KR20190132537A - Self-Stop Polishing Compositions and Methods for Bulk Oxide Flattening - Google Patents

Abstract

The present invention provides a chemical-mechanical polishing composition comprising an abrasive, a self-stopping agent, an aqueous carrier, and optionally a cationic polymer, and provides a method suitable for polishing a substrate.

Description

Self-Stop Polishing Compositions and Methods for Bulk Oxide Flattening

In the fabrication of integrated circuits and other electronic devices, multilayer conductors, semiconductors, and dielectric materials are deposited on or removed from the substrate surface. As layers of material are sequentially deposited on and removed from the substrate, the top surface of the substrate may be non-planar and require planarization. Planarizing or "polishing" the surface is a process by which material is removed from the surface of the substrate to form a generally flat, planar surface. Planarization is useful for removing unwanted surface topography and surface defects such as rough surfaces, aggregated material, crystal lattice damage, scratches, and contaminated layers or materials. Planarization is also useful for forming features on substrates by removing excess deposited material used to fill features and provide a flat surface for subsequent levels of metallization and processing.

Compositions and methods for planarizing or polishing the surface of a substrate are well known in the art. Chemical mechanical planarization or chemical mechanical polishing (CMP) is a common technique used to planarize a substrate. CMP utilizes a chemical composition known as a CMP composition or more simply a polishing composition (also referred to as a polishing slurry) to selectively remove material from the substrate. The polishing composition is typically applied to the substrate by contacting the surface of the substrate with a polishing pad (eg, polishing cloth or polishing disk) saturated with the polishing composition. Polishing of the substrate is typically further assisted by the chemical action of the polishing composition and / or the mechanical action of the abrasive suspended in the polishing composition or incorporated into the polishing pad (eg, a fixed abrasive polishing pad).

As the size of integrated circuits decreases and the number of integrated circuits on a chip increases, the components that make up the circuit must be placed closer to each other to accommodate the limited space available on a typical chip. Efficient isolation between circuits is important to ensure optimal semiconductor performance. For that purpose, shallow trenches are etched into the semiconductor substrate and filled with insulating material to isolate the active regions of the integrated circuit. More particularly, shallow trench isolation (STI) is a process in which a silicon nitride layer is formed on a silicon substrate, shallow trenches are formed through etching or photolithography, and a dielectric layer is deposited to fill the trench. Due to the change in trench depth formed in this manner, it is typically necessary to deposit excess dielectric material on top of the substrate to ensure complete filling of all trenches. Dielectric material (eg, silicon oxide) depends on the topography underneath the substrate.

Thus, after the dielectric material is disposed, the surface of the deposited dielectric material is characterized by an uneven combination of raised areas of the dielectric material separated by trenches in the dielectric material, wherein the raised areas and trenches of the dielectric material Aligned with the corresponding raised regions and trenches of the surface. The area of the substrate surface including the elevated dielectric material and trenches is referred to as the pattern field of the substrate, for example "pattern material", "pattern oxide" or "pattern dielectric". The pattern field is characterized by a "step" which is the difference in the height of the raised region of the dielectric material with respect to the trench height.

Excess dielectric material is typically removed by a CMP process, which additionally provides a planar surface for further processing. During removal of the elevated region material, a certain amount of material from the trench will also be removed. This removal of material from the trench is referred to as "trench corrosion" or "trench loss". Trench loss is the amount of material removed from the trench (in thickness, eg, angstroms) in achieving planarization of the pattern dielectric material by removing the initial step. Trench loss was calculated as the initial trench thickness minus the final trench thickness. Preferably, the rate of material removal from the trench is much lower than the rate of removal from the raised area. Thus, when the material in the elevated region is removed (at a faster rate compared to the material removed from the trench), the pattern dielectric is in the "blanket" region of the processed substrate surface, for example "blanket dielectric" or "blanket oxide." A highly planarized surface, which may be referred to as ".

The polishing composition may be characterized according to its polishing rate (ie, removal rate) and its planarization efficiency. Polishing rate refers to the rate of removal of material from the surface of a substrate and is usually expressed as a unit of length (eg per minute) in length (eg per minute). Different removal rates associated with different areas of the substrate, or different steps of the polishing step, may be important in evaluating process performance. The "pattern removal rate" is the rate of removal of the dielectric material from the elevated region of the patterned dielectric layer at the stage of the process, during which the substrate exhibits a substantial step. "Blanket removal rate" refers to the rate of removal of dielectric material from the planarized (ie, "blanket") region of the patterned dielectric layer when the step is significantly (substantially overall) reduced. Planarization efficiency relates to step reduction (ie step reduction divided by trench loss) relative to the amount of material removed from the substrate. Specifically, the polishing surface, for example the polishing pad, must first contact the "high point" of the surface and remove the material to form a planar surface. Processes where a planar surface is achieved with less material removal are believed to be more efficient than processes requiring more material removal to achieve planarity.

Often the removal rate of silicon oxide pattern material can be rate-limiting for the dielectric polishing step during the STI process, so high removal rates of silicon oxide pattern are desirable to increase device throughput. However, if the blanket removal rate is too fast, overpolishing of oxides in the exposed trenches results in trench erosion and increased device defects. Overpolishing and associated trench loss can be avoided when the blanket removal rate is lowered.

In certain polishing applications, the CMP composition preferably exhibits a “self-stop” behavior where the removal rate decreases when a large percentage of the “high point” (ie, elevated area) of the surface is removed. In self-stop polishing applications, while there is a significant step on the substrate surface, the removal rate is effectively high, then the removal rate is lowered as the surface becomes effectively planar. In various dielectric polishing steps (eg, of the STI process), the removal rate of the patterned dielectric material (eg, dielectric layer) is typically a speed-limiting factor of the overall process. Thus, high removal rates of pattern dielectric material are desirable to increase throughput. Good efficiency in the form of relatively low trench losses is also desirable. In addition, if the removal rate of the dielectric remains high after achieving planarization, overpolishing occurs and a trench loss is added.

The benefit of the self-stopping slurry comes from the reduced blanket removal rate, which creates a wide end window. For example, self-stop behavior allows polishing of substrates having a reduced dielectric film thickness, allowing a reduced amount of material to be deposited on the structured underlying layer. In addition, motor torque endpoint detection can be used for more effective monitoring of the final topography. The substrate can be polished under lower trench losses by preventing over-polishing or unnecessary removal of the dielectric after planarization.

Self-stopping CMP compositions have now been developed based on ceria / anionic polyelectrolyte systems. For example, US patent application publication 2008/0121839 discloses a polishing composition comprising an inorganic abrasive, a polyacrylic acid / maleic acid copolymer, and a gemini surfactant. Korean Patent No. 10-1524624 discloses a polishing composition (English abstract) comprising ceria, carboxylic acid and mixed amine compound. International Patent Application Publication No. WO2006 / 115393 discloses a polishing composition comprising ceria, hydroxycarboxylic acid and amino alcohol. However, as the structure of semiconductor devices becomes more complex, especially as the NAND technology moves from 2D to 3D, current self-stopping CMP compositions due to the use of anionic polymers result in electrostatic repulsion between the abrasive and the silicon oxide surface. This is a problem due to the limited step reduction rate caused by.

There remains a need for compositions and methods for chemical-mechanical polishing of silicon oxide-containing substrates that will also provide improved planarization efficiency while providing useful removal rates. The present invention provides such polishing compositions and methods. The above and other advantages of the present invention as well as additional inventive features will be apparent from the description of the invention provided herein.

The present invention provides a chemical-mechanical polishing composition comprising an abrasive, a self-stopping agent, an aqueous carrier, and optionally a cationic compound, and a method suitable for polishing a substrate using the polishing composition of the present invention.

More specifically, the invention relates to (a) an abrasive, (b) a self-stopping agent of formula QB wherein Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, and B is a bonding group, wherein A bonding group has a structure; C (O) —X—OH or —C (O) —OH, wherein X is a C 1 -C 2 alkyl group), and (c) an aqueous carrier, and has a pH of about 3 to about 9 It provides a chemical-mechanical polishing composition having a.

The present invention also provides an abrasive comprising (a) ceria, (b) kojic acid (5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one), crotonic acid ((E) -2 Butenoic acid), tiglic acid ((2E) -2-methylbut-2-enoic acid), valeric acid (pentanoic acid), 2-pentenoic acid, maltol (3-hydroxy-2-methyl-4H-pyran-4 -One), a self-terminating agent selected from benzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, caffeic acid, ethyl maltol, potassium sorbate, sorbic acid, and combinations thereof, and (c ) And a chemical-mechanical polishing composition comprising an aqueous carrier and having a pH of about 3 to about 9.

The present invention is also selected from (a) an abrasive comprising ceria, (b) a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), and combinations thereof A chemical-mechanical polishing composition comprising a self-stopping agent, (c) optionally a cationic polymer and (d) an aqueous carrier, having a pH of about 3 to about 9.

Wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocyclic alkyl, and heterocyclic aryl, each of which may be substituted or unsubstituted;

Wherein each X ¹ -X ³ is independently selected from N, O, S, sp ² -hybridized carbon, and CY ¹ Y ² , wherein each Y ¹ and Y ² are independently hydrogen, hydroxyl, C ₁ -C ₆ alkyl, halogen, and combinations thereof, each Z ¹ -Z ³ is independently selected from hydrogen, hydroxyl, C ₁ -C ₆ alkyl, and combinations thereof, each of which is substituted or unsubstituted Can be;

Wherein Z is selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkynyl, and aryl (eg, phenyl, benzyl, naphthyl, azulene, anthracene, pyrene, etc.) And X ¹ and X ² are independently selected from hydrogen, hydroxy, amino, and C ₁ -C ₆ alkyl, wherein X ¹ and X ² together with the attached carbon can form sp ² -hybridized carbon; , n is 1 or 2, p is 0-4, M is selected from hydrogen and a suitable counterion (eg, Group I metal), each of which may be substituted or unsubstituted;

Wherein X, Y and Z are independently selected from H, O, S, NH and CH ₂ , and R ¹ , R ² and R ³ are independently H, alkyl, alkenyl, alkynyl, aryl, halo and haloalkyl And M is selected from hydrogen and a suitable counterion.

The present invention further provides (i) a substrate comprising a patterned dielectric layer on the surface of the substrate, the patterned dielectric layer comprising a raised region (eg, an active area to a peripheral area) of a dielectric material, wherein the patterned dielectric The initial step of the layer is one describing the oxide thickness range (eg, active versus peripheral), (iii) providing the chemical-mechanical polishing composition described herein, (iv) polishing the substrate with a polishing pad and chemical- Contacting the mechanical polishing composition, (v) moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to polish at least a portion of the patterned dielectric layer on the surface of the substrate to polish the substrate. Provides a method of mechanically polishing.

1 (unscaled) shows a cross-sectional view of an example substrate to illustrate active regions, trench regions, steps and trench losses.
Figure 2 shows the polishing performance of the substrate according to the pitch width and pattern density of the polishing composition of the present invention.

The present invention relates to (a) an abrasive, (b) a self-stopping agent of formula QB wherein Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, B is a bonding group, wherein the bonding group is a structure; C (O) —X—OH or —C (O) —OH, wherein X is a C 1 -C 2 alkyl group), and (c) an aqueous carrier and having a pH of about 3 to about 9 Provide a mechanical polishing composition.

The polishing composition of the present invention comprises an abrasive. The abrasive of the polishing composition is preferably suitable for polishing nonmetallic portions of the substrate (eg, pattern dielectric material, blanket dielectric material, pattern oxide material, blanket oxide material, etc.). Suitable abrasives include ceria (eg CeO ₂ ), zirconia (eg ZrO ₂ ), silica (eg SiO ₂ ), and combinations thereof.

In a preferred embodiment, the abrasive is selected from ceria, zirconia and combinations thereof. In another preferred embodiment, the abrasive is ceria.

Both ceria and zirconia abrasives are well known in the CMP art and are commercially available. Examples of suitable ceria abrasives include in particular wet processed ceria, calcined ceria, and metal-doped ceria. Examples of suitable zirconia abrasives include in particular metal-doped zirconia and nonmetal-doped zirconia. Among the metal doped zirconia are cerium-, calcium-, magnesium-, or yttrium-doped zirconia, which preferably has a dopant element weight percentage in the range of 0.1-25%.

Ceria abrasives suitable for use in the polishing compositions of the present invention, and methods for their preparation, are disclosed in US Patent Application No. 14 / 639,564 filed March 5, 2015, entitled "Polishing Composition Containing Ceria Abrasive" (current US Patent No. 9,505,952). And US patent application Ser. No. 15 / 207,973, filed Jul. 12, 2016, entitled "Methods and Compositions for Processing Dielectric Substrate," published herein in U.S. Patent Application Publication No. 2017/0014969. Included by reference.

Preferred abrasives are wet processed ceria particles. The polishing composition may comprise a single type of abrasive particle or a plurality of different types of abrasive particles based on size, composition, method of manufacture, particle size distribution, or other mechanical or physical properties. Ceria abrasive particles can be prepared by a variety of different processes. For example, the ceria abrasive particles can be precipitated ceria particles or condensation-polymerized ceria particles comprising colloidal ceria particles.

Ceria abrasive particles can be prepared by any suitable process. By way of example, the ceria abrasive particles can be wet-processed ceria particles prepared according to the following process. Typically, the first step in the synthesis of wet-processed ceria particles is to dissolve the ceria precursor in water. The ceria precursor may be any suitable ceria precursor and may include a ceria salt with any suitable filler, for example Ce ³⁺ or Ce ⁴⁺ . Suitable ceria precursors include, for example, cerium nitrate III, cerium IV ammonium nitrate, cerium carbonate III, cerium sulfate IV and cerium chloride III. Preferably, the ceria precursor is cerium nitrate III.

The pH of the ceria precursor solution can typically be increased to form amorphous Ce (OH) ₃ . The pH of the solution can be increased to any suitable pH. For example, the pH of the solution can be increased to a pH of at least about 10, a pH of at least about 10.5, a pH of at least about 11, or a pH of at least about 12. Typically, the solution will have a pH of about 14 or less, such as a pH of about 13.5 or less, or a pH of about 13 or less. Any suitable base can be used to increase the pH of the solution. Suitable bases include, for example, KOH, NaOH, NH ₄ OH, and tetramethylammonium hydroxide. Organic bases such as ethanolamine and diethanolamine are also suitable. As the pH increases, the solution will become white and turbid, resulting in the formation of amorphous Ce (OH) ₃ .

The ceria precursor solution is typically mixed for several hours. For example, the solution may be at least about 1 hour, for example at least about 2 hours, at least about 4 hours, at least about 6 hours, at least about 8 hours, at least about 12 hours, at least about 16 hours, at least about 20 hours, or May be mixed for at least about 24 hours. Typically, the solution is mixed for about 1 hour to about 24 hours, for example about 2 hours, about 8 hours, or about 12 hours. When mixing is complete, the solution can be transferred to a pressurized vessel and heated.

The ceria precursor solution may be heated to any suitable temperature. For example, the solution may be heated to a temperature of at least about 50 ° C., such as at least about 75 ° C., at least about 100 ° C., at least about 125 ° C., at least about 150 ° C., at least about 175 ° C., or at least about 200 ° C. . Alternatively or additionally, the solution may be about 500 ° C. or less, for example about 450 ° C. or less, about 400 ° C. or less, about 375 ° C. or less, about 350 ° C. or less, about 300 ° C. or less, about 250 ° C. or less, about 225 ° C. Or to a temperature of about 200 ° C. or less. Thus, the solution can be heated to a temperature within a range limited to any two of the aforementioned endpoints. For example, the solution may be about 50 ° C. to about 300 ° C., such as about 50 ° C. to about 275 ° C., about 50 ° C. to about 250 ° C., about 50 ° C. to about 200 ° C., about 75 ° C. to about 300 ° C., about Heated to a temperature of 75 ° C to about 250 ° C, about 75 ° C to about 200 ° C, about 100 ° C to about 300 ° C, about 100 ° C to about 250 ° C, or about 100 ° C to about 225 ° C.

The ceria precursor solution is typically heated for several hours. For example, the solution may be at least about 1 hour, for example at least about 5 hours, at least about 10 hours, at least about 25 hours, at least about 50 hours, at least about 75 hours, at least about 100 hours, or at least about 110 hours. Can be heated. Alternatively or additionally, the solution may be heated for up to about 200 hours, for example up to about 180 hours, up to about 165 hours, up to about 150 hours, up to about 125 hours, up to about 115 hours, or up to about 100 hours. Can be. Thus, the solution can be heated for a limited period of time to any two of the aforementioned endpoints. For example, the solution may be from about 1 hour to about 150 hours, such as from about 5 hours to about 130 hours, from about 10 hours to about 120 hours, from about 15 hours to about 115 hours, or from about 25 hours to about 100 hours. Can be heated.

After heating, the ceria precursor solution may be filtered to separate precipitated ceria particles. The precipitate can be washed with excess water to remove unreacted ceria precursors. The mixture of precipitate and excess water can be filtered after each washing step to remove impurities. If properly cleaned, the ceria particles may be dried for further processing, for example sintering, or the ceria particles may be redispersed directly.

Ceria particles may optionally be dried and sintered before redispersion. The terms “sinter” and “calcination” are used interchangeably herein to refer to the heating of ceria particles under the conditions described below. Sintering of the ceria particles affects the degree of crystallization thereof produced. While not wishing to be bound by any particular theory, it is believed that the ceria particles are sintered at high temperatures and reduce defects in the crystal lattice structure of the particles for extended periods of time. Any suitable method may be used to sinter the ceria particles. By way of example, the ceria particles may be dried and then sintered at elevated temperature. Drying can be carried out at room temperature or at elevated temperature. In particular, drying may be performed at a temperature of about 20 ° C. to about 40 ° C., for example about 25 ° C., about 30 ° C., or about 35 ° C. Alternatively or additionally, drying may be performed at an elevated temperature of about 80 ° C. to about 150 ° C., for example about 85 ° C., about 100 ° C., about 115 ° C., about 125 ° C., or about 140 ° C. After the ceria particles have dried, they can be ground to produce a powder. Grinding can be performed using any suitable grinding material, such as zirconia.

The ceria particles may be sintered in any suitable oven and at any suitable temperature. For example, the ceria particles may be at least about 200 ° C., such as at least about 215 ° C., at least about 225 ° C., at least about 250 ° C., at least about 275 ° C., at least about 300 ° C., at least about 350 ° C., or at least about 375 ° C. Can be sintered at a temperature. Alternatively or additionally, the ceria particles may be about 1000 ° C. or less, for example about 900 ° C. or less, about 750 ° C. or less, about 650 ° C. or less, about 550 ° C. or less, about 500 ° C. or less, about 450 ° C. or less, or about 400 It may be sintered at a temperature of not more than ℃. Thus, the ceria particles can be sintered at a temperature limited to any two of the aforementioned endpoints. For example, the ceria particles may be from about 200 ° C. to about 1000 ° C., for example from about 250 ° C. to about 800 ° C., from about 300 ° C. to about 700 ° C., from about 325 ° C. to about 650 ° C., from about 350 ° C. to about 600 ° C., Sintered at a temperature of about 350 ° C. to about 550 ° C., about 400 ° C. to about 550 ° C., about 450 ° C. to about 800 ° C., about 500 ° C. to about 1000 ° C., or about 500 ° C. to about 800 ° C.

The ceria particles may be sintered for any suitable time. For example, the ceria particles may be sintered for at least about 1 hour, for example at least about 2 hours, at least about 5 hours, or at least about 8 hours. Alternatively or additionally, the ceria particles may be sintered for up to about 20 hours, up to about 18 hours, up to about 15 hours, up to about 12 hours, or up to about 10 hours. Thus, the ceria particles can be sintered for a limited period of time to any two of the aforementioned endpoints. For example, the ceria particles may be from about 1 hour to about 20 hours, such as from about 1 hour to about 15 hours, from about 1 hour to about 10 hours, from about 1 hour to about 5 hours, from about 5 hours to about 20 hours, Or from about 10 hours to about 20 hours.

Ceria particles may also be sintered at various temperatures and for various periods of time within the ranges described above. For example, the ceria particles can be sintered in a zone furnace, which exposes the ceria particles to one or more temperatures for various periods of time. By way of example, the ceria particles may be sintered for at least about 1 hour at a temperature of about 200 ° C. to about 1000 ° C., followed by at least about 1 hour at different temperatures within the range of about 200 ° C. to about 1000 ° C. .

Ceria particles are typically redispersed in a suitable carrier, for example an aqueous carrier, in particular water. When the ceria particles are sintered, the ceria particles are redispersed after completion of the sintering. Any suitable process may be used to redisperse the ceria particles. Typically, ceria particles are redispersed by lowering the pH of the mixture of ceria particles and water using a suitable acid. As the pH is lowered, the surface of the ceria particles generates a cationic zeta potential. This cationic zeta potential creates a repulsive force between the ceria particles, which facilitates their redispersion. Any suitable acid can be used to lower the pH of the mixture. Suitable acids include, for example, hydrochloric acid and nitric acid. Organic acids that are highly water soluble and have hydrophilic functional groups are also suitable. Suitable organic acids include, for example, acetic acid. Acids with polyvalent anions such as H ₃ PO ₄ and H ₂ SO ₄ are generally not preferred. The pH of the mixture can be lowered to any suitable pH. For example, the pH of the mixture may be lowered to about 2 to about 5, for example about 2.5, about 3, about 3.5, about 4, or about 4.5. Typically, the pH of the mixture does not drop below about 2.

Redispersed ceria particles are typically comminuted to reduce their particle size. Preferably, the ceria particles are milled simultaneously with redispersion. Milling can be performed using any suitable milling material, such as zirconia. Grinding may be performed using an sonication or wet-jet procedure. After milling, the ceria particles can be filtered to remove any remaining large particles. For example, the ceria particles may be filtered using a filter having a pore size of about 0.3 μm or more, for example about 0.4 μm or more, or about 0.5 μm or more.

The abrasive particles (eg ceria abrasive particles) preferably have a median particle size of about 40 nm to about 100 nm. The particle size of a particle is the diameter of the smallest sphere that contains the particle. The particle size of the abrasive particles can be measured using any suitable technique. For example, the particle size of the abrasive particles can be measured by a disk centrifuge, ie differential centrifugal sedimentation (DCS). Suitable disk centrifuge particle size measurement instruments are commercially available, for example, from CPS Instruments (Preyriville, Louisiana), for example from CPS disk centrifuge model DC24000UHR. Unless otherwise specified, the median particle size values reported and claimed herein are based on disc centrifuge measurements.

By way of example, the abrasive particles (eg, ceria abrasive particles) may be at least about 40 nm, for example at least about 45 nm, at least about 50 nm, at least about 55 nm, at least about 60 nm, at least about 65 nm, about 70 have a median particle size of at least nm, at least about 75 nm, or at least about 80 nm. Alternatively or additionally, the abrasive particles may be about 100 nm or less, for example about 95 nm or less, about 90 nm or less, about 85 nm or less, about 80 nm or less, about 75 nm or less, about 70 nm or less, or about 65 It can have a median particle size of less than or equal to nm. Thus, the abrasive particles may have an average particle size within a range limited to any two of the aforementioned endpoints. For example, the abrasive particles may be from about 40 nm to about 100 nm, for example from about 40 nm to about 80 nm, from about 40 nm to about 75 nm, from about 40 nm to about 60 nm, from about 50 nm to about 100 nm, About 50 nm to about 80 nm, about 50 nm to about 75 nm, about 50 nm to about 70 nm, about 60 nm to about 100 nm, about 60 nm to about 80 nm, about 60 nm to about 85 nm, or about It may have a median particle size of 65 nm to about 75 nm. Preferably, the abrasive particles have a median particle size of about 60 nm to about 80 nm, such as a median particle size of about 65 nm, a median particle size of about 70 nm, or a median particle size of about 75 nm.

The chemical-mechanical polishing composition may comprise any suitable amount of abrasive. If the composition comprises too little abrasive, the composition may not exhibit a sufficient removal rate. In contrast, when the polishing composition comprises too much ceria abrasive, the polishing composition may exhibit undesirable polishing performance, may not be cost effective, and / or may lack stability. Thus, the abrasive may be present in the polishing composition at a concentration of about 5 wt% or less, for example about 4 wt% or less, about 3 wt% or less, about 2 wt% or less, or about 1 wt% or less. Alternatively or additionally, the abrasive may comprise at least about 0.001% by weight, such as at least about 0.005%, at least about 0.01%, at least about 0.05%, at least about 0.1%, or at least about 0.5% by weight in the polishing composition. May be present in concentration. Thus, the abrasive may be present in the polishing composition in a concentration limited to any two of the aforementioned endpoints. For example, the abrasive may comprise about 0.001% to about 5% by weight, such as about 0.005% to about 4%, about 0.01% to about 3%, about 0.05% to about 2% by weight in the polishing composition. %, Or from about 0.1% to about 1% by weight.

Typically, the polishing composition does not include a substantial amount of abrasive suitable for polishing metals (eg, copper, silver, tungsten, etc.) on the surface of the substrate. For example, the polishing composition typically does not include substantial amounts of certain metal oxides (eg, alumina) suitable for polishing metal surfaces. Typically, the polishing composition comprises less than 0.1 weight percent abrasive in addition to the ceria and zirconia abrasive based on the total weight of the abrasive in the polishing composition. For example, the polishing composition may comprise 0.05 wt% or less of abrasives other than ceria and zirconia abrasives, or 0.01 wt% or less of abrasives other than ceria and zirconia abrasives. More specifically, the polishing composition may comprise 0.05 wt% or less of metal oxides other than ceria and zirconia or 0.01 wt% or less of metal oxides other than ceria and zirconia.

The abrasive is preferably suspended in the polishing composition, more specifically in the aqueous carrier component of the polishing composition. More specifically, when the abrasive comprises particles, the abrasive particles are preferably suspended in the polishing composition, and the abrasive particles are preferably colloidally stable. The term colloid refers to a suspension of abrasive particles in an aqueous carrier. Colloidal stability refers to the maintenance of the suspension over time. In the present invention, when the abrasive particles are placed in a 100 ml graduated cylinder and allowed to stand without stirring for 2 hours, the particle concentration ([B]; g / ml) in the lower 50 ml of the graduated cylinder and the top 50 ml of the graduated cylinder The difference of the particle concentration ([T]; g / ml) in the divided by the initial concentration ([C]; g / ml) of the particles in the abrasive composition is 0.5 or less (ie, {[B]-[T]} / [ C] ≦ 0.5) is considered to be colloidally stable. The value of {[B]-[T]} / [C] is preferably 0.3 or less, and more preferably 0.1 or less.

The polishing composition of the present invention comprises a self-stopping agent. Self-stopping agents are compounds that promote a relatively high pattern removal rate and a relatively low blanket removal rate and, when planarizing during polishing, facilitate a transition from a high pattern removal rate to a relatively low blanket removal rate. While not wishing to be bound by any particular theory, self-stopping agents are ligands that promote self-stop behavior by attaching to the abrasive (eg, to ceria or zirconia) to provide steric hindrance between the abrasive and the hydrophilic oxide surface. It is believed to work. The binding of the self-stopping agent to the abrasive can be assessed using any suitable technique, for example isothermal titration calorimetry (ITC).

While not wishing to be bound by any particular theory, it is believed that the self-stopping agent promotes a non-linear response to a given downward force (DF) on a tetraethoxysilane (TEOS) blanket dielectric material. During polishing, the pattern dielectric material undergoes a higher effective downward force (DF) than that of the blanket dielectric material, since the contact diffuses only to a portion of the pattern dielectric material that comes into contact with the pad. Higher effective DFs applied to TEOS pattern dielectric materials result in a “high” removal rate (eg, pattern removal rate) polishing method with a TEOS removal rate of about 8,000 GPa / min, where lower effective DF is about This results in a “stop” polishing scheme with a TEOS removal rate (eg, blanket removal rate) of less than 1,000 ms / minute. The difference between the "high" approach and the "stop" approach is typically distinguished such that a "high" removal rate or a "stop" removal rate is observed for a given DF. Thus, self-stopping agents are believed to enable a "high" removal rate (ie, a pattern removal rate), preferably even when the applied DF is in a "stop" manner when measured with a blanket wafer.

It is also noted that the mechanism is not only dependent on the DF, since the trench oxide removal rate on the pattern dielectric material is higher than the blanket removal rate despite having a lower effective DF in the trench than on the blanket wafer. For example, in some abrasive applications, the concentration of self-stopping agent plays a role in the observed effect, at low concentrations the self-stopping agent acts as a rate enhancer (eg, a "high" removal rate Observed), at higher concentrations self-stop behavior is observed (eg, "stop" removal rates are observed). Thus, some rate enhancers may have a dual action. For example, when the polishing composition comprises picolinic acid at a lower concentration, picolinic acid may function as a rate enhancer. However, when the polishing composition comprises picolinic acid at a higher concentration, the picolinic acid can function as a self-stopping agent. Typically, picolinic acid functions as a rate enhancer at concentrations below about 1000 ppm (eg, about 500 ppm, about 250 ppm, etc.) by weight.

In some embodiments of the invention, the self-stopping agent is of formula QB, wherein Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, and B is a bonding group, such as -C (O)- C-OH, -C (O) -CC-OH or -C (O) -OH. For example, in some embodiments the present invention includes an abrasive, a self-terminating agent of Formula QB, a cationic compound and an aqueous carrier (eg, water), and from about 3 to about 9 (eg, about 6.5) To a polishing composition having a pH of about 8.5).

In some embodiments of the invention, the self-stopping agent is of formula QB, wherein Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, B is a bonding group, wherein the bonding group is a structure: C (O) -X-OH or -C (O) -OH. X is a C1-C2 alkyl group. When the self-stopping agent is a compound of Formula Q-B as described herein, Q can be any suitable hydrophobic group, or any suitable group that confers steric hindrance. Suitable hydrophobic groups include saturated and unsaturated hydrophobic groups. Hydrophobic groups can be linear or branched, and can include ring structures including linear or branched alkyl groups, cycloalkyl groups, and aromatic, heterocyclic, and fused ring systems.

In one embodiment, Q is selected from alkyl groups, cycloalkyl groups, aromatic groups, heterocyclic groups, heteroaromatic groups, and combinations thereof.

Q may be an alkyl group. Suitable alkyl groups are, for example, linear or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon groups having 1 to 30 carbon atoms (eg, C ₁ -C ₃₀ alkyl groups, C ₁ -C ₂₄ alkyl _Groups , C ₁ -C ₁₈ alkyl groups, C ₁ -C ₁₂ alkyl groups, or even C ₁ -C ₆ alkyl groups, for example at least one carbon atom (ie methyl), at least two carbon atoms (eg For example, ethyl, vinyl), at least three carbon atoms (eg, propyl, isopropyl, propenyl, etc.), at least four carbon atoms (butyl, isobutyl, sec-butyl, butane, etc.), at least 5 carbon atoms (pentyl, isopentyl, sec-pentyl, neo-pentyl, etc.), at least 6 carbon atoms (hexyl, etc.), at least 7 carbon atoms, at least 8 carbon atoms, at least 9 carbon atoms, at least 10 Carbon atoms, at least 11 carbon atoms, at least 12 carbon atoms, at least 13 carbon atoms, at least 1 4 carbon atoms, at least 15 carbon atoms, at least 16 carbon atoms, at least 17 carbon atoms, at least 18 carbon atoms, at least 19 carbon atoms, at least 20 carbon atoms, at least 25 carbon atoms, or at least 30 Carbon atoms.

Substituted groups refer to groups in which one or more carbon-bonded hydrogens have been replaced with non-hydrogen atoms. Exemplary substituents include, for example, hydroxyl groups, keto groups, esters, amides, halogens (eg fluorine, chlorine, bromine and iodine), amino groups (primary, secondary, tertiary and / Or class 4), and combinations thereof.

Q may be a cycloalkyl group. Suitable cycloalkyl groups include, for example, saturated or unsaturated, substituted or unsubstituted cycloalkyl groups (eg, C ₃ -C ₂₀ cyclic groups) having 3 to 20 carbon atoms. For example, suitable cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and combinations thereof. Suitable unsaturated cycloalkyl groups also include, for example, cyclobutene, cyclopentene, cyclohexene and combinations thereof.

Q may be an aromatic group. Suitable aromatic groups include, for example, substituted or unsubstituted aromatic groups having 1 to 20 carbon atoms. For example, suitable aromatic groups include phenyl, benzyl, naphthyl, azulene, anthracene, pyrene, and combinations thereof.

Q may be a heteroaromatic group. "Heteroatom" is defined herein as any atom other than carbon and hydrogen atoms. Suitable heteroatom-containing functional groups are for example hydroxyl groups, carboxylic acid groups, ester groups, ketone groups, amino groups (eg primary, secondary and tertiary amino groups), amido groups, imidos Groups, thiol ester groups, thioether groups, nitrile groups, nitro groups, halogen groups, and combinations thereof.

Suitable heterocyclic groups include, for example, cyclic hydrocarbon compounds containing 1 to 20 carbon atoms and containing nitrogen, oxygen, sulfur, phosphorus, boron and combinations thereof. Heterocyclic compounds may be saturated and unsaturated, substituted or unsubstituted. Heterocyclic compounds refer to 5-, 6- or 7-membered ring systems having one or more heteroatom atoms (eg, N, O, S, P or B) contained as part of the ring system. Exemplary heterocyclic compounds are, for example, triazoles, aminotriazoles, 3-amino-1,2,4-triazoles, 3-amino-1,2,4-triazole-5-carboxylic acids, 3-amino-5-mercapto-1,2,4-triazole, 4-amino-5-hydrazino-1,2,4-triazole-3-thiol, thiazole, 2-amino-5-methyl Thiazole, 2-amino-4-imidazoleacetic acid, heterocyclic N-oxide, 2-hydroxypyridine-N-oxide, 4-methylmorpholine-N-oxide, and picolinic acid N-jade Seeds and the like. Other exemplary heterocyclic compounds include, for example, pyron compounds, pyridine compounds (including regioisomers and stereoisomers), pyrrolidine, delta-2-pyrroline, imidazolidine, delta-2-imidazoline, Delta-3-pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, quinuclidin, indolin, isoindolin, chroman, isochroman, and combinations thereof.

Suitable heteroaromatic groups are, for example, pyridine, thiophene, furan, pyrrole, 2H-pyrrole, imidazole, pyrazole, isoxazole, furazane, isothiazole, pyran (2H), pyrazine, pyrimidine, pyridazine, Isobenzofuran, indolizin, indole, 3H-indole, 1H-indazole, purine, isoindole, 4aH-carbazole, carbazole, beta-carboline, 2H-chromen, 4H-quinolizine, isoquinoline, Quinoline, quinoxaline, 1,8-naphthyridine, phthalazine, quinazoline, cinnoline, pteridine, xanthene, tetralin, phenothiazine, phenazine, perimidine, 1,7-phenanthroline , Phenanthridine, acridine and combinations thereof.

In some embodiments, Q is substituted with one or more substituents. Suitable substituents may include, for example, any suitable compound / group described herein. For example, suitable substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, heteroaromatic groups, and combinations thereof.

In some embodiments, Q is unsubstituted. In other embodiments, Q is a group that confers steric hindrance. For example, Q may not be particularly hydrophobic, but may be a bulky component that prevents chemical reactions or interactions that would otherwise occur in related molecules with smaller Q groups. Non-limiting examples of self-stopping agents having such Q groups are maltol, ethyl maltol and kojic acid.

In some embodiments, the linking group B is selected from carboxylic acid groups, hydroxylsamic acid groups, hydroxylamine groups, hydroxyl groups, keto groups, sulfate groups, phosphate groups and combinations thereof.

In some embodiments, the self-stopping agent QB is kojic acid, maltol, ethyl maltol, propyl maltol, hydroxamic acid, benzhydroxysamic acid, salicylic hydroxamic acid, benzoic acid, 3,4-dihydroxybenzoic acid, 3, 5-dihydroxybenzoic acid, caffeic acid, sorbic acid, and combinations thereof.

In addition, salts of the self-stopping agent of Formulation Q-B are suitable for use in the polishing compositions of the present invention.

In some embodiments, the self-stopping agent is koji acid, maltol, ethyl maltol, propyl maltol, tiglic acid, angelic acid, benzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, caffeic acid, Sorbic acid, potassium sorbate, and combinations thereof.

In some embodiments, the self-stopping agent of Formulation Q-B is selected from a compound of Formula (I), a compound of Formula (II), a compound of Formula (III), a compound of Formula (IV), and combinations thereof.

The compound of formula (I) has the structure

Wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocyclic alkyl, and heterocyclic aryl, each of which may be substituted or unsubstituted.

The compound of formula (II) has the structure

Wherein each X ¹ -X ³ is independently selected from N, O, S, sp ² hybridized carbon, and CY ¹ Y ² , wherein each Y ¹ and Y ² are independently hydrogen, hydroxyl, C _1- C ₆ alkyl, halogen, and combinations thereof, each Z ¹ -Z ³ is independently selected from hydrogen, hydroxyl, C ₁ -C ₆ alkyl, and combinations thereof, each of which may be substituted or unsubstituted Can be.

The compound of formula (III) has the structure

Z is from N, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkynyl, and aryl (eg, phenyl, benzyl, naphthyl, azulene, anthracene, pyrene, etc.) Selected; X ¹ and X ² are independently selected from hydrogen, hydroxy, amino, and C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl; Wherein X ¹ and X ² together with the attached carbon may form sp ² -hybridized carbon, n is 1 or 2, p is 0-4 and M is hydrogen and a suitable counterion (eg, I Group metal), each of which may be substituted or unsubstituted.

The compound of formula (IV) has the structure

Wherein X, Y and Z are independently selected from H, O, S, NH, and CH ₂ , and R ¹ , R ² and R ³ are independently H, alkyl, alkenyl, alkynyl, aryl, halo and halo Alkyl is selected and M is selected from hydrogen and a suitable counterion.

The polishing composition may comprise any suitable amount of self-stopping agent (eg, a compound of Formula Q-B). If the composition comprises too little self-stopping agent, the composition may not exhibit suitable self-stopping behavior. In contrast, when the polishing composition comprises too much self-stopping agent, the composition may exhibit undesirable polishing performance, may not be cost effective and / or lack stability. Thus, the polishing composition may comprise up to about 2 weight percent, for example up to about 1 weight percent, up to about 0.5 weight percent, up to about 0.1 weight percent, or up to about 0.01 weight percent self-stopping agent. Alternatively or additionally, the polishing composition may comprise at least about 0.0001 wt%, for example at least about 0.0005 wt%, at least about 0.001 wt%, at least about 0.005 wt%, at least about 0.01 wt% or at least about 0.05 wt% self-stop It may include the agent. Thus, the polishing composition may comprise a self-stopping agent at a concentration limited to any two of the aforementioned endpoints. For example, the self-stopping agent may be present in the polishing composition in an amount from about 0.0001% to about 2% by weight, such as from about 0.0005% to about 1%, from about 0.001% to about 0.5%, from about 0.005% to It may be present at a concentration of about 0.1%, or about 0.01% to about 0.05% by weight.

In some embodiments, the polishing compositions of the present invention comprise up to about 0.5 weight percent (eg, up to about 5,000 ppm) of self-stopping agents. In some embodiments, the polishing composition comprises up to about 2,500 ppm (0.25 wt.%), For example up to about 2,000 ppm, up to about 1,500 ppm, up to about 1,000 ppm, or up to about 500 ppm self-stopping agent.

In some embodiments, the polishing compositions of the present invention comprise a self-stopping agent in combination with a leveling agent (ie, cationic compound), which is also referred to as a topography control agent. While not wishing to be bound by any particular theory, cationic compounds act as planarizers to enhance the topography of the polished substrate, which typically degrades the oxide removal rate by binding the cationic compound to the negatively charged oxide surface. It seems to be because The cationic compound also improves the planarization efficiency of the self-stopping composition under higher pH polishing conditions (eg, having a pH of about 6.5 to about 8.5, a pH of about 7.0 to 8.5).

The cationic compound can be a polymer comprising a monomer selected from quaternary amines, cationic polyvinyl alcohol, cationic cellulose, and combinations thereof. Thus, cationic polymers may include quaternary amines, cationic polyvinyl alcohols, cationic celluloses, and combinations thereof.

Suitable quaternary amine monomers include, for example, vinylimidazolium, methacryloyloxyethyltrimethylammonium halide, diallyldimethylammonium halide and combinations thereof. Thus, suitable cationic polymers are, for example, poly (vinylimidazolium), poly (methacryloyloxyethyltrimethylammonium) halides such as poly (methacryloyloxyethyltrimethylammonium) chloride (polyMADQUAT), poly ( Diallyldimethylammonium) halides such as poly (diallyldimethylammonium) chloride (polyDADMAC), poly [bis (2-chloroethyl) ether-alt-1,3-bis [3- (dimethylamino) propyl] urea] ( That is, a copolymer of polyquaternium-2), vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate (ie polyquaternium-11), a copolymer of vinylpyrrolidone and quaternized vinylimidazole ( Terpolymers of polyquaternium-16), vinylcaprolactam, vinylpyrrolidone, and quaternized vinylimidazole (ie polyquaternium-46), and 3-methyl-1-vinylimidazolium methyl From sulphate-N-vinylpyrrolidone copolymer (ie polyquaternium-44) Comprises a quaternary amine. In addition, suitable cationic polymers are cationic polymers for personal care such as Ruviquat® Supreme, Rubiquart® Hold, Rubiquart® UltraCare, Rubiquart® FC 370, Rubiquart® FC 550, Rubiquart FC 552, RubyQuartx Excellence, and combinations thereof. Any combination of the cationic polymers mentioned herein can be used.

In one embodiment, the cationic polymer is a quaternary amine and the cationic polymer is a poly (methacryloyloxyethyltrimethylammonium) halide, for example polyMADQUAT.

In one embodiment, the cationic polymer is a quaternary amine and the cationic polymer is poly (vinylimidazolium).

The cationic polymer can be any suitable cationic polyvinyl alcohol or cationic cellulose. Preferably, the cationic polymer is cationic polyvinyl alcohol. For example, the cationic polyvinyl alcohol may be Nippon Gosei GOHSEFIMER K210 ™ polyvinyl alcohol product.

If present, the cationic polymer (ie, quaternary amine, cationic polyvinyl alcohol, cationic cellulose, or a combination thereof) as a whole may be present in any suitable concentration in the polishing composition. Typically, the cationic polymer is from about 1 ppm to about 500 ppm, for example from about 1 ppm to about 475 ppm, from about 1 ppm to about 450 ppm, from about 1 ppm to about 425 ppm, from about 1 ppm to about 400 ppm, about 1 ppm to about 375 ppm, about 1 ppm to about 350 ppm, about 1 ppm to about 325 ppm, about 1 ppm to about 300 ppm, about 1 ppm to about 275 ppm, about 1 ppm to about 250 ppm , About 1 ppm to about 225 ppm, about 1 ppm to about 200 ppm, about 1 ppm to about 175 ppm, about 1 ppm to about 150 ppm, about 1 ppm to about 125 ppm, about 1 ppm to about 100 ppm, about 1 ppm to about 75 ppm, about 1 ppm to about 50 ppm, about 1 ppm to about 40 ppm, about 1 ppm to about 25 ppm, about 5 ppm to about 225 ppm, about 5 ppm to about 100 ppm, about 5 ppm To about 50 ppm, about 10 ppm to about 215 ppm, about 10 ppm to about 100 ppm, about 15 ppm to about 200 ppm, about 25 ppm to about 175 ppm, about 25 ppm to about 100 ppm, or about 30 ppm to At a concentration of about 150 ppm exist. Unless stated otherwise, the ppm concentrations listed herein reflect the weight-based ratio of components to the total weight of the polishing composition.

If the cationic polymer is poly (vinylimidazolium), the cationic polymer is preferably from about 1 ppm to about 10 ppm, for example about 2 ppm, about 5 ppm, about 6 ppm, about 7 ppm in the polishing composition. , About 8 ppm, or about 9 ppm. More preferably, when the cationic polymer is poly (vinylimidazolium), the cationic polymer is preferably in the polishing composition from about 1 ppm to about 5 ppm, for example about 2 ppm, about 3 ppm or about 4 It is present at a concentration of ppm.

The polishing composition may be an anionic copolymer of carboxylic acid monomer, sulfonated monomer, or phosphonated monomer with acrylate, polyvinylpyrrolidone, or polyvinyl alcohol (eg, 2-hydroxyethylmethacrylic acid and meta Copolymers of acrylic acid); It may optionally include additives selected from nonionic polymers, wherein the nonionic polymer is selected from polyvinylpyrrolidone or polyethylene glycol; Silanes, wherein the silanes are amino silanes, ureido silanes, or glycidyl silanes; N-oxides of functionalized pyridine (eg picolinic acid N-oxide); Starch; Cyclodextrins (eg, alpha-cyclodextrins or beta-cyclodextrins), and combinations thereof.

If the additive is a nonionic polymer and the nonionic polymer is polyvinylpyrrolidone, the polyvinylpyrrolidone may have any suitable molecular weight. For example, polyvinylpyrrolidone may be from about 10,000 g / mol to about 1,000,000 g / mol, for example about 20,000 g / mol, about 30,000 g / mol, about 40,000 g / mol, about 50,000 g / mol, or It may have a molecular weight of about 60,000 g / mol. If the additive is a nonionic polymer and the nonionic polymer is polyethylene glycol, the polyethylene glycol may have any suitable molecular weight. For example, polyethylene glycol can have a molecular weight of about 200 g / mol to about 200,000 g / mol, for example about 8000 g / mol, or about 100,000 g / mol.

If the additive is a silane, the silane can be any suitable amino silane, ureido silane or glycidyl silane. For example, the silane may be 3-aminopropyltrimethoxysilane, 3-aminopropylsilanetriol, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilanetriol, (N, N) -dimethyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, ureidopropyltriethoxysilane, or 3-glycidopropyldimethylethoxysilane.

Preferably, when the polishing composition comprises an additive, the additive is a copolymer of 2-hydroxyethylmethacrylic acid and methacrylic acid, polyvinylpyrrolidone, aminopropylsilanetriol, picolinic acid N-oxide , Starch, alpha-cyclodextrin, beta-cyclodextrin, and combinations thereof.

Additives (ie, carboxylic acid monomers, sulfonated monomers, or anionic copolymers of phosphonated monomers and acrylates, polyvinylpyrrolidone, or polyvinyl alcohol as a whole; silanes; N-oxides of functionalized pyridine Starch; cyclodextrin; or a combination thereof) may be present in any suitable concentration in the chemical-mechanical polishing composition. Preferably, the additive is about 1 ppm to about 500 ppm, for example about 5 ppm to about 400 ppm, about 10 ppm to about 400 ppm, about 15 ppm to about 400 ppm, about 20 ppm to about 400 in the polishing composition. ppm, about 25 ppm to about 400 ppm, about 10 ppm to about 300 ppm, about 10 ppm to about 250 ppm, about 30 ppm to about 350 ppm, about 30 ppm to about 275 ppm, about 50 ppm to about 350 ppm, Or at a concentration of about 100 ppm to about 300 ppm. More preferably, the additive is about 1 ppm to about 300 ppm, for example about 1 ppm to about 275 ppm, about 1 ppm to about 250 ppm, about 1 ppm to about 100 ppm, about 1 ppm to about in the polishing composition. 50 ppm, about 10 ppm to about 250 ppm, about 10 ppm to about 100 ppm, or about 35 ppm to about 250 ppm.

The polishing composition optionally comprises, in addition to one or more additives described herein, cationic polymers described herein, ie carboxylic acid monomers, sulfonated monomers, or anionic copolymers of phosphonated monomers and acrylates, polyvinylpyrrolidone or polyvinyl. N-oxides of alcohols, nonionic polymers, silanes, functionalized pyridine; Starch; And cyclodextrins. Alternatively, the polishing composition does not have one or more of the additives described above, that is, an anionic copolymer of carboxylic acid monomers, sulfonated monomers, or phosphonated monomers and acrylates, polyvinylpyrrolidone, or polyvinyl Alcohol; Nonionic polymers; Silanes; N-oxides of functionalized pyridine; Starch; And cationic polymers without one or more of cyclodextrins.

The polishing composition comprises an aqueous carrier. The aqueous carrier comprises water (eg deionized water) and may contain one or more water-miscible organic solvents. Examples of organic solvents that can be used include alcohols such as propenyl alcohol, isopropyl alcohol, ethanol, 1-propanol, methanol, 1-hexanol and the like; Aldehydes such as acetylaldehyde and the like; Ketones such as acetone, diacetone alcohol, methyl ethyl ketone and the like; Esters such as ethyl formate, propyl formate, ethyl acetate, methyl acetate, methyl lactate, butyl lactate, ethyl lactate and the like; Ethers including sulfoxides such as dimethyl sulfoxide (DMSO), tetrahydrofuran, dioxane, diglyme and the like; Amides such as N, N-dimethylformamide, dimethylimidazolidinone, N-methylpyrrolidone and the like; Polyhydric alcohols and derivatives thereof such as ethylene glycol, glycerol, diethylene glycol, diethylene glycol monomethyl ether and the like; And nitrogen-containing organic compounds such as acetonitrile, amylamine, isopropylamine, imidazole, dimethylamine and the like. Preferably, the aqueous carrier is water alone, ie there is no organic solvent present.

The pH of the polishing composition of the present invention is about 3 to about 9. Typically, the polishing composition has a pH of about 3 or greater. In addition, the pH of the polishing composition is typically about 9 or less. For example, the polishing composition may be about 3.5 to about 9, for example about 4 to about 9, about 4.5 to about 9, about 5 to about 9, about 5.5 to about 9, about 6 to about 9, about 6.5 to about 9, about 7 to about 9, about 7.5 to about 9, about 8 to about 9, or about 8.5 to about 9. Alternatively, the polishing composition may be about 3 to about 8.5, for example about 3 to about 8, about 3 to about 7.5, about 3 to about 7, about 3 to about 6.5, about 3 to about 6, about 3 to about It may have a pH of 5.5, about 3 to about 5, about 3 to about 4.5, about 3 to about 4, or about 3 to about 3.5. Thus, the polishing composition may have a pH limited to any two of these endpoints.

Preferably, the polishing composition has a pH of about 3 to about 5, or about 7.0 to about 8.5. For example, in a preferred embodiment the polishing composition comprises an abrasive, a self-stopping agent of Formula Q-B described herein, and an aqueous carrier, wherein the pH of the polishing composition is about 3 to about 5.

In another preferred embodiment, the polishing composition comprises an abrasive, a self-stopping agent of Formula Q-B as described herein, a cationic polymer, and an aqueous carrier, wherein the pH of the polishing composition is about 7.0 to about 9.0. In some preferred embodiments, the polishing compositions of the present invention comprise an abrasive, a self-stopping agent of formula (I) as described herein, a cationic polymer, and an aqueous carrier, wherein the pH of the polishing composition is from about 7.0 to about 9.0.

The polishing composition may comprise a pH-adjusting agent and a pH buffer. The pH-adjusting agent can be any suitable pH-adjusting agent. For example, the pH-adjusting agent can be an alkyl amine, alcohol amine, quaternary amine hydroxide, ammonia, or a combination thereof. In particular, the pH-adjusting agent may be triethanolamine (TEA), tetramethylammonium hydroxide (TMAH or TMA-OH), or tetraethylammonium hydroxide (TEAH or TEA-OH). In some embodiments, the pH-adjusting agent is triethanolamine.

The pH-adjusting agent may be present in any suitable concentration in the polishing composition. Preferably, the pH-adjusting agent maintains a pH in the polishing composition at a concentration sufficient to achieve and / or maintain the pH of the polishing composition within the pH ranges set forth herein, for example from about 3 to about 9, or It is present at a concentration sufficient to maintain a pH of 3 to about 5, or to maintain a pH of about 7.0 to about 8.5.

The polishing composition may contain any suitable buffer. For example, suitable buffers may include phosphates, sulfates, acetates, malonates, oxalates, borates, ammonium salts, azoles and the like. In some embodiments, the buffer is 1H-benzotriazole.

The polishing composition, if present, may contain any suitable amount of buffer. For example, the buffer may be present in a polishing composition at a concentration of at least about 0.0001%, for example at least about 0.0005%, at least about 0.001%, at least about 0.005%, at least about 0.01%, or at least about 0.1% by weight. May exist. Alternatively or additionally, the buffer may be up to about 2% by weight, for example up to about 1.8%, up to about 1.6%, up to about 1.4%, up to about 1.2%, or about 1% by weight in the polishing composition. It may be present in the following concentrations. Thus, the buffer may be present in the polishing composition at a concentration limited to any two of the aforementioned endpoints. For example, the buffer may comprise about 0.0001% to about 2% by weight, such as about 0.005% to about 1.8%, about 0.01% to about 1.6%, or about 0.1% to about 1% by weight in the polishing composition. It may be present at a concentration by weight.

The polishing composition optionally further includes one or more other additives. Exemplary additional ingredients include speed enhancers, conditioners, scale inhibitors, dispersants, and the like. Preferably, the rate enhancer is an organic carboxylic acid that activates abrasive particles or a substrate by forming a supercoordinating compound (eg, a coordinating or hexagonal silicon compound). Suitable rate enhancers include, for example, picolinic acid and 4-hydroxybenzoic acid. Abrasive compositions include viscosity enhancers and coagulants (eg, polymeric rheology control agents such as, for example, urethane polymers), dispersants, biocides (eg, KATHON ™ LX), and the like. Surfactants and / or rheology control agents. Suitable surfactants include, for example, cationic surfactants, anionic surfactants, anionic polyelectrolytes, nonionic surfactants, amphoteric surfactants, fluorinated surfactants, mixtures thereof, and the like. By way of example, additional components may include Breeze S20 (polyethylene glycol octadecyl ether) and polyethylene glycol (eg PEG8000).

The polishing composition can be prepared by any suitable technique, many of which are known to those skilled in the art. The polishing composition can be prepared in a batch or continuous process. In general, the polishing composition may be prepared by combining the components described herein in any order. As used herein, the term "component" means any component (eg, abrasive, self-stopping agent, cationic compound, etc.) as well as any combination of components (eg, abrasive, self-stopping agent, cationic compound). And the like).

For example, self-stopping agents can be added to the aqueous carrier (eg, water) at the desired concentration (s). The pH can then be adjusted (as desired) and the abrasive can be added to the mixture at the desired concentration to form the polishing composition. The polishing composition may be prepared prior to use, and one or more components are added to the polishing composition immediately prior to use (eg, within about 1 minute before use, or within about 1 hour before use, or within about 7 days before use). do. The polishing composition may also be prepared by mixing the components at the surface of the substrate during the polishing operation.

The polishing composition may also be provided as a concentrate intended to be diluted with an appropriate amount of aqueous carrier, in particular water, before use. In such embodiments, the polishing composition concentrate may comprise a polishing agent, a self-stopping agent, a cationic polymer (if present) and an aqueous carrier when each component of the polishing composition is diluted for each component upon dilution of the concentrate with an appropriate amount of water. It may be included in an amount such that it can be present in the polishing composition in an amount within the appropriate ranges mentioned above. In addition, as will be appreciated by those skilled in the art, the concentrate may contain an appropriate fraction of water present in the final polishing composition to ensure that the other components are at least partially or completely dissolved in the concentrate.

Although the polishing composition may be prepared considerably before or even just before use, the polishing composition may also be prepared by mixing the components of the polishing composition at or near the point of use. As used herein, the term “point of use” refers to the point where the polishing composition is applied to the substrate surface (eg, the polishing pad or the substrate surface itself). If the polishing composition is to be prepared using use-point mixing, the components of the polishing composition are stored separately in two or more storage devices.

In order to prepare the polishing composition at or near the point of use by mixing the components contained in the storage device, the storage device typically has a point of use (eg, platens, polishing pads, Or one or more flow lines) leading to the substrate surface). The term "flow line" means a flow path from an individual storage vessel to the point of use of the components stored there. One or more flow lines may each directly lead to a point of use, or in situations where more than one flow line is used, two or more of the flow lines may be combined into a single flow line at any point and lead to a point of use. Can be. In addition, one or more other flow lines (e.g., individual flow lines or combined flow lines) before one or more other devices (e.g. pumping devices, measuring devices, Mixing device, etc.) first.

The components of the polishing composition may be delivered independently at the point of use (eg, the components are delivered to the substrate surface where the components are mixed during the polishing process), or the components may be combined just before being delivered to the point of use. Less than 10 seconds before the component reaches the point of use, preferably less than 5 seconds before reaching the point of use, more preferably less than 1 second before reaching the point of use, or even at the point of use When combined at the same time as delivery (eg, when the components are combined at the dispenser), the components are combined "just before delivery to the point of use". If the components are combined within 5 m of the point of use, for example within 1 m of the point of use or even within 10 cm of the point of use (eg within 1 cm of the point of use), the components are also referred to as “points of use. Immediately before delivery ".

If two or more of the components of the polishing composition are combined before reaching the point of use, the components can be combined and delivered to the point of use without the use of a mixing device. Alternatively, one or more flow lines may reach the mixing device to facilitate the combination of two or more components. Any suitable mixing device can be used. For example, the mixing device may be a nozzle or jet (eg, a high pressure nozzle or jet) through which two or more components flow. Alternatively, the mixing device may comprise one or more inlets through which two or more components of the polishing composition are introduced into the mixer, and the mixed components leave the mixer directly or through other elements of the apparatus (eg, one or more flow lines). Through) at least one outlet to the point of use. Also, the mixing device may comprise more than one chamber, each chamber having at least one inlet and at least one outlet, where two or more components are combined in each chamber. If a container-type mixing device is used, the mixing device preferably comprises a mixing mechanism that facilitates the combination of the components. Mixing mechanisms are generally known in the art and include stirrers, blenders, agitators, paddled baffles, gas sparger systems, vibrators and the like.

The invention also provides a method of chemically-mechanically polishing a substrate using the CMP compositions of the invention described herein. In one embodiment, the present invention provides a substrate comprising (i) on a surface of a substrate a patterned dielectric layer comprising a raised region of dielectric material and a trenched region of dielectric material, wherein the initial of the patterned dielectric layer The step is the difference between the height of the elevated region of the dielectric material and the height of the trench region of the dielectric material), (ii) providing a polishing pad, (iii) providing a chemical-mechanical polishing composition described herein, ( iv) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition, (v) moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to polish at least a portion of the patterned dielectric layer on the surface of the substrate to polish the substrate. A method of chemically-mechanically polishing a substrate is provided.

More specifically, the invention provides a substrate comprising (i) a patterned dielectric layer on a surface of the substrate, the patterned dielectric layer comprising a raised region of dielectric material and a trenched region of dielectric material, wherein the initial step of the patterned dielectric layer is Is the difference between the height of the elevated region of the dielectric material and the height of the trench region of the dielectric material), (ii) providing a polishing pad, (iii) (a) abrasive, (b) a self-stopping agent of formula QB Wherein Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, and B is a bonding group having the structure C (O) -X-OH or -C (O) -OH, wherein X is C1 -C2 alkyl group), (c) an aqueous carrier, (d) optionally a cationic polymer, and having a pH of about 3 to about 9, (iv) a substrate with a polishing pad and Contacting with the chemical-mechanical polishing composition, (v) polishing pad and chemical-mechanical lead Provided is a method for chemically-mechanically polishing a substrate comprising moving the composition to a substrate to polish the substrate by grinding at least a portion of the patterned dielectric layer on the surface of the substrate.

The present invention also provides a substrate comprising (i) a patterned dielectric layer on a surface of a substrate, the patterned dielectric layer comprising a raised region of dielectric material and a trenched region of dielectric material, wherein the initial step of the patterned dielectric layer is a dielectric The difference between the height of the elevated region of the material and the height of the trench region of the dielectric material), (ii) providing a polishing pad, (iii) (a) an abrasive comprising ceria, (b) kojic acid, maltol, Self-stopping agent selected from caffeic acid, crotonic acid, tiglic acid, 2-pentenoic acid, 2-hydroxynicotinic acid, ethyl maltol, potassium sorbate, sorbic acid, diperiprone, valeric acid and combinations thereof, (c) aqueous Providing a chemical-mechanical polishing composition comprising a carrier and having a pH of about 3 to about 9, (iv) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition, (v) the polishing pad and the chemical- Mechanical polishing composition to the substrate Provides a method of mechanically polished - a substrate, which comprises grinding at least a portion of the copper to the dielectric layer pattern on the surface of the substrate to polish the substrate chemistry.

The present invention also provides a substrate comprising (i) a patterned dielectric layer comprising a raised region of dielectric material and a trenched region of dielectric material on a surface of the substrate, wherein the initial step of the patterned dielectric layer is a dielectric material The difference between the height of the raised region and the height of the trench region of the dielectric material), (ii) providing a polishing pad, (iii) (a) abrasive, (b) a self-selected compound of formula (I) Providing a chemical-mechanical polishing composition comprising a stopper, (c) an aqueous carrier, (d) a cationic polymer, and having a pH of about 7 to about 9, (iv) polishing the substrate with a polishing pad and chemical-mechanical polishing Contacting the composition, (v) moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to polish at least a portion of the patterned dielectric layer on the surface of the substrate to polish the substrate.Mach provides a method.

Wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocyclic alkyl and heterocyclic aryl, each of which may be substituted or unsubstituted.

The present invention also provides a substrate comprising (i) a patterned dielectric layer comprising a raised region of dielectric material and a trenched region of dielectric material on a surface of the substrate, wherein the initial step of the patterned dielectric layer is a dielectric material The difference between the height of the raised region and the height of the trench region of the dielectric material), (ii) providing a polishing pad, (iii) (a) abrasive, (b) a formula (II), (III) or ( Providing a chemical-mechanical polishing composition comprising a self-stopping agent selected from the compound of IV), (c) an aqueous carrier and having a pH of about 3 to about 9, (iv) polishing the substrate with a polishing pad and chemical-mechanical Contacting the polishing composition, (v) polishing the substrate by polishing the substrate by contacting the polishing pad and the chemical-mechanical polishing composition against the substrate to grind at least a portion of the patterned dielectric layer on the surface of the substrate. Polishing with Provides a way.

Wherein each X ¹ -X ³ is independently selected from N, O, S, sp ² hybridized carbon, and CY ¹ Y ² , wherein each Y ¹ and Y ² are independently hydrogen, hydroxyl, C _1- C ₆ alkyl, halogen, and combinations thereof, each Z ¹ -Z ³ is independently selected from hydrogen, hydroxyl, C ₁ -C ₆ alkyl, and combinations thereof, each of which may be substituted or unsubstituted Can be.

Z is from N, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkynyl, and aryl (eg, phenyl, benzyl, naphthyl, azulene, anthracene, pyrene, etc.) And X ¹ and X ² are independently selected from hydrogen, hydroxy, amino, and C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, wherein X ¹ and X ² together with the attached carbon Can form a ² -hybridized carbon, n is 1 or 2, p is 0-4, M is selected from hydrogen and a suitable counterion (eg, a Group I metal), each of which is substituted or unsubstituted Can be.

Wherein X, Y and Z are independently selected from H, O, S, NH and CH ₂ , and R ¹ , R ² and R ³ are independently H, alkyl, alkenyl, alkynyl, aryl, halo and haloalkyl And M is selected from hydrogen and a suitable counterion.

The present invention also provides a substrate comprising (i) a patterned dielectric layer comprising a raised region of dielectric material and a trenched region of dielectric material on a surface of the substrate, wherein the initial step of the patterned dielectric layer is a dielectric material The difference between the height of the raised region and the height of the trench region of the dielectric material), (ii) providing a polishing pad, (iii) (a) an abrasive comprising ceria, (b) hydroxamic acid such as acetohydride A chemical having a pH of about 7 to about 9, comprising a self-stopping agent selected from lactic acid, benzhydroxamic acid, salicylic acid, and combinations thereof, (c) a cationic polymer, and (d) an aqueous carrier Providing a mechanical polishing composition, (iv) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition, (v) moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to provide a pattern on the surface of the substrate. Provided are a method for chemically-mechanically polishing a substrate, comprising grinding at least a portion of the entire layer to polish the substrate.

The polishing composition of the present invention is useful for polishing any suitable substrate. The polishing composition is particularly useful for polishing a substrate comprising a silicon oxide layer. Suitable substrates include, but are not limited to, flat panel displays, integrated circuits, memory or rigid disks, metals, semiconductors, interlayer dielectric (ILD) devices, microelectromechanical systems (MEMS), 3D NAND devices, ferroelectrics, and magnetic heads. Does not. The polishing composition is particularly well suited for planarizing or polishing substrates that have undergone shallow trench isolation (STI) processing. Preferably, the substrate comprises one having a region of patterned dielectric material comprising a dielectric-containing (eg, silicon oxide-containing) surface, particularly a raised dielectric region separated by a trench region of the dielectric material. The substrate may further comprise at least one other layer, for example an insulating layer. The insulation layer can be a metal oxide, porous metal oxide, glass, organic polymer, fluorinated organic polymer, or any other suitable high or low-k insulation layer. The insulating layer may comprise, consist essentially of, or consist of silicon oxide, silicon nitride, or a combination thereof. The silicon oxide layer may comprise, consist essentially of, or consist of any suitable silicon oxide, many of which are known in the art. For example, silicon oxide layers include tetraethoxysilane (TEOS), high density plasma (HDP) oxide, borophosphosilicate glass (BPSG), high aspect ratio process (HARP) oxide, spin on dielectric (SOD) oxide, chemical vapor deposition (CVD) oxide, plasma-enhanced tetraethyl ortho silicate (PETEOS), thermal oxide, or undoped silicate glass. The substrate may further comprise a metal layer. The metal may comprise, consist essentially of, or consist of any suitable metal, many of which are known in the art and are, for example, copper, tantalum, tungsten, titanium, platinum, for example , Ruthenium, iridium, aluminum, nickel, or a combination thereof.

In accordance with the present invention, the substrate may be planarized or polished by any suitable method using the polishing composition described herein. The polishing method of the present invention is particularly suitable for use with chemical-mechanical polishing (CMP) apparatus. Typically, a CMP device is a platen that moves in use and has a velocity resulting from orbit, straight or circular motion; A polishing pad in contact with the platen and moving with the platen in motion; And a carrier that secures the substrate by bringing the substrate to be polished into contact with and moving relative to the surface of the polishing pad. Polishing the substrate places the substrate in contact with the polishing composition and typically the polishing pad of the invention, followed by polishing at least a portion of the surface of the substrate, such as silicon oxide, or one or more of the substrate materials described herein. The composition is performed by grinding the substrate, typically by polishing pads. Any suitable polishing condition can be used to polish the substrate in accordance with the present invention.

The substrate may be planarized or polished with the chemical-mechanical polishing composition along with any suitable polishing pad (eg, polishing surface). Suitable polishing pads include, for example, woven and nonwoven polishing pads. Moreover, suitable polishing pads may include any suitable polymer of varying density, hardness, thickness, compressibility, ability to bounce on compression, and compression modulus. Suitable polymers are, for example, polyvinylchloride, polyvinylfluoride, nylon, fluorocarbons, polycarbonates, polyesters, polyacrylates, polyethers, polyethylenes, polyamides, polyurethanes, polystyrenes, polypropylenes, Hybrid products thereof and mixtures thereof.

Although the compositions and methods of the present invention exhibit self-stop behavior, the CMP apparatus may further comprise an in situ polishing endpoint detection system, many of which are known in the art. Techniques for inspecting and monitoring the polishing process by analyzing light or other radiation reflected from the surface of the workpiece are known in the art. Such methods include, for example, US Patent No. 5,196,353, US Patent No. 5,433,651, US Patent No. 5,609,511, US Patent No. 5,643,046, US Patent No. 5,658,183, US Patent No. 5,730,642, US Patent No. 5,838,447, US Patent No. 5,872,633, US Patent No. 5,893,796, US Pat. No. 5,949,927, and US Pat. No. 5,964,643. Preferably, checking or monitoring the progress of the polishing process for the workpiece to be polished makes it possible to determine the polishing end point, i.e. when to terminate the polishing process for a particular workpiece.

For substrates of any type of device, the substrate surface may include a continuous but structured (non-planar and non-flat) layer of dielectric material overlying the underlying layer that also includes the surface structure or topography. This structured non-planar region of the dielectric material surface is referred to as a "pattern dielectric." It is produced from a dielectric material disposed over the heterogeneous structure of the underlying layer to fill trenches or holes present in the underlying layer. In order to ensure complete filling of all trenches or holes, etc., and to ensure complete coverage on the surface of the underlying layer containing trenches or holes, the dielectric material is deposited in excess. The dielectric material will follow the non-uniform topography of the underlying layer, which creates a deposited continuous dielectric surface characterized by raised areas separated by trenches. The elevated area will be the location of active polishing and material removal, meaning the location where most dielectric material is removed. The pattern dielectric material is also characterized as being referred to as a "step", which is the height of the dielectric material in the raised region relative to the height of the dielectric material in adjacent trenches.

The polishing composition of the present invention is particularly well suited for planarizing or polishing substrates that have undergone shallow trench isolation (STI) or similar processes, where the dielectric is coated on the structured underlying layer to create regions of patterned dielectric material. For substrates that have undergone shallow trench isolation, typical steps may range from about 1,000 angstroms to about 7,000 angstroms.

Certain embodiments of the described polishing compositions are also useful for planarizing or polishing a substrate that is a 3D NAND flash memory device during processing. In such substrates, the underlying layer is made of a semiconductor layer comprising trenches, holes, or other structures having high aspect ratios, eg, at least 10: 1, 30: 1, 60: 1 or 80: 1. When a surface having such a high aspect ratio structure is coated by a dielectric material, the resulting pattern dielectric will have a high step, such as substantially greater than about 7,000 angstroms, for example greater than about 10,000 angstroms, greater than about 20,000 angstroms, greater than about 30,000 angstroms. , Or more than about 40,000 Angstroms or more.

The dielectric material of any of the devices described herein can comprise, consist essentially of, or consist of any suitable dielectric material, including various forms of silicon oxide and silicon oxide-based dielectric materials, many of which are It is well known. For example, dielectric materials comprising silicon oxide or silicon oxide-based dielectric layers include tetraethoxysilane (TEOS), high density plasma (HDP) oxide, phosphosilicate glass (PSG), borophosphosilicate glass (BPSG) Any one or more of high aspect ratio process (HARP) oxide, dielectric phase spin (SOD) oxide, chemical vapor deposition (CVD) oxide, plasma-enhanced tetraethyl ortho silicate (PETEOS), thermal oxide or undoped silicate glass It may comprise, consist of, or consist essentially of. In the past, some examples of substrates that require planarization of the pattern dielectric have been silicon nitride layers (eg, "silicon nitride caps" or "liners"), for example structured semiconductor layers, at locations below the active polishing region of the pattern dielectric material. It was made to include a "cap" on the land surface of the. Silicon nitride is designed to stop polishing and removing the dielectric material in the active region upon reaching the silicon nitride layer. The silicon nitride layer functions to stop the removal of material in the polishing step in a manner intended to reduce trench loss and dishing in the final topography. However, this step adds significant cost to the manufacturing process and may still not completely prevent dishing.

According to the method of the present invention, the substrate may comprise a silicon nitride liner positioned at the intended end of the dielectric polishing and removal step. In other embodiments, the substrate does not require a silicon nitride "liner" or "cap" disposed at the location where the step of removing the dielectric from the active region ends, and may optionally and preferably exclude.

Preferably, the pattern dielectric material is planarized and polished to reduce the initial step between the raised region (with initial height) and the trench (with initial trench thickness). In order to achieve this planarization effectively and efficiently, the method of the present invention has a high removal rate of the elevated region of the (active) pattern dielectric material, with a substantially lower removal rate of the dielectric material of the trench. Most preferably, the method also exhibits self-stop behavior.

During CMP polishing or planarization, the dielectric material is removed from the raised areas and in smaller amounts from the trenches. During polishing, the height of the raised area decreases and eventually becomes essentially the same as the height of the trench. This may mean that the step is reduced to less than 1,000 angstroms, for example less than 900 angstroms, less than 500 angstroms, less than 300 angstroms or less than 250 angstroms. Reducing the height of the raised region removes the pattern of the raised region of the trenches, effectively removing the pattern, and patterning the "blanket dielectric", which means a field of planarizing dielectric, ie a substantially planarized region of the dielectric material. Or "blanket oxide".

Depending on the substrate to be polished, the initial step may be at least 1,000 angstroms, for example at least 2,000 angstroms, or at least 5,000 angstroms, and substantially greater than 7,000 angstroms, for example at least as measured before beginning the step of CMP processing. 10,000 angstroms, at least 20,000 angstroms, at least 30,000 angstroms, or at least 40,000 angstroms. After polishing, the step is reduced and the trench thickness is reduced.

1 illustrates an example substrate having an initial step h ₀ and an initial trench thickness t ₀ . The stepped material may be mostly a dielectric, such as TEOS, BPSG or other amorphous silica-containing material. The key step in 3D NAND dielectric (and other bulk oxide removal) processing is to reduce the step (h ₁ ) (eg, less than about 1,000 GPa, or about 900 GPa, with minimal trench loss (t ₀ -t ₁ ). Less than). For good planarization efficiency, the final step must be achieved without significant trench loss. This requires a polishing composition that has a higher removal rate in the active (ie elevated) region than in the trench region. In addition, preferred polishing compositions will produce "self-stop" or "stop on plane" behavior, allowing for a more effective final polishing without causing overpolishing. Preferably, the polishing composition of the present invention has a much higher pattern removal rate (removal rate in the active region) compared to the removal rate on the blanket (substantially flat) dielectric material.

The removal rate of the dielectric material in the active region is referred to as the removal rate of the pattern material (eg, the pattern removal rate) or the “pattern removal rate” or “active removal rate”. The pattern removal rate achieved using the methods and polishing compositions described herein can be any suitable rate and is very partial depending on the dimensions (eg, pitch and width) of the raised region for any given process and substrate. Will vary. According to a preferred method, the removal rate of the pattern dielectric material is at least about 2,000 angstroms per minute, preferably at least about 4,000 angstroms per minute, for example at least about 5,000 angstroms per minute, at least about 6,000 angstroms per minute, at least about 10,000 angstroms per minute, at least per minute About 14,000 angstroms or at least about 15,000 angstroms per minute.

According to a preferred method, the pattern dielectric can be processed into a flattened surface for less than 5 minutes, for example less than 3 minutes, less than 2 minutes, or less than 1 minute by CMP processing of the pattern dielectric. This may be achieved for a substrate having a patterned dielectric material, including a step of at least 7,000 angstroms, for example at least 10,000 angstroms, at least 20,000 angstroms, at least 30,000 angstroms, or at least 40,000 angstroms. It is believed that the surface is effectively planarized when achieving a reduced step (ie, "residual" step) of less than 1,000 Angstroms (by polishing). Thus, the polishing compositions and methods of the present invention may provide residual steps of less than 1,000 angstroms, such as less than 900 angstroms, less than 500 angstroms, less than 300 angstroms, or less than 250 angstroms.

Furthermore, according to a preferred polishing method using the polishing composition as described herein, trench loss will be reduced compared to the polishing composition that does not contain a self-stopping agent (eg, a compound of formula QB) as described herein. And the planarization efficiency can be improved. Trench loss refers to the difference between the thickness of the trench before CMP processing (t ₀ ) and the thickness of the trench after CMP processing (t ₁ ), ie the trench loss is t ₀ -t ₁ (for a given processing time or result). (FIG. 1). Preferably, the amount of trench loss that will occur during polishing to planarization, or during a given amount of processing time (eg, less than 1,000 angstroms, such as less than 900 angstroms, less than 500 angstroms, less than 300 angstroms, or less than 250 angstroms). Defined as the "residual" step may be reduced by the presence of a self-stopping agent as described herein in the polishing composition as described herein. Thus, the polishing methods described herein are similar using the same process conditions and equipment but with a polishing composition that does not contain a self-stopping agent as described herein (eg, a polishing composition that does not contain a compound of Formula QB). It results in substantially less (eg, at least 10% less) trench loss than the trench loss that would occur in polishing the same type of substrate. Preferably, the method of the present invention for polishing a substrate provides a trench loss of less than about 2,000 angstroms (eg, less than about 1,500 angstroms, less than about 1,000 angstroms, less than about 500 angstroms, or less than about 250 angstroms).

Lower trench losses can be reflected in planarization efficiency, which refers to step reduction reduction divided by trench loss. According to a preferred method of the present invention, the planarization efficiency can be improved by the presence of a self-stopping agent as described herein in the polishing composition as described herein. Thus, the polishing methods described herein are similar types using the same process conditions and equipment but of the same type as polishing compositions (eg, polishing compositions that do not contain a compound of Formula QB) that do not contain the self-stopping agents described herein. This results in a planarization efficiency that is substantially greater (eg, at least 10% greater) than the planarization efficiency that would occur in polishing the substrate of the substrate. Preferably, the present method of polishing the substrate provides a planarization efficiency of at least about 2.0, preferably at least about 3.0, such as at least about 3.5.

Preferred methods can also exhibit self-stop behavior and provide a rate of removal of the dielectric material from the blanket dielectric material (less than 1,000 angstroms, less than 900 angstroms, less than 500 angstroms, less than 300 angstroms, or less than 200 angstroms). (Ie, "blanket removal rate") is significantly lower than the removal rate of the pattern dielectric material. Self-stop behavior is believed to occur when the rate of removal of the blanket dielectric material is less than about 1,000 angstroms per minute. Thus, in a preferred embodiment, the method of the invention removes blanket dielectric material of less than about 1,000 angstroms per minute, for example, less than about 800 angstroms per minute, less than about 500 angstroms per minute, less than about 300 angstroms per minute, or less than about 200 angstroms per minute. To provide speed.

By another means, self-stop behavior can be measured by comparing the removal rate of the blanket dielectric material with the removal rate of the pattern dielectric material. The ratio of low blanket removal rate to pattern removal rate shows good self-stop behavior. Thus, in a preferred embodiment, the ratio of the removal rate of the blanket dielectric material to the removal rate of the pattern dielectric material is less than about 1, for example less than about 0.5, less than about 0.3, or less than about 0.1. Thus, the polishing methods of the present invention are similar using the same process conditions and equipment but with a polishing composition that does not contain a self-stopping agent as described herein (eg, a polishing composition that does not contain a compound of formula QB). This results in a ratio of the blanket removal rate to the pattern removal rate being substantially less (eg, at least about 10% less) than the ratio of the blanket removal rate to the pattern removal rate that will occur to polish the same type of substrate.

In one embodiment, the present invention includes a patterned dielectric layer comprising an initial step of at least about 1,000 Angstroms, wherein the initial step is reduced to less than about 900 Angstroms during polishing to produce a planarization dielectric, wherein the rate of removal of the planarization dielectric Provides a method that is less than about 1,000 Angstroms per minute.

In one embodiment, the present invention provides a method comprising removing at least about 10,000 angstroms of raised regions of a dielectric material from the surface of a patterned dielectric layer.

In one embodiment, the present invention provides a method wherein the ratio of the removal rate of the elevated region of the dielectric material to the removal rate of the trench region of the dielectric material is greater than about 5, preferably greater than about 10, greater than about 15, or greater than about 20. to provide.

In one embodiment, the present invention provides a method wherein the removal rate of an elevated region of dielectric material is greater than about 1000 Angstroms per minute. Thus, in a preferred embodiment, the removal rate of the elevated region of the dielectric material is greater than about 2,000 angstroms per minute, for example, greater than about 4,000 angstroms per minute, greater than about 5,000 angstroms per minute, greater than about 6,000 angstroms per minute, greater than about 10,000 angstroms per minute, Or greater than about 15,000 Angstroms per minute.

In one embodiment, the present invention provides a method wherein the pattern dielectric layer comprises a dielectric material selected from silicon oxide, tetraethoxysilane, phosphosilicate glass, borophosphosilicate glass, and combinations thereof.

Embodiment

(1) In embodiment (1), (a) an abrasive, (b) a self-stopping agent of formula QB, wherein Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, and B is a bonding group Wherein the bonding group has a structure; -C (O) -X-OH or -C (O) -OH, where X is a C1-C2 alkyl group (e.g., formulas (II), (III) and Any of (IV)); And (c) an aqueous carrier, wherein a chemical-mechanical polishing composition having a pH of about 3 to about 9 is presented.

(2) In embodiment (2), the polishing composition of embodiment (1) is provided, wherein the abrasive is selected from ceria, zirconia and combinations thereof.

(3) In embodiment (3), the polishing composition of embodiment (2) is provided wherein the abrasive is ceria.

(4) In embodiment (4), the polishing composition of any one of embodiments (1) to (3) is provided, wherein the abrasive is present in the polishing composition at a concentration of about 0.001% to about 5% by weight.

(5) In embodiment (5), any one of embodiments (1) to (4) wherein Q is selected from alkyl groups, cycloalkyl groups, aromatic groups, heterocyclic groups, heteroaromatic groups, and combinations thereof Abrasive composition is presented.

(6) In embodiment (6), the polishing composition of embodiment (5) is provided wherein Q is substituted with one or more groups selected from hydroxyl groups, alkyl groups, halogens, amine groups, or any combination thereof. .

(7) In embodiment (7), QB is maltol, kojic acid, crotonic acid, tiglic acid, 2-pentenic acid, valeric acid, benzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid The polishing composition of embodiment (1) is selected from caffeic acid, ethyl maltol, potassium sorbate, sorbic acid, and combinations thereof.

(8) In embodiment (8), the polishing composition of any one of embodiments (1) to (7), wherein the self-stopping agent is present in the polishing composition at a concentration of less than about 0.5% by weight.

(9) In embodiment (9), the polishing composition of any one of embodiments (1) to (8) is further provided comprising a cationic polymer.

(10) In embodiment (10), the polishing composition of embodiment (9) is provided wherein the cationic polymer comprises a monomer selected from quaternary amines, cationic polyvinyl alcohol, cationic cellulose and combinations thereof.

(11) In embodiment (11), the cationic polymer comprises a quaternary amine monomer, wherein the quaternary amine monomer is vinylimidazolium, methacryloyloxyethyltrimethylammonium halide, diallyldimethylammonium halide and An abrasive composition of embodiment (10) is selected that is selected from the combination.

(12) In embodiment (12), the cationic polymer is poly (vinylimidazolium), poly (methacryloyloxyethyltrimethylammonium) chloride, poly (diallyldimethylammonium) chloride, polyquaternium-2 and An abrasive composition of embodiment (9) is selected that is selected from combinations thereof.

(13) In embodiment (13), the polishing composition of any one of embodiments (1) to (12) having a pH of about 6.5 to about 8.5 is presented.

(14) In embodiment (14), the polishing composition of any one of embodiments (1) to (12) having a pH of about 3 to about 5 is presented.

(15) In embodiment (15), the polishing composition of any one of embodiments (1) to (14) is further provided comprising a rate enhancer and / or a pH buffer.

(16) In embodiment (16), (a) an abrasive comprising ceria, (b) kojic acid, crotonic acid, tiglic acid, valeric acid, 2-pentenic acid, maltol, benzoic acid, 3,4-dihydroxy A self-terminating agent selected from benzoic acid, 3,5-dihydroxybenzoic acid, caffeic acid, ethyl maltol, potassium sorbate, sorbic acid, and combinations thereof, and (c) an aqueous carrier, wherein the carrier is from about 3 to about 9 A chemical-mechanical polishing composition having a pH is presented.

(7) In embodiment (17), the polishing composition of embodiment (16) having a pH of about 3 to about 5 is shown.

(18) From embodiment (18), from poly (vinylimidazolium), poly (methacryloyloxyethyltrimethylammonium) chloride, poly (diallyldimethylammonium) chloride, polyquaternium-2, and combinations thereof A polishing composition of embodiment (16) is further provided that further includes a leveling agent comprising a selected cationic polymer.

(19) In embodiment (19), the polishing composition of embodiment (18) is shown having a pH of about 6.5 to about 8.5.

(20) In embodiment (20), (a) an abrasive comprising ceria, (b) a self-terminating agent selected from compounds of formula (I), (c) aluminum salts, 2- (dimethylamino) ethyl methacryl Rate, diallyldimethylammonium, poly (vinylimidazolium), poly (methacryloyloxyethyltrimethylammonium) halide, poly (diallyldimethylammonium) halide, polyquaternium-2, polyquaternium-11, poly Quaternium-16, Polyquaternium-46, Polyquaternium-44, RubyQuart Supreme, RubyQuart Hold, RubyQuart Ultracare, RubyQuart FC 370, RubyQuart FC 550, RubyQuart FC 552, RubyQuart Excellence, And a cationic compound selected from combinations thereof, and (d) an aqueous carrier, wherein a chemical-mechanical polishing composition having a pH of about 7 to about 9 is presented.

Wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocyclic alkyl and heterocyclic aryl, each of which may be substituted or unsubstituted.

(21) In embodiment (21), the polishing composition of embodiment (20) having a pH of about 7 to about 9 is presented.

(22) In embodiment (22), (i) providing a substrate comprising a patterned dielectric layer on the surface of the substrate, the patterned dielectric layer comprising an elevated region of the dielectric material and a trenched region of the dielectric material, wherein the patterned dielectric layer The initial step of is the difference between the height of the raised region of the dielectric material and the height of the trench region of the dielectric material), (ii) providing a polishing pad, (iii) any of embodiments (1)-(21) Providing a chemical-mechanical polishing composition of (i) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition, (v) moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to A method of chemically-mechanically polishing a substrate is provided that includes polishing at least a portion of a patterned dielectric layer to polish the substrate.

(23) In embodiment (23), the initial step is reduced to less than about 900 angstroms during polishing to produce a planarized dielectric, the removal rate of the planarized dielectric being less than about 1,000 angstroms per minute, wherein the patterned dielectric layer has an initial of at least about 1,000 angstroms. A polishing method of embodiment (22) is provided that includes a step.

(24) In embodiment (24), a method of polishing of embodiment (22) or embodiment (23) is provided, comprising removing at least about 10,000 angstroms of raised regions of the dielectric material from the patterned dielectric layer.

(25) The method of any one of embodiments (22) to (24), wherein in the embodiment (25), the ratio of the removal rate of the elevated region of the dielectric material to the removal rate of the trench region of the dielectric material is greater than about 5. Presented.

(26) In embodiment (26), the polishing method of any one of embodiments (22) to (25) is provided wherein the removal rate of the elevated region of the dielectric material is greater than about 1,000 angstroms per minute.

(27) The embodiments (22) to (27), wherein the pattern dielectric layer comprises a dielectric material selected from silicon oxide, tetraethoxysilane, phosphosilicate glass, borophosphosilicate glass, and combinations thereof. The polishing method of any one of (26) is presented.

Example

The following examples further illustrate the invention but, of course, should not be understood as limiting its scope.

In the examples the following abbreviations are used: PEG8000 refers to polyethylene glycol having a molecular weight of 8,000 g / mol; pMADQUAT refers to polyMADQUAT; SHA refers to salicylic hydroxamic acid; BHA refers to benzhydrosamic acid; BTA refers to 1H-benzotriazole; TEA refers to triethanolamine; POU refers to a point of use; RR refers to the removal rate; AA refers to the active region; TA refers to trench regions; BW refers to TEOS blanket wafers; SH refers to the step.

Example 1

This example demonstrates the effect on polishing performance in polishing compositions comprising those of self-stopping agents, optionally in combination with cationic compounds.

The patterned substrate was polished with 14 polishing compositions (ie, polishing compositions 1A-1N). Abrasive compositions 1A-1N were prepared by mixing abrasive compositions C1 and C2 (shown in Table 1 below) and additive formulations F1-F15 (shown in Table 2 below) in a 7: 3 volume ratio.

The abrasive compositions C1 and C2 contained ceria abrasive, picolinic acid and water as shown in Table 1. HC60 and HC30 ceria abrasives are commercially available from Rhodia. H-30 ceria abrasive is the wet process ceria described in the previous application (US Published Patent Application 2016/0257855). Abrasive compositions C1 and C2 each had a pH of 4.2.

Table 1: Abrasive Composition

Additive Formulation F4-F15 contained cationic compounds (pMADQUAT)), self-stopping agents (SHA or BHA), and additives (BTA) as shown in Table 2. The pH of each additive formulation F3-F15 was adjusted using triethanolamine (TEA). The additive formulations F1 and F2 did not contain a base and had a pH of 4.2.

Table 2: Additive Formulations

Individually patterned coupon substrates (SKW Associates, Inc.) comprising 250 μm TEOS features (approximately 20,000 μs thick features) with a 50% pattern density initially coated on a patterned silicon substrate having a step of approximately 8,000 μs. (A square cut with 40 mm on each side of the SKW7-2 wafer from SKW Associates, Inc.) on POLI-300 (G & P Tech. Inc.) with a 200 mm CMP platen. Polishing was performed using IC1010 ™ pads (Rohm and Haas Electronic Materials) at 20.68 kPa (3 psi) down force at platen speeds and head speeds of 120 rpm and 110 rpm, respectively, for 60 seconds. The total flow rate of the polishing composition was 200 mL / min. The results are shown in Table 3.

Table 3: Effect of Cationic Compounds and pH on Polishing Performance

As is evident from the results presented in Table 3, polishing compositions 1A and 1B comprising an abrasive formulation with a self-stopping agent (hydroxysamic acid) at an acidic pH (pH 4.2) are preferably active area removal versus trench area removal. The ratio of was shown in the range of about 3-6. Thus, polishing compositions 1A and 1B are preferably "self-stop" compositions that planarize the pattern material while preserving the trench material.

The polishing composition 1I comprising both self-stopping and cationic compounds showed that the ratio of active area removal to trench area removal at pH of 6.1 was approximately 8.6 and active area removal was 777 kPa. Thus, polishing composition 1I is also a “self-stop” composition that planarizes the pattern material while preserving the trench material.

The polishing compositions 1C-1H and 1J-1N comprising both a self-stopping agent and a cationic compound have a ratio of active area removal to trench area removal in the range of about 5.76: 1 to about 50: 1 at a pH of 7.6-8.8 and about Active area removal of 4,700 mm 3 to about 9,000 mm 3 was shown. Thus, polishing compositions 1C-1H and 1J-1N are "self-stop" compositions that planarize the pattern material while preserving the trench material.

Example 2

This example demonstrates the effect on polishing performance in polishing compositions comprising those of self-stopping agents, optionally in combination with cationic compounds.

The patterned substrate was polished with three kinds of polishing compositions (ie, polishing compositions 2A-2C). Abrasive compositions 2B and 2C were prepared using the abrasive composition and additive formulation described in Example 1 (7: 3 volume ratio). Composition 2A (comparative) contained only abrasive formulation C2.

Individual patterns obtained from Silyb Inc. comprising TEOS (features approximately 10,000 mm thick) initially coated at varying widths and densities on a patterned silicon substrate having a step of approximately 5,000 mm 3 3 psi downward force on plated speeds and head speeds of 93 rpm and 87 rpm, respectively, for various times on AP-300 ^™ (CTS Co., Ltd.) with 300 mm CMP platens Under IC1010 ™ pads. The total flow rate of the polishing composition was 250 mL / min.

Table 4: Description of Polishing Compositions 2A-2C

The remaining active thicknesses before and after polishing according to the pitch and pattern density as a result of Example 2 are shown graphically in FIG. 2.

As is apparent from the results shown in FIG. 2, the polishing composition 2C of the present invention containing the polishing agent, benzhydroxamic acid, and polyMADQUAT at a pH (POU) of 7.7, compared to the polishing compositions 2A and 2B, has a polishing time. As increasing, it exhibited a low pattern density dependency, with a stop with uniform topography across the substrate (polishing composition 2C polishing for 90 seconds).

Additional abrasive performance data is presented in Table 5 and FIG. 2. The data in Table 5 shows the remaining active thickness including 900 μm TEOS features (50% pattern density) on the wafer over polishing time.

Table 5: Residual Silicon Oxide with Polishing Time

As is apparent from the results presented in Table 5 and FIG. 2, the polishing composition 2C initially exhibited a lower polishing rate on the pattern material, but the rate decreased as the step reduction decreased compared to the comparative examples (polishing compositions 2A and 2B). Uniformly degraded on the wafer. This example is further formulated in a pH range of about 7.0 to about 8.5 at the point of use with a self-stopping agent (eg, hydroxamic acid) and a cationic compound (eg, pMADQUAT), as compared to the control polishing composition. Verified self-stop polishing composition with respect to topography variation (pattern density dependence) across the substrate and within wafer polishing rate variation (WIWNU).

Example 3

This example demonstrates the effect on the self-stopping agent of the present invention and the polishing performance in the pH range, optionally in combination with cationic compounds.

The pattern substrate and the TEOS-coated silicon substrate were polished using the 14 polishing compositions (ie, polishing compositions 3A-3N) described in Table 7 below. The polishing composition was prepared by mixing the abrasive composition (shown in Table 1) and the additive formulations shown in Table 6 in a 7: 3 volume ratio.

Additive Formulations G1-G5 do not contain cationic compounds, whereas Formulations G6-G14 contain cationic compounds (ie, pMADQUAT or rubyquat supreme). All formulations contained a self-stop agent and additional ingredients as shown in Table 6.

Table 6: Additive Formulations

900 μm TEOS features (approximately 10,000 μs thick features) with a 50% pattern density obtained from patterned wafers from Silicon Inc. and initially coated on a patterned silicon substrate having a step of approximately 5,000 μs ). TEOS blanket wafers were obtained from WRS material. Test wafers were polished for 60 and 90 seconds on patterned and blanket wafers, respectively, using a MIRRA ™ polishing tool (Applied Materials, Inc.). NexPlanar® E6088 (Cabot Microelectronics Corporation) polishing pads were used on a 200 mm platen using 3 psi downforce and at 93 rpm and 87 rpm, respectively. Total slurry flow rate was 150 mL / min. The results are shown in Table 7.

Table 7: Effect of additives and POU pH on polishing performance

As is evident from the results presented in Table 7, all polishing compositions including abrasive formulations with self-stopping agents exhibited high step removal rates on patterns and low oxide removal rates on blanket wafers. This indicates that a significant removal rate drop occurs on the pattern wafer as it is planarized. The ratio of step removal rate to oxide blanket removal rate ranged from approximately 4 to 24, depending on the type of self-stopping agent in combination with the POU pH and the cationic compound.

All publications, including the publications, patent applications, and patents cited above are hereby incorporated by reference to the same extent when each reference is individually and specifically incorporated by reference and its entirety is set forth herein.

In the context of describing the present invention, the singular and “at least one” and similar referents should be construed to encompass both the singular and the plural unless the context clearly dictates otherwise or otherwise clearly contradicts the context. The use of the term “at least one” (eg, “at least one of A and B”) following one or more of the items listed is from an item listed unless otherwise indicated herein or otherwise clearly contradicted by context. It should be construed as meaning one item selected (A or B) or any combination of two or more of the listed items (A and B). The terms "comprising", "having", "including" and "including" are to be interpreted as open-ended terms (ie, meaning "including but not limited to") unless stated otherwise. do. Reference to a range of values herein is intended to serve as a shorthand way of individually referring to each individual value within a range, unless otherwise indicated herein, each individual value cited individually herein. It is included in the specification as it becomes. Unless otherwise indicated herein or otherwise clearly contradicted by context, all methods described herein may be performed in any suitable order. The use of any and all examples, or exemplary language (eg, “such as”) provided herein, is intended to further illustrate the invention and is not intended to limit the scope of the invention unless otherwise claimed. Do not raise. The phraseology in the specification should not be construed as indicating any non-claimed element as essential to the practice of the invention.

Preferred embodiments of the invention are described herein, including the best mode known to the inventors for carrying out the invention. Modifications of the preferred embodiments thereof will become apparent to those skilled in the art upon reading the above specification. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as explicitly described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable legislation. Moreover, unless otherwise indicated herein or otherwise clearly contradicted by context, any combination of the above-described elements in all possible variations of the invention is included in the invention.

Claims (20)

(a) an abrasive selected from ceria, zirconia and combinations thereof,
(b) a self-stopping agent selected from compounds of formula (II), compounds of formula (III), compounds of formula (IV), and combinations thereof

Wherein each X ¹ -X ³ is independently selected from N, O, S, sp ² -hybridized carbon, and CY ¹ Y ² , wherein each Y ¹ and Y ² are independently hydrogen, hydroxyl, C ₁ -C ₆ alkyl, halogen, and combinations thereof, each Z ¹ -Z ³ is independently selected from hydrogen, hydroxyl, C ₁ -C ₆ alkyl, and combinations thereof, each of which is substituted or unsubstituted Can be;

Where Z is N, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkynyl, and aryl (eg, phenyl, benzyl, naphthyl, azulene, anthracene, pyrene, etc.) And X ¹ and X ² are independently selected from hydrogen, hydroxy, amino, and C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, wherein X ¹ and X ² together with the attached carbon sp ² -hybridized carbon can be formed, n is 1 or 2, p is 0-4, M is selected from hydrogen and a suitable counterion (eg, Group I metal), each of which is substituted or Can be unsubstituted;

Wherein X, Y and Z are independently selected from H, O, S, NH and CH ₂ , and R ¹ , R ² and R ³ are independently H, alkyl, alkenyl, alkynyl, aryl, halo and haloalkyl Is selected from M and hydrogen is selected from a suitable counterion, and
(c) aqueous carrier
A chemical-mechanical polishing composition comprising: and having a pH of about 3 to about 9 The polishing composition of claim 1 further comprising a rate enhancer. The polishing composition of claim 1, wherein the abrasive is present in the polishing composition at a concentration of about 0.001% to about 5% by weight. The method of claim 1 wherein the self-stopping agent is maltol, ethyl maltol, kojic acid, benzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, caffeic acid, ethyl maltol, sorbic acid, butyric acid, valeric Acids, hexanoic acid, tiglic acid, angelic acid, crotonic acid, sorbic acid, diferipron, 2-hydroxy nicotinic acid, 2-pentenoic acid, 3-pentenoic acid, other saturated and unsaturated alkyl carboxylic acids, salts thereof, and Polishing composition selected from combinations thereof. The polishing composition of claim 1, wherein the self-stopping agent is present in the polishing composition at a concentration of about 1% by weight or less. The polishing composition of claim 1 further comprising a cationic compound selected from polymers, oligomers, small molecules, salts, and combinations thereof. The polishing composition of claim 6, wherein the cationic compound is a polymer or oligomer comprising a monomer selected from quaternary amines, cationic polyvinyl alcohol, cationic cellulose and combinations thereof. The method of claim 7, wherein the cationic compound is a polymer or oligomer comprising a quaternary amine monomer, wherein the quaternary amine monomer is vinylimidazolium, methacryloyloxyethyltrimethylammonium halide, diallyldimethylammonium halide and its A polishing composition selected from the combination. The method of claim 6, wherein the cationic compound is 2- (dimethylamino) ethyl methacrylate, diallyldimethylammonium, poly (vinylimidazolium), poly (methacryloyloxyethyltrimethylammonium) halide, poly (di Allyldimethylammonium) halide, polyquaternium-2, polyquaternium-11, polyquaternium-16, polyquaternium-46, polyquaternium-44, rubyquat supreme, rubyquat hold, rubyquat ultracare, ruby A polishing composition that is a cationic oligomer or cationic polymer selected from quart FC 370, ruby quart FC 550, ruby quart FC 552, ruby quart Excellence, and combinations thereof. The polishing composition of claim 1 having a pH of about 6.0 to about 8.5. The polishing composition of claim 1 having a pH of about 3 to about 5. 6. (a) an abrasive selected from ceria, zirconia and combinations thereof,
(b) a self-terminating agent selected from compounds of formula (I)

Wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, heterocyclic alkyl and heterocyclic aryl, each of which may be substituted or unsubstituted,
(c) cationic polymers,
(d) aqueous carrier
And a chemical-mechanical polishing composition comprising a pH of about 7 to about 9. 9. 13. The polishing composition of claim 12, wherein the self-stopping agent is selected from hydroxamic acid, acetohydroxysamic acid, benz hydroxamic acid, salicylic hydroxamic acid and combinations thereof. The method of claim 12, wherein the cationic polymer is 2- (dimethylamino) ethyl methacrylate, diallyldimethylammonium, poly (vinylimidazolium), poly (methacryloyloxyethyltrimethylammonium) halide, poly (di Allyldimethylammonium) chloride, polyquaternium-2, polyquaternium-11, polyquaternium-16, polyquaternium-46, polyquaternium-44, rubyquat supreme, rubyquat hold, rubyquat ultracare, ruby A polishing composition selected from Quart FC 370, RubyQuart FC 550, RubyQuart FC 552, RubyQuart Excellence, and combinations thereof. 13. The polishing composition of claim 12 further comprising a rate enhancer. The polishing composition of claim 12, wherein the self-stopping agent is present in the polishing composition at a concentration of about 1% by weight or less. The polishing composition of claim 12, wherein the abrasive is ceria. The polishing composition of claim 12, wherein the abrasive is present in the polishing composition at a concentration of about 0.001% to about 5% by weight. (i) providing a substrate comprising a patterned dielectric layer on a surface of the substrate,
(ii) providing a polishing pad;
(iii) providing the chemical-mechanical polishing composition of claim 1;
(iv) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition; And
(v) polishing the substrate by moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to grind at least a portion of the patterned dielectric layer on the surface of the substrate.
And chemically-mechanically polishing the substrate. (i) providing a substrate comprising a patterned dielectric layer on a surface of the substrate,
(ii) providing a polishing pad;
(iii) providing the chemical-mechanical polishing composition of claim 12;
(iv) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition; And
(v) polishing the substrate by moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to grind at least a portion of the patterned dielectric layer on the surface of the substrate.
And chemically-mechanically polishing the substrate.

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