Cleaning composition and application thereof, leveling process and electronic device

Abstract

The invention provides a cleaning composition and application thereof, a leveling process and an electronic device. The cleaning composition comprises an anionic surfactant and an organic acid complexing agent, the anionic surfactant comprises one or more of ammonium dodecyl sulfate and dodecylbenzene sulfonic acid; the organic acid complexing agent comprises a first complexing agent containing a carboxylic acid group and a second complexing agent containing a phosphonic acid group, and / or the organic acid complexing agent comprises a third complexing agent containing a carboxylic acid group and a phosphonic acid group; in the cleaning composition, the mass percentage content of the anionic surfactant is less than 0.5%; the pH value of the cleaning composition is greater than 7 and less than or equal to 12. According to the cleaning composition, the foam amount can be effectively reduced by performing proper component matching and pH value regulation and control on the cleaning composition, grinding materials and other impurities remaining on the surface of a workpiece can be effectively removed by applying the cleaning composition to cleaning of the leveling workpiece, and the comprehensive performance of a semiconductor device is remarkably improved.

Description

Technical Field

[0001] This application relates to the field of semiconductor device fabrication, specifically to a cleaning composition and its application, a planarization process, and electronic devices. Background Technology

[0002] In semiconductor device manufacturing, planarization is a crucial process aimed at improving the surface smoothness of the substrate. However, after planarization, a large amount of abrasive particles, organic matter, and other contaminants remain on the substrate surface, leading to a decrease in the reliability and electrical performance of semiconductor devices. Furthermore, some of these residues cannot be removed by subsequent processes. Therefore, cleaning solutions are needed to clean the planarized substrate surface and remove these contaminants. To improve cleaning effectiveness, some cleaning solutions add surfactants. However, this often generates excessive foam during the cleaning process, triggering machine alarms. The residue left after foam bursting can also severely affect the surface properties of the substrate, thereby impacting the reliability of the semiconductor device. Summary of the Invention

[0003] In view of this, this application provides a cleaning composition and its application, a planarization process, and an electronic device. By selecting a special anionic surfactant and an organic acid complexing agent and controlling the cleaning composition within a suitable pH range, this application can effectively reduce the amount of foam generated by the addition of surfactants. When applied to the cleaning of planarized workpieces, it can effectively remove residual abrasives and other impurities from their surfaces, significantly improving the overall performance of semiconductor devices.

[0004] The first aspect of this application provides a cleaning composition comprising an anionic surfactant, an organic acid complexing agent, and a solvent; the anionic surfactant comprising one or more of dodecyl ammonium sulfate and dodecylbenzene sulfonic acid; the organic acid complexing agent comprising a first complexing agent containing a carboxylic acid group and a second complexing agent containing a phosphonic acid group, and / or, the organic acid complexing agent comprising a third complexing agent containing a carboxylic acid group and a phosphonic acid group; wherein the mass percentage of the anionic surfactant in the cleaning composition is less than 0.5%; and the pH value of the cleaning composition is greater than 7 and less than or equal to 12.

[0005] In some embodiments of this application, the first complexing agent includes one or more of aminotriacetic acid, ethylenediaminetetraacetic acid, and hydroxyethylethylenediaminetriacetic acid; the second complexing agent includes one or more of hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid; and the third complexing agent includes 2-phosphonobutane-1,2,4-tricarboxylic acid. By selecting organic acid complexes with carboxylic acid and phosphonic acid groups, the surface charge of the substrate and residual abrasive can be effectively controlled, enhancing the electrostatic repulsion between the abrasive and the substrate surface, thereby effectively removing residual abrasive from the substrate surface.

[0006] In some embodiments of this application, the mass ratio of the anionic surfactant to the organic acid complexing agent in the cleaning composition is (0.01-1):1. By controlling the mass ratio of the anionic surfactant to the organic acid complexing agent within the aforementioned suitable range, the synergistic effect of the two can be further enhanced, thereby increasing the negative charge on the substrate and abrasive surface while reducing the number of defects on the substrate surface, thus further improving the overall performance of the semiconductor device.

[0007] In some embodiments of this application, the molar ratio of the carboxylic acid group to the phosphonic acid group in the organic acid complexing agent is (0.02-5):1. By controlling the molar ratio of the carboxylic acid group to the phosphonic acid group in the organic acid complexing agent within the above-mentioned suitable range, the surface charge of the substrate and residual abrasive can be effectively regulated, thereby effectively removing residual abrasive from the substrate surface. Simultaneously, it can chelate metal ions in the system, reducing residual metal impurities on the smoothed substrate surface after cleaning, and improving the reliability of the device.

[0008] In some embodiments of this application, the molecular weight of the organic acid complexing agent is less than 1000. By controlling the molecular weight of the organic acid complexing agent within the aforementioned small range, the smoothed substrate surface cleaned by the cleaning composition can have lower surface residue and higher cleanliness.

[0009] In some embodiments of this application, the cleaning composition further includes a defoamer, which is a polyether-type compound. By selecting a suitable defoamer, foaming caused by anionic surfactants can be further reduced, thereby further improving the cleaning effect and efficiency of the composition on the substrate surface.

[0010] In some embodiments of this application, the surface zeta potential of the abrasive in the cleaning composition is less than or equal to -35mV, and the abrasive includes one or more of silica sol, cerium oxide, and aluminum oxide.

[0011] In some embodiments of this application, the surface zeta potential of the substrate in the cleaning composition is less than or equal to -35mV; the substrate comprises one or more of polycrystalline silicon, silicon nitride, and silicon oxide.

[0012] The second aspect of this application provides the application of the cleaning composition or dilution thereof provided in the first aspect in the cleaning process of semiconductor fabrication. The composition provided in this application can be applied in the planarization process, which is beneficial to improving the stability of the planarization process and improving the planarization effect.

[0013] A third aspect of this application provides a leveling process, comprising: A leveling composition is used to level the workpiece to be leveled, resulting in a leveled workpiece. The leveled workpiece is cleaned using the cleaning composition or its dilution provided in the first aspect to obtain a cleaned leveled workpiece.

[0014] The leveling process provided in this application has high stability, good leveling effect, and the leveled workpieces produced have excellent comprehensive performance.

[0015] Fourthly, this application provides an electronic device comprising a cleaned and planarized workpiece obtained using the planarization process described in the third aspect. This workpiece exhibits a high degree of planarization, resulting in good overall performance of the electronic device.

[0016] In some embodiments of this application, the electronic device includes a semiconductor device. The high degree of planarization of the cleaned and planarized workpiece facilitates the formation of a multilayer wiring structure on the substrate, promotes the refinement of the semiconductor device, and results in semiconductor devices containing this planarized workpiece exhibiting high precision and excellent overall performance. Detailed Implementation

[0017] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0018] With the development of semiconductor technology, the requirements for the precision of semiconductor devices are becoming increasingly stringent, leading to greater complexity in the multilayer wiring structures of substrates during semiconductor fabrication. In semiconductor fabrication, the multilayer wiring structure of the substrate requires multiple film deposition and etching processes, which can easily create micron / nanometer-level height differences on the substrate surface, hindering subsequent processes. Therefore, planarization is typically used to eliminate these height differences and improve surface smoothness. However, planarization leaves a large amount of organic matter, abrasive particles, and grinding pad debris on the substrate surface. Some of these residues, such as mask particles, can interact with the substrate surface through electrostatic attraction and chemical bonding, making them difficult to remove through subsequent cleaning processes. To improve cleaning effectiveness, some cleaning solutions add surfactants. However, this often generates excessive foam during cleaning, triggering machine alarms. Furthermore, the residue left after foam bursting can severely affect the surface properties of the substrate, thus impacting the reliability of semiconductor devices.

[0019] To address the aforementioned technical problems, this application provides a cleaning composition and its application, a leveling process, and an electronic device. The cleaning composition comprises an anionic surfactant, an organic acid complexing agent, and a solvent. The anionic surfactant includes one or more of ammonium dodecyl sulfate and dodecylbenzene sulfonic acid. The organic acid complexing agent includes a first complexing agent containing a carboxylic acid group and a second complexing agent containing a phosphonic acid group, and / or, the organic acid complexing agent includes a third complexing agent containing both carboxylic acid and phosphonic acid groups. The mass percentage of the anionic surfactant in the cleaning composition is less than 0.5%, and the pH value of the cleaning composition is greater than 7 and less than or equal to 12. This application, by selecting specific anionic surfactants and organic acid complexing agents and controlling the cleaning composition within a suitable pH range, can effectively reduce the amount of foam generated by the addition of surfactants. By selecting ammonium dodecyl sulfate and / or dodecylbenzene sulfonic acid as anionic surfactants and combining them with organic acid complexing agents containing carboxylic acid and phosphonic acid groups, the amount of anionic surfactant used can be effectively reduced. This allows for better cleaning results with less surfactant, and the lower anionic surfactant content significantly reduces foaming caused by surfactant addition, thereby reducing foam breakage residue and effectively preventing machine alarms. This improves the safety and stability of the cleaning process and the cleanliness of the resulting substrate surface. Furthermore, the organic acid complexing agent containing carboxylic acid and phosphonic acid groups, in synergy with the aforementioned special anionic surfactants, can effectively regulate the Zeta potential of the substrate surface and the Zeta potential of residual abrasive particles after substrate surface smoothing. This results in both the substrate and abrasive surfaces carrying a strong negative charge, significantly enhancing the "negative-negative" charge repulsion between the substrate and abrasive, thus improving the removal effect of residual abrasive particles after substrate surface smoothing. In a moderately alkaline environment with a pH of 7-12, the system contains a relatively high amount of OH-. - This pH value can introduce more negative charges, significantly enhancing the charge repulsion between the substrate and the abrasive, thus improving the removal of residual abrasive. Furthermore, under this pH condition, the precipitation of planarization byproducts such as silica byproducts can be reduced, facilitating the formation of soluble salts from these byproducts which are subsequently removed with the cleaning solution, thereby reducing impurities on the substrate surface caused by polishing byproducts. Applying this cleaning composition to the cleaning of planarized workpieces can effectively remove residual abrasive and other impurities from their surface, and also effectively reduce the number of surface defects, thereby improving the stability of semiconductor device fabrication processes and contributing to enhanced overall semiconductor device performance.

[0020] In this application, the anionic surfactant includes one or more of ammonium dodecyl sulfate and dodecylbenzene sulfonic acid. In some embodiments of this application, the anionic surfactant includes ammonium dodecyl sulfate. In other embodiments of this application, the anionic surfactant includes dodecylbenzene sulfonic acid. In still other embodiments of this application, the anionic surfactant includes both ammonium dodecyl sulfate and dodecylbenzene sulfonic acid. These anionic surfactants can synergistically work with organic acid complexing agents, allowing for better cleaning results with less surfactant. Furthermore, these anionic surfactants do not introduce metal ion impurities into the system, significantly improving the cleaning efficiency and effectiveness of the cleaning composition.

[0021] In this application, the mass percentage of anionic surfactant in the cleaning composition is less than 0.5%. A lower content of anionic surfactant in the cleaning composition significantly reduces foaming caused by the added surfactant, thereby reducing foam breakage residue and effectively preventing machine alarms, thus improving the safety and stability of the cleaning process and the cleanliness of the resulting substrate surface. In some embodiments of this application, the mass percentage of anionic surfactant in the cleaning composition is less than 0.2%. Further limiting the content of anionic surfactant in the cleaning composition to the above range can further reduce foaming during the cleaning process, thereby further improving the cleaning effect. In some specific embodiments, the mass percentage of anionic surfactant in the cleaning composition may be, for example, 0.02%, 0.03%, 0.05%, 0.06%, 0.08%, 0.09%, 0.1%, 0.12%, 0.14%, 0.15%, 0.18%, 0.2%, 0.25%, 0.2%, 0.3%, 0.35%, 0.4%, or 0.45%.

[0022] In some embodiments of this application, the organic acid complexing agent includes a first complexing agent containing a carboxylic acid group (-COOH) and a second complexing agent containing a phosphonic acid group (-PO3H2), and / or, the organic acid complexing agent includes a third complexing agent containing both a carboxylic acid group and a phosphonic acid group. In some embodiments of this application, the organic acid complexing agent includes a first complexing agent containing a carboxylic acid group and a second complexing agent containing a phosphonic acid group, i.e., the organic complexing agent includes a combination of a first complexing agent having only a carboxylic acid group and a second complexing agent having only a phosphonic acid group. In some specific embodiments, the first complexing agent includes one or more of aminotriacetic acid, ethylenediaminetetraacetic acid, and hydroxyethylethylenediaminetriacetic acid; the second complexing agent includes one or more of hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid. In other embodiments of this application, the organic acid complexing agent includes a third complexing agent containing both a carboxylic acid group and a phosphonic acid group, i.e., the organic complexing agent includes a third complexing agent having both a carboxylic acid group and a phosphate group. In some specific embodiments, the third complexing agent may be, for example, 2-phosphonobutane-1,2,4-tricarboxylic acid. By selecting an organic acid complex containing carboxylic acid and phosphonic acid groups, the surface charge of the substrate and residual abrasive can be effectively controlled. The phosphonic acid groups can be anchored to the surfaces of the abrasive and substrate through strong coordination bonds, providing a high and stable negative charge density; while the carboxylic acid groups can adsorb at sites not covered by the phosphonic acid groups, or further interact with the adsorbed phosphonic acid molecules through hydrogen bonds, increasing the charge repulsion. The two work synergistically to increase the negative zeta potential of the substrate and abrasive surfaces, enhance the electrostatic repulsion between the abrasive and substrate surfaces, thereby effectively removing residual abrasive from the substrate surface.

[0023] In some embodiments of this application, the molecular weight of the organic acid complexing agent in the cleaning composition is less than 1000. In some embodiments of this application, the molecular weight of the organic acid complexing agent in the cleaning composition may be less than 800. In still other embodiments of this application, the molecular weight of the organic acid complexing agent in the cleaning composition may be less than 600. By controlling the molecular weight of the organic acid complexing agent within the aforementioned smaller range, the number of hydrophobic segments can be reduced, and adhesion to the hydrophobic substrate surface can be reduced, thereby resulting in a smoothed substrate surface cleaned by the cleaning composition having lower surface residue and higher cleanliness. In this application, the molecular weight of the organic acid complexing agent can be determined by, but is not limited to, high-resolution mass spectrometry, gel permeation chromatography, etc.

[0024] In some embodiments of this application, the mass percentage of the organic acid complexing agent in the cleaning composition is 0.005%-5%. In some specific embodiments, the mass percentage of the organic acid complexing agent in the cleaning composition may be, for example, 0.005%, 0.01%, 0.02%, 0.03%, 0.05%, 0.06%, 0.1%, 0.11%, 0.15%, 0.25%, 0.3%, 0.35%, 0.5%, 0.51%, 0.6%, 0.8%, 1%, 1.01%, 1.5%, 2%, 3%, 4%, or 5%. By controlling the content of the organic acid complexing agent within the above range, the surface charge of the substrate and residual abrasive can be further controlled. This allows the abrasive and substrate surfaces to have strong charge repulsion while minimizing the corrosion of the substrate surface by the cleaning composition and reducing the number of defects on the substrate surface. In some embodiments of this application, the mass percentage of the organic acid complexing agent in the cleaning composition may be 0.01%-2.5%. Further control over the content of organic acid complexing agents in the cleaning composition can further promote the removal of residual abrasives from the substrate surface.

[0025] In some embodiments of this application, the molar ratio of carboxylic acid groups to phosphonic acid groups in the organic acid complexing agent is (0.02-5):1. In some specific embodiments, the molar ratio of carboxylic acid groups to phosphonic acid groups in the organic acid complexing agent can be, for example, 0.02:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 2:1, 2.5:1, 3:1, 4:1, or 5:1. By controlling the molar ratio of carboxylic acid groups to phosphonic acid groups in the organic acid complexing agent within the above-mentioned suitable range, the surface charge of the substrate and residual abrasive can be effectively regulated, the negative Zeta potential of the substrate and residual abrasive can be increased, and the electrostatic repulsion between the residual abrasive and the substrate surface can be enhanced, thereby effectively removing the residual abrasive on the substrate surface; at the same time, it can also chelate metal ions in the system, reduce the residual metal impurities on the smoothed substrate surface after cleaning, and improve the reliability of the device. In some embodiments of this application, the molar ratio of carboxylic acid groups to phosphonic acid groups in the organic acid complexing agent can be (0.1-2.5):1. In this application, the molar ratio of carboxylic acid groups to phosphonic acid groups in the organic acid complexing agent can be determined, but is not limited to, by methods such as high-resolution mass spectrometry and gel permeation chromatography.

[0026] In some embodiments of this application, the mass ratio of anionic surfactant to organic acid complexing agent in the cleaning composition is (0.01-1):1. In some specific embodiments, the mass ratio of anionic surfactant to organic acid complexing agent in the cleaning composition can be, for example, 0.01:1, 0.02:1, 0.03:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1:1. By controlling the mass ratio of anionic surfactant to organic acid complexing agent within the above-mentioned suitable range, the synergistic effect of the two can be further enhanced, further strengthening the negative charge on the substrate and abrasive surface while reducing the number of defects on the substrate surface, thereby further improving the overall performance of the semiconductor device. In some embodiments, the mass ratio of anionic surfactant to organic acid complexing agent in the cleaning composition can be (0.1-1):1.

[0027] In this application, the solvent includes water. In some specific embodiments of this application, the solvent may be, for example, ultrapure water.

[0028] In some embodiments of this application, the cleaning composition further includes a defoamer, which is a polyether-type compound. In some specific embodiments, the defoamer may be one or more of the following: polypropylene glycol, polyethylene glycol, glycerol, polyethylene glycol-polypropylene glycol-polyethylene glycol copolymer (PEG-PPG-PEG copolymer), and polypropylene glycol-polypropylene glycol copolymer (PPG-PEG-PPG copolymer). By selecting a suitable defoamer, foam generated by anionic surfactants can be further reduced, thereby further improving the cleaning effect and efficiency of the composition on the substrate surface.

[0029] In some embodiments of this application, the pH value of the cleaning composition is greater than 7 and less than or equal to 12. In some specific embodiments of this application, the pH value of the cleaning composition can be, for example, 7.1, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or 12. By controlling the pH value of the cleaning composition under the above-mentioned semi-alkaline conditions, this application ensures that the cleaning composition contains a relatively high amount of OH-. - This introduces more negative charges into the system, significantly enhancing the electrostatic repulsion between the substrate and the abrasive, thereby improving the removal of residual abrasive. In some embodiments of this application, the pH value of the cleaning composition can be 8-10. By further controlling the pH value of the cleaning composition within the above range, the cleaning effect of the cleaning composition can be further improved, substrate surface corrosion can be inhibited, and the number of defects on the substrate surface can be reduced, thereby improving the stability of the semiconductor device fabrication process and contributing to the improvement of the overall performance of the semiconductor device.

[0030] In some embodiments of this application, the pH value of the cleaning composition is controlled by adding a pH adjuster. In some specific embodiments of this application, the pH adjuster may be one or more of ammonia, ammonium acetate, alkali metal hydroxides, amine compounds, and quaternary ammonium compounds. Specifically, alkali metal hydroxides may be potassium hydroxide; amine compounds may be ethanolamine, triethanolamine, tromethamine, etc.; and quaternary ammonium compounds may be tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. The above-mentioned pH adjusters can effectively adjust the pH value of the cleaning composition to an ideal range without affecting the good performance of other components in the cleaning composition. In the embodiments of this application, the mass percentage of the pH adjuster in the cleaning composition is determined according to the actual required pH value.

[0031] In some embodiments of this application, the cleaning composition further includes other additives, including but not limited to one or more of antibacterial agents, abrasive particles, and oxidants. In some specific embodiments, the antibacterial agent may be one or more of phenoxyethanol, benzyl alcohol, and parabens; the abrasive particles may be silica sol; and the oxidant may be hydrogen peroxide.

[0032] In the embodiments of this application, the types and contents of each component in the cleaning composition can be determined by, but are not limited to, methods such as infrared spectroscopy, nuclear magnetic resonance, high-resolution mass spectrometry, and gel permeation chromatography.

[0033] In some embodiments of this application, the surface Zeta potential of the abrasive in the above-described cleaning composition is less than or equal to -35 mV, and the abrasive is one or more of silica sol, alumina, and cerium oxide. In some specific embodiments, the abrasive may be, for example, silica sol. In this application, silica sol specifically refers to a stable colloidal solution formed by dispersing nanoscale silica particles in water. In some embodiments, the solid content of the silica particles in the silica sol is 0.01%-20%; the D50 particle size of the silica particles in the silica sol is 10 nm-200 nm. In some specific embodiments, the solid content of the silica particles in the silica sol can be, for example, 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 8%, 10%, 15%, or 20%; the D50 particle size of the silica in the silica sol can be, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, or 200 nm. In some embodiments, the solid content of the silica particles in the silica sol can be 0.1%-5%; the D50 particle size of the silica particles in the silica sol can be 10 nm-200 nm.

[0034] In some embodiments of this application, the surface of the planarized workpiece contains abrasive particles, and the surface Zeta potential of the abrasive particles in the cleaning composition is less than or equal to -30 mV. By using the cleaning composition provided in this application, the abrasive surface can have a higher negative potential, thereby enhancing the electrostatic repulsion between the abrasive and the similarly negatively charged substrate surface, thus effectively removing residual abrasive particles from the substrate surface. In some embodiments of this application, the surface Zeta potential of the abrasive in the cleaning composition is less than or equal to -35 mV. In some embodiments of this application, the surface Zeta potential of the abrasive in the cleaning composition is less than or equal to -40 mV. In this application, the surface Zeta potential of the abrasive in the cleaning composition is measured simulating the cleaning process using the cleaning composition, not a potential test on the surface of the abrasive after cleaning. Specifically, a dynamic light scattering instrument is used to test the surface Zeta potential of the abrasive placed in the cleaning composition. During the test, the planarization composition containing abrasive particles is added to the cleaning composition provided in this application at a content of 10 wt%, and the surface Zeta potential of the abrasive in the cleaning composition is measured.

[0035] In some embodiments of this application, the surface Zeta potential of the substrate in the above-described cleaning composition is less than or equal to -30mV, and the substrate includes one or more of polycrystalline silicon, silicon nitride, and silicon oxide. In some embodiments of this application, the workpiece to be planarized is the substrate, which includes a substrate, a metal layer, a dielectric layer, and a barrier layer. The substrate may be, for example, one or more of polycrystalline silicon, monocrystalline silicon, silicon-germanium, and germanium; the metal layer may be, for example, one or more of aluminum, copper, and tungsten; the dielectric layer may be, for example, silicon dioxide; and the barrier layer may be, for example, one or more of silicon nitride and silicon oxide.

[0036] In some embodiments of this application, the substrate comprises polycrystalline silicon and silicon nitride, and the surface Zeta potential of the substrate in the cleaning composition is less than or equal to -30mV. By using the cleaning composition provided in this application, the substrate surface can also have a high negative potential, thereby enhancing the electrostatic repulsion with the similarly negatively charged abrasive surface, thus achieving effective removal of residual abrasive from the substrate surface. In some embodiments of this application, the surface Zeta potential of the substrate in the cleaning composition is less than or equal to -35mV. In some embodiments of this application, the surface Zeta potential of the substrate in the cleaning composition is less than or equal to -40mV. In this application, the surface Zeta potential of the substrate in the cleaning composition is measured simulating the cleaning process using the cleaning composition, not a potential test on the substrate surface after cleaning. Specifically, a solid surface Zeta potential analyzer is used to test the substrate. During testing, a sample containing polycrystalline silicon and silicon nitride is cut into 1 cm × 2 cm pieces and placed in the cleaning composition provided in this application for testing.

[0037] This application also provides the application of the cleaning composition or its dilution in the cleaning process of semiconductor fabrication. The cleaning composition described in any of the above embodiments can be used, but is not limited to, in the planarization process of semiconductor fabrication. The cleaning composition provided in this application can be used in the planarization process, which is beneficial to improving the stability of the planarization process and improving the planarization effect.

[0038] This application also provides a leveling process, including: S101: The workpiece to be flattened is flattened using a flattening composition to obtain a flattened workpiece; S102: The leveled workpiece is cleaned using the cleaning composition or its dilution described in any one of the above embodiments to obtain a cleaned leveled workpiece. The leveling process provided in this application can improve the leveling degree of the leveled workpiece, and the surface of the cleaned leveled workpiece has fewer contaminants, which is beneficial to subsequent processes.

[0039] In one embodiment of this application, the workpiece to be planarized is used as a substrate, which can be applied to the fabrication of semiconductor devices. In this embodiment, the substrate includes a silicon substrate, a metal layer, a dielectric layer, and a barrier layer, as well as the aforementioned substrate with surface modification or added supporting layers. The silicon substrate may include, but is not limited to, polycrystalline silicon; the barrier layer may include, but is not limited to, silicon nitride or silicon oxide. After planarizing the substrate using a planarization composition, the abrasive in the planarization composition easily adheres to the substrate surface and leaves behind a large amount of contaminants. Therefore, a cleaning composition is needed to clean the residual contaminants and abrasive. The cleaning composition provided in this application can regulate the surface Zeta potential of the abrasive and the substrate surface, forming a strong electrostatic repulsion force, thereby effectively removing contaminants and abrasive from the substrate surface. Furthermore, this cleaning composition is less prone to foaming during the cleaning process, which is beneficial for improving the stability and cleaning effect of the planarization process, reducing substrate surface defects, and improving the performance of semiconductor devices.

[0040] In one embodiment of this application, the planarization process can be, for example, chemical mechanical polishing (CMP). CMP combines chemical and physical methods to planarize the substrate surface, thereby obtaining electronic devices with high flatness, fewer surface defects (such as scratches, pits, ripples, orange peel, pinholes, haze, etc.), and higher precision. In this embodiment, the planarization process can occur during the front-end processing of electronic devices, such as before and after etching, thin film deposition, and ion implantation in component manufacturing; the planarization process can also occur during the back-end processing, such as before and after packaging and testing.

[0041] The planarization process provided in this application embodiment can be used in the manufacture of semiconductor devices such as integrated circuits.

[0042] This application provides a substrate prepared by the planarization process described in any of the above embodiments. The substrate provided by this application has a high degree of planarization, high surface cleanliness, few contaminants, and few surface defects, which is beneficial for subsequent processes and can improve the overall performance of electronic devices.

[0043] This application also provides an electronic device comprising the substrate described above, exhibiting excellent overall performance. In some embodiments of this application, the electronic device includes a semiconductor device. The substrate has a high degree of planarity, which is beneficial for the formation of a multilayer wiring structure on the substrate, promoting the refinement of the semiconductor device. Semiconductor devices containing this substrate exhibit high precision and excellent overall performance.

[0044] The effects of the technical solution in this application will be further illustrated below with specific examples.

[0045] Example 1 The cleaning composition comprises: 0.03% by weight of the anionic surfactant ammonium dodecyl sulfate, 0.05% by weight of the organic acid complexing agent triacetic acid, 0.30% by weight of the organic acid complexing agent hydroxyethylidene diphosphonic acid, 0.3% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 8.5 using ammonia as a pH adjuster.

[0046] Example 2 The cleaning composition comprises: 0.09% by weight of the anionic surfactant ammonium dodecyl sulfate, 0.05% by weight of the organic acid complexing agent triacetic acid, 0.30% by weight of the organic acid complexing agent ethylenediaminetetramethylenephosphonic acid, 0.03% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 9 using ammonia as a pH adjuster.

[0047] Example 3 The cleaning composition comprises: 0.18% by weight of the anionic surfactant ammonium dodecyl sulfate, 0.05% by weight of the organic acid complexing agent triacetic acid, 0.30% by weight of the organic acid complexing agent diethylenetriamine pentamethylphosphonic acid, 0.03% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 9.5 using ammonia as a pH adjuster.

[0048] Example 4 The cleaning composition comprises: 0.03% by weight of the anionic surfactant ammonium dodecyl sulfate, 0.05% by weight of the organic acid complexing agent ethylenediaminetetraacetic acid, 0.10% by weight of the organic acid complexing agent hydroxyethylidene diphosphonic acid, 0.03% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 9 using ammonia as a pH adjuster.

[0049] Example 5 The cleaning composition comprises: 0.09% by weight of the anionic surfactant ammonium dodecyl sulfate, 0.10% by weight of the organic acid complexing agent ethylenediaminetetraacetic acid, 0.10% by weight of the organic acid complexing agent ethylenediaminetetramethylenephosphonic acid, 0.03% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 8 using ammonia as a pH adjuster.

[0050] Example 6 The cleaning composition comprises: 0.18% by weight of the anionic surfactant ammonium dodecyl sulfate, 0.15% by weight of the organic acid complexing agent ethylenediaminetetraacetic acid, 0.10% by weight of the organic acid complexing agent diethylenetriaminepentamethylenephosphonic acid, 0.03% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 7.5 using ammonia as a pH adjuster.

[0051] Example 7 The cleaning composition comprises: 0.18% by weight of the anionic surfactant dodecylbenzenesulfonic acid, 0.50% by weight of the organic acid complexing agent hydroxyethyl ethylenediamine triacetic acid, 0.10% by weight of the organic acid complexing agent hydroxyethylidene diphosphonic acid, 0.03% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 10 using ammonia as a pH adjuster.

[0052] Example 8 The cleaning composition comprises: 0.18% by weight of the anionic surfactant dodecylbenzenesulfonic acid, 0.50% by weight of the organic acid complexing agent hydroxyethyl ethylenediamine triacetic acid, 0.10% by weight of the organic acid complexing agent ethylenediaminetetramethylenephosphonic acid, 0.03% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 8.5 using ammonia as a pH adjuster.

[0053] Example 9 The cleaning composition comprises: 0.18% by weight of the anionic surfactant ammonium dodecyl sulfate, 1% by weight of the organic acid complexing agent hydroxyethyl ethylenediamine triacetic acid, 0.50% by weight of the organic acid complexing agent diethylenetriamine pentamethylphosphonic acid, 0.03% by weight of the defoamer polypropylene glycol, and the balance being water as a solvent. The pH of the cleaning composition is adjusted to 9 using diethanolamine as a pH adjuster.

[0054] Example 10 The difference from Example 1 is that the pH of the cleaning composition was adjusted to 7.5 using ammonia as a pH adjuster.

[0055] Example 11 The difference from Example 1 is that the pH of the cleaning composition was adjusted to 12 using ammonia as a pH adjuster.

[0056] Example 12 The difference from Example 1 is that the organic acid complexing agent is 0.35% by mass of 2-phosphonobutane-1,2,4-tricarboxylic acid.

[0057] Example 13 The difference from Example 1 is that the mass percentage of nitrotriacetic acid is 0.01%, the mass percentage of hydroxyethyl ethylenediamine triacetic acid is 1.5%, and the molar ratio of the carboxylic acid group in nitrotriacetic acid to the phosphonic acid group in hydroxyethyl ethylenediamine triacetic acid is 0.01:1.

[0058] Example 14 The difference from Example 1 is that the mass percentage of nitrotriacetic acid is 0.40%, the mass percentage of hydroxyethyl ethylenediamine triacetic acid is 0.06%, and the molar ratio of the carboxylic acid group in nitrotriacetic acid to the phosphonic acid group in hydroxyethyl ethylenediamine triacetic acid is 10:1.

[0059] Example 15 The difference from Example 1 is that the mass percentage of ammonium dodecyl sulfate is 0.01%, the mass percentage of nitric acid triacetic acid is 0.5%, and the mass percentage of hydroxyethylidene diphosphonic acid is 0.5%.

[0060] Example 16 The difference from Example 1 is that the mass percentage of ammonium dodecyl sulfate is 0.35%.

[0061] Example 17 The difference from Example 1 is that the defoamer polypropylene glycol is not present.

[0062] Example 18 The difference from Example 1 is that nitroglycerin is replaced with polyacrylic acid with a molecular weight of 6000.

[0063] Comparative Example 1 The difference from Example 3 is that no organic acid complexing agent is added.

[0064] Comparative Example 2 The difference from Example 1 is that no anionic surfactant is added.

[0065] Comparative Example 3 The difference from Example 1 is that ammonium dodecyl sulfate is replaced with dodecyl polyoxyethylene ether (AEO-15).

[0066] Comparative Example 4 The difference from Example 1 is that the mass percentage of ammonium dodecyl sulfate is 1%.

[0067] Comparative Example 5 The difference from Example 1 is that no aminotriacetic acid is added, and the mass percentage of hydroxyethylidene diphosphonic acid is 0.35%.

[0068] Comparative Example 6 The difference from Example 1 is that hydroxyethylidene diphosphonic acid is not added, and the mass percentage of aminotriacetic acid is 0.35%.

[0069] Comparative Example 7 The difference from Example 1 is that the pH of the cleaning composition was adjusted to 5 using ammonia as a pH adjuster.

[0070] Comparative Example 8 The difference from Example 17 is that the organic acid complexing agents aminotriacetic acid and hydroxyethylidene diphosphonic acid are not added.

[0071] The components and their contents of the cleaning compositions prepared in Examples 1-18 and Comparative Examples 1-8 are shown in Table 1.

[0072] Performance testing A 12-inch diameter substrate was planarized. The substrate included a polycrystalline silicon substrate and silicon nitride and silicon oxide layers. The planarization process used a silica sol as the abrasive (the silica sol contained 2% solid silica, the D50 particle size of the silica particles was 65 nm, and the solvent was ultrapure water). The grinding pressure was 1.5 PSI, the flow rate of the planarization composition was 250 mL / min, and the grinding time was 60 s. The cleaning compositions obtained in Examples 1-18 and Comparative Examples 1-8 were used to clean the planarized substrate, and the substrate was dried to obtain the cleaned substrate. The number of defects larger than 0.120 μm on the substrate surface was detected using a defect detector, and the results are shown in Table 2.

[0073] The pH values ​​of the cleaning compositions prepared in Examples 1-18 and Comparative Examples 1-8 were measured using a pH meter, and the results are shown in Table 1.

[0074] The surface Zeta potential of the abrasive in the cleaning compositions obtained in Examples 1-18 and Comparative Examples 1-8 was tested using a dynamic light scattering instrument. During the test, a planarization composition containing silica sol abrasive was added to the above cleaning composition after being diluted 6 times at a content of 10 wt%. The surface Zeta potential of the abrasive in the cleaning composition was measured, and the results are shown in Table 2.

[0075] The surface Zeta potential of the substrate was tested using an electric solid surface analyzer. During the test, the substrate containing the polycrystalline silicon substrate and the silicon nitride layer was cut into samples of 1 cm × 2 cm and placed in the cleaning compositions obtained in Examples 1-18 and Comparative Examples 1-8. The surface Zeta potential of the substrate in the cleaning composition was measured, and the results are shown in Table 2.

[0076] Table 1

[0077] Note: In Table 1, K12-A is ammonium dodecyl sulfate; LABS is dodecylbenzenesulfonic acid; AEO-15 is dodecyl polyoxyethylene ether; NTA is aminotriacetic acid; EDTA is ethylenediaminetetraacetic acid; HEDTA is hydroxyethylethylenediaminetriacetic acid; HEDP is hydroxyethylidene diphosphonic acid; EDTMP is ethylenediaminetetramethylenephosphonic acid; DTPMPA is diethylenetriaminepentamethylenephosphonic acid; PBTCA is 2-phosphonobutane-1,2,4-tricarboxylic acid; PPG is polypropylene glycol.

[0078] Table 2

[0079] As can be seen from the data in Table 1, the cleaning compositions provided in Examples 1-18 of this application can effectively adjust the Zeta potential of the substrate and abrasive surface by selecting appropriate anionic surfactants and organic acid complexing agents and controlling the pH value and the content of each component within a suitable range. This can effectively remove residual abrasive and other impurities from the substrate surface, and can also significantly reduce substrate surface defects and improve the overall performance of the device.

[0080] As can be seen from the data of Comparative Examples 1 and 3, Comparative Examples 5 and 6 and Example 1, Comparative Examples 8 and 17, the embodiments of this application, by selecting appropriate types and combinations of organic acid complexing agents, can be combined with anionic surfactants to significantly reduce the surface zeta negative potential of abrasive silica sol and substrate polycrystalline silicon and silicon nitride, thereby improving the cleaning effect of the composition on residual abrasive. Furthermore, by selecting appropriate types and combinations of organic acid complexing agents, the number of defects on the substrate surface can also be effectively reduced.

[0081] As can be seen from the data of Comparative Examples 2-4 and Example 1, by selecting a suitable anionic surfactant and controlling its content within a suitable range, the present application embodiments can be combined with organic acid complexing agents to significantly reduce the surface zeta negative potential of abrasive silica sol and substrate polycrystalline silicon and silicon nitride, thereby improving the cleaning effect of the composition on residual abrasive.

[0082] As can be seen from the data of Comparative Example 7 and Examples 1, 10, and 11, the embodiments of this application can significantly reduce the surface zeta negative potential of abrasive silica sol and substrate polycrystalline silicon and silicon nitride by controlling the pH value of the cleaning composition in a suitable alkaline environment. This is because the alkaline environment can bring more negative charges, significantly enhance the charge repulsion between the substrate and the abrasive, and improve the removal effect of residual abrasive.

[0083] It should be understood that the use of the terms "first," "second," and various numerical designations in this document is merely for descriptive convenience and is not intended to limit the scope of this application.

[0084] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone, where A and B can be singular or plural. The character " / " generally indicates that the related objects before and after it have an "or" relationship.

[0085] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0086] In this application, "-" indicates a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, meaning that the value of a can be between 0.5 and 15, and includes the endpoint values ​​of 0.5 and 15.

[0087] The above description represents the preferred embodiments of this application, but should not be construed as limiting the scope of this application. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this application, and these improvements and modifications are also considered to be within the scope of protection of this application.

Claims

1. A cleaning composition characterized in that, The cleaning composition comprises an anionic surfactant, an organic acid complexing agent, and a solvent; the anionic surfactant comprises one or more of ammonium lauryl sulfate and dodecylbenzenesulfonic acid; the organic acid complexing agent comprises a first complexing agent comprising a carboxylic acid group and a second complexing agent comprising a phosphonic acid group, and / or the organic acid complexing agent comprises a third complexing agent comprising a carboxylic acid group and a phosphonic acid group; the mass percentage content of the anionic surfactant in the cleaning composition is less than 0.5%; the pH value of the cleaning composition is greater than 7 and less than or equal to 12.

2. The cleaning composition of claim 1, wherein, The first complexing agent comprises one or more of nitrilotriacetic acid, ethylenediaminetetraacetic acid, and hydroxyethylethylenediaminetriacetic acid; the second complexing agent comprises one or more of hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylene phosphonic acid, and diethylenetriamine pentamethylene phosphonic acid; the third complexing agent comprises 2-phosphonobutane-1,2,4-tricarboxylic acid.

3. The cleaning composition according to claim 1 or 2, wherein In the cleaning composition, the mass ratio of the anionic surfactant to the organic acid complexing agent is (0.01-1):

1.

4. The cleaning composition according to claim 1 or 2, wherein In the organic acid complexing agent, the molar ratio of the carboxylic acid group to the phosphonic acid group is (0.02-5):

1.

5. The cleaning composition of claim 1 or 2, wherein The molecular weight of the organic acid complexing agent is less than 1000.

6. The cleaning composition of claim 1 or 2, wherein The cleaning composition further comprises a defoaming agent, which is a polyether type compound.

7. The cleaning composition of claim 1 or 2, wherein The surface Zeta potential of the abrasive in the cleaning composition is less than or equal to -35 mV, the abrasive comprising one or more of silica sol, cerium oxide, and aluminum oxide; The surface Zeta potential of the substrate in the cleaning composition is less than or equal to -35 mV; the substrate comprising one or more of polysilicon, silicon nitride, and silicon oxide.

8. Use of a cleaning composition or a dilution thereof in a cleaning process for the production of semiconductors, characterized in that The cleaning composition is the cleaning composition according to any one of claims 1-7.

9. A planarization process characterized by, Comprising: flatting the workpiece to be flat using a flatting composition to obtain a flatting workpiece after flatting; cleaning the flatting workpiece after flatting using the cleaning composition according to any one of claims 1-7 or a dilution thereof to obtain a cleaned flatting workpiece.

10. An electronic device, characterized by The electronic device comprises the cleaned flatting workpiece obtained by the flatting process according to claim 9.

11. The electronic device of claim 10, wherein the first and second conductive layers are formed of a conductive material selected from the group consisting of silver, gold, copper, aluminum, and combinations thereof. The electronic device comprises a semiconductor device. The electronic device comprises a semiconductor device.

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