TW200938614A - CMP slurry composition and process for planarizing copper containing surfaces provided with a diffusion barrier layer - Google Patents

Abstract

A CMP slurry composition for planarizing surfaces comprising copper and a diffusion barrier layer comprising: an abrasive, an oxidizer, a corrosion inhibitor, a monomeric polyhydroxy compound, a base, the slurry composition having a pH of from 7 to 13.

Description

200938614 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to the manufacture of integrated circuits, particularly regarding the chemical-mechanical polishing of button barrier layers used in copper metallization. [Prior Art] - As the integrated circuit device shrinks, the semiconductor device geometry reaches a minimum physical size of 0.18 - micron' and as the circuit speed and performance increase, copper has replaced the lower electrical interconnect material. The need for interconnect resistivity, good electromigration resistance, and good deposition characteristics that allow efficient filling of vias and contacts has been used as an interconnect material in entangled circuits. Copper metallization structures are typically formed by the so-called damascene process. An insulating layer called an interlayer electrolyte (ILD) separates the metal layer in the multilayer metallization structure. An ILD dielectric layer composed of a bottom layer and a top low dielectric constant layer has an area etched to the interior of the metal line to be embedded. A barrier layer is deposited to prevent copper from diffusing into the 54 dielectric. This barrier layer is generally composed of a Ta or Ta compound. A copper seed layer is then deposited, followed by an electroplated copper layer. Excess copper is then removed by a process known as chemical mechanical polishing (CMP). CMp improves surface material removal over long and short distances by mechanically abrading the surface under chemical etchant selection. To this end, CMp utilizes a polishing slurry that contains both an abrasive and a chemically active component. Generally, in copper damascene processing, CMP is performed in two steps. The first CMp step removes excess copper from the wafer surface, and may remove some or all of the 134940.doc 200938614 and then perform a second CMP step, the purpose of which is to completely remove the dielectric surface between the Cu lines. & layer and 2) flatten the surface to compensate for the cu dish-shaped depression and surname. For the second purpose, the second CMp step needs to have the best selectivity between the dielectric, the dielectric and the barrier, so that the Cu dishing generated during the first step cMp is most suitably compensated. A polished surface (both Cu and _2) that is equally important for such structures is related to surface damage/roughness and & quality on the surface. (10) Post-cleaning only removes solid particles and ionic contamination of the material (10) The sputum designed to polish the layer containing the nucleus usually contains abrasives (eg, sorghum, titanium dioxide, oxidizing, oxidizing agents (eg hydrogen peroxide), blocks Acid unloading or potassium ferricyanide) and other additives as needed. If an invasive polishing method is used to remove the chemically blunt and mechanically hard layer comprising the group, it will generally damage the soft surface layer placed under the layer, such as a low or a κ material.

Ta barrier polishing results in dishing and dishing, depending on polishing selection. Selective 1-shaped depressions and inverted dish-shaped depressions refer to recessed and convex metal interconnects, respectively, compared to adjacent dielectric films. . A preferred abrasive for the Ta barrier throwing liquid is oxygen cutting, but other abrasives such as alumina can be used. The benefits of using a dioxic abrasive instead of the alumina abrasive commonly used in other CMP applications include: 1) increased Ta removal rate, 2) enhanced ability to polish oxide dielectrics for planarization, and 3) Reduce the possibility of damage to oxides and surfaces. A conventional dioxic slurry for Ta barrier polishing comprises 20 to 200 nm diameter pores of porphyrin suspended in water 134940.doc 200938614 medium. To avoid copper rot (4) during and after polishing, compounds that inhibit steel corrosion (such as benzotrisole or mountain-three sputum (hereinafter referred to as "three saliva, ·)) are generally soluble in the liquid medium, suspended The pH of the liquid is adjusted between pH 7 and pH 1 〇.5, which is the range of empirical values that produce the minimum corrosion rate. The effect of different tests in the CMP slurry was investigated in a thin solid film 498 (2〇〇6)6〇63. It was found that K〇H is a pH regulator suitable for a colloidal cerium oxide-based CMP slurry. ❹

The by-product of the polishing process causes the slurry medium to contain dissolved or insoluble dielectric, copper and buttons in addition to the liquid component. In the prior art, after the copper CMp of the cerium oxide slurry was used, two solid defects were also found after using the copper CMp of the alumina slurry (the presence of Si 〇 2). These defects include precipitation and copper stains. Compounds (also known as "Cu passivators'), such as triazole compounds, which inhibit copper corrosion in the slurry were found to substantially increase the occurrence of such defects. The precipitation residue contained in a portion of the conductor material negatively affects device yield and reliability', e.g., causing short circuits and/or leakage between the two wires. Residues and precipitates Also prevent the dielectric barrier from effectively sealing the top surface of the copper wire, causing copper to diffuse into the dielectric and provide an electromigration path on the surface of the copper atom. In WO 02/05 1955, a slurry for etching a barrier layer comprising a cerium oxide abrasive, a copper corrosion inhibitor (for example triazole or benzotriazole) and a polyvinyl alcohol (PVA), ρνΑ· Poly(vinyl acetate) copolymer, PVA-polyethylene copolymer, sorbitol, glycerin, polypropylene decylamine, ethylene glycol, di(ethylene glycol), poly(ethylene glycol) (PEG) , polyoxyethyl glyceryl ether (GEO) 'polydimethyl siloxane-ethylene oxide copolymer 134940.doc 200938614 (DMSiO-EO), polyepoxy surfactant, octyl anti-epoxy Fully analog of ethane, nonylphenol polyethylene oxide, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyethylene oxide surfactant, polyoxypropyl Gan (4) Organic Addition of (GPO), Organic Amine, N, N•Diethylcyclohexylamine (dca) and Polyethylamine_) The results of the experiment are based on specific oxidizing agents, triterpenes, and dices. A slurry consisting of diol) (〇£(}) and 1) 1^ about 9 water is provided. Low molecular organic additives such as DEG are reported to result in worse results than polymeric additives such as PEG. The use of oxidizing agents is not disclosed. WO 02/059393 relates to an acid-based barrier sCMp slurry having an almost 1:1 removal rate for ~ and Ta/TaN to achieve a single step polishing. The common slurries described herein include abrasives (such as ceria or alumina), oxidants (such as HN〇3, H2〇2), and corrosion inhibitors (such as BTA). The slurry additionally uses other additives such as mono- and polyhydroxy compounds (e.g., ethanol, propanol, or glycerin). KOH can be used as a pH adjuster. Further, WO 〇 2/〇 59393 discloses an alkaline slurry comprising a base such as KOH or NHaOH and an oxidizing agent such as H2〇2 or (nh4)2S208, optionally with various other additives. Polyhydroxy compounds are used only in acid slurries. In WO 2004/033574, the slurry flattens the copper-containing surface (especially the Cu/Ta surface). The slurry contains an abrasive (such as cerium oxide having an average particle diameter of 100 nm or more) and an oxidizing agent (such as H2 〇 2). , corrosion inhibitors (such as BTA), specific amphoteric nonionic surfactants and organic acids. According to Example 1, the pH system was adjusted from KOH to pH 10. The slurry contains further components as needed. One of these is a complexing agent such as a di-, tri-, or polyhydric alcohol such as ethylene glycol, coke tea, coke hunts, tannins, and the like. 134940.doc -9· 200938614 However, while the design of barrier CMP slurries is highly advanced, there is still a need for barrier CMp slurries and methods that provide extremely high polishing rates and reduced dishing and corrosion. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a CMp slurry which provides increased button removal rates and low scratch and low corrosion of low copper layer dishing and dielectric layers. It is a further object of the present invention to provide a barrier CMp slurry that is easily adjusted to a predetermined selectivity for the removal rate of the button or TaN, dielectric and copper. [Embodiment] According to a first aspect of the present invention, there is provided a slurry composition for planarizing a surface comprising copper and a diffusion film layer, the slurry comprising: - an abrasive; - an oxidizing agent; - a residual inhibitor; - a monomer Sexual polyol; • Test; ❹ The slurry composition has a pH of 7 to 13. This can achieve extremely high barrier polishing rates. Other advantages of the invention will be apparent from the following description of the preferred embodiments. In a preferred embodiment, the barrier CMP slurry does not comprise a polymeric polyhydroxy compound. According to a second aspect of the present invention, there is provided a method of polishing a substrate comprising at least one metal layer (the metal layer comprising copper) and at least one diffusion barrier layer, the method comprising: 134940.doc • 10. 200938614 i) The material is contacted with a chemical-mechanical polishing composition comprising: • an abrasive, • a heterocyclic compound containing N, a monomeric polyhydroxy compound, an assay, an oxidizing agent as needed, and a phlegm; Adjusting to a value of 7 to 13, and U1) oxidizing at least a portion of at least one metal layer and at least a portion of at least one diffusion barrier layer, iv) grinding at least one metal layer and at least one diffusion barrier layer to planarize the substrate. According to a further aspect of the present invention, there is provided a method of adjusting a removal rate selectivity r(Ta)/r(Cu) and/or r(dielectric)/r(Cu) of a slurry of a polishing substrate, the substrate The method comprises at least one metal layer, at least one diffusion barrier layer and at least one dielectric layer, wherein the metal layer comprises copper, the method comprises adding a monomeric polyhydroxy compound to the slurry to increase the removal rate selectivity r(Ta) /r(Cu) and / or r (dielectric) / r (Cu) until a specific removal rate selectivity r (Ta) / r (Cu) and / or r (dielectric) / r (Cu Where 'r(Ta) is the removal rate of the diffusion barrier layer, r(Cu) is the removal rate of at least one metal layer containing copper and r (dielectric) is the removal of the dielectric layer rate. Another aspect of the invention is the removal rate selectivity r(Ta)/r of the monomeric polyol in the polishing slurry comprising at least one metal layer, at least one diffusion barrier layer and at least one dielectric layer. Use of Cu) and / or r (dielectric) / r (Cu) 'The metal layer contains copper, where r (Ta) is the diffusion barrier layer removal rate 134940.doc -11- 200938614 rate r (Cu) The removal rate of at least one metal layer containing copper, and r (dielectric) is the removal rate of the dielectric layer. The invention is further illustrated by the following preferred examples, which are not intended to limit the scope of the invention. The abrasive may have any suitable particle size and is selected from the group consisting of ceria, cerium oxide, titanium dioxide, lead oxide, co-formed particles thereof, polymer particles, polymer coated particles thereof, coated with a polymer. Bauxite and its group

. a group of people. The abrasive is preferably a cerium oxide abrasive or an alumina abrasive coated with a polymeric dielectric (for example, an alumina abrasive coated with polystyrene sulfonic acid). The polishing is easily performed by a hard abrasive (for example, alumina). In the case of abrasives, such as a soft metal layer (for example, steel), a cerium oxide abrasive and a polymer-coated alumina abrasive are preferred. The abrasive generally has an average primary particle diameter of 1 Å nm or more, preferably 2 Å nm or more, and most preferably 25 nm or more. In this paper, the term "particle size" is synonymous with "average particle diameter". The average primary particle size is generally 1 micron or less, more preferably 500 nm or less, even more preferably 100 nm or less, and most preferably 8 Å nm or less. The abrasive preferably has a primary particle size of from 2 Å to 1 Å nm, especially even ribs nm. The particle size can be determined by sieve analysis or optical methods such as transmission electron microscopy. The reference method for determining the average diameter is by means of transmission electron microscopy. The particles may have a monomodal, bimodal or multimodal particle size distribution with a simple unimodal distribution. The abrasive may be composed of one or more types of abrasive particles, preferably using a single particle type. J34940.doc 12 200938614 The abrasive preferably comprises a dioxin. The preferred amount of the abrasive is a silica dioxide. The best abrasive consists mainly of cerium oxide. The ruthenium dioxide-based particles are preferably produced by a sol-gel process. Ο

The abrasive of any of the embodiments described herein is preferably stable. Glue refers to the abrasive particles (4) in the liquid carrier. The colloidal stability refers to the suspension and the time remains unchanged. In the present invention, when the abrasive is placed in a 100 1 cylinder and allowed to stand without agitation for 2 hours, the particle concentration of the bottom end W of the cylinder ([] 乂 g / mW τ ) and the top of the cylinder 5 〇 ... particle concentration ([ The difference in (10) is divided by the initial concentration of the particles in the polishing composition (indicated by [c]wg/mi) is less than or equal to 0.8, and the abrasive is considered to be colloidal stability. The β usually abrasive particles can be prepared by any known method as long as the foreign ion contains 罝 as low as * affects the semiconductor processing. The content of foreign ions in the ruthenium dioxide is preferably less than 1 ppm. Colloidal silica is preferably used as an abrasive. Asphalt cerium oxide having a high removal rate can also be used 'but generally produces more severe scratch defects and poor colloidal stability and is therefore not a priority. In a preferred embodiment, the colloidal cerium oxide is prepared by a sol gel process from tetramethyl orthoformate (TMOS) or tetraethyl orthophthalate (TE〇s). The dioxide dream is commercially available, for example, from Fuso Chemicals. When such a type of cerium oxide is utilized, the stability of hydrogen peroxide in the slurry is particularly high. The abrasive can be of any suitable shape. The abrasive may be spherical or non-spherical, non-spherical. The non-spherical particles are, for example, the blue shape described in US 2005/0258139 A1 and available from Fuso. Alternatively, the shape may be a knot as described in w 〇 03/042322 A1. In particular, the enamel-shaped particles exhibit an increased polishing rate and a polishing rate of the Ta/TaN barrier layer to copper increased by 134940.doc 13 200938614. Although the fuso pl3 particle size is small, the removal rate for Ta is significantly higher than the removal rate of the reference cerium oxide, and the copper removal rate is reduced. The polishing slurry generally comprises from 0.1% by weight to 3% by weight, preferably from 1% by weight to 25% by weight, even more preferably from 3% by weight to 20% by weight, even more preferably from 5% by weight to 18% by weight, most preferably 7% by weight Up to 15% by weight of abrasive. The barrier CMP slurry according to the present invention further comprises an oxidizing agent. The oxidizing agent can be any compound suitable for oxidizing the barrier substrate. Oxides may be omitted from the slurry and replaced or supplemented by electrochemical methods. In an electrochemical polishing system, the means for oxidizing the substrate preferably comprises means for applying a time varying potential to the substrate, e.g., as described in U.S. Patent No. 6,379,223. The chemical oxidant can be any suitable oxidant. Suitable oxidizing agents include inorganic and organic per-compounds, bromates, nitrates, sulphonates, chromates, iodates, irons and copper salts (eg, nitrates, sulfates, ethylenediamine-tetraacetic acid) EDTA) and citrate), rare earths and transition metal oxides (for example, tetraoxide), potassium ferricyanide, potassium dichromate, iodic acid, and the like. According to the invention, the per-compound is a compound comprising at least one peroxy group 〇 〇 〇 ) or a compound comprising an element present in the highest oxidation state. Examples of compounds containing at least one peroxy group include, but are not limited to, pervaporated hydrogen and its adducts such as urea hydrogen peroxide and percarbonate, organic pervaporates such as benzamidine peroxide, peracetic acid And di-tert-butyl peroxide, monopersulfate (SO52·), double persulfate do〆) and sodium peroxide. Examples of compounds containing the elements present in the highest oxidation state include, but are not limited to, periodic acid, periodate, high bromate, perbromate, high gas and high 134,940.doc •14-200938614 (tetra) acid , (iv) acid salt and per-acid salt. The oxidizing agent is preferably over. The polishing system, especially the cMP system (especially the polishing combination), generally comprises from 0.01% by weight to 5% by weight, preferably from 3% by weight to more preferably from 0.05% by weight to 3% by weight, preferably 〇〇 5 wt% by weight of oxidant.

The corrosion inhibitor can be any suitable corrosion inhibitor. Generally, the corrosion inhibitor is an organic compound containing a functional group containing a hetero atom. The corrosion inhibitor is preferably a rhodium-containing heterocyclic compound. For example, the corrosion inhibitor is a heterocyclic organic compound having at least one or a heterocyclic ring as a reactive functional group, wherein the heterocyclic ring contains at least a nitrogen atom, such as a "sitting compound. The corrosion inhibitor is preferably a triazole compound, more preferably hydrazine, 2,4•triazole, '2,3-seat, or benzobisazole. The corrosion inhibitor used in the polishing system is generally 0.0001 to 3% by weight, preferably 〇1 to 2 by weight. The optimum is 0.002 to 0.3% by weight. The most preferred is benzotriazole because it does not significantly affect the removal rate of Ta/TaN and oxide. Since benzotriacetate and other rot (iv) preparations have a low degree of resolution in water, it is preferred to dissolve the stupid triazole in the monomeric polyol when the barrier CMp slurry is produced. The liquid carrier is used to assist the application of the abrasive to the surface of a suitable substrate to be polished, and as a suspending medium for the abrasive and other components of the barrier CMp slurry or a mixture or suspension medium. The liquid carrier is preferably an aqueous carrier and may be only water, may comprise water and a suitable solvent in admixture with water, or may be an emulsion. Suitable solvents to be mixed with the aqueous phase include alcohols such as methanol, ethanol and the like. The aqueous carrier is preferably substantially composed of water, preferably deionized water. 134940.doc • 15· 200938614 The polishing composition further comprises a base which increases the pH to a strong base. The higher the pH, the higher the removal rate of the dielectric film (including TEOS, FSG, and black diamond (BD) films). Higher pH values also improve the removal rate of tantalum and tantalum nitride films. The copper film removal rate decreases as the pH increases. The polishing composition has a pH of from 7 to 13. It is preferred to use a pH having a pH of 8 to 12, more preferably a pH of 8.5 to 11, and most preferably a slurry having a pH of 9 to 1 〇. The test may be any strong or weak base such as an alkali metal hydroxide, ammonia, a first, second or third ammonium hydroxide, a quaternized hydroxide such as tetramethylammonium hydroxide (TMAH) or the like. KOH is best used because KOH has an improved effect on the polishing rate of the button and no corrosion to copper compared to other bases. The alkali concentration is preferably from 0.01 to 5% by weight, more preferably from 0.2 to 3% by weight, most preferably from 0.05 to 2% by weight. The test (good KOH) needs to be pure enough to avoid rapid decomposition of hydrogen peroxide. Excessive metal impurities (e.g., Fe, Cu) are preferably less than 1 ppm. It has been surprisingly found that monomeric polyols such as ethylene glycol improve the removal rate of Ta, TaN and oxide (dielectric). In contrast, polyols reduce the rate of copper removal. Therefore, a monomeric polyhydroxy compound, particularly ethylene glycol or propylene glycol, can be used as a removal rate enhancer for Ta, TaN and oxide layers, and a copper removal rate reducing agent. If Ta/TaN* Si〇2 is present in combination with copper, the removal rate selectivity of the slurry should be adjusted. Figure 1 shows the dependence of Ta, oxide and removal rate on the ethylene glycol content of the slurry prepared according to Example 1 (see Table 1). The removal rate of Ta and oxide increased significantly with increasing ethylene glycol content, from less than 134940.doc -16 to 200938614 600 to still 700 A/min, and from about 330 to about 430 A/min, respectively. The copper removal rate is significantly reduced from about 450 to about 350 A/min. Monomeric polyols also improve polishing uniformity, as shown in Figure 2. The slurry was prepared according to Example 1. The non-uniformity can be determined from the 49 point measurement on the wafer. The unevenness ^^; can be calculated by NU [%] = standard deviation (RRn) / RRm by the removal rate RR across the points on the wafer, where RRm is the average of the removal rates. Choose a point that is at least 5 from the edge. The polishing composition further comprises a monomeric polyol. The polyhydroxy group according to the present invention means a compound containing two or more hydroxyl groups, preferably two, three or four vials. Further, the monomeric polyol has a function as a button surface removal rate repellent. On the other hand, it acts as a dissolution promoter for a corrosion inhibitor, a wetting agent, and a lubricant. The monomeric polyhydroxy composition is preferably selected from the group consisting of the compound of formula I, HO-CCR'R^n-OH (1) wherein R1 is Η, CVC4 alkyl, R2 is Η, C丨-C4 alkyl or 〇H and n is 2 to 6. More preferably, the monomeric polyhydroxy compound is selected from the group consisting of a compound of the formula wherein R1 and R2 are each a hydrazine or a Ci-C2 alkyl group and η is 2 to 4. The monomeric polyhydroxy compound is preferably selected from the group consisting of ethylene glycol. Propylene glycol or glycerin, especially ethylene glycol. The barrier CMP slurry preferably contains from 0.1 to 2% by weight, more preferably from 2 to 15% by weight, even more preferably from 0.3 to 10% by weight, even more preferably from 3 to 8% by weight, even better. 4 to 6% by weight, even more preferably 4 to 5% by weight, most preferably 0.5 to 4 by weight. /. The amount of monomeric polyol. 134940.doc 17 200938614 The monomeric polyol is preferably penetrating and completely soluble in a liquid carrier such as water. The CMP system can be packaged as needed - one or more pH adjusters, modifiers, or buffers. The pH adjuster can be (partially) compensated for J J horse strength or weak acid to adjust the pH to the desired value. Bismuth can be organic or inorganic, and organic acids are preferred. Suitable pH adjusting agents, conditioning agents, or buffering agents may include, for example, sulfuric acid, hydrochloric acid, acetic acid, nitric acid, acid acid, citric acid, squama, and mixtures thereof. The best pH regulator is acetic acid because it increases the copper removal rate and improves the copper surface flatness.

❹ The CMP system further satisfies ^, ‘a with its constituents as needed. These other components include mis- or chelating agents, biocides, antifoaming agents, and the like. Surfactants can also be used in barrier CMP slurries. It is preferred to use a nonionic surfactant, if any. In a preferred embodiment, an ethoxylated aliphatic alcohol (e.g., Trit® DF16 from Dow Chemical) can be used to reduce the rate of removal of the black diamond film of the cover layer by a nonionic surfactant. In a preferred embodiment, the slurry consists essentially of an abrasive, an oxidizing agent, a heterocyclic compound containing N, a monomeric poly-based compound, 35, a liquid carrier, and optionally an organic acid, all of which are selected individually. From a single compound or a mixture of compounds. In another preferred embodiment, the slurry is primarily composed of cerium oxide, an oxidizing agent, a heterocyclic compound containing N, a monomeric polyol, and a liquid carrier with an optional organic acid and/or a nonionic surfactant. composition. In another embodiment, the slurry consists essentially of an abrasive, an oxidizing agent, a triterpene compound, a test, ethylene glycol and water, and optionally an organic acid and/or a nonionic surfactant. In another embodiment, the slurry is mainly composed of an abrasive, 134940.doc -18 - 200938614 Η"2, a triterpenoid, KOH, ethylene glycol, water, and optionally acetic acid and/or a nonionic surfactant. composition. In a preferred embodiment, the slurry consists essentially of cerium oxide, H2 cerium 2, benzotriazole, K 〇 H, ethylene glycol, citric acid, a nonionic surfactant, and water. The barrier CMP slurry is used to polish (or planarize) a substrate comprising a copper layer and a barrier layer. The substrate is typically a microelectronic (e.g., semiconductor) substrate and, if desired, a dielectric layer. The dielectric layer may have any suitable ruthenium (e.g., 3.5 or more, or 3.5 or less). For example, the dielectric layer may be ruthenium oxide or organically modified bismuth glass, such as carbon doped ruthenium dioxide. Formed by etching an etched trench or via hole into a dielectric layer, such as hafnium oxide. The trench or via is then lined with a thin barrier film, such as by physical vapor deposition (PVD), or via Chemical vapor deposition (CVD). Then, a copper layer is deposited on the barrier film to completely fill the trench and via holes and cover the barrier film. The first CMp process is performed to remove the conductor metal layer downward until the barrier film. The barrier CMp slurry of the present invention is subjected to a first human CMP process to remove the barrier film and any excess conductive metal layer down to the dielectric material. During the first CMP process, the via hole or trench Unacceptable conductor metal layer dish (4), and unwanted dielectric material scratches or corrosion. Combination of components, especially ethylene glycol in the barrier CMp slurry can reduce the copper layer dishing during the barrier layer removal ^, and / or reduce dielectric Scratch and/or rot #. The diffusion barrier layer is preferably such that the CMP system is particularly suitable for use with chemical mechanical polishing (cMp). The device typically comprises a pressure plate (when used, it is at 134940.doc) 200938614 motion state with speed due to orbital, linear or circular motion), a polishing pad that contacts the platen and moves with the platen as it moves, and a bracket that holds the substrate to contact and relative Polishing the surface of the polishing pad to be contacted with the substrate to be polished to polish the substrate to be polished.) generally contacting the polishing pad via the substrate and then moving the polishing pad relative to the substrate (generally having the polishing composition of the present invention interposed therebetween) Polishing the substrate to polish at least a portion of the substrate' to polish the substrate. The CMP device can be any suitable CMP device, as is known in the art. All percentages, ppm or ratios are relative to the respective mixture. The weight of the total weight, unless otherwise stated, is incorporated herein by reference. Example 1: A similar patterned substrate comprising copper, button and cerium oxide dioxide is used. Polished by an aqueous button barrier slurry containing the following components: a) Abrasive. Colloidal, spherical ceria (Fus〇 Quartr〇n pL3, average particle size 30 nm, 茧 shape) b) Oxidizer: H202

c) Alkali: KOH d) Monomeric poly-based compounds: ethylene glycol; and e) Corrosion inhibitors: benzotriazoles The concentrations and additional components and process conditions are listed. Table i and Figure i show the effect of ethylene glycol on the removal rate of the group and oxide removal rate and the reduction rate of copper removal rate. In addition, Table i and Figure 2 show the removal rate uniformity when using ethylene glycol. 134940.doc •20· 200938614 Table 1 1 2 3 Ceria type Fuso PL3 Fuso PL3 Fuso PL3 cerium oxide [° /〇] 10 10 10 0.09 0.09 0.09 Organic acid [%] Acetic acid acetate Γ%1 0,17 0,17 0,17 pH 8,7 8,7 8,7 H2O2(30%) [%1 0.35 0.35 0.35 Ethylene Glycol 0% 1% 2% BTA [ppm] 0 0 0 Surfactant [%] 0 0 0 Polishing Pressure [kPa] 20.7 (3 psi) 20.7 (3 psi) 20.7 (3 psi) Pad Polytex Polytex Polytex Ta 586 653 719 Cu 454 367 346 Removal rate [A/min] Oxide 337 392 441 Ta 4,05% 3,2 2,7 Cu 8,5 6,6 5,3 Unevenness [%] Oxide 6 3,2 3,3

The H202 concentration in the table refers to the content of 30% H2〇2 in water (unlike the above description regarding the absolute H2〇2 content). Example 2: Example 1 was repeated to change the composition in the barrier CMP slurry. All relevant data are listed in Table 2. Table 2: 4 5 6 7 8 9 cerium oxide type Bayer 50CK Bayer 100CK Fuso PL3 Fuso PL3 Fuso PL3 Fuso PL3 cerium oxide [%] 10 10 14 19 14 14 organic acid 0.09% acetic acid 0.09% acetic acid 0.14% acetic acid 0.06% Oxalic acid 0.15% citric acid 0.15% citric acid KOH [%] 0.10 0,10 0.25 0.40 0.25 0.25 pH 8.7 8.7 9.6 9.5 9.8 9.8 H2O2 (30%) [%] 0.35 0.35 0.35 0.35 0.70 0.70 Ethylene glycol [%] 1 1 1 1 2 2 BTA [ppm] 0 0 100 100 0 0 Surfactant [ppm] 0 0 0 0 0 200 Triton X-100 Polishing pressure [Pa] 20.7 20.7 13.8 10.3 13.8 13.8 (3psi) (3psi) (2 psi (1.5 psi) (2 psi) (2 psi) -21 - 134940.doc 200938614 4 5 6 7 8 9 Pad Polytex Polytex Polytex Polytex Hard Cushion Removal Rate Ta 290 254 700 548 660 810 [A/min] Cu 313 355 300 216 469 488 Oxide 224 299 666 363 827 944 BD - - - 763 925 360 Unevenness Ta 6.3 6.6 5.2 8 8.36 4.5 [%] Cu 14 16 6.1 10.2 10 10 Oxide 10.3 8.7 5.1 1.6 6.8 6.6 BD - - - 11.4 7.5 21.6 [Simple description of the diagram] Figure 1 Correlation between removal rate and monomeric polyol concentration; Figure 2 removal rate Compound concentration unevenness and related monomeric polyhydroxy

❿ -22- 134940.doc

Claims (1)

200938614 X. Patent Application Range: 1. A CMP slurry composition for planarizing a surface comprising copper and a diffusion barrier layer, comprising: - an abrasive; - an oxidizing agent; - a silver rot inhibitor, - a monomeric polyhydroxy group Compound; - test, φ The slurry composition has a pH of 7 to 13. 2. The CMP slurry composition of claim 1 which does not comprise a polymeric polyhydroxy compound. 3. The CMP slurry composition of claim 1, which is mainly composed of: - an abrasive; - an oxidizing agent; - a heterocyclic compound containing N; - a monomeric or oligomeric polyhydroxy compound; And - liquid carrier. 4. The CMP slurry composition of any one of claims 1 to 3, wherein the abrasive comprises cerium oxide. The CMP slurry composition of any one of claims 1 to 3, wherein the abrasive is non-spherical. 6. The CMP slurry composition of any of claims 1 to 3, wherein the abrasive has an average diameter of from 20 to 100 nm, especially from 25 to 80 nm. The CMP slurry composition of any one of clauses (1), wherein the oxidizing agent comprises hydrogen peroxide. The poly-liquid composition of (10) according to any one of claims 1 to 3, wherein the residual inhibitor is a heterocyclic compound containing N, especially benzotriazole, 6-tolyltriazole 1,2,3-triazole, i24 one or two π sitting and combinations thereof. The CMp slurry composition according to any one of claims 3 to 3, wherein the monomeric polyol is a dihydroxy compound having 2 to 6 carbon atoms. ® W The clear liquid composition of claim 9, wherein the di-based compound is selected from the group consisting of ethylene glycol and propylene glycol. The CMP slurry composition according to any one of claims 1 to 3, wherein the monomeric poly-based compound is present in the CMP slurry in an amount of from 0.3 to 1 M% by weight, especially from 4 to 5% by weight. The CMp slurry composition according to any one of the preceding claims, wherein the base is KOH. 13. The CMp slurry composition of any of claims 3 to 3, wherein the slurry has a pH of from 8.5 to 11, especially from 9 to 10.5. 14. Use of a CMp slurry composition according to any one of claims 1 to 13 for planarizing a substrate comprising at least one metal layer comprising copper and a diffusion barrier material. 15. A method of polishing a substrate comprising at least one metal layer and at least one diffusion barrier layer, the metal layer comprising copper, the method comprising: 1) contacting a substrate with a chemical-mechanical polishing composition, the composition comprising : 134940.doc 200938614 _Abrasives, "resistance inhibitors, -monomeric polyols, -test, - oxidizing agents as needed; ii) adjusting the pH to values between 7 and 13, and • iii) Oxidizing at least a portion of the at least one diffusion barrier layer, W) grinding at least one metal layer comprising copper and at least a portion of the diffusion barrier layer to planarize the substrate. The method of claim 15, wherein at least one of the metal layer comprising copper and the at least one diffusion barrier layer are oxidized by a chemical oxidant. 17. The method of claim 15 or 16, wherein at least one of the metal layer comprising copper and the at least one diffusion barrier layer are oxidized by electrochemical means. 18. The method of claim 15 or 16, wherein the slurry of any one of claims 1 to 14 is used. 19. The method of claim 15 or 16, wherein the rate of removal of the diffusion barrier layer is at least 100 times faster than copper. 20. The method of claim 15 or 16, wherein the diffusion barrier layer comprises tantalum or .TaN. 21. A method of adjusting a slurry removal rate selection and/or "(dielectric) / r (Cu) to polish a substrate comprising at least one metal layer, at least one diffusion barrier layer and at least a dielectric layer comprising copper'. The method comprises adding a monomeric poly-based compound to the poly-liquid to increase the removal rate selectivity r(Ta)/r(Cu) and/or r (dielectric /r(Cu) up to 134940.doc 200938614 to obtain a specific removal rate selectivity r(Ta)/r(Cu) and/or r(dielectric)/r(Cu), where r(Ta) is diffusion The removal rate of the barrier layer, r(Cu) is the removal rate of at least one metal layer containing copper, and r (dielectric) is the removal rate of the dielectric layer. 22. A monomeric polyhydroxy compound The use of polishing a substrate to adjust a slurry removal rate selectivity r(Ta)/r(Cu) and/or 1 (dielectric)/r(Cu)a, the substrate comprising at least one metal layer, at least one a diffusion barrier layer and at least one dielectric layer 'where the metal layer comprises copper, wherein r(Ta) is a removal rate of the diffusion barrier layer, r(Cu) is a removal rate of at least one metal layer containing copper and r (dielectric) Layer removal rate. 134940.doc