KR102671229B1 - Self-stopping polishing compositions and methods for bulk oxide planarization - 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 substrates.

Description

Self-stopping polishing compositions and methods for bulk oxide planarization

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

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 substrates. CMP utilizes chemical compositions known as CMP compositions or more simply polishing compositions (also referred to as polishing slurries) to selectively remove material from a substrate. The polishing composition is typically applied to the substrate by contacting the surface of the substrate with a polishing pad (e.g., a 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 (e.g., 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 together to conform to 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 area of the integrated circuit. More specifically, shallow trench isolation (STI) is a process in which a layer of silicon nitride is formed on a silicon substrate, a shallow trench is formed through etching or photolithography, and a dielectric layer is deposited to fill the trench. Because of the variation 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. The dielectric material (eg, silicon oxide) follows the underlying topography of the substrate.

Accordingly, after the dielectric material has been disposed, the surface of the deposited dielectric material is characterized by a non-uniform combination of raised areas of dielectric material separated by trenches in the dielectric material, with the raised areas of dielectric material and the trenches forming the underlying dielectric material. They are aligned with corresponding raised areas and trenches of the surface. The region of the substrate surface containing the raised dielectric material and the trench is referred to as the patterned field of the substrate, e.g., “patterned material,” “patterned oxide,” or “patterned dielectric.” The pattern field is characterized by a "step", which is the difference in the height of the raised areas of dielectric material relative to the trench height.

Excess dielectric material is typically removed by a CMP process, which provides an additional planar surface for further processing. During removal of the raised area material, an amount of material from the trench will also be removed. This removal of material from the trench is referred to as “trench erosion” or “trench loss.” Trench loss is the amount of material (in thickness, for example, Angstroms (Å)) removed from the trench to achieve planarization of the patterned dielectric material by removing the initial steps. 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 material removal from the raised area. Therefore, when the material in the raised areas is removed (at a faster rate compared to material removed from the trench), the patterned dielectric is transferred to the "blanket" area of the machined substrate surface, i.e., the "blanket dielectric" or "blanket oxide." This results in a highly flattened surface that can be referred to as ".

Polishing compositions can be characterized according to their polishing rate (i.e., removal rate) and their planarization efficiency. Polishing rate refers to the rate of removal of material from the surface of a substrate, and is typically expressed as units of length (thickness, e.g., Angstroms (Å)) per unit of time (e.g., per minute). Different removal rates associated with different regions of the substrate, or different stages of the polishing step, may be important in evaluating process performance. “Pattern removal rate” is the rate of removal of dielectric material from the raised areas of the patterned dielectric layer at a 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 (i.e., “blanket”) region of the patterned dielectric layer at the end of the polishing step when the step has been significantly (substantially) reduced. Planarization efficiency relates to step reduction (i.e. step reduction divided by trench loss) relative to the amount of material removed from the substrate. Specifically, a polishing surface, such as a polishing pad, must first contact the "high spots" of the surface and remove material to form a planar surface. Processes that achieve a planar surface while removing less material are believed to be more efficient than processes that require the removal of more material to achieve the planar surface.

Often the removal rate of the silicon oxide pattern material can be rate-limiting for the dielectric polishing step during the STI process, and therefore a high removal rate of the silicon oxide pattern is desirable to increase device throughput. However, if the blanket removal rate is too fast, overabundance of oxide in the exposed trenches results in trench erosion and increased device failure. Overabrasion and associated trench loss can be avoided if the blanket removal rate is slowed.

In certain polishing applications, it is desirable for the CMP composition to exhibit "self-resting" behavior where the removal rate decreases when a large percentage of the "high spots" (i.e., raised areas) of the surface are removed. In self-stop polishing applications, the removal rate is effectively high as long as there is a significant step in the substrate surface, and then the removal rate slows down as the surface becomes effectively planar. In various dielectric polishing steps (e.g., those of STI processes), the rate of removal of patterned dielectric material (e.g., dielectric layer) is typically the rate-limiting factor of the overall process. Accordingly, high removal rates of patterned dielectric material are desirable to increase throughput. Good efficiency in the form of relatively low trench losses is also desirable. Additionally, if the rate of dielectric removal remains high after planarization is achieved, over-abrasion occurs and trench loss is added.

The benefits of self-sustaining slurries result from reduced blanket removal rates, which create wide endpoint windows. For example, self-stopping behavior allows polishing of substrates with reduced dielectric film thickness, allowing a reduced amount of material to be deposited on the structured underlying layer. Additionally, motor torque endpoint detection can be used for more effective monitoring of the final topography. The substrate can be polished with lower trench loss by preventing overpolishing or unnecessary removal of dielectric after planarization.

Self-suspending 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 comprising ceria, carboxylic acid and mixed amine compounds (English abstract). International Patent Application Publication No. WO2006/115393 discloses a polishing composition comprising ceria, hydroxycarboxylic acid and amino alcohol. However, as the structures of semiconductor devices become more complex, especially as NAND technology moves from 2D to 3D, the use of anionic polymers makes it difficult for current self-stopping CMP compositions to overcome electrostatic repulsion between the abrasive and the silicon oxide surface. It is becoming a problem due to the limited speed of step reduction caused by .

There remains a need for compositions and methods for chemical-mechanical polishing of silicon oxide-containing substrates that will provide useful removal rates while also providing improved planarization efficiency. The present invention provides such polishing compositions and methods. These and other advantages of the invention, as well as additional inventive features, will become 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 present invention relates to (a) an abrasive, (b) a self-stopping agent of the formula Q-B, where Q is a substituted or unsubstituted hydrophobic group, or a sterically hindering group, and B is a linking group, where The linking group has the structure: C(O)-X-OH or -C(O)-OH, wherein It provides a chemical-mechanical polishing composition having a.

In addition, the present invention provides (a) an abrasive containing 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-stopping 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 ) a chemical-mechanical polishing composition comprising an aqueous carrier and having a pH of about 3 to about 9.

The present invention also provides (a) an abrasive comprising ceria, (b) a compound selected from 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, and having a pH of from about 3 to about 9 is provided.

where 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 ​ ​ ​ ​ ​} _​ -C ₆ alkyl, halogen, and combinations thereof, and 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 selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkynyl, and aryl (e.g., 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 ^{, where} X ¹ and , n is 1 or 2, p is 0-4, M is selected from hydrogen and a suitable counterion (e.g., a Group I metal), each of which may be substituted or unsubstituted;

_wherein ^{​ ​ ​} and M is selected from hydrogen and a suitable counterion.

The present invention further provides a substrate comprising (i) a patterned dielectric layer comprising raised regions (e.g., active regions to peripheral regions) of dielectric material on a surface of the substrate, wherein the patterned dielectric layer (i) providing a polishing pad, (iii) providing a chemical-mechanical polishing composition described herein, (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 grind at least a portion of the patterned dielectric layer on the surface of the substrate. It includes polishing, and provides a method for chemically-mechanically polishing a substrate.

Figure 1 (not to scale) shows a cross-sectional view of an example substrate to illustrate the active area, trench area, steps and trench losses.
Figure 2 shows the polishing performance of a substrate according to the pitch width and pattern density of the polishing composition of the present invention.

The present invention provides (a) an abrasive, (b) a self-stopping agent of the formula Q-B, wherein Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, and B is a linking group, wherein the linking group has the structure: C(O)-X-OH or -C(O)-OH, wherein A mechanical polishing composition is provided.

The polishing composition of the present invention includes an abrasive. The abrasive of the polishing composition is preferably suitable for polishing non-metallic portions of the substrate (e.g., patterned dielectric material, blanket dielectric material, patterned 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 abrasives and zirconia abrasives are well known in the CMP art and are commercially available. Examples of suitable ceria abrasives include wet-processed ceria, calcined ceria, and metal-doped ceria, among others. Examples of suitable zirconia abrasives include, among others, metal-doped zirconia and non-metal-doped zirconia. Among the metal doped zirconias are preferably cerium-, calcium-, magnesium-, or yttrium-doped zirconia with dopant element weight percentages 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 U.S. Patent Application No. 14/639,564, filed March 5, 2015 (now U.S. Patent No. 9,505,952), entitled “Polishing Composition Containing Ceria Abrasive.” and U.S. Patent Application No. 15/207,973, filed July 12, 2016, entitled “Methods and Compositions for Processing Dielectric Substrate,” published as U.S. Patent Application Publication No. 2017/0014969, the disclosures of which are incorporated herein by reference. Incorporated by reference.

The preferred abrasive is wet processed ceria particles. The polishing composition may include a single type of abrasive particle or multiple different types of abrasive particles based on size, composition, manufacturing method, particle size distribution, or other mechanical or physical properties. Ceria abrasive particles can be manufactured by a variety of different processes. For example, the ceria abrasive particles can be precipitated ceria particles, including colloidal ceria particles, or condensation-polymerized ceria particles.

Ceria abrasive particles can be manufactured by any suitable process. As an 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 dissolving the ceria precursor in water. The ceria precursor may be any suitable ceria precursor and may include a ceria salt with any suitable charge, for example Ce ³⁺ or Ce ⁴⁺ . Suitable ceria precursors include, for example, cerium III nitrate, cerium IV ammonium nitrate, cerium III carbonate, cerium IV sulfate, and cerium III chloride. Preferably, the ceria precursor is cerium III nitrate.

The pH of the ceria precursor solution is typically increased to form amorphous Ce(OH) ₃ . The pH of the solution may be increased to any suitable pH. For example, the pH of the solution may be increased to a pH greater than about 10, a pH greater than about 10.5, a pH greater than about 11, or a pH greater than about 12. Typically, the solution will have a pH of about 14 or less, for example a pH of about 13.5 or less, or a pH of about 13 or less. Any suitable base may 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 cloudy, and amorphous Ce(OH) ₃ is formed.

Ceria precursor solutions are typically mixed for several hours. For example, the solution may be maintained for 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 Mixing may occur for approximately 24 hours or more. Typically, the solution is mixed for about 1 hour to about 24 hours, such as 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 have a temperature below about 500°C, such as below about 450°C, below about 400°C, below about 375°C, below about 350°C, below about 300°C, below about 250°C, below about 225°C. It may be heated to a temperature of less than or equal to about 200°C. Accordingly, the solution can be heated to a temperature within a range limited by any two of the end points mentioned above. For example, the solution may have a temperature of 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 It can be 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 maintained for at least about 1 hour, such as 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. It can be heated. Alternatively or additionally, the solution may be heated for up to about 200 hours, such as 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. You can. Accordingly, the solution can be heated for a limited period of time to any two of the above-mentioned endpoints. For example, the solution may be maintained for about 1 hour to about 150 hours, such as about 5 hours to about 130 hours, about 10 hours to about 120 hours, about 15 hours to about 115 hours, or about 25 hours to about 100 hours. It can be heated.

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

The ceria particles may optionally be dried and sintered prior to redispersion. The terms “sintering” and “calcining” are used interchangeably herein to refer to heating of ceria particles under the conditions described below. Sintering of ceria particles affects their resulting crystallinity. Without wishing to be bound by any particular theory, it is believed that sintering the ceria particles at high temperatures reduces defects in the crystal lattice structure of the particles over an extended period of time. Any suitable method may be used to sinter the ceria particles. As an example, ceria particles can be dried and then sintered at elevated temperatures. Drying can be carried out at room temperature or at elevated temperature. In particular, drying may be carried out 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 carried out 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 are dried, they can be ground to produce a powder. Grinding may 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 heated above about 200°C, for example above about 215°C, above about 225°C, above about 250°C, above about 275°C, above about 300°C, above about 350°C, or above about 375°C. It can be sintered at any temperature. Alternatively or additionally, the ceria particles may have a temperature below about 1000°C, such as below about 900°C, below about 750°C, below about 650°C, below about 550°C, below about 500°C, below about 450°C, or below about 400°C. It can be sintered at temperatures below ℃. Accordingly, ceria particles can be sintered at temperatures limited to any two of the above-mentioned endpoints. For example, the ceria particles may have a temperature of about 200°C to about 1000°C, such as about 250°C to about 800°C, about 300°C to about 700°C, about 325°C to about 650°C, about 350°C to about 600°C, It can be 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 can be sintered for at least about 1 hour, such as 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 no more than about 20 hours, no more than about 18 hours, no more than about 15 hours, no more than about 12 hours, or no more than about 10 hours. Accordingly, the ceria particles can be sintered for a limited period of time to any two of the above-mentioned endpoints. For example, the ceria particles may be heated 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, Alternatively, it may be sintered for about 10 hours to about 20 hours.

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

The ceria particles are typically redispersed in a suitable carrier, for example an aqueous carrier, especially water. When the ceria particles are sintered, the ceria particles are redispersed after completion of sintering. Any suitable process may be used to redisperse the ceria particles. Typically, the ceria particles are redispersed by lowering the pH of the mixture of ceria particles and water using a suitable acid. As the pH decreases, the surface of the ceria particle develops a cationic zeta potential. This cationic zeta potential creates a repulsive force between ceria particles, which facilitates their redispersion. Any suitable acid may 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 undesirable. The pH of the mixture may be lowered to any suitable pH. For example, the pH of the mixture may be lowered from about 2 to about 5, such as about 2.5, about 3, about 3.5, about 4, or about 4.5. Typically, the pH of the mixture does not fall below about 2.

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

The abrasive particles (e.g., 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 containing the particle. The particle size of abrasive particles can be measured using any suitable technique. For example, the particle size of abrasive particles can be measured by disk centrifugation, i.e. differential centrifugal sedimentation (DCS). Suitable disk centrifuge particle size measurement instruments are commercially available, for example, from CPS Instruments (Prairieville, Louisiana), for example, in the CPS disk centrifuge model DC24000UHR. Unless otherwise specified, median particle size values reported and claimed herein are based on disk centrifugation measurements.

By way of example, the abrasive particles (e.g., ceria abrasive particles) can 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, at least about 70 nm. It may have a median particle size of greater than or equal to about 75 nm, or greater than or equal to about 80 nm. Alternatively or additionally, the abrasive particles may be about 100 nm or less, such as 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 nm or less. It may have a median particle size of less than nm. Accordingly, the abrasive particles may have an average particle size within a range limited by any two of the above-mentioned endpoints. For example, the abrasive particles can be about 40 nm to about 100 nm, such as about 40 nm to about 80 nm, about 40 nm to about 75 nm, about 40 nm to about 60 nm, 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, for example 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 include any suitable amount of abrasive. If the composition contains too little abrasive, the composition may not exhibit sufficient removal rates. In contrast, if the polishing composition includes too much ceria abrasive, the polishing composition may exhibit undesirable polishing performance, may not be cost-effective, and/or may lack stability. Accordingly, the abrasive may be present in the polishing composition in a concentration of up to about 5% by weight, for example up to about 4% by weight, up to about 3% by weight, up to about 2% by weight, or up to about 1% by weight. Alternatively or additionally, the abrasive may be present in the polishing composition in an amount of at least about 0.001% by weight, for example at least about 0.005% by weight, at least about 0.01% by weight, at least about 0.05% by weight, at least about 0.1% by weight, or at least about 0.5% by weight. It can exist in any concentration. Accordingly, the abrasive may be present in the polishing composition in a concentration limited to any two of the above-mentioned endpoints. For example, the abrasive may be present in the polishing composition in an amount of from about 0.001% to about 5% by weight, such as from about 0.005% to about 4% by weight, from about 0.01% to about 3% by weight, or from about 0.05% to about 2% by weight. %, or may be present in a concentration of 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 (e.g., copper, silver, tungsten, etc.) on the surface of a substrate. For example, polishing compositions typically do not include substantial amounts of certain metal oxides (e.g., alumina) suitable for polishing metal surfaces. Typically, the polishing composition includes less than 0.1 weight percent of abrasives other than ceria abrasives and zirconia abrasives, based on the total weight of abrasives in the polishing composition. For example, the polishing composition may include 0.05 weight percent or less of an abrasive other than ceria abrasive and zirconia abrasive, or 0.01 weight percent or less of an abrasive other than ceria abrasive and zirconia abrasive. More specifically, the polishing composition may include 0.05% by weight or less of metal oxides other than ceria and zirconia or 0.01% by weight or less of metal oxides other than ceria and zirconia.

The polishing agent is preferably suspended in the polishing composition, more specifically in the aqueous carrier component of the polishing composition. More specifically, when the abrasive contains 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 a suspension over time. In the present invention, when the abrasive particles are placed in a 100 ml graduated cylinder and left to stand without stirring for 2 hours, the particle concentration ([B]; g/ml) in the lower 50 ml of the graduated cylinder and the upper 50 ml of the graduated cylinder The difference in particle concentration ([T]; g/ml) divided by the initial concentration of particles in the abrasive composition ([C]; g/ml) is 0.5 or less (i.e., {[B]-[T]}/[ [C]≤0.5), it is considered colloidally stable. The value of {[B]-[T]}/[C] is preferably 0.3 or less, more preferably 0.1 or less.

The polishing composition of the present invention includes a self-stopping agent. Self-stoppers are compounds that promote relatively high pattern removal rates and relatively low blanket removal rates and, upon planarization during polishing, promote the transition from high pattern removal rates to relatively low blanket removal rates. Without wishing to be bound by any particular theory, a self-stopping agent is a ligand that promotes self-stopping behavior by attaching to an abrasive (e.g., ceria or zirconia) and providing 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, such as isothermal titration calorimetry (ITC).

Without wishing to be bound by any particular theory, it is believed that the self-restoring agent promotes a non-linear response to a given downward force (DF) on the tetraethoxysilane (TEOS) blanket dielectric material. During polishing, the patterned dielectric material experiences a higher effective downward force (DF) than that of the blanket dielectric material because the contact spreads to only a small portion of the patterned dielectric material that comes into contact with the pad. The higher effective DF applied to the TEOS patterned dielectric material results in a “high” removal rate (e.g., pattern removal rate) polishing regime with a TEOS removal rate of approximately 8,000 Å/min, where the lower effective DF is approximately This results in a “stationary” polishing regime with a TEOS removal rate (e.g., blanket removal rate) of less than 1,000 Å/min. The difference between "high" and "stationary" regimes is typically broken down such that for a given DF either a "high" or a "quiescent" removal rate is observed. Accordingly, it is believed that self-rest agents enable desirably “high” removal rates (i.e. pattern removal rates), even when the applied DF is in a “stationary” mode as measured with a blanket wafer.

Additionally, note that the mechanism is not dependent on DF alone, since the trench oxide removal rate on the patterned 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 polishing applications, the concentration of the self-stopping agent plays a role in the observed effect, since at low concentrations the self-stopping agent acts as a rate enhancer (e.g., at “high” removal rates the self-stopping agent acts as a rate enhancer). observed), at higher concentrations self-arresting behavior is observed (e.g., a “stationary” removal rate is observed). Accordingly, some rate enhancers may have a dual action. For example, if the polishing composition includes lower concentrations of picolinic acid, picolinic acid may function as a rate enhancer. However, when the polishing composition includes picolinic acid in higher concentrations, picolinic acid can function as a self-stopping agent. Typically, picolinic acid functions as a rate enhancer at concentrations less than about 1000 ppm by weight (e.g., about 500 ppm, about 250 ppm, etc.).

In some embodiments of the invention, the self-stopping agent is of the formula Q-B, where Q is a substituted or unsubstituted hydrophobic group, or a group that imparts steric hindrance, and B is a linking group such as -C(O)- C-OH, -C(O)-C-C-OH or -C(O)-OH. For example, in some embodiments the invention comprises an abrasive, a self-stopping agent of Formula Q-B, a cationic compound, and an aqueous carrier (e.g., water), and has about 3 to about 9 (e.g., about 6.5 to about 8.5).

In some embodiments of the invention, the self-stopping agent is of the formula Q-B, where Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, and B is a linking group, wherein the linking group has the structure: It has C(O)-X-OH or -C(O)-OH. Here, X is a C1-C2 alkyl group. When the self-stopping agent is a compound of formula Q-B as described herein, Q may be any suitable hydrophobic group, or any suitable group that imparts steric hindrance. Suitable hydrophobic groups include saturated and unsaturated hydrophobic groups. Hydrophobic groups may be linear or branched and may include linear or branched alkyl groups, cycloalkyl groups, and ring structures, including 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 (e.g. C ₁ -C ₃₀ alkyl groups, C ₁ -C ₂₄ alkyl group, C _l -C ₁₈ alkyl group, C ₁ -C ₁₂ alkyl group, or even C ₁ -C ₆ alkyl group), for example at least 1 carbon atom (i.e. methyl), at least 2 carbon atoms (i.e. e.g. ethyl, vinyl), at least 3 carbon atoms (e.g. propyl, isopropyl, propenyl, etc.), at least 4 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 14 carbon atoms, at least 15 carbon atoms, at least 16 carbon atoms, at least 17 carbon atoms, at least 18 carbon atoms atoms, at least 19 carbon atoms, at least 20 carbon atoms, at least 25 carbon atoms, or at least 30 carbon atoms.

A substituted group refers to a group in which one or more carbon-bonded hydrogens have been replaced by a non-hydrogen atom. Exemplary substituents include, for example, hydroxyl groups, keto groups, esters, amides, halogens (e.g. fluorine, chlorine, bromine and iodine), amino groups (primary, secondary, tertiary and/or or level 4), and combinations thereof.

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

Q may be an aromatic group. Suitable aromatic groups include substituted or unsubstituted aromatic groups having, for example, 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 include, for example, hydroxyl groups, carboxylic acid groups, ester groups, ketone groups, amino groups (e.g. primary, secondary and tertiary amino groups), amido groups, imido groups. 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 can be saturated and unsaturated, substituted or unsubstituted. Heterocyclic compounds refer to 5-, 6-, or 7-membered ring systems with one or more heteroatoms (e.g., N, O, S, P, or B) contained as part of the ring system. Exemplary heterocyclic compounds include, for example, triazole, aminotriazole, 3-amino-1,2,4-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid, 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-oxide. Includes seeds, etc. Other exemplary heterocyclic compounds include, for example, pyrone compounds, pyridine compounds (including regioisomers and stereoisomers), pyrrolidine, delta-2-pyrroline, imidazolidine, delta-2-imidazoline, Includes delta-3-pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, quinuclidine, indoline, isoindoline, chroman, isochroman, and combinations thereof.

Suitable heteroaromatic groups include, for example, pyridine, thiophene, furan, pyrrole, 2H-pyrrole, imidazole, pyrazole, isoxazole, furazane, isothiazole, pyran (2H), pyrazine, pyrimidine, pyridazine, Isobenzofuran, indolizine, indole, 3H-indole, 1H-indazole, purine, isoindole, 4aH-carbazole, carbazole, beta-carboline, 2H-chromene, 4H-quinolizine, isoquinoline, Quinoline, quinoxaline, 1,8-naphthyridine, phthalazine, quinazoline, cinnoline, pteridine, xanthene, tetraline, 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 imparts 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-terminating agents with such Q groups are maltol, ethyl maltol, and kojic acid.

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

In some embodiments, the self-stopping agent Q-B is kojic acid, maltol, ethyl maltol, propyl maltol, hydroxamic acid, benzhydroxamic acid, salicylhydroxamic acid, benzoic acid, 3,4-dihydroxybenzoic acid, 3, selected from 5-dihydroxybenzoic acid, caffeic acid, sorbic acid, and combinations thereof.

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

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

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

Compounds of formula (I) have the structure:

where 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.

Compounds of formula (II) have the structure:

^{wherein each ​ ​ ​ ​ ​} _​ C ₆ alkyl, halogen, and combinations thereof, and 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. You can.

Compounds of formula (III) have the structure:

Z is selected from N, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkynyl, and aryl (e.g., phenyl, benzyl, naphthyl, azulene, anthracene, pyrene, etc.) being selected; X ¹ and X ² are independently selected from hydrogen, hydroxy, amino, and C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl; where ^{X 1 and} group metals), each of which may be substituted or unsubstituted.

Compounds of formula (IV) have the structure:

_wherein ^{​ ​ ​} is selected from alkyl, and M is selected from hydrogen and a suitable counterion.

The polishing composition may include any suitable amount of a self-stopping agent (e.g., a compound of formula Q-B). If the composition contains too little self-stopping agent, the composition may not exhibit adequate self-stopping behavior. In contrast, if the polishing composition includes too much self-stopping agent, the composition may exhibit undesirable polishing performance, may not be cost-effective, and/or may lack stability. Accordingly, the polishing composition may include up to about 2% by weight, for example, up to about 1% by weight, up to about 0.5% by weight, up to about 0.1% by weight, or up to about 0.01% by weight of self-stopping agent. Alternatively or additionally, the polishing composition may have at least about 0.0001 weight percent, such as at least about 0.0005 weight percent, at least about 0.001 weight percent, at least about 0.005 weight percent, at least about 0.01 weight percent, or at least about 0.05 weight percent self-restoring. may include provisions. Accordingly, the polishing composition may include a self-stopping agent in a concentration limited to any two of the above-mentioned endpoints. For example, the self-stopping agent may be present in the polishing composition in an amount of from about 0.0001% to about 2% by weight, such as from about 0.0005% to about 1% by weight, from about 0.001% to about 0.5% by weight, from about 0.005% to about 0.005% by weight. It may be present in a concentration of about 0.1% by weight, or from about 0.01% to about 0.05% by weight.

In some embodiments, the polishing compositions of the present invention include up to about 0.5 weight percent (e.g., up to about 5,000 ppm) of a self-stopping agent. In some embodiments, the polishing composition comprises about 2,500 ppm (0.25% by weight) or less of a self-stopping agent, such as about 2,000 ppm or less, about 1,500 ppm or less, about 1,000 ppm or less, or about 500 ppm or less.

In some embodiments, the polishing compositions of the present invention include a self-stopping agent in combination with a leveling agent (i.e., a cationic compound), also referred to as a topography control agent. Without wishing to be bound by any particular theory, cationic compounds act as levelers to improve the topography of the polished substrate, which typically slows down the oxide removal rate by binding to the negatively charged oxide surface. It is believed that it is because they are told to do so. Cationic compounds also improve the planarization efficiency of self-stopping compositions under higher pH polishing conditions (e.g., having a pH of about 6.5 to about 8.5, a pH of about 7.0 to 8.5).

The cationic compound may be a polymer comprising monomers selected from quaternary amines, cationic polyvinyl alcohol, cationic cellulose, and combinations thereof. Accordingly, the cationic polymer may include quaternary amines, cationic polyvinyl alcohol, cationic cellulose, and combinations thereof.

Suitable quaternary amine monomers include, for example, vinylimidazolium, methacryloyloxyethyltrimethylammonium halide, diallyldimethylammonium halide, and combinations thereof. Accordingly, 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] ( i.e. polyquaternium-2), a copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate (i.e. polyquaternium-11), a copolymer of vinylpyrrolidone and quaternized vinylimidazole ( i.e. polyquaternium-16), a terpolymer of vinylcaprolactam, vinylpyrrolidone, and quaternized vinylimidazole (i.e. polyquaternium-46), and 3-methyl-1-vinylimidazolium methyl. and a quaternary amine selected from sulfate-N-vinylpyrrolidone copolymers (i.e. polyquaternium-44). Additionally, suitable cationic polymers include cationic polymers for personal care, such as Luviquat® Supreme, Luviquat® Hold, Luviquat® Ultracare, Luviquat® FC 370, Luviquat® FC 550, Luviquat® ® FC 552, Rubyquat® Excellence, and combinations thereof. Any combination of cationic polymers mentioned herein may be used.

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

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

The cationic polymer may 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 the Nippon Gosei GOHSEFIMER K210™ polyvinyl alcohol product.

If present, the cationic polymer (i.e., quaternary amine, cationic polyvinyl alcohol, cationic cellulose, or combinations thereof as a whole) may be present in the polishing composition in any suitable concentration. Typically, the cationic polymer is present in the polishing composition in an amount of about 1 ppm to about 500 ppm, for example about 1 ppm to about 475 ppm, about 1 ppm to about 450 ppm, about 1 ppm to about 425 ppm, 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, from about 10 ppm to about 215 ppm, from about 10 ppm to about 100 ppm, from about 15 ppm to about 200 ppm, from about 25 ppm to about 175 ppm, from about 25 ppm to about 100 ppm, or from about 30 ppm It is present in a concentration of approximately 150 ppm. Unless otherwise stated, ppm concentrations listed herein reflect the weight-based ratio of the components to the total weight of the polishing composition.

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

The polishing composition may be a carboxylic acid monomer, a sulfonated monomer, or an anionic copolymer of an acrylate with a phosphonated monomer, polyvinylpyrrolidone, or polyvinyl alcohol (e.g., 2-hydroxyethylmethacrylic acid and copolymer of acrylic acid); It may optionally include additives selected from nonionic polymers, wherein the nonionic polymer is polyvinylpyrrolidone or polyethylene glycol; silanes (where silane is amino silane, ureido silane, or glycidyl silane); N-oxides of functionalized pyridines (eg, picolinic acid N-oxide); starch; cyclodextrins (e.g., alpha-cyclodextrin or beta-cyclodextrin), 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, the polyvinylpyrrolidone may be from about 10,000 g/mol to about 1,000,000 g/mol, such as 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, such as about 8000 g/mol, or about 100,000 g/mol.

If the additive is a silane, the silane may be any suitable amino silane, ureido silane, or glycidyl silane. For example, silanes include 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 It may be 3-glycidopropyldimethylethoxysilane.

Preferably, if 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 (i.e., as a whole, carboxylic acid monomers, sulfonated monomers, or anionic copolymers of acrylates with phosphonated monomers, polyvinylpyrrolidone, or polyvinyl alcohol; silanes; N-oxides of functionalized pyridines) ; starch; cyclodextrin; or combinations thereof) may be present in the chemical-mechanical polishing composition. Preferably, the additive is present in the polishing composition in an amount of about 1 ppm to about 500 ppm, such as 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 ppm. ppm, from about 25 ppm to about 400 ppm, from about 10 ppm to about 300 ppm, from about 10 ppm to about 250 ppm, from about 30 ppm to about 350 ppm, from about 30 ppm to about 275 ppm, from about 50 ppm to about 350 ppm, or at a concentration of about 100 ppm to about 300 ppm. More preferably, the additive is present in the polishing composition in an amount of 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 It may be present in a concentration of 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, a cationic polymer described herein, i.e., an anionic copolymer of an acrylate with a carboxylic acid monomer, a sulfonated monomer, or a phosphonated monomer, polyvinylpyrrolidone, or polyvinyl N-oxides of alcohols, nonionic polymers, silanes, functionalized pyridines; starch; and cyclodextrin. Alternatively, the polishing composition does not have one or more of the additives described above, i.e., an anionic copolymer of an acrylate with a carboxylic acid monomer, a sulfonated monomer, or a phosphonated monomer, polyvinylpyrrolidone, or polyvinyl Alcohol; nonionic polymer; Silane; N-oxide of functionalized pyridine; starch; and a cationic polymer without one or more of cyclodextrins.

The polishing composition includes an aqueous carrier. Aqueous carriers include water (e.g., 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, etc.; aldehydes such as acetylaldehyde and the like; Ketones such as acetone, diacetone alcohol, methyl ethyl ketone, etc.; Esters such as ethyl formate, propyl formate, ethyl acetate, methyl acetate, methyl lactate, butyl lactate, ethyl lactate, etc.; Ethers containing sulfoxides, such as dimethyl sulfoxide (DMSO), tetrahydrofuran, dioxane, diglyme, etc.; Amides such as N,N-dimethylformamide, dimethylimidazolidinone, N-methylpyrrolidone, etc.; polyhydric alcohols and their derivatives such as ethylene glycol, glycerol, diethylene glycol, diethylene glycol monomethyl ether, etc.; and nitrogen-containing organic compounds such as acetonitrile, amylamine, isopropylamine, imidazole, dimethylamine, etc. Preferably, the aqueous carrier is water alone, i.e. there is no presence of organic solvents.

The pH of the polishing composition of the present invention is from about 3 to about 9. Typically, the polishing composition has a pH of about 3 or higher. Additionally, the pH of the polishing composition is typically about 9 or less. For example, the polishing composition may have a thickness of about 3.5 to about 9, such as 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 have a strength of about 3 to about 8.5, such as 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. Accordingly, the polishing composition may have a pH limited to any two of the above 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 from 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 from about 7.0 to about 9.0. In some preferred embodiments, the polishing composition of the present invention comprises 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 ranges from about 7.0 to about It is 9.0.

The polishing composition may include a pH-adjusting agent and a pH buffering agent. The pH-adjusting agent may 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 the polishing composition at any suitable concentration. Preferably, the pH-adjusting agent is present in the polishing composition at a concentration sufficient to achieve and/or maintain a pH of the polishing composition within the pH range set forth herein, e.g., maintaining a pH of about 3 to about 9, or about It is present in a concentration sufficient to maintain a pH of from 3 to about 5, or to maintain a pH of from about 7.0 to about 8.5.

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

The polishing composition may contain any suitable amount of buffering agent, if present. For example, the buffering agent may be present in the polishing composition at a concentration of at least about 0.0001% by weight, such as at least about 0.0005% by weight, at least about 0.001% by weight, at least about 0.005% by weight, at least about 0.01% by weight, or at least about 0.1% by weight. It can exist. Alternatively or additionally, the buffering agent may be present in the polishing composition in an amount of less than about 2% by weight, such as less than about 1.8% by weight, less than about 1.6% by weight, less than about 1.4% by weight, less than about 1.2% by weight, or less than about 1% by weight. It may be present in the following concentrations. Accordingly, the buffering agent may be present in the polishing composition in a concentration limited to any two of the above-mentioned endpoints. For example, the buffering agent may be present in the polishing composition in an amount of from about 0.0001% to about 2% by weight, such as from about 0.005% to about 1.8% by weight, from about 0.01% to about 1.6% by weight, or from about 0.1% to about 1% by weight. It may be present in a concentration of % by weight.

The polishing composition optionally further includes one or more other additives. Exemplary additional ingredients include speed enhancers, conditioners, scale inhibitors, dispersants, etc. Preferably, the rate enhancer is an organic carboxylic acid that activates the abrasive particles or substrate by forming a hypercoordinated compound (e.g., a penta- or hexa-coordinated silicon compound). Suitable rate enhancers include, for example, picolinic acid and 4-hydroxybenzoic acid. The polishing composition may include viscosity enhancers and coagulants (e.g., polymeric rheology control agents such as, e.g., urethane polymers), dispersants, biocides (e.g., KATHON™ LX), etc. Surfactants and/or rheology control agents may be included. 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 ingredients may include Breeze S20 (polyethylene glycol octadecyl ether) and polyethylene glycol (e.g. PEG8000).

Polishing compositions may be prepared by any suitable technique, many of which are known to those skilled in the art. The polishing composition may be manufactured in a batch or continuous process. In general, polishing compositions can be prepared by combining the components described herein in any order. As used herein, the term “ingredient” refers to individual components (e.g., abrasives, self-stopping agents, cationic compounds, etc.) as well as any combination of ingredients (e.g., abrasives, self-stopping agents, cationic compounds, etc.). etc.) includes.

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

The polishing compositions may also be provided as concentrates intended to be diluted with an appropriate amount of an aqueous carrier, especially water, before use. In this embodiment, the polishing composition concentrate contains an abrasive, a self-stopping agent, a cationic polymer (if present), and an aqueous carrier such that, upon dilution of the concentrate with an appropriate amount of water, each component of the polishing composition is It may be included in an amount such that it can be present in the polishing composition in an amount within the appropriate range mentioned above. Additionally, as will be appreciated by those skilled in the art, the concentrate may contain an appropriate proportion of water present in the final polishing composition to ensure that other components are at least partially or completely dissolved in the concentrate.

The polishing composition can be prepared significantly prior to use, or even immediately prior to use, but the polishing composition can 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 at which the polishing composition is applied to the substrate surface (e.g., a polishing pad or the substrate surface itself). If the polishing composition is to be prepared using point-of-use mixing, the components of the polishing composition are stored separately in two or more storage devices.

To prepare a polishing composition at or near the point-of-use by mixing the components contained in the storage device, the storage device typically contains a point-of-use polishing composition from each storage device (e.g., platen, polishing pad, or one or more flow lines leading to the substrate surface) are provided. The term “flow line” refers to the flow path from an individual storage container to the point of use of the ingredients stored therein. One or more flow lines may each lead directly 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 at any point into a single flow line leading to a point-of-use. You can. Additionally, any one or more flow lines (e.g., individual flow lines or combined flow lines) may be connected to one or more other devices (e.g., pumping devices, measuring devices, mixing device, etc.) may be reached first.

The components of the polishing composition may be delivered independently to the point of use (e.g., the components are delivered to the substrate surface and the components are mixed during the polishing process), or the components may be combined immediately prior to being delivered to the point of use. of the ingredient less than 10 seconds before it reaches the point-of-use, preferably less than 5 seconds before it reaches the point-of-use, more preferably less than 1 second before it reaches the point-of-use, or even at the point-of-use. When combined upon delivery (for example, when the components are combined in a dispenser), the components are combined “immediately before delivery to the point-of-use.” If an ingredient is combined within 5 m of the point of use, e.g. within 1 m of the point of use, or even within 10 cm of the point of use (e.g. within 1 cm of the point of use), then the ingredient is also “at the point of use.” It is combined “just before delivery.”

When two or more of the components of the polishing composition are combined before reaching the point-of-use, the components can be combined in a flow line and delivered to the point-of-use without the use of a mixing device. Alternatively, one or more flow lines may lead to a mixing device to facilitate combination of two or more components. Any suitable mixing device may 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 have one or more inlets through which the 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 device (e.g., one or more flow lines via) may be a vessel-type mixing device comprising at least one outlet that is delivered to the point of use. Additionally, the mixing device may include 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 vessel-type mixing device is used, the mixing device preferably includes a mixing mechanism to further facilitate the combination of ingredients. Mixing mechanisms are commonly known in the art and include stirrers, blenders, agitators, paddled baffles, gas sparger systems, vibrators, etc.

The present invention also provides a method of chemically-mechanically polishing a substrate using the inventive CMP composition described herein. In one embodiment, the present invention provides a substrate comprising (i) a patterned dielectric layer, on a surface of the substrate, comprising a raised region of dielectric material and a trench region of dielectric material, wherein an initial portion of the patterned dielectric layer The step 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) providing a chemical-mechanical polishing composition described herein, ( iv) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition, (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. Provided is a method of chemically-mechanically polishing a substrate, comprising:

More specifically, the present invention provides a substrate comprising (i) on a surface of the substrate, a patterned dielectric layer comprising a raised region of dielectric material and a trench region of dielectric material, wherein an initial step of the patterned dielectric layer 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) (a) an abrasive, (b) a self-stopping agent of formula Q-B. (where Q is a substituted or unsubstituted hydrophobic group, or a group imparting steric hindrance, B is a linking group having the structure C(O)-X-OH or -C(O)-OH, where -C2 alkyl group), (c) an aqueous carrier, (d) optionally a cationic polymer, and (iv) providing a chemical-mechanical polishing composition having a pH of about 3 to about 9, (iv) combining the substrate with a polishing pad and contacting the substrate with a chemical-mechanical polishing composition, (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. A chemical-mechanical polishing method is provided.

The present invention also provides (i) a substrate comprising, on a surface of the substrate, a patterned dielectric layer comprising a raised region of dielectric material and a trench region of dielectric material, wherein the initial step of the patterned dielectric layer is difference between the height of the raised 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, A self-restraining 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- A method of chemically mechanically polishing a substrate is provided, the method comprising polishing a substrate by moving a mechanical polishing composition across the substrate to grind at least a portion of a patterned dielectric layer on a surface of the substrate.

The invention also provides a substrate comprising (i) on a surface of the substrate, a patterned dielectric layer comprising a raised region of dielectric material and a trench region of dielectric material, wherein the initial steps of the patterned dielectric layer are (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) (a) an abrasive, (b) a magnetic material selected from a 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) combining a substrate with a polishing pad and chemical-mechanical polishing. contacting the substrate with the composition, (v) polishing the substrate by moving 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. Provides a method of polishing.

where 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 invention also provides a substrate comprising (i) on a surface of the substrate, a patterned dielectric layer comprising a raised region of dielectric material and a trench region of dielectric material, wherein the initial steps of the patterned dielectric layer are (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) (a) an abrasive, (b) Formula (II), (III) or ( IV) providing a chemical-mechanical polishing composition comprising a self-stopping agent selected from the compounds of (c) an aqueous carrier, and having a pH of about 3 to about 9; (iv) attaching the substrate to the polishing pad and the chemical-mechanical polishing composition; contacting the substrate with a polishing composition; (v) 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; Provides a method of polishing.

^{wherein each ​ ​ ​ ​ ​} _​ C ₆ alkyl, halogen, and combinations thereof, and 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. You can.

Z is selected from N, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkynyl, and aryl (e.g., phenyl, benzyl, naphthyl, azulene, anthracene, pyrene, etc.) selected, and X ¹ and X ² are independently selected from hydrogen, hydroxy, amino, and C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl ^, where X ¹ and ² - capable of forming a hybridized carbon, n is 1 or 2, p is 0-4, and M is selected from hydrogen and a suitable counterion (e.g., a Group I metal), each of which is substituted or unsubstituted. It can be.

_wherein ^{​ ​ ​} and M is selected from hydrogen and a suitable counterion.

The invention also provides a substrate comprising (i) on a surface of the substrate, a patterned dielectric layer comprising a raised region of dielectric material and a trench region of dielectric material, wherein the initial steps of the patterned dielectric layer are (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) (a) an abrasive comprising ceria, (b) a hydroxamic acid such as acetohyde. A chemical comprising a self-stopping agent selected from roxamic acid, benzhydroxamic acid, salicylhydroxamic acid, and combinations thereof, (c) a cationic polymer, and (d) an aqueous carrier, and having a pH of about 7 to about 9. -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 pattern the dielectric on the surface of the substrate. A method of chemically mechanically polishing a substrate is provided, the method comprising polishing the substrate by grinding at least a portion of the layer.

The polishing compositions of the present invention are useful for polishing any suitable substrate. The polishing composition is particularly useful for polishing substrates containing 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 a dielectric-containing (e.g. silicon oxide-containing) surface, particularly having regions of patterned dielectric material comprising raised dielectric regions separated by trench regions of dielectric material. The substrate may further include at least one other layer, for example an insulating layer. The insulating layer may be a metal oxide, porous metal oxide, glass, organic polymer, fluorinated organic polymer, or any other suitable high or low-κ insulating layer. The insulating layer may include, consist essentially of, or consist of silicon oxide, silicon nitride, or combinations 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, and chemical vapor deposition. (CVD) oxide, plasma-enhanced tetraethyl ortho silicate (PETEOS), thermal oxide, or undoped silicate glass. The substrate may further include a metal layer. The metal may comprise, consist essentially of, or consist of any suitable metal, many of which are known in the art, such as, for example, copper, tantalum, tungsten, titanium, platinum. , ruthenium, iridium, aluminum, nickel, or a combination thereof.

In accordance with the present invention, a substrate may be planarized or polished by any suitable method using the polishing compositions described herein. The polishing method of the present invention is particularly suitable for use with chemical-mechanical polishing (CMP) equipment. Typically, a CMP device includes a platen that moves when in use and has a velocity resulting from orbital, linear, or circular motion; a polishing pad that is in contact with the platen and moves with it during movement of the platen; and a carrier that holds the substrate to be polished by bringing it into contact with the surface of the polishing pad and moving it relative thereto. Polishing a substrate involves placing the substrate in contact with a polishing composition of the present invention and typically a polishing pad, 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. This is accomplished by polishing the substrate by grinding the composition and typically with a polishing pad. Substrates may be polished in accordance with the present invention using any suitable polishing conditions.

The substrate may be planarized or polished with a chemical-mechanical polishing composition in conjunction with any suitable polishing pad (e.g., polishing surface). Suitable polishing pads include, for example, woven and non-woven polishing pads. Moreover, suitable polishing pads may comprise any suitable polymer of varying density, hardness, thickness, compressibility, ability to bounce back upon compression, and compressive modulus. Suitable polymers include, for example, polyvinylchloride, polyvinylfluoride, nylon, fluorocarbons, polycarbonates, polyesters, polyacrylates, polyethers, polyethylene, polyamides, polyurethane, polystyrene, polypropylene, Includes their hybrid products and mixtures thereof.

Although the compositions and methods of the present invention exhibit self-pausing behavior, the CMP apparatus may further include in situ polishing end point detection systems, 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. These methods are described, for example, in US Pat. No. 5,196,353, US Pat. No. 5,433,651, US Pat. No. 5,609,511, US Pat. No. 5,643,046, US Pat. 5,893,796, U.S. Patent No. 5,949,927, and U.S. Patent No. 5,964,643. Preferably, checking or monitoring the progress of the polishing process on the workpiece to be polished allows determination of a polishing end point, i.e., when to terminate the polishing process for a particular workpiece.

For the substrate of any type of device, the substrate surface may include a continuous but structured (non-planar and non-planar) layer of dielectric material overlying an underlying layer that also includes a surface structure or topography. These structured non-planar regions of the surface of a dielectric material are referred to as “patterned dielectrics.” It is created from a dielectric material that is placed over the non-uniform structure of the underlying layer and fills the trenches or holes present in the underlying layer. To ensure complete filling of all trenches, holes, etc., and complete coverage on the surface of the underlying layer containing the trenches, holes, etc., an excess of dielectric material is deposited. The dielectric material will follow the non-uniform topography of the underlying layer, creating a deposited continuous dielectric surface characterized by raised areas separated by trenches. The raised area will be the location of active polishing and material removal, meaning this is where most of the dielectric material is removed. Patterned dielectric material is also characterized by what is referred to as a “step”, which is the height of the dielectric material in the raised area relative to the height of the dielectric material in the adjacent trench.

The polishing compositions of the present invention are particularly well suited for planarizing or polishing substrates that have undergone shallow trench isolation (STI) or similar processes, wherein a dielectric is coated on a 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 substrates that are 3D NAND flash memory devices in process. In such substrates, the underlying layer is made of a semiconductor layer that includes trenches, holes, or other structures with a high aspect ratio, for example, an aspect ratio of at least 10:1, 30:1, 60:1, or 80:1. When a surface having such a high aspect ratio structure is coated with a dielectric material, the resulting patterned dielectric may have a high step, such as substantially greater than about 7,000 Angstroms, such as greater than about 10,000 Angstroms, greater than about 20,000 Angstroms, greater than about 30,000 Angstroms. , or will exhibit a step difference of greater than or equal to about 40,000 Angstroms.

The dielectric material of any of the devices described herein may include, consist essentially of, or consist of any suitable dielectric material, including various types of silicon oxide and silicon oxide-based dielectric materials, many of which may be used. It is widely 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). , high aspect ratio process (HARP) oxide, spin on dielectric (SOD) oxide, chemical vapor deposition (CVD) oxide, plasma-enhanced tetraethyl orthosilicate (PETEOS), thermal oxide, or undoped silicate glass. It may comprise, consist of, or consist essentially of. In the past, some examples of substrates requiring planarization of the patterned dielectric material included a layer of silicon nitride (e.g. a "silicon nitride cap" or "liner") at a location below the active polishing area of the patterned dielectric material, such as a structured semiconductor layer. It was manufactured to include a “cap” on the land surface of the. The silicon nitride is designed to stop polishing and removal of dielectric material in the active area upon reaching the silicon nitride layer. The silicon nitride layer functions to halt the removal of material during 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 include a silicon nitride liner positioned at the intended distal location of the dielectric polishing and removal step. In other embodiments, the substrate does not require, and can optionally and preferably exclude, a silicon nitride “liner” or “cap” disposed at the end of the step of removing the dielectric from the active region.

Preferably, the patterned dielectric material is planarized and polished to reduce the initial step between the raised area (having the initial height) and the trench (having the initial trench thickness). To achieve this planarization effectively and efficiently, the method of the present invention has a high removal rate of the raised areas of (active) patterned dielectric material, along with a substantially lower removal rate of the dielectric material of the trenches. Most preferably, the method of the invention also exhibits self-stationary behavior.

During CMP polishing or planarization, dielectric material is removed from the raised areas and to a lesser extent from the trenches. During polishing, the height of the raised area decreases until it is essentially level with the height of the trench. This may mean that the step difference 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 area removes the pattern of the raised area of the trenches, effectively removing the pattern and reducing the pattern to a field of flattened dielectric, i.e. a "blanket dielectric", meaning a substantially flattened area of dielectric material. or converted to “blanket oxide”.

Depending on the substrate being 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 It may be 10,000 angstroms, at least 20,000 angstroms, at least 30,000 angstroms, or at least 40,000 angstroms. After polishing, the steps are reduced and the trench thickness is reduced.

Figure 1 shows an example substrate with an initial step (h ₀ ) and an initial trench thickness (t ₀ ). The material of the step may most often be a dielectric such as TEOS, BPSG or other amorphous silica-containing material. A key step in processing 3D NAND dielectrics (and other bulk oxide removal) is to reduce the step (h ₁ ) (e.g., to less than about 1,000 Å, or about 900 Å) while having minimal trench loss (t ₀ -t ₁ ). to less than). For good planarization efficiency, the final step should be achieved without significant trench loss. This requires a polishing composition that has a higher removal rate in the active (i.e., raised) area than in the trench area. Additionally, preferred polishing compositions will produce “self-stopping” or “stopping in plane” behavior, allowing for more effective final polishing that does not result in overpolishing. Preferably, the polishing composition of the present invention has a much higher pattern removal rate (removal rate in the active area) compared to the removal rate on a blanket (substantially flat) dielectric material.

The removal rate of dielectric material in the active region is referred to as the removal rate of pattern material (e.g., pattern removal rate) or “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 will vary greatly depending on the dimensions (e.g., pitch and width) of the raised area for any given process and substrate. will change. According to a preferred method, the rate of removal of the patterned 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 It may be about 14,000 angstroms or at least about 15,000 angstroms per minute.

According to a preferred method, the patterned dielectric can be machined to a planarized surface by CMP machining of the patterned dielectric in less than 5 minutes, such as less than 3 minutes, less than 2 minutes, or less than 1 minute. This can be achieved for a substrate with a patterned dielectric material comprising a step of at least 7,000 angstroms, such as at least 10,000 angstroms, at least 20,000 angstroms, at least 30,000 angstroms, or at least 40,000 angstroms. A surface is believed to be effectively planarized when it achieves a reduced step (by polishing) of less than 1,000 Angstroms (i.e., a “residual” step). Accordingly, the polishing compositions and methods of the present invention can provide a residual step 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.

Additionally, preferred polishing methods using polishing compositions as described herein may result in reduced trench loss compared to polishing compositions that do not contain a self-stopping agent (e.g., 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 ), i.e. the trench loss is (for a given processing time or result) t ₀ -t ₁ (Figure 1). Preferably, the amount of trench loss that will occur during polishing to planarization, or for a given amount of processing time (e.g., 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) can be reduced by the presence of a self-stopping agent as described herein in a polishing composition as described herein. Accordingly, the polishing method described herein can be prepared using the same process conditions and equipment and with a polishing composition that is similar but does not contain a self-stopping agent as described herein (e.g., a polishing composition that does not contain a compound of formula QB). Resulting in trench loss that is substantially less (e.g., at least 10% less) than would occur if 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 (e.g., 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 loss can be reflected in planarization efficiency, which refers to step reduction (Å) divided by trench loss (Å). 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. Accordingly, the polishing methods described herein may be of the same type using the same process conditions and equipment but with a polishing composition that does not contain the self-stopping agent described herein (e.g., a polishing composition that does not contain a compound of formula Q-B). This results in a planarization efficiency that is substantially greater (e.g., at least 10% greater) than the planarization efficiency that would result from polishing a substrate of Preferably, the method of the present invention for polishing a substrate provides a planarization efficiency of at least about 2.0, preferably at least about 3.0, such as at least about 3.5.

The preferred method may also exhibit self-shutdown behavior and the rate of removal of dielectric material from the blanket dielectric material (upon reaching a step of less than 1,000 Angstroms, less than 900 Angstroms, less than 500 Angstroms, less than 300 Angstroms, or less than 200 Angstroms). (i.e., “blanket removal rate”) is significantly lower than the removal rate of the patterned dielectric material. Self-shutdown behavior is believed to occur when the removal rate of blanket dielectric material is less than about 1,000 Angstroms per minute. Accordingly, in preferred embodiments, the method of the present invention removes less than about 1,000 angstroms per minute, such as 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. Provides speed.

By another means, self-stopping behavior can be measured by comparing the removal rate of the blanket dielectric material to the removal rate of the patterned dielectric material. A low ratio of blanket removal rate to pattern removal rate indicates good self-stopping behavior. Accordingly, in preferred embodiments, 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, such as less than about 0.5, less than about 0.3, or less than about 0.1. Accordingly, the polishing method of the present invention can be achieved using similar process conditions and equipment but with a polishing composition that does not contain a self-stopping agent as described herein (e.g., a polishing composition that does not contain a compound of Formula Q-B). This results in a ratio of blanket removal rate to pattern removal rate that is substantially less (e.g., at least about 10% less) than the ratio of blanket removal rate to pattern removal rate that would result in polishing the same type of substrate.

In one embodiment, the invention includes a patterned dielectric layer comprising an initial step of at least about 1,000 Angstroms, and reducing the initial step to less than about 900 Angstroms during polishing to produce a planarized dielectric, wherein the removal rate of the planarized dielectric is: A method is provided wherein is less than about 1,000 angstroms per minute.

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

In one embodiment, the present invention provides a method comprising: to provide.

In one embodiment, the present invention provides a method wherein the removal rate of elevated areas of dielectric material is greater than about 1000 Angstroms per minute. Accordingly, in preferred embodiments, the removal rate of the elevated region of dielectric material is greater than about 2,000 Angstroms per minute, such as 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 patterned dielectric layer includes 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 Q-B, wherein Q is a substituted or unsubstituted hydrophobic group, or a group that imparts steric hindrance, and B is a linking group wherein the linking group has the structure: -C(O)-X-OH or -C(O)-OH, where (IV) any of the compounds); and (c) an aqueous carrier, wherein the chemical-mechanical polishing composition has a pH of from about 3 to about 9.

(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), Q is selected from alkyl group, cycloalkyl group, aromatic group, heterocyclic group, heteroaromatic group and combinations thereof. A polishing 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 group, alkyl group, halogen, amine group, or any combination thereof. .

(7) In embodiment (7), Q-B is maltol, kojic acid, crotonic acid, tiglic acid, 2-pentenoic acid, valeric acid, benzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid. The polishing composition of embodiment (1) is provided, wherein the polishing composition 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) is provided, wherein the self-stopping agent is present in the polishing composition in 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 provided, further 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 A polishing composition of embodiment (10) selected from a combination is presented.

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

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

(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 provided.

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

(16) In embodiment (16), (a) an abrasive comprising ceria, (b) kojic acid, crotonic acid, tiglic acid, valeric acid, 2-pentenoic acid, maltol, benzoic acid, 3,4-dihydroxy a self-stopping 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, comprising 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 provided.

(18) In embodiment (18), from poly(vinylimidazolium), poly(methacryloyloxyethyltrimethylammonium) chloride, poly(diallyldimethylammonium) chloride, polyquaternium-2, and combinations thereof. The polishing composition of embodiment (16) is presented, further comprising a leveling agent comprising a selected cationic polymer.

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

(20) In embodiment (20), (a) an abrasive comprising ceria, (b) a self-stopping agent selected from a compound of formula (I), (c) an aluminum salt, 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, Rubyquat Supreme, RubyQuart Hold, RubyQuart UltraCare, RubyQuart FC 370, RubyQuart FC 550, RubyQuart FC 552, RubyQuart Excellence, and combinations thereof, and (d) an aqueous carrier, wherein the chemical-mechanical polishing composition has a pH of from about 7 to about 9.

where 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 provided.

(22) In embodiment (22), there is provided a substrate comprising: (i) on a surface of the substrate, a patterned dielectric layer comprising a raised region of dielectric material and a trench region of dielectric material, wherein the patterned dielectric layer the initial step 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). (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 the surface of the substrate. A method of chemically-mechanically polishing a substrate is provided, comprising polishing the substrate by grinding at least a portion of a patterned dielectric layer.

(23) In embodiment (23), the patterned dielectric layer has 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 planarized dielectric, and the removal rate of the planarized dielectric is less than about 1,000 Angstroms per minute. The polishing method of embodiment (22) is presented, comprising steps.

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

(25) In embodiment (25), the polishing method of any one of embodiments (22) through (24), wherein the ratio of the removal rate of the raised region of dielectric material to the removal rate of the trench region of dielectric material is greater than about 5. presented.

(26) In embodiment (26), the polishing method of any of embodiments (22) through (25) is provided wherein the removal rate of the raised regions of dielectric material is greater than about 1,000 Angstroms per minute.

(27) Embodiment (27), wherein the patterned dielectric layer comprises a dielectric material selected from silicon oxide, tetraethoxysilane, phosphosilicate glass, borophosphosilicate glass, and combinations thereof. (26) Any one of the polishing methods is presented.

Example

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

In the examples the following abbreviations are used: PEG8000 refers to polyethylene glycol with a molecular weight of 8,000 g/mol; pMADQUAT refers to polyMADQUAT; SHA refers to salicylhydroxamic acid; BHA refers to benzhydroxamic acid; BTA refers to 1H-benzotriazole; TEA refers to triethanolamine; POU refers to point of use; RR refers to the clearance rate; AA refers to the active area; TA refers to the trench area; BW refers to TEOS blanket wafer; SH refers to step.

Example 1

This example demonstrates the effect of a self-stopping agent, optionally in combination with a cationic compound, on polishing performance in a polishing composition comprising the same.

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

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 a wet processing ceria described in a previous application (US published patent application 2016/0257855). Abrasive compositions C1 and C2 each had a pH of 4.2.

Table 1: Abrasive composition

Additives Formulations F4-F15 contained a cationic compound (pMADQUAT)), a self-stopping agent (SHA or BHA), and an additive (BTA) as shown in Table 2. The pH of each additive formulation F3-F15 was adjusted using triethanolamine (TEA). Additive formulations F1 and F2 contained no base and had a pH of 4.2.

Table 2: Additive formulations

Individual patterned coupon substrates (SKW Associates, Inc.) containing 250 μm TEOS features (approximately 20,000 Å thick features) with 50% pattern density initially coated on patterned silicon substrates with a step of approximately 8,000 Å. (square cuts with each side of 40 mm from SKW7-2 wafers from SKW Associates, Inc.) on a POLI-300 (G&P Tech. Inc.) with a 200 mm CMP platen. Polished using an IC1010™ pad (Rohm and Haas Electronic Materials) at 20.68 kPa (3 psi) downward force with platen and head speeds of 120 rpm and 110 rpm, respectively, for 60 seconds. The total flow rate of polishing composition was 200 mL/min. The results are presented 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 (hydroxamic acid) at acidic pH (pH 4.2) are preferred for active zone removal versus trench zone removal. The ratio was approximately in the range of 3 to 6. Accordingly, polishing compositions 1A and 1B are preferably “self-stopping” compositions that planarize the pattern material while preserving the trench material.

Polishing composition 1I comprising both a self-stopping agent and a cationic compound demonstrated a ratio of active area removal to trench area removal of approximately 8.6 and an active area removal of 777 Å at a pH of 6.1. Accordingly, Polishing Composition 1I is also a “self-stopping” composition that planarizes the pattern material while preserving the trench material.

Polishing compositions 1C-1H and 1J-1N comprising both a self-stopping agent and a cationic compound have a ratio of active zone removal to trench zone removal ranging from about 5.76:1 to about 50:1 at a pH of 7.6-8.8 and a ratio of about. It showed removal of the active region from 4,700 Å to about 9,000 Å. Accordingly, polishing compositions 1C-1H and 1J-1N are “self-stopping” compositions that planarize the pattern material while preserving the trench material.

Example 2

This example demonstrates the effect of a self-stopping agent, optionally in combination with a cationic compound, on polishing performance in a polishing composition comprising the same.

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

Individual patterns obtained from Silyb Inc. containing TEOS (features approximately 10,000 Å thick) initially coated at various widths and densities on patterned silicon substrates with steps of approximately 5,000 Å. The processed substrate was subjected to 3 psi downward force on an AP-300 ^TM (CTS Co., Ltd.) with a 300 mm CMP platen at a platen speed and head speed of 93 rpm and 87 rpm, respectively, for various times. It was polished using an IC1010™ pad. The total flow rate of polishing composition was 250 mL/min.

Table 4: Description of polishing compositions 2A-2C

As a result of Example 2, the remaining active thickness before and after polishing according to pitch and pattern density is graphically shown in FIG. 2.

As is evident from the results shown in Figure 2, when compared to polishing compositions 2A and 2B, polishing composition 2C of the present invention containing abrasive, benzhydroxamic acid, and polyMADQUAT at pH (POU) of 7.7 has a polishing time of As the pattern increased, stopping occurred with a uniform topography across the substrate, showing low pattern density dependence (polishing composition 2C for 90 seconds).

Additional polishing performance data is presented in Table 5 and Figure 2. The data in Table 5 shows the remaining active thickness containing 900 μm TEOS features (50% pattern density) on the wafer as a function of polishing time.

Table 5: Residual silicon oxide depending on polishing time

As evident from the results presented in Table 5 and Figure 2, polishing composition 2C initially exhibited lower polishing rates on the patterned material, but the rate decreased as step reduction compared to the comparative examples (polishing compositions 2A and 2B). Degradation occurred uniformly on the wafer. This example further compares the control polishing composition to a self-stopping agent (e.g., hydroxamic acid) and a cationic compound (e.g., pMADQUAT) formulated with a pH range of about 7.0 to about 8.5 at the point of use. The advantages of the self-suspended polishing composition are demonstrated with respect to topographic variation across the substrate (pattern density dependence) and within wafer polishing rate variation (WIWNU).

Example 3

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

Patterned substrates and TEOS-coated silicon substrates were polished using 14 polishing compositions (i.e., polishing compositions 3A-3N) listed in Table 7 below. The polishing composition was prepared by mixing the polishing composition (listed in Table 1) and the additive formulation listed in Table 6 in a 7:3 volume ratio.

Additive formulations G1-G5 contained no cationic compounds, whereas formulations G6-G14 contained cationic compounds (i.e., pMADQUAT or Rubiquat Supreme). All formulations contained a self-sustaining agent and additional ingredients as shown in Table 6.

Table 6: Additive formulations

Patterned wafers were obtained from Siliv Inc. and had 900 μm TEOS features with 50% pattern density initially coated on patterned silicon substrates with a step of approximately 5,000 Å (features approximately 10,000 Å thick). ) was included. TEOS blanket wafers were obtained from WRS materials. Test wafers were polished using a MIRRA™ polishing tool (Applied Materials, Inc.) for 60 and 90 seconds for patterned and blanket wafers, respectively. A NexPlanar® E6088 (Cabot Microelectronics Corporation) polishing pad was used on a 200 mm platen using 3 psi downward force, and platen speed and head speed of 93 rpm and 87 rpm, respectively. The total slurry flow rate was 150 mL/min. The results are presented in Table 7.

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

As evident from the results presented in Table 7, all polishing compositions comprising 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 reduction in removal speed occurs on the patterned wafer as it is flattened. The ratio of step removal rate to oxide blanket removal rate ranged from approximately 4 to 24, depending on the POU pH and the type of self-stopping agent in combination with the cationic compound.

All references, including publications, patent applications, and patents, cited above are herein incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and set forth in its entirety herein.

In describing the present invention, the terms singular and "at least one" and similar referents should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradictory from the context. The use of the term "at least one" following one or more listed items (e.g., "at least one of A and B") refers to the term "at least one of A and B") from the listed item, unless otherwise indicated herein or clearly contradictory from the context. It should be interpreted to mean one selected item (A or B) or any combination of two or more of the listed items (A and B). The terms “including,” “having,” “including,” and “including” should be construed as open-ended terms (i.e., meaning “including but not limited to”) unless otherwise stated. do. References to ranges of values herein are intended to serve only as a shorthand method of referring individually to each individual value falling within the range, unless otherwise indicated herein, and each individual value is individually cited herein. It is included in the specification as available. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended only to further illustrate the invention and not to limit the scope of the invention unless otherwise claimed. do not raise Phrases 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 for carrying out the invention known to the inventors. Modifications of the preferred embodiments may also become apparent to those skilled in the art upon reading the above specification. The inventors expect that skilled artisans will employ such variations as appropriate, and the inventors do not intend the invention to be practiced otherwise than as explicitly described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations of the invention is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

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 ​ ​ ​ ​ ​} _​ -C ₆ alkyl, halogen, and combinations thereof, and 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 selected from N, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkynyl, and aryl, phenyl, benzyl, naphthyl, azulene, anthracene, or pyrene, ¹ and X ² are independently selected from hydrogen, hydroxy, amino, and C ₁ ^-C ₆ alkyl, C ₁ -C ₆ alkenyl ^, where X ¹ and n is 1 or 2, p is 0-4, M is selected from hydrogen and a suitable counterion, or a Group I metal, each of which may be substituted or unsubstituted;

_wherein ^{​ ​ ​} M is selected from hydrogen and a suitable counterion, and
(c) aqueous carrier
Including,
The self-stopping agents include maltol, ethyl maltol, kojic acid, benzoic acid, caffeic acid, sorbic acid, butyric acid, valeric acid, hexanoic acid, tiglic acid, angelic acid, crotonic acid, diperiprone, 2-hydroxynicotinic acid, 2- selected from pentenoic acid, 3-pentenoic acid, salts thereof, and combinations thereof,
A chemical-mechanical polishing composition having a pH of 3 to 9. The polishing composition of claim 1 further comprising a speed enhancer, wherein the speed enhancer is an organic carboxylic acid. The polishing composition of claim 1, wherein the abrasive is present in the polishing composition at a concentration of 0.001% to 5% by weight. delete The polishing composition of claim 1, wherein the self-stopping agent is present in the polishing composition in a concentration of less than 1% by weight. 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. 8. The method of claim 7, wherein the cationic compound is a polymer or oligomer comprising quaternary amine monomers, wherein the quaternary amine monomers are vinylimidazolium, methacryloyloxyethyltrimethylammonium halide, diallyldimethylammonium halide and the like. A polishing composition selected from a combination. The method of claim 6, wherein the cationic compound is 2-(dimethylamino)ethyl methacrylate, diallyldimethylammonium, poly(vinylimidazolium), poly(methacryloyloxyethyltrimethylammonium) halide, poly(dimethylammonium), Allyldimethylammonium) halide, polyquaternium-2, polyquaternium-11, polyquaternium-16, polyquaternium-46, polyquaternium-44, Rubyquat Supreme, RubyQuart Hold, RubyQuart UltraCare, Ruby A polishing composition that is a cationic oligomer or cationic polymer selected from Quart FC 370, Rubyquat FC 550, Rubyquat FC 552, Rubyquat Excellence, and combinations thereof. The polishing composition of claim 1, having a pH of 6.0 to 8.5. The polishing composition of claim 1, having a pH of 3 to 5. (a) an abrasive selected from ceria, zirconia and combinations thereof,
(b) a self-stopping agent selected from compounds of formula (I)

where 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 polymer,
(d) aqueous carrier
Including,
The cationic polymer contains a quaternary amine,
A chemical-mechanical polishing composition having a pH of 7.5 to 9. 13. The polishing composition of claim 12, wherein the self-stopping agent is selected from hydroxamic acid, acetohydroxamic acid, benzhydroxamic acid, salicylhydroxamic 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(dimethylammonium), Allyldimethylammonium) chloride, polyquaternium-2, polyquaternium-11, polyquaternium-16, polyquaternium-46, polyquaternium-44, Rubyquat Supreme, RubyQuart Hold, RubyQuart UltraCare, Ruby A polishing composition selected from Rubyquat FC 370, RubyQuart FC 550, RubyQuart FC 552, RubyQuart Excellence, and combinations thereof. 13. The polishing composition of claim 12, further comprising a speed enhancer, wherein the rate enhancer is an organic carboxylic acid. 13. The polishing composition of claim 12, wherein the self-stopping agent is present in the polishing composition at a concentration of 1 weight percent or less. 13. The polishing composition of claim 12, wherein the abrasive is ceria. 13. The polishing composition of claim 12, wherein the abrasive is present in the polishing composition at a concentration of 0.001% to 5% by weight. (i) providing a substrate comprising a patterned dielectric layer on a surface of the substrate;
(ii) providing polishing pads;
(iii) providing the chemical-mechanical polishing composition of claim 1;
(iv) contacting the substrate with a polishing pad and a 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.
A method for chemically-mechanically polishing a substrate, comprising: (i) providing a substrate comprising a patterned dielectric layer on a surface of the substrate;
(ii) providing polishing pads;
(iii) providing the chemical-mechanical polishing composition of claim 12;
(iv) contacting the substrate with a polishing pad and a 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.
A method for chemically-mechanically polishing a substrate, comprising: