Washing liquid composition

Abstract

To provide a washing liquid composition that has high pH stability and shows excellent washability for organic residues and abrasives containing cobalt (Co) for a substrate having a cobalt (Co) contact hole and / or cobalt (Co) wiring.SOLUTION: A washing liquid composition for washing a substrate having a cobalt (Co) contact plug and / or cobalt (Co) wiring contains one or two or more types of hydroxylamine derivatives as reductant agents, one or two or more types of surface active agents, one or two or more types of pH adjusting agents, and water, where pH is equal to or larger than 3 and equal to or smaller than 9.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a cleaning solution composition used for cleaning a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring. [Background technology]

[0002] In recent years, with the advancement of miniaturization of devices and the development of multi-layer wiring structures, there has been a demand for more precise planarization of substrate surfaces at each stage of semiconductor substrate manufacturing. To address this, a new technology called chemical mechanical polishing (CMP) has been introduced in which a wafer is pressed against an abrasive cloth called a buff while a mixture of abrasive particles and chemicals is supplied, and then the buff is rotated, combining chemical and physical actions to polish and planarize insulating films and metal materials.

[0003] Chemical mechanical polishing (CMP) is performed using a slurry containing silicon compounds such as alumina and silicon oxide, and cerium compounds such as cerium oxide as abrasives. After chemical mechanical polishing (CMP), the substrate surface becomes contaminated by particles such as alumina, silica, or cerium oxide particles contained in the slurry, as well as metal impurities derived from the constituent materials of the surface being polished and the chemicals contained in the slurry. These contaminants cause pattern defects, poor adhesion, and poor electrical properties, so they must be completely removed before the next process.

[0004] Traditionally, tungsten (W) has been used for contact plugs to raise electrodes such as the gate, source, and drain of transistors onto the insulating film. However, with the trend toward miniaturization, cobalt (Co) has come to be used in advanced devices as a material with lower electrical resistance than W. Furthermore, the middle of line (MOL), which electrically connects these contact plugs to the upper layer wiring, is also shifting from copper (Cu) to cobalt (Co) as the technology becomes more miniaturized.

[0005] Cobalt (Co) has been used as a barrier metal or liner to prevent metal diffusion in copper (Cu) wiring in the semiconductor manufacturing process (Patent Document 1). However, the cobalt (Co) used as a barrier metal or liner is very thin, and foreign matter called organic residue derived from the slurry and abrasive grains are unlikely to remain on the cobalt (Co) after chemical mechanical polishing (CMP). On the other hand, the area of ​​cobalt (Co) contact plugs and wiring (MOL) is larger than that of barrier metals and liners, and organic residues and abrasive grains are likely to remain after chemical mechanical polishing (CMP). A cleaning solution composition for use after chemical mechanical polishing (CMP) for substrates having such cobalt (Co) contact plugs and wiring has been proposed, and its excellent cleaning properties against organic residues and abrasive grains containing cobalt (Co) have been confirmed (Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] US Patent Application Publication No. 2020 / 0199500 [Patent Document 2] JP 2020-45453 A Summary of the Invention [Problem to be solved by the invention]

[0007] The present inventors have encountered a problem that, in a cleaning solution composition for use after chemical mechanical polishing (CMP) of a substrate having the above-mentioned cobalt (Co) contact plug or wiring, when a reducing agent selected from the group consisting of five- or six-membered ring compounds having two or more hydroxyl groups directly bonded to a ring, such as ascorbic acid, is used, the cleaning properties for organic residues and abrasive grains containing cobalt (Co) are good, but the pH of the cleaning solution composition changes over time and becomes unstable. Therefore, the present inventors have carried out research with the objective of providing a cleaning solution composition that has high pH stability while ensuring good cleaning properties against organic residues and abrasive grains containing cobalt (Co) as a cleaning solution composition intended for substrates having cobalt (Co) contact plugs and / or cobalt (Co) wiring. That is, the objective of the present invention is to provide a cleaning solution composition that exhibits good cleaning properties against organic residues and abrasive grains containing cobalt (Co) and further has high pH stability in substrates having cobalt (Co) contact plugs and / or cobalt (Co) wiring. [Means for solving the problem]

[0008] In the course of intensive research to solve the above problems, the present inventors have found that a cleaning liquid composition containing one or more hydroxylamine derivatives as a reducing agent, one or more surfactants, one or more pH adjusters, and water, and having a pH of 3 to 9, exhibits good cleaning properties for organic residues and abrasive grains containing cobalt (Co) and also exhibits high pH stability. As a result of further research, the present inventors have completed the present invention.

[0009] That is, the present invention relates to the following. [1] A cleaning solution composition for cleaning a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring, comprising one or more hydroxylamine derivatives as a reducing agent, one or more surfactants, one or more pH adjusters, and water, and having a pH of 3 or more and 9 or less. [2] The cleaning liquid composition according to [1] above, further comprising one or more anticorrosive agents. [3] The cleaning liquid composition according to [1] or [2] above, wherein the hydroxylamine derivative is selected from the group consisting of N,N-diethylhydroxylamine, N-methylhydroxylamine, and N,N-dimethylhydroxylamine.

[0010] [4] The cleaning liquid composition according to any one of the above [1] to [3], wherein the surfactant is a polysulfonic acid compound. [5] The cleaning liquid composition according to any one of the above [1] to [4], wherein the pH adjuster is a quaternary ammonium compound. [6] The cleaning liquid composition according to [5] above, wherein the quaternary ammonium compound is trimethyl-2-hydroxyethylammonium hydroxide. [7] The cleaning liquid composition according to any one of the above [2] to [6], wherein the corrosion inhibitor is a nitrogen-containing ring compound. [8] The cleaning composition according to [7] above, wherein the nitrogen-containing ring compound is 3-mercapto-1,2,4-triazole.

[0011] [9] A concentrate composition for a cleaning liquid composition according to any one of [1] to [8] above, the concentrate composition being used to obtain the cleaning liquid composition by diluting it 10 to 1,000 times.

[10] A method for cleaning a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring, comprising a step of contacting a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring with the cleaning liquid composition according to any one of [1] to [8] above.

[0012]

[11] A method for producing a semiconductor substrate, comprising a step of contacting a substrate having a cobalt (Co) contact plug and / or cobalt (Co) wiring with the cleaning liquid composition according to any one of the above [1] to [8].

[12] A method for manufacturing a semiconductor substrate according to

[11] , comprising a step of chemically mechanically polishing (CMP) the substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring prior to the step of contacting the substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring with the substrate.

[13] The method for producing a semiconductor substrate according to

[11] or

[12] , wherein the step of contacting a substrate having a cobalt (Co) contact plug and / or cobalt (Co) wiring is a step of cleaning the substrate having a cobalt (Co) contact plug and / or cobalt (Co) wiring. Effect of the Invention

[0013] The cleaning liquid composition of the present invention can effectively remove metal impurities and fine particles, particularly organic residues and abrasive grains containing cobalt (Co), which is a reaction product between cobalt (Co) and an organic corrosion inhibitor in a slurry, in a short time when cleaning the surface of a metal material of a substrate that has been subjected to polishing, etching, chemical mechanical polishing (CMP), or the like in the manufacturing process of an electronic device such as a semiconductor element. The cleaning solution compositions of the present invention also exhibit high pH stability over time. The cleaning liquid composition of the present invention further contains an anticorrosive agent, thereby making it possible to suppress corrosion of metal materials such as cobalt (Co) in a substrate having a cobalt (Co) contact plug and / or cobalt (Co) wiring. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 shows the pH of the cleaning liquid compositions of Examples 1 to 4 and Comparative Examples 1 to 3 immediately after preparation (0 day) and one week after preparation (7 days). [Diagram 2] FIG. 2 is a graph showing the cleaning properties of the cleaning liquid compositions of Examples 5 to 13 and Comparative Examples 4 to 8 for removing post-CMP residues on a Co-containing substrate. [Diagram 3] FIG. 3 is a graph showing the cleaning properties of the cleaning liquid compositions of Comparative Examples 9 and 10 for removing post-CMP residues on a Co-containing substrate. [Figure 4] FIG. 4 is a graph showing the cleaning properties of the cleaning liquid compositions of Comparative Examples 11 and 12 for removing post-CMP residues on a Co-containing substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below based on preferred embodiments of the present invention.

[0016] The present invention relates to a cleaning solution composition for cleaning a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring, the cleaning solution composition comprising one or more hydroxylamine derivatives as a reducing agent, one or more surfactants, one or more pH adjusters, and water, and having a pH of 3 or more and 9 or less.

[0017] Since cobalt (Co) corrodes under acidic conditions, a weakly alkaline to alkaline pH is generally selected for the cleaning solution. Here, ascorbic acid and catechol, which are common reducing agents used in the semiconductor field, are deprotonated in the above pH range, so while their reducing properties are increased, their decomposition is also promoted, and they have a problem of poor stability.

[0018] The reducing agent used in the present invention is a hydroxylamine derivative. A hydroxylamine derivative is a compound in which one or two hydrogens (H) bonded to nitrogen (N) in hydroxylamine (NH2OH) are substituted with an alkyl group, preferably an alkyl group having 1 to 2 carbon atoms. A hydroxylamine derivative is more stable than unsubstituted hydroxylamine (NH2OH). On the other hand, hydroxylamine derivatives have the property that their reactivity increases by forming a complex with a metal (ion). In other words, in a cleaning solution composition for cobalt (Co), the reactivity is selectively increased at the interface between cobalt (Co) and the cleaning solution composition, and the hydroxylamine derivatives exhibit reducing properties. Therefore, the cleaning liquid composition of the present invention containing the above-mentioned hydroxylamine derivative is weakly alkaline, but maintains high stability, and exhibits excellent reducing properties at the cobalt (Co) / cleaning liquid composition interface during use, thereby exerting a cleaning effect.

[0019] The hydroxylamine derivatives include N,N-diethylhydroxylamine, N-methylhydroxylamine, and N,N-dimethylhydroxylamine, and preferably N,N-diethylhydroxylamine. The hydroxylamine derivatives can be used alone or in combination of two or more. The concentration of the hydroxylamine derivative in the cleaning liquid composition is not limited to this value, but is preferably 0.1 mM to 100 mM, and particularly preferably 1 mM to 10 mM.

[0020] From the viewpoint of stability, the cleaning liquid composition of the present invention preferably does not contain ascorbic acid, pyrogallol, or methyl gallic acid.

[0021] The surfactant used in the present invention is appropriately selected depending on the fine particles and substrate to be removed, and is not particularly limited. Examples of the surfactant include polysulfonic acid compounds, polycarboxylic acid compounds, and polyphosphonic acid compounds, and preferably polysulfonic acid compounds. Examples of the polysulfonic acid compound include naphthalenesulfonic acid formaldehyde condensation products, polystyrenesulfonic acid, ligninsulfonic acid, and salts thereof, and preferably naphthalenesulfonic acid formaldehyde condensation products. The surfactant may be used alone or in combination of two or more. The concentration of the surfactant in the cleaning liquid composition is not limited to this range, but is preferably 1 ppm to 10,000 ppm, and particularly preferably 1 ppm to 100 ppm.

[0022] The pH adjuster used in the present invention is not particularly limited as long as it can adjust the pH to a predetermined level. Examples of the pH adjuster include quaternary ammonium compounds, potassium hydroxide, sodium hydroxide, and aqueous ammonium solutions, and preferably quaternary ammonium compounds.

[0023] Examples of the quaternary ammonium compound include, but are not limited to, tetramethylammonium hydroxide (TMAH), trimethyl-2-hydroxyethylammonium hydroxide (choline hydroxide), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, and methyltris(2-hydroxyethyl)ammonium hydroxide. Preferred are trimethyl-2-hydroxyethylammonium hydroxide (choline hydroxide), tetraethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, and methyltris(2-hydroxyethyl)ammonium hydroxide. Particularly preferred is trimethyl-2-hydroxyethylammonium hydroxide (choline hydroxide). One or more pH adjusters can be used.

[0024] From the viewpoint of suppressing toxicity to the human body, the cleaning liquid composition of the present invention preferably does not contain tetramethylammonium hydroxide (TMAH), which is a quaternary ammonium compound.

[0025] The cleaning liquid composition of the present invention contains water.

[0026] The pH of the cleaning liquid composition of the present invention is from 3 to 9. From the viewpoint of cleaning properties of cobalt (Co)-containing organic residues and abrasive grains, the pH is preferably from 6 to 9.

[0027] In one embodiment, the cleaning liquid composition of the present invention may contain a corrosion inhibitor. The anticorrosive agent is not limited to these, but examples thereof include nitrogen-containing ring compounds and thiol compounds, and is preferably a nitrogen-containing ring compound.

[0028] Examples of the nitrogen-containing ring compound include, but are not limited to, pyrrole, pyrazoline, pyrazole, imidazole, triazole, imidazoline, oxazoline, oxazole, isoxazole and derivatives thereof. Specific examples include 1H-pyrrole, 1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrolidine, pyrrolidone, γ-butyrolactam, γ-valerolactam, proline, prolyl, hyglic acid, hygroyl, minalin, 1H-pyrazole, 1-pyrazoline, 2-pyrazoline, pyrazolidine, pyrarizolidone, 3-pyrazolone, 4-pyrazolone, 5-pyrazolone, 1H-pyrazole-4-carboxylic acid, 1-methyl-1H-pyrazoline, Examples of the imidazoline-5-carboxylic acid, 5-methyl-1H-pyrazole-3-carboxylic acid, 3,5-pyrazoledicarboxylic acid, 3-amino-5-hydroxypyrazole, 1H-imidazole, 2-imidazoline, 3-imidazoline, 4-imidazoline, imidazolidine, imidazolidone, ethyleneurea, hydantoin, allantoin, histidine, histidyl, histamine, 1,2,3-triazole, 1,2,4-triazole, 1-hydroxybenzotriazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 4-ano-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole. As the nitrogen-containing compound, from the viewpoints of industrial availability and high water solubility, preferred are pyrazole, 3,5-pyrazoledicarboxylic acid, 3-amino-5-hydroxypyrazole, imidazole, triazole, 3-mercapto-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, histidine, and histamine, and particularly preferred is 3-mercapto-1,2,4-triazole.

[0029] One or more kinds of anticorrosive agents can be used. The concentration of the anticorrosive agent in the cleaning liquid composition is not limited to this value, but is preferably 0.01 mM to 100 mM, and particularly preferably 0.1 mM to 10 mM.

[0030] The organic residue includes, but is not limited to, organic residues containing cobalt (Co), which are dimers or oligomers of organometallic complexes cross-linked by cobalt (Co) generated by the reaction of cobalt (Co) with an organic corrosion inhibitor such as benzotriazole (BTA) contained in a chemical mechanical polishing (CMP) slurry during a chemical mechanical polishing (CMP) process, and are poorly soluble. The organic residues on the substrate to be cleaned with the cleaning solution composition according to the present invention may contain cobalt (Co) at a high concentration. In order to dissolve the organic residues containing cobalt (Co) in the cleaning solution composition, there is a method of breaking the coordinate bond between cobalt (Co) and the organic corrosion inhibitor by changing the pH of the cleaning solution composition, and converting it into a low molecular weight compound.

[0031] Among organic residues containing cobalt (Co), dimers and oligomers of organometallic complexes cross-linked by cobalt (Co) generated by the reaction of cobalt (Co) with an organic corrosion inhibitor such as benzotriazole (BTA) during a chemical mechanical polishing (CMP) process include, but are not limited to, cobalt (Co)-benzotriazole (BTA) complexes.

[0032] The Co-BTA complex refers to a complex formed by crosslinking cobalt (Co) and benzotriazole (BTA), and examples of such complex include, but are not limited to, Co-BTA complexes and compounds in which inorganic substances derived from slurry, such as silicon oxide (SiO2), are mixed with Cu-BTA complexes.

[0033] The substrate having a cobalt (Co) contact plug and / or cobalt (Co) wiring in the present invention is not limited to a substrate obtained after chemical mechanical polishing (CMP), and examples thereof include a substrate immediately after CMP and a substrate immediately after processing an upper insulating film by dry etching after forming a cobalt (Co) contact plug and / or cobalt (Co) wiring. Among these, a substrate immediately after chemical mechanical polishing (CMP) is preferable.

[0034] The chemical mechanical polishing (CMP) in the present invention can be performed in accordance with known chemical mechanical polishing, and is not limited thereto. Examples of such methods include a polishing method using abrasive grains such as silicon oxide (SiO2) or alumina (Al2O3), and an abrasive-less polishing method using electrolytic water. Of these, silicon oxide (SiO2) or alumina (Al2O 3) This is a polishing method that uses abrasive grains such as

[0035] The cleaning liquid composition of the present invention can be obtained by diluting the concentrate composition of the present invention. The cleaning liquid composition of the present invention can be obtained by diluting the concentrate composition, for example, but not limited to, 10 times or more, preferably 10 to 1000 times, and more preferably 50 to 200 times, but the dilution amount can be appropriately determined depending on the composition.

[0036] Since the cleaning liquid composition of the present invention is mostly composed of water, when a dilution and mixing device is installed in the production line of electronic devices, it can be supplied as an undiluted composition and diluted with a diluting liquid containing water (including a diluting liquid consisting only of ultrapure water) immediately before use. This has the advantage of contributing to reduced transportation costs, reduced carbon dioxide gas emissions during transportation, and reduced production costs for electronic device manufacturers.

[0037] The cleaning solution composition of the present invention is suitable for use on a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring, and is particularly suitable for use on a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring and no copper (Cu). It is also suitable for use on a substrate after chemical mechanical polishing (CMP), and here, in addition to various wirings on the substrate surface and barrier metal materials (CoTi-based compounds, Ta-based compounds, Ru, etc.) and insulating film materials (SiO2, low-k), fine particles and metal impurities contained in the slurry may be present on the substrate surface after chemical mechanical polishing (CMP). The fine particles are, for example, mainly alumina, silica, and cerium oxide, and the metal impurities include copper (Cu) dissolved and redeposited in the slurry during polishing, iron (Fe) derived from the oxidizing agent in the slurry, and cobalt (Co) organometallic complexes formed by the reaction of a cobalt (Co) corrosion inhibitor contained in the slurry with cobalt (Co).

[0038] In the present invention, the barrier metal refers to cobalt (Co), titanium (Ti)-based compounds, tantalum (Ta)-based compounds, ruthenium (Ru), etc., which are used in a layer (barrier metal layer) formed between a contact plug or wiring of a semiconductor substrate and an insulating film in order to prevent the metal in the contact plug or wiring from diffusing into the insulating film.

[0039] Low-k materials are materials with low dielectric constants used for interlayer insulating films, and include, but are not limited to, porous silicon, silicon-containing organic polymers, TEOS (tetraethoxysilane), etc. Specific examples include Black Diamond (manufactured by Applied Materials, Inc.) and Aurora (manufactured by ASM International).

[0040] The present invention also relates to a method for cleaning a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring, comprising a step of contacting a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring with the cleaning solution composition of the present invention.

[0041] The present invention still further relates to a method for producing a semiconductor substrate, comprising a step of contacting a substrate having a cobalt (Co) contact plug and / or cobalt (Co) wiring with the cleaning liquid composition of the present invention. In one embodiment, a method for producing a semiconductor substrate includes a step of chemically mechanically polishing (CMP) a substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring prior to a step of contacting the substrate having a cobalt (Co) contact plug and / or a cobalt (Co) wiring with the cleaning liquid composition of the present invention.

[0042] Examples of the contacting step include, but are not limited to, a cleaning step after chemical mechanical polishing (CMP) and a cleaning step after processing an insulating film on a top layer of a cobalt (Co) contact plug by dry etching. Examples of the contacting method include, but are not limited to, a single-wafer cleaning method using brush scrubbing in combination, a single-wafer cleaning method in which a cleaning solution is sprayed from a spray or nozzle, a batch-type spray cleaning method, and a batch-type immersion cleaning method. Among these, the single-wafer cleaning method using brush scrubbing in combination and the single-wafer cleaning method in which a cleaning solution is sprayed from a spray or nozzle are preferred, and the single-wafer cleaning method using brush scrubbing in combination is particularly preferred.

[0043] The atmosphere in which the contact is performed is not limited to this, but examples thereof include air, a nitrogen atmosphere, and a vacuum, etc. Among these, air and a nitrogen atmosphere are preferable. The contact time is not particularly limited since it is appropriately selected depending on the purpose, but is 0.5 to 5 minutes in the case of a single-wafer cleaning method in which brush scrubbing is used in combination and a single-wafer cleaning method in which a cleaning solution is sprayed from a spray or a nozzle, and is 0.5 to 30 minutes in the case of a batch-type spray cleaning method and a batch-type immersion cleaning method. The temperature is not particularly limited as it is appropriately selected depending on the purpose, but is 20°C to 50°C in the case of a single wafer cleaning method in which brush scrubbing is used in combination and a single wafer cleaning method in which a cleaning solution is sprayed from a spray or nozzle, and is 20°C to 100°C in the case of a batch type spray cleaning method and a batch type immersion cleaning method. The above-mentioned contact conditions can be appropriately combined depending on the purpose.

[0044] Examples of the semiconductor substrate include, but are not limited to, silicon, silicon carbide, silicon nitride, gallium arsenide, gallium nitride, gallium phosphide, indium phosphide, etc. Among these, silicon, silicon carbide, gallium arsenide, and gallium nitride are preferable, and silicon and silicon carbide are particularly preferable. EXAMPLES

[0045] Next, the cleaning liquid composition of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these.

[0046] 1. pH stability test 1.1. Preparation of cleaning solution composition First, cleaning liquid compositions according to Examples 1 to 4 and Comparative Examples 1 to 3 were prepared. Specifically, as shown in Table 1, a reducing agent, a surfactant, and / or a pH adjuster were added to water and mixed to prepare cleaning liquid compositions according to Examples 1 to 4 and Comparative Examples 1 to 3.

[0047] Evaluation The pH of the prepared cleaning liquid composition was measured using a pH meter (manufactured by DKK-TOA, model number: HM-25R) on the day of preparation (day 0) and one week after preparation (day 7). The results are shown in Table 1 and Figure 1. [Table 1] In Table 1, DEHA is N,N-diethylhydroxylamine, and IONET D2 is a naphthalenesulfonic acid formaldehyde condensate.

[0048] The cleaning solutions of Examples 1 to 4 had a stable pH even one week after production, and were particularly stable at a pH of 6 to 9. On the other hand, the cleaning solution compositions of Comparative Examples 1 to 3 were found to have a change in pH of 0.5 or more one week after production.

[0049] 2. Cleaning ability of the cleaning solution composition for cobalt (Co) wafers 2.1. Preparation of cleaning solution composition Cleaning liquid compositions according to Examples 5 to 13 and Comparative Examples 4 to 9 were prepared. Specifically, the cleaning liquid compositions according to Examples 5 to 13 and Comparative Examples 4 to 9 were prepared by adding a reducing agent, a surfactant, a pH adjuster, and / or an anticorrosive agent as shown in Table 2 to water and mixing them. Comparative Example 10 is an aqueous solution prepared by dissolving tetramethylammonium hydroxide (TMAH) in water and adjusting the pH. Comparative Examples 11 and 12 are cleaning liquid compositions to be applied after CMP manufactured by Kanto Chemical Co., Ltd., and Comparative Example 11 is an alkaline post-CuCMP cleaning liquid for cobalt (Co) barrier metal, and Comparative Example 12 is an acidic post-CuCMP cleaning liquid for tantalum (Ta) barrier metal. Comparative Examples 11 and 12 do not contain a hydroxylamine derivative.

[0050] 2.2. Preparation of CMP polishing fluid A slurry using silicon oxide (manufactured by Resonac) was diluted with ultrapure water (DIW) to obtain a CMP polishing liquid.

[0051] 2.3. Preparation of wafer to be polished A cobalt (Co) substrate having the following structure was prepared (PVD-Co 2kÅ / Ti / Th-SiO2 / Si, manufactured by Advanced Materials Technology Co., Ltd.).

[0052] 2.4. Cobalt (Co) Wafer Polishing and Cleaning The wafer to be polished was polished for 30 seconds using the CMP polishing solution with a polishing device (CMP polishing device manufactured by G&P Technology, model number: POLI-762). After the polishing was completed, the wafer was rinsed for 10 seconds with 100 mL of ultrapure water (DIW) while rotating. The rinsed wafer was cleaned for 60 seconds by rolling a polyvinyl alcohol brush (manufactured by AION Co., Ltd.) over the wafer while rotating using each of the cleaning solution compositions listed in Tables 2 to 4. The cleaned wafer was rinsed for 30 seconds with 300 mL of ultrapure water (DIW) while rotating, and further dried at 25°C for 30 seconds while rotating to obtain a wafer for measurement.

[0053] 2.5. Measuring the number of defects on the surface of a cobalt (Co) wafer The number of defects on the surface of the measurement wafer was measured using a surface inspection device (manufactured by Takano Corporation, model number: WM-10) to evaluate the cleaning properties of the cleaning liquid composition. The evaluation results are shown in Tables 2 to 4 and Figures 2 to 4.

[0054] 2.6. Results [Table 2] In Table 2, DEHA is N,N-diethylhydroxylamine, IONET D2 is naphthalenesulfonic acid formaldehyde condensate, and mTAZ is 3-mercapto-1,2,4-triazole.

[0055] [Table 3] [Table 4]

[0056] All of the cleaning liquid compositions of Examples 5 to 13 showed the number of defects in the first three figures, and in particular, the cleaning liquid composition of Example 10 showed the most excellent cleaning properties. The cleaning liquid compositions of Examples 5 to 13 showed good cleaning properties equal to or better than the cleaning liquid compositions of Comparative Examples 6 to 8, which had poor pH stability but good cleaning properties, and showed cleaning properties far superior to the TMAH aqueous solution of Comparative Example 10 and the commercially available cleaning liquid compositions of Comparative Examples 11 and 12. Furthermore, since the number of defects increased in the cleaning liquid composition of Comparative Example 4, it was found that a surfactant is essential for improving the cleaning performance in a cleaning liquid composition using a hydroxylamine. Furthermore, the cleaning liquid composition of Comparative Example 5 had insufficient cleaning properties despite containing the same components as those of Examples 6 to 13, indicating that cleaning properties cannot be guaranteed when the pH is 12.

Claims

1. A cleaning solution composition for cleaning substrates having cobalt (Co) contact plugs and / or cobalt (Co) wiring, comprising one or more hydroxylamine derivatives as a reducing agent, one or more surfactants, one or more pH adjusting agents, and water, wherein the pH is 3 or higher and 9 or lower.

2. The cleaning solution composition according to claim 1, further comprising one or more corrosion inhibitors.

3. The cleaning solution composition according to claim 1, wherein the hydroxylamine derivative is selected from the group consisting of N,N-diethylhydroxylamine, N-methylhydroxylamine, and N,N-dimethylhydroxylamine.

4. The cleaning solution composition according to claim 1, wherein the surfactant is a polysulfonic acid compound.

5. The cleaning solution composition according to claim 1, wherein the pH adjusting agent is a quaternary ammonium compound.

6. The cleaning solution composition according to claim 5, wherein the quaternary ammonium compound is trimethyl-2-hydroxyethylammonium hydroxide.

7. The cleaning solution composition according to claim 2, wherein the corrosion inhibitor is a nitrogen-containing ring compound.

8. The cleaning composition according to claim 7, wherein the nitrogen-containing ring compound is 3-mercapto-1,2,4-triazole.

9. A stock solution composition for a cleaning solution composition according to any one of claims 1 to 8, the stock solution composition used to obtain the cleaning solution composition by diluting it 10 to 1000 times.

10. A method for cleaning a substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring, comprising the step of bringing a cleaning solution composition according to any one of claims 1 to 8 into contact with the substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring.

11. A method for manufacturing a semiconductor substrate, comprising the step of bringing a cleaning solution composition according to any one of claims 1 to 8 into contact with a substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring.

12. A method for manufacturing a semiconductor substrate according to claim 11, comprising the step of chemically mechanically polishing (CMP) a substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring before bringing the substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring into contact with the substrate.

13. A method for manufacturing a semiconductor substrate according to claim 11, wherein the step of bringing a substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring into contact is a step of cleaning the substrate having cobalt (Co) contact plugs and / or cobalt (Co) wiring.

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