Composition as well as application and leveling process thereof

Abstract

The invention provides a composition and application and a leveling process thereof, the composition comprises a corrosion inhibitor, a pH regulator, a wetting agent and a solvent, the pH value of the composition is 1-5.5, the corrosion inhibitor comprises one or more of chlorhexidine and chlorhexidine salt, and the wetting agent comprises one or more of chlorhexidine and chlorhexidine salt. The wetting agent comprises an anionic polycarboxylic acid electrolyte and / or an anionic polycarboxylate electrolyte. The acidic composition can be used for cleaning a workpiece containing a metal substrate, under the synergistic effect of all the components and under the condition that the composition is controlled to be at the proper pH value, the good cleaning effect can be achieved while corrosion protection on the metal substrate is achieved, preparation of electronic devices is facilitated, and the comprehensive performance of the electronic devices is improved.

Description

Technical Field

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

[0002] With the continuous development of electronic device technology, the industry's requirements for high density and miniaturization of electronic devices are becoming increasingly stringent. This has led to increasingly complex multilayer wiring structures on the substrates during electronic device fabrication, resulting in significant height differences on the substrate surface. Currently, planarization compositions are used to planarize the substrates and improve surface smoothness. However, after the planarization process, a large number of abrasive particles, organic matter, and other contaminants remain on the substrate surface, which can damage the integrity of the substrate surface structure and severely affect the yield of electronic devices. Therefore, cleaning agents are needed to clean the substrate surface and remove contaminants. Because the substrate surface is a composite surface with complex interface properties, existing cleaning solutions are insufficient to simultaneously protect the substrate surface metal from corrosion and remove contaminants. This can easily lead to excessive corrosion of the substrate surface metal, increasing surface defects and hindering the improvement of the overall performance and structural reliability of electronic devices. Therefore, a cleaning composition with strong cleaning ability and good metal protection is needed to improve cleaning performance, inhibit surface metal corrosion, and enhance the overall performance of electronic devices. Summary of the Invention

[0003] In view of this, this application provides a composition and its application, as well as a planarization process. The composition can be used to clean workpieces containing metal substrates. Through the synergistic effect of each component and by adjusting the pH within a suitable range, corrosion protection of the metal substrate can be achieved. At the same time, it can also improve the wettability and negative charge effect of the workpiece surface, thereby improving the cleaning effect on the workpiece surface and enhancing the cleaning ability of the composition. The composition has both excellent cleaning and protective effects, and its application in the preparation of electronic devices can improve the overall performance of electronic devices.

[0004] In a first aspect, this application provides a composition comprising a corrosion inhibitor, a pH adjuster, a wetting agent, and a solvent. The pH value of the composition is 1-5.5. The corrosion inhibitor comprises one or more of chlorhexidine and chlorhexidine salts, and the wetting agent comprises anionic polycarboxylate electrolytes and / or anionic polycarboxylate salt electrolytes. Through the combination of these components, the pH of the composition can be controlled at a suitable value, achieving strong cleaning power while enhancing the corrosion resistance of the corrosion inhibitor, improving the protection of the substrate surface metal, and achieving excellent cleaning and protective effects, which is beneficial to improving the overall performance of electronic devices.

[0005] Optionally, the anionic polycarboxylic acid electrolyte includes one or more of polyacrylic acid, polymaleic acid, and acrylic-maleic acid copolymers. The aforementioned wetting agent can improve the wettability of the substrate surface and enhance its affinity for water, while also strengthening the negative charge on the substrate surface, thereby reducing the bonding strength between the abrasive particles and the substrate surface. Under this dual effect, the composition can improve the cleaning effect on residues on the substrate surface.

[0006] Optionally, the weight-average molecular weight of the anionic polycarboxylic acid electrolyte is 500-1,000,000. A suitable molecular weight range can further improve the cleaning effect of the composition and the compatibility between the components.

[0007] Optionally, in the composition, the corrosion inhibitor is present in a mass percentage of 0.0001%-0.3%; and / or, the wetting agent is present in a mass percentage of 0.0001%-0.3%. Appropriate amounts of corrosion inhibitor and wetting agent enhance the protection of the substrate surface metal without affecting the cleaning effect.

[0008] Optionally, the composition further includes one or more of guanidine, guanidine carbonate, guanidine nitrate, guanidine sulfate, guanidine acetate, diguanidine hydrogen phosphate, aminoguanidine, aminoguanidine bicarbonate, aminoguanidine sulfonate, aminoguanidine hydrochloride, and aminoguanidine nitrate. These guanidine compounds can synergistically interact with chlorhexidine and / or chlorhexidine salts in the composition to further enhance the cleaning effect of the composition.

[0009] Optionally, the composition further includes a chelating agent comprising a small molecule acid, including one or more of tartaric acid, glycolic acid, gluconic acid, malic acid, lactic acid, mandelic acid, salicylic acid, and citric acid. The chelating agent can further enhance the protective effect on the base metal and slow down the metal corrosion rate.

[0010] Optionally, the chelating agent in the composition comprises 0.01%-10% by mass. An appropriate amount of chelating agent can form a stable complex with metal ions, significantly reducing the concentration of free metal ions in the composition, thereby blocking the negative effects of free metal ions and further improving the cleaning effect.

[0011] Secondly, this application provides an application of a composition used in a leveling process.

[0012] The composition provided in this application can be used in the leveling process, which helps to improve the stability of the leveling process and improve the leveling effect.

[0013] Thirdly, this application provides a leveling process, including:

[0014] A leveling composition is used to level the workpiece to be leveled, resulting in a workpiece precursor.

[0015] The planarized workpiece precursor is cleaned using the composition described in the first aspect to obtain a cleaned planarized workpiece.

[0016] Optionally, the planarized workpiece comprises tungsten metal, wherein the static corrosion rate of the tungsten metal is less than or equal to... The lower the static corrosion rate, the better the corrosion protection of the metal and the better the cleaning effect, which is beneficial to the manufacturing process of electronic devices.

[0017] Optionally, the planarized workpiece includes tungsten metal, and the planarized workpiece undergoes a wetting performance test, with the measured contact angle being less than or equal to 10°. A smaller measured contact angle indicates better wettability of the workpiece surface, thereby improving the cleaning effect on abrasive particles on the workpiece surface.

[0018] The leveling process provided in this application has high stability, good leveling effect, and the leveled workpieces produced have excellent comprehensive performance. Detailed Implementation

[0019] 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.

[0020] With the development of electronic device technology, the integration density of integrated circuits in electronic devices is increasing, and the requirements for high density and miniaturization of electronic devices are also becoming more stringent. This has led to greater complexity in the multilayer wiring structure of the substrate during electronic device fabrication. In electronic device fabrication, the multilayer wiring structure of the substrate is formed through multiple film deposition and etching processes, which easily creates nanoscale height differences on the substrate surface, hindering subsequent processes. Currently, planarization compositions are used for planarization treatment to eliminate these height differences and improve substrate flatness. However, after planarization, the negatively charged abrasive particles in the planarization composition form a strong attraction with the substrate, leaving a large amount of abrasive particles, organic matter, and other contaminants on the substrate surface. This can damage the integrity of the substrate surface, leading to microstructural defects, low breakdown, channel breakdown, soft breakdown, increased leakage current, and chip short circuits, severely impacting yield. Therefore, the degree of contaminant removal is a crucial factor determining the quality of electronic device products. Because the surface of electronic device substrates is a composite surface, containing various metals, nitrides, and oxides, its interface properties are complex. Existing acidic cleaning compositions protect the metal and reduce corrosion, but they also cause the nitride surface to become positively charged, which binds to abrasive particles and hinders cleaning. Alkaline cleaning compositions can accelerate the cleaning of nitride surfaces, but they cause severe corrosion of the metal. Therefore, existing cleaning solutions struggle to remove surface contaminants while simultaneously providing corrosion protection to the substrate metal, leading to excessive corrosion of the substrate structure, increased surface defects, and significant obstacles to subsequent processes. This ultimately hinders the improvement of the electrical performance and structural reliability of electronic devices.

[0021] To address the aforementioned technical problems, this application provides a composition comprising a corrosion inhibitor, a pH adjuster, a wetting agent, and a solvent. The composition has a pH value of 1-5.5. The corrosion inhibitor includes one or more of chlorhexidine and chlorhexidine salts, and the wetting agent includes anionic polycarboxylate electrolytes and / or anionic polycarboxylate salt electrolytes. This composition can be used to clean workpieces containing metal substrates, nitrides, and oxides. By controlling the composition within a suitable pH range, on the one hand, under these specific acidic conditions, the guanidinium groups on chlorhexidine and chlorhexidine salts undergo protonation, increasing their charge density and thus enhancing their adsorption on the surface of the metal substrate (e.g., tungsten metal), forming a protective film on the metal substrate surface and reducing corrosion. On the other hand, within this pH range, the probability of tungsten metal itself corroding is lower. Furthermore, the composition also includes a wetting agent with excellent hydrophilic properties, which can improve the wettability of nitride and oxide surfaces and increase the affinity of nitride and oxide surfaces for water. This makes it easier to remove residual abrasive particles on the surface as the surface's affinity for water is enhanced, improving the cleaning effect of the composition. Therefore, this application provides a composition with good cleaning effect and strong metal corrosion resistance, which is beneficial to the manufacturing process of electronic devices and improves the overall performance of electronic devices.

[0022] In this application, the pH of the cleaning solution composition is 1-5.5. The acidic composition enhances corrosion protection of the metal substrate, reduces the corrosion rate, and allows the components to work synergistically, increasing the affinity of abrasive particles and other contaminants for water and their repulsion of the substrate surface. This reduces contaminant residue on the substrate surface, improves the cleaning effect of the composition, and reduces surface contamination of the workpiece. Specifically, the pH of the composition can be, but is not limited to, 1, 2, 2.5, 3, 3.5, 4, 4.5, 5, or 5.5. In one embodiment of this application, the pH of the composition can be 1-3.5. In another embodiment of this application, the pH of the composition can be 3-5, which can further enhance the cleaning and metal protection effects of the composition.

[0023] In this application, the corrosion inhibitor can form a strong binding force with the metal substrate on the substrate surface, forming a protective film on the metal substrate surface. This reduces corrosion of the substrate surface metal, especially the metal substrate itself, preventing corrosion of the metal substrate by the composition during the cleaning process and improving the cleaning effect. Specifically, the corrosion inhibitor may include, but is not limited to, one or more of chlorhexidine and chlorhexidine salts. For example, chlorhexidine salts may include, but are not limited to, one or more of chlorhexidine hydrochloride, chlorhexidine citrate, chlorhexidine disglucose, chlorhexidine glutamate, chlorhexidine acetate, and chlorhexidine phosphate. In one embodiment of this application, the corrosion inhibitor may be chlorhexidine. In this application, the type and content of the corrosion inhibitor in the composition may be characterized by, but is not limited to, titration, LC-MS (liquid chromatography-mass spectrometry), GC-MS (gas chromatography-mass spectrometry), infrared spectroscopy, ultraviolet spectroscopy, and nuclear magnetic resonance spectroscopy.

[0024] In one embodiment of this application, the corrosion inhibitor includes one or more of chlorhexidine and chlorhexidine salts. On one hand, compared to other guanidine compounds, the corrosion inhibitor provided in this application is a biguanide compound, meaning the molecule contains two guanidine groups. The positive charge of the biguanide group and the negative charge of the metal surface form a strong adsorption through electrostatic interaction. Furthermore, the steric hindrance of the molecule containing two guanidine groups is relatively large. After adsorption on the metal surface, the molecule is not easily replaced by other ions in the solution or components of the cleaning solution, thereby forming a dense and stable protective film on the metal surface, effectively blocking the contact between corrosive media (such as water, oxygen, acidic / alkaline ions, etc.) and the metal substrate. On the other hand, in the molecular structure of chlorhexidine and chlorhexidine salts, the two guanidine groups are usually linked to long hydrophobic chains (e.g., C14 alkyl chains) through imino groups (-NH-). This structure gives chlorhexidine and chlorhexidine salts strong lipophilicity and interfacial penetration ability, allowing them to penetrate organic contaminants (such as organic additives remaining in polishing solutions) or the micropores of inorganic oxide layers on the metal surface, and then directly adsorb onto the metal substrate surface, forming an "anchoring" effect. This penetrating ability not only enhances the adhesion of corrosion inhibitors but also builds a more complete and stable protective film on the metal surface, reducing local defects (such as pores or cracks) and thus improving overall corrosion resistance. These corrosion inhibitors can effectively prevent metal corrosion during the cleaning process, largely avoiding adverse effects on subsequent manufacturing processes.

[0025] In one embodiment of this application, the mass percentage of corrosion inhibitor in the composition is 0.0001%-0.3%. An appropriate amount of corrosion inhibitor enhances the protection of the substrate surface metal without affecting the cleaning effect. Specifically, the mass percentage of corrosion inhibitor in the composition can be, but is not limited to, 0.0001%, 0.0005%, 0.001%, 0.002%, 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, or 0.3%, etc. In one embodiment of this application, the mass percentage of corrosion inhibitor in the composition can be 0.0001%-0.01%. In another embodiment of this application, the mass percentage of corrosion inhibitor in the composition can be 0.01%-0.3%.

[0026] In this application, a pH adjuster can maintain the composition at a suitable pH to improve its cleaning effect. Specifically, the pH adjuster can be, but is not limited to, an organic amine. For example, organic amines can include, but are not limited to, one or more of triethanolamine, diethanolamine, and ethanolamine. In one embodiment of this application, the pH adjuster can be triethanolamine. In another embodiment of this application, the pH adjuster can be diethanolamine. In this application, the type and content of the pH adjuster in the composition can be characterized by, but is not limited to, titration, LC-MS (liquid chromatography-mass spectrometry), GC-MS (gas chromatography-mass spectrometry), infrared spectroscopy, nuclear magnetic resonance spectroscopy, etc.

[0027] In one embodiment of this application, the mass percentage of the pH adjuster in the composition is 0.1%-0.5%. An appropriate amount of pH adjuster regulates the overall pH of the composition, which is beneficial for the synergistic effect of each component. Specifically, the mass percentage of the corrosion inhibitor in the composition can be, but is not limited to, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.25%, 0.4%, 0.45%, or 0.5%. In one embodiment of this application, the mass percentage of the pH adjuster in the composition can be 0.1%-0.3%. In another embodiment of this application, the mass percentage of the pH adjuster in the composition can be 0.3%-0.5%.

[0028] In this application, the composition includes a wetting agent with dual functions: it improves the wettability of the substrate surface, enhancing its affinity for water, and it strengthens the negative charge on the substrate surface, thereby reducing the bonding strength between the abrasive particles and the substrate surface. This dual action improves the cleaning effect of the composition on substrate surface residues. Specifically, the wetting agent may include, but is not limited to, anionic polycarboxylic acid electrolytes and / or anionic polycarboxylate salt electrolytes. For example, anionic polycarboxylic acid electrolytes are derived from monomers containing at least two carboxyl groups, which can further enhance the improvement of substrate wettability and the strength of the negative charge on the substrate surface. Exemplarily, anionic polycarboxylic acid electrolytes may include, but are not limited to, one or more of polyacrylic acid, polymaleic acid, and acrylic acid-maleic acid copolymers; anionic polycarboxylate salt electrolytes are salt electrolytes of the aforementioned anionic polycarboxylic acid electrolytes. In one embodiment of this application, the anionic polycarboxylic acid electrolyte may be polyacrylic acid. In another embodiment of this application, the anionic polycarboxylic acid electrolyte includes polymaleic acid. The aforementioned anionic polycarboxylic acid electrolyte can adsorb onto the interface between a liquid (such as water or organic solvent) and a solid through the ionization of carboxylic acid groups, thereby significantly reducing the surface tension of the liquid and enhancing the liquid's ability to spread on hydrophobic substrates. The flexibility of the molecular chains and the distribution of polar groups in the anionic polycarboxylic acid electrolyte can dynamically adjust the solid-liquid contact angle.

[0029] In one embodiment of this application, the weight-average molecular weight of the anionic polycarboxylate electrolyte is 500-1,000,000. A suitable molecular weight range can further improve the cleaning effect of the composition and the compatibility between the components. Specifically, the weight-average molecular weight of the anionic polycarboxylate electrolyte can be, for example, 500, 1000, 2000, 2500, 5000, 6000, 8000, 10000, 50000, 100000, 200000, 500000, 800000, or 1,000000. In one embodiment of this application, the mass percentage of the wetting agent in the composition can be 2,500-800,000. In this application, the weight-average molecular weight of the anionic polycarboxylate electrolyte in the composition can be characterized by, but is not limited to, GPC (Gel Permeation Chromatography).

[0030] In one embodiment of this application, the mass percentage of the wetting agent in the composition is 0.0001%-0.3%. An appropriate amount of lubricant can improve the cleaning effect of the composition. Specifically, the mass percentage of the wetting agent can be, but is not limited to, 0.0001%, 0.0005%, 0.001%, 0.002%, 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, or 0.3%, etc. In one embodiment of this application, the mass percentage of the wetting agent in the composition can be 0.0001%-0.01%. In another embodiment of this application, the mass percentage of the wetting agent in the composition can be 0.01%-0.3%. In this application, the type and content of the anionic polycarboxylic acid electrolyte in the composition can be characterized by, but is not limited to, titration, LC-MS (liquid chromatography-mass spectrometry), GC-MS (gas chromatography-mass spectrometry), infrared spectroscopy, nuclear magnetic resonance spectroscopy, etc.

[0031] In one embodiment of this application, the composition further includes one or more of guanidine, guanidine carbonate, guanidine nitrate, guanidine sulfate, guanidine acetate, diguanidine hydrogen phosphate, aminoguanidine, aminoguanidine bicarbonate, aminoguanidine sulfonate, aminoguanidine hydrochloride, and aminoguanidine nitrate. The aforementioned guanidine compounds can synergistically interact with chlorhexidine and / or chlorhexidine salts in the composition to further enhance the cleaning effect of the composition. In this application, the type and content of the chelating agent in the composition can be characterized by, but not limited to, titration, LC-MS (liquid chromatography-mass spectrometry), GC-MS (gas chromatography-mass spectrometry), infrared spectroscopy, and nuclear magnetic resonance spectroscopy.

[0032] In one embodiment of this application, the composition further includes a chelating agent, which can further enhance the protective effect on the base metal and slow down the metal corrosion rate. Specifically, the chelating agent may include, but is not limited to, small molecule acids, including one or more of tartaric acid, glycolic acid, gluconic acid, malic acid, lactic acid, mandelic acid, salicylic acid, and citric acid. In one embodiment of this application, the chelating agent may be citric acid. In another embodiment of this application, the chelating agent may be glycolic acid. In this application, the chelating agent and its content in the composition may be characterized by, but is not limited to, titration, LC-MS (liquid chromatography-mass spectrometry), GC-MS (gas chromatography-mass spectrometry), infrared spectroscopy, nuclear magnetic resonance spectroscopy, etc.

[0033] In one embodiment of this application, the chelating agent in the composition is 0.01%-10% by mass. An appropriate amount of chelating agent can form a stable complex with metal ions (e.g., the chelating agent citric acid can form a complex with Fe). 3+This process forms a [Fe(Cit)]-complex, significantly reducing the concentration of free metal ions in the composition, thereby blocking the negative effects of free metal ions and further enhancing the cleaning effect. Specifically, the mass percentage of the chelating agent can be, but is not limited to, 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 5%, 6%, 8%, or 10%.

[0034] In one embodiment of this application, the solvent in the composition includes, but is not limited to, solvents commonly used in the art. Specifically, it may be one or more of water, alcohol solvents, or ether solvents. In some specific embodiments of this application, alcohol solvents include, but are not limited to, methanol, ethanol, isopropanol, ethylene glycol, glycerol, etc.; ether solvents include, but are not limited to, ethylene glycol monomethyl ether, propylene glycol methyl ether, etc. The above solvents can fully dissolve and disperse the various components in the composition, thereby obtaining a composition with good homogeneity.

[0035] In one embodiment of this application, the composition may be prepared by, for example, mixing a corrosion inhibitor, a pH adjuster, a wetting agent and a solvent to obtain the composition described in the above embodiment.

[0036] This application also provides applications of the composition, which can be, but is not limited to, used in a leveling process.

[0037] This application also provides a leveling process, including:

[0038] S101: The workpiece to be flattened is flattened using a flattening composition to obtain a workpiece precursor;

[0039] S102: The workpiece precursor is cleaned using the composition described in any one of the above embodiments to obtain a planarized workpiece. The planarization process provided in this application can improve the planarization degree of the workpiece, and at the same time, the surface of the planarized workpiece has fewer contaminants, which is beneficial to subsequent processes.

[0040] In one embodiment of this application, the workpiece to be planarized is used as a substrate and can be applied in the fabrication of electronic devices. The substrate surface includes silicon nitride, silicon oxide, and a metal substrate (such as tungsten). After planarizing the substrate with a planarizing composition, the acidic composition causes abrasive particles to adhere to the workpiece surface, leaving a large amount of residual contaminants. Therefore, the composition is needed to clean these residual contaminants. The composition provided in any of the above embodiments of this application can, while providing corrosion protection to the metal substrate surface, enhance the removal of residual contaminants from the workpiece surface through the synergistic effect of its components, achieving strong corrosion protection and strong cleaning ability, which is beneficial to improving the overall performance of electronic devices.

[0041] In one embodiment of this application, the composition can be used to clean workpieces containing tungsten metal, thereby reducing corrosion of the tungsten metal, improving its anti-corrosion effect, and after the leveling process, the static corrosion rate of the tungsten metal is less than or equal to... A lower static corrosion rate results in better corrosion protection and cleaning of the metal, which is beneficial for the fabrication of electronic devices. Specifically, the static corrosion rate of tungsten can be, but is not limited to, [a certain value]. or Etc. In one embodiment of this application, the static corrosion rate of tungsten metal can be... This can further improve the corrosion protection effect on the base metal. In another embodiment of this application, the static corrosion rate of tungsten metal can be... In this application, the static corrosion rate of tungsten metal includes, but is not limited to, determining the tungsten content using inductively coupled plasma atomic emission spectrometry and then calculating the static corrosion rate of tungsten metal.

[0042] In one embodiment of this application, the planarized workpiece includes tungsten metal. The planarized workpiece undergoes a wetting performance test, and the measured contact angle is less than or equal to 10°. A smaller measured contact angle indicates better wettability of the workpiece surface cleaned using the composition of this application, thereby improving the cleaning effect on abrasive particles on the workpiece surface. Specifically, the contact angle measured in the wetting performance test of the planarized workpiece can be, for example, 1°, 2°, 3°, 4°, 5°, 6°, 7°, 8°, 9°, or 10°. The method for the wetting performance test in this application can, for example, involve grinding and cleaning the planarized workpiece precursor using the composition provided in this application, drying it, and then measuring the contact angle.

[0043] 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.

[0044] In one embodiment of this application, the substrate includes a base material and a dielectric layer on the surface of the base material. The dielectric layer may be formed of, but is not limited to, one or more materials selected from silicon oxide, silicon nitride, aluminum oxide, low dielectric constant materials, and metallic materials. In one embodiment of the application, the dielectric layer may be composed of silicon oxide and silicon nitride. In another embodiment of this application, the dielectric layer may be composed of silicon oxide, silicon nitride, and tungsten metal.

[0045] This application also provides a method for fabricating a semiconductor device, comprising:

[0046] S201. Prepare a substrate containing a substrate and a dielectric layer on the surface of the substrate;

[0047] S202. The substrate is flattened to obtain a flattened workpiece precursor.

[0048] S203. The smoothing workpiece precursor is cleaned using the composition described in any one of the above embodiments to obtain a smoothing workpiece.

[0049] This method results in semiconductor devices with high yield and excellent overall performance.

[0050] The technical solution of this application will be further described below through specific embodiments.

[0051] Example 1

[0052] The composition comprises 0.001% by weight of a corrosion inhibitor (chlorhexidine digluconate), 0.1% by weight of a wetting agent (polyacrylic acid Mw=6000), 0.1% by weight of a pH adjuster (triethanolamine), 0.1% by weight of a chelating agent (citric acid), and the balance being water as a solvent.

[0053] Example 2

[0054] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.005%.

[0055] Example 3

[0056] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.01%.

[0057] Example 4

[0058] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.0001%.

[0059] Example 5

[0060] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.3%.

[0061] Example 6

[0062] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.005% and the pH adjuster has a mass percentage of 0.3%.

[0063] Example 7

[0064] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.005% and the wetting agent (acrylic acid-maleic acid copolymer) has a mass percentage of 0.1%.

[0065] Example 8

[0066] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.005% and the wetting agent has a mass percentage of 0.3%.

[0067] Example 9

[0068] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.005%, the wetting agent has a mass percentage of 0.3%, and the pH adjuster (diethanolamine) has a mass percentage of 0.1%.

[0069] Example 10

[0070] The difference from Example 1 is that the corrosion inhibitor has a mass percentage of 0.005%, the wetting agent has a mass percentage of 0.3%, and the pH adjuster (ethanolamine) has a mass percentage of 0.1%.

[0071] Example 11

[0072] The difference from Example 1 is that the molecular weight of the polyacrylic acid is Mw = 2500.

[0073] Example 12

[0074] The difference from Example 1 is that the molecular weight of the polyacrylic acid is Mw = 800,000.

[0075] Example 13

[0076] The difference from Example 1 is that the corrosion inhibitor is chlorhexidine citrate.

[0077] Example 14

[0078] The difference from Example 1 is that the corrosion inhibitor is chlorhexidine.

[0079] Comparative Example 1

[0080] The difference from Example 1 is that no corrosion inhibitor is added, and the wetting agent has a mass percentage of 0.3%.

[0081] Comparative Example 2

[0082] The difference from Example 1 is that no wetting agent is added, and the corrosion inhibitor has a mass percentage of 0.005%.

[0083] Comparative Example 3

[0084] The difference from Example 1 is that the wetting agent is polylysine.

[0085] Comparative Example 4

[0086] The difference from Example 1 is that the pH adjuster is 20% by mass, so that the pH of the composition is 10.

[0087] Comparative Example 5

[0088] The difference from Example 1 is that the corrosion inhibitor is benzotriazole.

[0089] Comparative Example 6

[0090] The difference in Example 1 is that the corrosion inhibitor is guanidine sulfate.

[0091] Performance testing

[0092] pH of the composition: The pH of the composition was measured by inserting a calibrated pH meter into the composition solutions of Examples 1-14 and Comparative Examples 1-6. The pH values ​​of the compositions were obtained by reading the pH values. The results are shown in Table 1.

[0093] Static corrosion rate of tungsten metal: The corrosion rate of the substrates obtained after cleaning with the compositions of Examples 1-14 and Comparative Examples 1-6 was tested. A 2-inch tungsten wafer was placed in 50g of the composition solution and reacted for 60 minutes. The composition solution was taken and the tungsten content was obtained by inductively coupled plasma atomic emission spectrometry. The static corrosion rate of tungsten metal was then calculated. The results are shown in Table 1.

[0094] Surface defects: After mounting the Si wafers with deposited tungsten, silicon oxide, and silicon nitride films into the chemical mechanical polishing (CMP) equipment, the products used were subjected to a CMP process at 60 rpm and 1 psi for 60 seconds. The Si wafers were then placed in a cleaning chamber and cleaned for 15 seconds in Brush 1 using Examples 1-14 and Comparative Examples 1-6 respectively. The number of defects (specifically, defects greater than or equal to 0.12 μm) on the surface of the Si wafers was measured using a measuring device. The results are shown in Table 1.

[0095] Wetting performance: The wetting performance of 2-inch tungsten wafer substrates obtained after cleaning with the compositions of Examples 1-14 and Comparative Examples 1-6 were tested. The substrates were polished and cleaned with polishing equipment and the compositions for 1 minute. After drying, 1.8 μL of pure water was dropped onto the substrate surface. The static contact angle was measured after 10 seconds. The results are shown in Table 2.

[0096] Table 1

[0097]

[0098]

[0099] As shown in Table 1, the compositions provided in Examples 1-14 of this application, by selecting appropriate components and adjusting their pH within a suitable range, can, on the one hand, control the static corrosion rate of tungsten metal within a small range when used for cleaning substrates, thus providing good protection and corrosion prevention for tungsten metal. On the other hand, compared with Comparative Examples 1-6, the compositions provided in this application show fewer surface defects on tungsten metal, oxides, and silicon nitride after cleaning the substrate, indicating that the compositions provided in this application have a better cleaning effect. Therefore, the compositions provided in Examples 1-14 of this application, when used for cleaning substrates, combine good cleaning effect with strong metal corrosion prevention capability.

[0100] Table 2

[0101] Contact angle (°) Example 1 9 Example 2 9 Example 3 9 Example 4 9 Example 5 10 Example 6 10 Example 7 9 Example 8 6 Example 9 6 Example 10 6 Example 11 9 Example 12 8 Example 13 9 Example 14 9 Comparative Example 1 8 Comparative Example 2 20 Comparative Example 3 18 Comparative Example 4 15 Comparative Example 5 9 Comparative Example 6 9

[0102] As can be seen from Table 2, the contact angle measured after cleaning the substrate surface using the compositions provided in Examples 1-14 of this application is relatively small, indicating that the compositions provided in this application have a good wetting effect.

[0103] 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.

[0104] 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 are in an "or" relationship.

[0105] 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), sa-c, bc, or abc, where a, b, and c can be single or multiple.

[0106] 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.

[0107] 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 composition, characterized in that, The composition comprises a corrosion inhibitor, a pH adjuster, a wetting agent, and a solvent. The pH value of the composition is 1-5.

5. The corrosion inhibitor comprises one or more of chlorhexidine and chlorhexidine salts. The wetting agent comprises anionic polycarboxylate electrolytes and / or anionic polycarboxylate salt electrolytes.

2. The composition according to claim 1, characterized in that, The anionic polycarboxylic acid electrolyte includes one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, and acrylic-maleic acid copolymer.

3. The composition according to claim 1, characterized in that, The weight-average molecular weight of the anionic polycarboxylic acid electrolyte is 500-1,000,000.

4. The composition according to claim 1, characterized in that, The chlorhexidine salt includes one or more of chlorhexidine hydrochloride, chlorhexidine citrate, chlorhexidine disglucuronide, chlorhexidine glutamate, chlorhexidine acetate, and chlorhexidine phosphate.

5. The composition according to claim 1, characterized in that, In the composition, the corrosion inhibitor comprises 0.0001%-0.3% by mass; and / or, In the composition, the wetting agent has a mass percentage of 0.0001%-0.3%.

6. The composition according to claim 1, characterized in that, The composition further includes one or more of guanidine, guanidine carbonate, guanidine nitrate, guanidine sulfate, guanidine acetate, diguanidine hydrogen phosphate, aminoguanidine, aminoguanidine bicarbonate, aminoguanidine sulfonate, aminoguanidine hydrochloride, and aminoguanidine nitrate.

7. The composition according to claim 1, characterized in that, The composition further includes a chelating agent comprising a small molecule acid, wherein the small molecule acid comprises one or more of tartaric acid, glycolic acid, gluconic acid, malic acid, lactic acid, mandelic acid, salicylic acid and citric acid. In the composition, the chelating agent is present in a mass percentage of 0.01%-10%.

8. The application of the composition according to any one of claims 1-7, characterized in that, The composition is used in a leveling process.

9. A leveling process, characterized in that, include: A leveling composition is used to level the workpiece to be leveled, resulting in a workpiece precursor. The smoothed workpiece precursor is cleaned using the composition according to any one of claims 1-7 to obtain the smoothed workpiece.

10. The leveling process as described in claim 9, characterized in that, The smoothed workpiece comprises tungsten metal, wherein the static corrosion rate of the tungsten metal in the composition is less than or equal to that of... And / or, The smoothed workpiece includes tungsten metal, and the smoothed workpiece undergoes a wetting performance test, with the measured contact angle being less than or equal to 10°.

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