Composition, application of composition, cleaning agent and application of cleaning agent

Abstract

The embodiment of the invention provides a composition and application thereof, and a cleaning agent and application thereof. The composition can be used for providing a cleaning agent. The cleaning agent can be obtained after the composition is compounded with an oxidizing agent, the etching rate of the cleaning agent to AlN is stable, high-selectivity etching of AlN to AlOx is achieved, the cleaning agent can be well compatible with metal cobalt, and preparation of a high-performance semiconductor device is facilitated; in addition, the composition can be recycled and reused.

Description

Technical Field

[0001] The present application relates to the technical field of semiconductor device preparation, and in particular to a composition and its application, a cleaning agent and its application. Background Art

[0002] With the development of the semiconductor industry, in order to enrich or optimize the performance of semiconductor devices, more and more materials are introduced into semiconductor devices or the production and manufacturing process of semiconductor devices; for example, metal nitrides, metal oxides, etc. In different semiconductor devices or their manufacturing processes, the same material may play different roles or be used to form different structures. Aluminum nitrides (such as AlN) and aluminum oxides (such as AlO x ,0 <x≤1.5)为例,二者可以同为刻蚀停止层的材料,或者作为半导体制程中的不同的保护层等;在一些应用场景下,AlN层与AlO x The layers are in contact with each other, and high selectivity for AlN etching is required to maintain AlO x The outline of the layer.

[0003] In addition, due to the good conductivity of metallic cobalt, the use of cobalt to prepare interconnection lines can effectively reduce the power consumption and size of semiconductor devices. Cobalt has a small crystallization rate, few grain boundaries, weak diffusion, and low chemical activity, which is more conducive to the preparation of high-integration, high-precision semiconductor devices. Therefore, in the preparation of some semiconductor devices, the wiring metal cobalt under the etching stop layer. Therefore, when etching AlN, it is also necessary to have good compatibility with metallic cobalt. Therefore, it is urgent to provide a new cleaning agent that can achieve AlN to AlO at the same time. X The higher etching selectivity of AlN, the higher compatibility with metallic cobalt, and the higher selective etching of AlN to Co. Summary of the invention

[0004] In view of this, the present application provides a composition and its application, a cleaning agent and its application. The cleaning agent formed by compounding the above composition with an oxidant has a stable etching rate for AlN, achieving the etching rate of AlN to AlO x The composition can be etched with higher selectivity and is better compatible with metallic cobalt; in addition, the composition can also be recycled and reused.

[0005] In a first aspect, an embodiment of the present application provides a composition, including a first protective agent, a second protective agent and a solvent;

[0006] The first protecting agent includes substituted or unsubstituted 1,2,3-triazole and / or substituted or unsubstituted pyrazole, and the second protecting agent includes substituted or unsubstituted benzoic acid and / or substituted or unsubstituted phthalic acid;

[0007] In the composition, the mass content of the first protective agent is greater than or equal to the mass content of the second protective agent.

[0008] The cleaning agent provided by the above-mentioned composition and the oxidant can simultaneously realize the cleaning of AlN to AlO x The high selective etching of AlN and the certain etching selectivity of Co have good compatibility and can remove the AlN layer without damaging AlO x The cleaning agent provided by the composition of the present application can also achieve the effect of AlN on AlO x , and the etching selectivity of AlN to Co can be flexibly adjusted in a wide range to meet the needs of different application scenarios. In addition, the above composition will not damage low-dielectric materials (including materials with a dielectric constant ≤ 3.5), so that when the cleaning agent provided by the above composition is used to clean the workpiece, the outline of the structure formed by the low-dielectric material will not be damaged. Due to the high stability of the first protective agent and the second protective agent, the stability of the removal rate of AlN by the final cleaning agent can be improved, which is beneficial to the preparation of high-precision semiconductor devices; at the same time, the recycling of the composition can also be achieved, thereby significantly extending the service life of the composition.

[0009] In some embodiments of the present application, the mass ratio of the first protective agent to the second protective agent is 1:1 to 20:1. x The etching selectivity ratio of AlN to Co and the etching selectivity ratio of AlN to Co are controlled within a relatively high range, which is more conducive to the preparation of high-precision and high-integration semiconductor devices.

[0010] In some embodiments of the present application, the first protective agent accounts for 1%-5% of the mass of the composition. x The selectivity ratio is more conducive to inhibiting the etching of metal cobalt by the cleaning agent, and the risk of the first protective agent being adsorbed and remaining on the surface of the workpiece is also smaller, thereby providing a cleaning agent with better comprehensive performance.

[0011] In some embodiments of the present application, the substituted 1,2,3-triazole includes The R 11 , R 12 Each is independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, wherein the aryl group includes a phenyl group and a benzyl group; and the R 11 , R 12 It is not a hydrogen atom at the same time; thus, it has good compatibility with the cleaning agent system, is stable and soluble, will not affect the removal of AlN, can exist stably in the system, and can protect the metal cobalt; it is conducive to the realization of AlN to AlO xAnd the selective etching of AlN to Co.

[0012] and / or, the substituted pyrazole comprises The R 21 , R 22 , R 23 Each is independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, wherein the aryl group includes a phenyl group and a benzyl group; and the R 21 , R 22 , R 23 The above materials have good compatibility with the cleaning agent system, are stable and soluble, will not affect the removal of AlN, can exist stably in the system, and are conducive to the realization of AlN to AlO x And the selective etching of AlN to Co.

[0013] In some embodiments of the present application, the substituted benzoic acid includes The R 31 , R 32 , R 33 , R 34 Each is independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, wherein the aryl group includes a phenyl group and a benzyl group; and the R 31 , R 32 , R 33 , R 34 Not all hydrogen atoms at the same time;

[0014] And / or, the substituted phthalic acid comprises The R 41 , R 42 , R 43 , R 44 Each is independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, wherein the aryl group includes a phenyl group and a benzyl group; and the R 41 , R 42 , R 43 , R 44 Not all are hydrogen atoms.

[0015] In some embodiments of the present application, the composition further comprises a chelating agent; the chelating agent comprises one or more of trans-1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminetriacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, and diethylenetriaminepentaacetic acid; the mass proportion of the chelating agent in the composition is 0.001%-1%. The chelating agent can reduce the risk of free metal ions inducing the decomposition of the oxidant (e.g., H2O2) in the cleaning agent, slow down the decomposition rate of the oxidant, and improve the etching stability of the cleaning agent.

[0016] In some embodiments of the present application, the composition further includes a solubilizer; the solubilizer includes one or more of N-methylmorpholine-N-oxide and N-ethylmorpholine-N-oxide; the mass proportion of the solubilizer in the composition is 1%-30%. The solubilizer can not only promote the dissolution of each component, but also improve the uniformity of the final cleaning agent, which is beneficial to the application and storage stability of the cleaning agent.

[0017] In some embodiments of the present application, the composition further comprises a buffer; the buffer comprises one or more of 1,8-diazabicyclo[5.4.0]undec-7-ene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and phosphoric acid. The buffer is used to adjust the pH value of the composition.

[0018] In some embodiments of the present application, the pH value of the composition is 6-8. This facilitates the removal of AlN by the cleaning agent.

[0019] In some embodiments of the present application, the solvent includes water and / or an organic solvent;

[0020] The organic solvent includes aprotic solvents and / or ether alcohol solvents, and the aprotic solvent includes one or more of dimethyl sulfoxide, cyclopentane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone; the ether alcohol solvent includes one or more of diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, glycerol, ethylene glycol, and propylene glycol; the mass proportion of the organic solvent in the composition is 0.1%-50%, and the mass proportion of the water in the composition is 1%-99%. Water is used to dissolve the components in the composition, and the aprotic solvent is used to dissolve the photosensitive materials commonly used in the semiconductor device process and the ash of the photosensitive materials has a certain solubility; the alcohol ether solvent has amphiphilic properties (hydrophilic and lipophilic), can effectively reduce the surface tension of the composition, and has a high wettability to the wafer surface.

[0021] The second aspect of the embodiment of the present application provides an application of the composition provided in the first aspect of the embodiment of the present application in the field of cleaning agents. Specifically, the composition provided in the first aspect of the embodiment of the present application can be used to provide a cleaning agent.

[0022] The third aspect of the embodiment of the present application provides a cleaning agent, including an oxidant and the aforementioned composition provided in the first aspect of the embodiment of the present application; the oxidant includes hydrogen peroxide. Since the composition provided in the embodiment of the present application is compounded with the oxidant, the cleaning agent can simultaneously achieve the effect of AlN on AlO x , and a high selective etching ratio of AlN to Co, and the above etching ratio can be flexibly adjusted within a large range; and the cleaning agent has good stability during use, and is very effective for AlN, AlO x The removal rate of Co is stable, which can play a vital role in some process scenarios of semiconductor manufacturing. In addition, in practical applications, the cleaning agent can be compounded in the cleaning equipment, and the composition and oxidant can be delivered to the equipment through different pipelines. For example, the oxidant can be replenished through the spiking mode, which can realize the flexible regulation of the ratio of the oxidant and the composition, and can also realize the recycling and reuse of the composition, effectively extending the service life of the composition, up to 24 hours or more.

[0023] A fourth aspect of the embodiments of the present application provides a cleaning method, comprising: contacting the cleaning agent provided by the embodiments of the present application with the workpiece to be cleaned; or, mixing the aforementioned cleaning agent provided by the embodiments of the present application with an oxidant and then contacting the workpiece to be cleaned.

[0024] The cleaning method has strong process controllability, simple operation and is suitable for large-scale industrial production.

[0025] In some embodiments of the present application, the aforementioned composition provided in the embodiments of the present application is mixed with an oxidant, wherein the oxidant is replenished through the spiking mode of the equipment. This helps to keep the etching rate of the cleaning agent on AlN stable, and the cleaning agent can be used in a circulation mode for more than 24 hours.

[0026] A fifth aspect of the embodiments of the present application provides a method for preparing a semiconductor device, comprising:

[0027] Forming a patterned film layer on a substrate containing a hard mask, transferring the pattern of the patterned film layer to the hard mask, and etching the substrate to obtain a patterned substrate;

[0028] The patterned substrate is cleaned by using the cleaning agent provided in the embodiment of the present application, or by using a mixture of the above composition and an oxidant provided in the embodiment of the present application to clean the patterned substrate.

[0029] The above-mentioned preparation method has strong process reliability, is suitable for large-scale industrial production, and is also beneficial to improving the production efficiency and production yield of semiconductor devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is the change of pH value of the composition of Example 1 at 60°C over time;

[0031] Figure 2A Example 1 cleaning agent for AlO x The etching rate variation curve with time;

[0032] Figure 2B Example 1 cleaning agent for AlO x The etching rate variation curve with time;

[0033] Figure 2C The etching rate of Co by the cleaning agent of Example 1 changes with time;

[0034] Figure 2D The etching rate of the cleaning agent of Example 1 on NDC (doped silicon carbide film) changes with time;

[0035] Figure 2E The etching rate of the NFDARC layer (nitrogen-free dielectric anti-reflection layer) by the cleaning agent of Example 1 changes with time;

[0036] Figure 2F This is a curve showing the change of etching rate of semiconductor ODC material by the cleaning agent in Example 1 over time;

[0037] Figure 2G The etching rate of TEOS (SiO2 layer deposited by using tetraethoxysilane TEOS as raw material) by the cleaning agent of Example 1 changes with time;

[0038] Figure 2H This is a curve showing the change in etching rate of DLK (dense low k, dense low k material) by the cleaning agent in Example 1 over time. DETAILED DESCRIPTION

[0039] With the development of the semiconductor industry, its manufacturing process is developing towards nodes below 10nm; and, in order to enrich or optimize the performance of semiconductor devices, more and more materials are introduced into semiconductor devices or the production and manufacturing process of semiconductor devices; for example, metal nitrides, metal oxides, etc. In the manufacturing process of semiconductors, the etch stop layer is a widely used structure, which is mainly used to prevent the continuation of etching, so that the etching behavior stops at the changed structure, thereby protecting the underlying material from being damaged. In addition, as the critical dimensions of semiconductors continue to decrease and the patterns continue to become more complex, it is difficult to remove part of the film layer with high selectivity to more accurately retain the pattern information while achieving contour control of other structures. Common etch stop layer materials include titanium nitride and aluminum oxide. In different semiconductor devices or their manufacturing processes, there may be some differences in the structures that need to be selectively etched based on differences in structural design. In some preparation scenarios, the AlN layers are in contact with each other, and it is necessary to achieve AlN to AlO x In addition, due to the good conductivity of metallic cobalt, the use of cobalt to prepare interconnection lines can effectively reduce the power consumption and size of semiconductor devices, and cobalt has a small crystallization rate, few grain boundaries, weak diffusion, and low chemical activity, which is more conducive to the preparation of high-integration, high-precision semiconductor devices; therefore, in the preparation of some semiconductor devices, the wiring metal cobalt under the etching stop layer is used. Therefore, when etching AlN, it is also necessary to achieve a certain etching selectivity ratio of AlN to Co. Therefore, it is urgent to provide a new cleaning agent that can simultaneously achieve AlN to AlO x A higher selective etching ratio of AlN and a certain etching selectivity of AlN to Co.

[0040] In the prior art, the reagents used for selective etching generally include an oxidant and a composition containing a protective agent and other components. However, in order to meet the requirements of long-term storage and transportation, the oxidant is generally mixed with the above composition to form a cleaning agent before use. The properties of the cleaning agent depend to a certain extent on the formulation design of the composition. Therefore, it is essentially necessary to provide a composition that can be used to be compounded with an oxidant to form a cleaning agent that can achieve the technical goal.

[0041] In order to solve the above technical problems, the present application provides a composition in an embodiment, comprising a first protective agent, a second protective agent and a solvent;

[0042] The first protecting agent includes substituted or unsubstituted 1,2,3-triazole and / or substituted or unsubstituted pyrazole, and the second protecting agent includes substituted or unsubstituted benzoic acid and / or substituted or unsubstituted phthalic acid;

[0043] In the above composition, the mass content of the first protective agent is greater than or equal to the mass content of the second protective agent.

[0044] The above-mentioned composition provided by the embodiments of the present application can be used to provide a cleaning solution, which can be used in the preparation of semiconductor devices.

[0045] After the above-mentioned composition is compounded with an oxidant, a cleaning solution can be obtained, and this cleaning solution can achieve the selective etching of AlN to AlO x Specifically, under the cooperation of a first protecting agent of azole type and a second protecting agent of benzoic acid or phthalic acid type with specific relative contents, while not affecting the etching rate of the cleaning agent on AlN, it can show high compatibility with AlO x so as to achieve a high selective etching of AlN to AlO x Furthermore, under the synergistic effect of the first protecting agent and the second protecting agent with specific ratios, the composition shows strong protection for Co and can effectively inhibit the removal of Co by the cleaning agent. Therefore, the cleaning agent provided by the above-mentioned composition can simultaneously achieve a high selective etching of AlN to AlO x and a certain etching selectivity ratio of AlN to Co, with good compatibility, and can achieve the effect of removing the AlN layer without damaging the AlO x layer and the cobalt metal layer. It should also be noted that the cleaning agent provided by the composition of the present application can also achieve flexible regulation of the etching selectivity ratio of AlN to AlO x and AlN to Co within a large range to meet the requirements of different application scenarios. In addition, the above-mentioned composition will not damage low dielectric materials (including materials with a dielectric constant ≤ 3.5), so when using the cleaning agent provided by the above-mentioned composition to clean a workpiece, it will not damage the profile of the structure formed by the low dielectric material. Also, due to the high stability of the first protecting agent and the second protecting agent, the stability of the removal rate of AlN by the final cleaning agent can be improved, which is beneficial to the preparation of high-precision semiconductor devices; at the same time, the recycling of the composition can be realized, thus significantly extending the service life of the composition.

[0046] In addition, the above-mentioned protecting agent has certain water solubility. Even when water is used as the main solvent of the composition, after the cleaning process, the protecting agent is easily detached from the surface of the workpiece, which is more beneficial to the preparation of semiconductor devices. At the same time, the cleaning agent provided by the above-mentioned composition has a relatively small etching rate and a stable etching rate for other film layer materials that often appear in the semiconductor device substrate, such as low dielectric material film layers. In some embodiments of the present application, AlO x , 0 < x ≤ 1.5.

[0047] In some embodiments of the present application, the mass ratio of the first protecting agent to the second protecting agent is 1:1 to 20:1. In this way, it is more beneficial to reduce the etching rates of the cleaning solution on AlO x and metallic cobalt, and can maintain the etching rate of the cleaning solution on AlO x at a relatively high level, which is beneficial to simultaneously achieving the high selective etching of AlN to AlOx The etching selectivity of AlN to Co and the etching selectivity of AlN to Co are controlled within a relatively high range, which is more conducive to the preparation of high-precision and high-integration semiconductor devices. Specifically, the mass ratio of the first protective agent to the second protective agent can be, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, etc.

[0048] In some embodiments of the present application, the first protective agent accounts for 1%-5% of the mass of the composition. x The selectivity ratio is more conducive to inhibiting the etching of metal cobalt by the cleaning agent, and the risk of the first protective agent being adsorbed and remaining on the surface of the workpiece is also smaller, thereby providing a cleaning agent with better comprehensive performance. Specifically, the mass proportion of the first protective agent in the etching composition can be, for example, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%.

[0049] In some embodiments of the present application, the second protective agent accounts for 0.05%-5% of the mass of the composition. The mass ratio of the second protective agent in the etching composition can be, for example, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55, 0.6, 0.65, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%. On the premise that the relative dosages of the first protective agent and the second protective agent are within the scope defined in the present application, further limiting the dosage of the second protective agent within the above range is more conducive to inhibiting the etching of metallic cobalt by the cleaning agent.

[0050] In some embodiments of the present application, the first protective agent includes substituted or unsubstituted 1,2,3-triazole; the substituted 1,2,3-triazole includes R 11 、R 12 Each independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group (-COOH), a hydroxyl group (-OH), a mercapto group (-SH), and an aryl group, the aryl group includes a phenyl group and a benzyl group, and R 11 、R 12 are not simultaneously hydrogen atoms. The above materials have good compatibility with the cleaning agent system, are stable, easily soluble, do not affect the removal of AlN, can stably exist in the system, and can achieve the protection of metallic cobalt; it is conducive to realizing the selective etching of AlN on AlO x and AlN on Co. In the embodiments of the present application, the C1-C4 alkyl group can be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The number of carbon atoms in the alkoxy group can be 1-4, and the alkoxy group can be, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group. In this way, it is conducive to its dissolution in the cleaning agent. Substituted or unsubstituted 1,2,3-triazole is more conducive to reducing the etching rates of the cleaning agent on AlO x and Co, so that the cleaning agent shows a higher AlN / AlO x and AlN / Co selective etching ratio.

[0051] In some embodiments of the present application, the substituted pyrazole includes R 21 、R 22 、R 23 are each independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group (-COOH), a hydroxyl group (-OH), a mercapto group (-SH), and an aryl group, and the aryl group includes a phenyl group and a benzyl group; R 21 、R 22 、R 23 are not simultaneously hydrogen atoms. The above materials have good compatibility with the cleaning agent system, are stable and easily soluble, do not affect the removal of AlN, can stably exist in the system, and are conducive to realizing the selective etching of AlN on AlO x and the selective etching of AlN on Co. In the embodiments of the present application, the C1-C4 alkyl group can be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The number of carbon atoms in the alkoxy group can be 1-4, and the alkoxy group can be, for example, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Thus, it is conducive to its dissolution in the cleaning agent.

[0052] In some embodiments of the present application, the second metal protectant includes a substituted or unsubstituted phthalic acid. The substituted or unsubstituted phthalic acid cooperates with the first metal protectant to be more conducive to reducing the etching rate of the cleaning agent on AlO x . In some embodiments of the present application, the substituted phthalic acid includes R 41 、R 42 、R 43 、R 44 are each independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, and the aryl group includes a phenyl group and a benzyl group; and R 41 、R 42 、R 43 、R 44 are not simultaneously hydrogen atoms. In the embodiments of the present application

[0053] , the C1-C4 alkyl group can be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The number of carbon atoms in the alkoxy group can be 1-4, and the alkoxy group can be, for example, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Thus, it is conducive to its dissolution in the cleaning agent.

[0054] In some embodiments of the present application, the substituted benzoic acid includes R 31 、R 32 、R 33 、R 34 are each independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, and the aryl group includes a phenyl group and a benzyl group; and R 31 、R32 , R 33 , R 34 are not simultaneously hydrogen atoms. In the embodiments of the present application, the C1-C4 alkyl group can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. The number of carbon atoms in the alkoxy group can be 1-4, and the alkoxy group can be, for example, methoxy, ethoxy, propoxy, butoxy. Thus, it is beneficial to its dissolution in the cleaning agent.

[0055] In some embodiments of the present application, the first protective agent includes 1,2,3-triazole, and the second protective agent includes phthalic acid. At this time, it is beneficial to further improve the etching selectivity of AlN to AlO x .

[0056] In some embodiments of the present application, the composition further includes a chelating agent. The chelating agent can be used to chelate aluminum ions (Al 3+ ) generated after the cleaning agent etches the workpiece, reduce the risk of free metal ions causing the decomposition of the oxidant (for example, H2O2) in the cleaning agent, slow down the decomposition rate of the oxidant, and improve the etching stability of the cleaning agent. In some embodiments of the present application, the chelating agent includes one or more of trans-1,2-cyclohexanediaminetetraacetic acid (CDTA), ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylenediaminetriacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, and diethylenetriaminepentaacetic acid. In some embodiments of the present application, the mass ratio of the chelating agent in the composition is 0.001%-1%. Thus, it will not affect the etching rate of the cleaning agent to AlN, and can effectively and quickly chelate the metal ions generated by the reaction, effectively alleviating the decomposition of the oxidant. Specifically, the mass ratio of the chelating agent in the composition can be, for example, 0.001%, 0.002%, 0.005%, 0.006%, 0.008%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%. In some specific embodiments, the chelating agent includes trans-1,2-cyclohexanediaminetetraacetic acid. Thus, the chelating effect on metal ions is better during the application process of the cleaning agent, which is more beneficial to improving the etching stability of the cleaning agent.

[0057] In some embodiments of the present application, the composition further comprises a solubilizer. The solubilizer can not only promote the dissolution of each component, improve the uniformity of the finally obtained cleaning agent, and facilitate the application and storage stability of the cleaning agent. In some embodiments of the present application, the solubilizer comprises one or more of N-methylmorpholine-N-oxide and N-ethylmorpholine-N-oxide. The above two agents can not only act as solubilizers, but also stabilize the oxidant; at the same time, the above two reagents also have a certain alkalinity and can play the role of a buffer to stabilize the pH value of the composition and the cleaning agent formed by subsequent compounding, thereby further improving the etching stability of the cleaning agent for AlN and extending the recycling service life of the composition.

[0058] In some embodiments of the present application, the mass percentage of the solubilizer in the composition is 1%-30%. In this way, it is beneficial to form a uniform and stable composition and cleaning agent, which is beneficial to the application of the cleaning agent and does not affect the etching of AlN by the cleaning agent. Further, when the solubilizer is selected from N-methylmorpholine-N-oxide and / or N-ethylmorpholine-N-oxide, controlling its mass percentage in the composition within the above range is also beneficial to regulating the pH value of the composition within the target range. Specifically, the mass percentage of the solubilizer in the composition can be, for example, 1%, 2%, 5%, 6%, 8, 10%, 12%, 15%, 16%, 18%, 20%, 22%, 25%, 26%, 28%, 30%.

[0059] In some embodiments of the present application, the composition further comprises a buffer. The buffer is used to regulate the pH value of the composition. In some embodiments of the present application, the buffer comprises one or more of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetramethylammonium hydroxide, tetraethylammonium hydroxide, and phosphoric acid. The above reagents have good compatibility with the composition of the present application and the cleaning agent formed by compounding, and can regulate the pH value of the composition.

[0060] In some embodiments of the present application, the pH value of the composition is 6-8. In this way, it is beneficial to the removal of AlN by the cleaning agent.

[0061] In some embodiments of the present application, the solvent includes water and / or organic solvents; the organic solvents include aprotic solvents and / or ether alcohols. In some embodiments of the present application, the solvent includes water and organic solvents; the organic solvents include aprotic solvents and ether alcohols; the mass percentage of water in the composition is 1%-99%, and the mass percentage of the organic solvent in the composition is 0.1%-50%. Thus, water is used to dissolve the components in the composition, the aprotic solvent is used to dissolve the photosensitive materials commonly used in the semiconductor device manufacturing process and has a certain solubility for the ash of the photosensitive materials; the alcohol ether solvents have amphiphilic properties (hydrophilic and lipophilic), can effectively reduce the surface tension of the composition, and have a high wettability to the surface of the wafer. In some embodiments of the present application, the aprotic solvent includes one or more of dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone. In some embodiments of the present application, the alcohol ether solvents include one or more of diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, glycerol, ethylene glycol, and propylene glycol. In some specific embodiments, the aprotic solvent includes dimethyl sulfoxide, and the alcohol ether solvent includes diethylene glycol butyl ether. Specifically, the mass percentage of water in the composition can be, for example, 1%, 1.5%, 2%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 20%, 22%, 25%, 28%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 98.5%, 98.9%, 99%, etc. Specifically, the mass percentage of the organic solvent in the composition can be, for example, 0.1%, 0.5%, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, etc.

[0062] In the present application, detection methods such as nuclear magnetic resonance and mass spectrometry can be used to detect the presence of each component in the composition provided in the embodiments of the present application, and nuclear magnetic resonance combined with an internal standard sample can be used to determine the mass percentage of each component in the composition.

[0063] The embodiments of the present application also provide an application of the foregoing composition in the field of cleaning agents. Specifically, the foregoing composition can be used to provide a cleaning agent, which can be used in the preparation of semiconductor devices, and can be specifically applied to cleaning the patterned substrate obtained by the patterning process, so as to facilitate the obtaining of high-performance and high-precision semiconductor devices.

[0064] The present application also provides a cleaning agent, which includes an oxidant and the aforementioned composition provided by the embodiments of the present application; the oxidant includes hydrogen peroxide. Since the composition provided by the embodiments of the present application is compounded with the oxidant, the cleaning agent can simultaneously achieve a relatively high selective etching ratio of AlN to AlO x and AlN to Co, and can realize flexible regulation of the above etching ratio selection within a large range; moreover, the cleaning agent has good stability during use, and the removal rates of AlN, AlO x and Co are stable, and it can play a crucial role in some process scenarios of semiconductor manufacturing processes. In addition, in actual applications, the cleaning agent can be compounded in the cleaning equipment, and the composition and the oxidant can be transported to the equipment through different pipelines. For example, the oxidant can be replenished in a spiking mode, which can realize flexible regulation of the ratio of the oxidant to the composition, and can also realize the recycling of the composition, effectively extending the service life of the composition to reach 24 hours or more.

[0065] In the implementation of the present application, those skilled in the art can determine the ratio of the oxidant to the composition according to actual production needs. In some embodiments of the present application, the oxidant includes hydrogen peroxide, and the mass ratio of the oxidant to the composition is 1:1 to 1:30. Further regulating the ratio of the composition to the oxidant can regulate the etching rate and regulate the etching selectivity ratio of AlN / AlO x and AlN / Co within a certain range. Specifically, the mass ratio of the oxidant to the composition can be, for example, 1:1, 1:2, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, 1:22, 1:25, 1:28, 1:30.

[0066] In some embodiments of the present application, the etching selectivity ratio of the cleaning agent to AlN and AlO x ≥4.5:1, 0 < x < 1.5. Specifically, using the cleaning agent provided by the embodiments of the present application, the etching selectivity ratio of AlN to AlO x can be, for example, 4.5:1, 5:1, 8:1, 10:1, 12:1, 14:1, 15:1, 18:1, 20:1, 22:1, 25:1, 28:1, 30:1, 32:1, 35:1, 38:1, 40:1, 45:1, 48:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 100:1, 105:1, 110:1, 115:1, 120:1, 125:1, 130, 135:1, 140:1, 145:1, 150:1, 155:1, 160:1, etc.

[0067] In some embodiments of the present application, the etching selectivity of the cleaning agent for AlN and Co is ≥1.67:1. Specifically, using the cleaning agent provided in the embodiments of the present application, the etching selectivity of AlN for Co can be, for example, 1.67:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1, 15:1, 18:1.

[0068] The embodiments of the present application also provide a cleaning method, including: contacting the workpiece to be cleaned with the cleaning agent provided in the embodiments of the present application; or, mixing the aforementioned cleaning agent provided in the embodiments of the present application with an oxidant and then contacting the workpiece to be cleaned with the mixture.

[0069] The above cleaning method has strong process controllability, is easy to operate, and is suitable for large-scale industrial production.

[0070] In some embodiments of the present application, the aforementioned composition provided in the embodiments of the present application is mixed with an oxidant, wherein the oxidant is replenished through the spiking mode of the equipment. In this way, it is beneficial to keep the etching rate of the cleaning agent for AlN stable, and the cleaning agent can be used in a circulation mode, and the service time can reach more than 24 hours.

[0071] The embodiments of the present application also provide a method for preparing a semiconductor device, including:

[0072] Forming a patterned film layer on a substrate containing a hard mask, transferring the pattern of the patterned film layer to the hard mask, and etching the substrate to obtain a patterned substrate;

[0073] Cleaning the patterned substrate with the cleaning agent provided in the embodiments of the present application, or cleaning the patterned substrate with a mixture of the aforementioned composition provided in the embodiments of the present application and an oxidant.

[0074] The above preparation method has strong process reliability, is suitable for large-scale industrial production, and is also beneficial to improving the production efficiency and production yield of semiconductor devices.

[0075] The technical solutions of the present application will be further described below with multiple embodiments.

[0076] Example 1

[0077] A composition is composed of the following components by mass content: 1.25% of a first protective agent (specifically pyrazole), 0.5% of a second protective agent (specifically phthalic acid), 9% of a solubilizer (specifically N-methylmorpholine-N-oxide), 8% of an aprotic solvent (specifically sulfolane), 30% of an ether alcohol solvent (specifically diethylene glycol monobutyl ether), and the balance is water.

[0078] Example 2

[0079] A composition consists of the following components by mass content: 1% of the first protective agent (specifically 1,2,3-triazole), 0.05% of the second protective agent (specifically benzoic acid), 0.05% of the chelating agent (specifically CDTA), 8% of the solubilizer (specifically N-methylmorpholine-N-oxide), 0.1% of the buffer (specifically tetramethylammonium hydroxide), 10% of the aprotic solvent (specifically a dimethyl sulfoxide and sulfolane mixture with a mass ratio of 8:2), 25% of the ether alcohol solvent (specifically diethylene glycol butyl ether), and the balance being water.

[0080] Example 3

[0081] A composition consists of the following components by mass content: 5% of the first protective agent (specifically pyrazole), 5% of the second protective agent (specifically salicylic acid), 0.12% of the chelating agent (specifically DTPA), 10% of the solubilizer (specifically N-ethylmorpholine-N-oxide), 3.7% of the buffer (specifically TEAH), 10% of the aprotic solvent (specifically a dimethyl sulfoxide and sulfolane mixture with a mass ratio of 8:2), 20% of the ether alcohol solvent (specifically DPM), and the balance being water.

[0082] Example 4

[0083] A composition consists of the following components by mass content: 1.25% of the first protective agent (specifically 1,2,3-triazole), 0.3% of the second protective agent (specifically phthalic acid), 0.1% of the chelating agent (specifically EDTA), 8% of the solubilizer (specifically N-methylmorpholine-N-oxide), 0.5% of the buffer (specifically TMAH), 10% of the aprotic solvent (specifically a dimethyl sulfoxide and sulfolane mixture with a mass ratio of 1:1), 30% of the ether alcohol solvent (specifically BDG), and the balance being water.

[0084] Example 5

[0085] A composition consists of the following components by mass content: 0.5% of the first protective agent (specifically 1,2,3-triazole), 0.3% of the second protective agent (specifically phthalic acid), 0.1% of the chelating agent (specifically EDTA), 8% of the solubilizer (specifically N-methylmorpholine-N-oxide), 0.5% of the buffer (specifically TMAH), 10% of the aprotic solvent (specifically a dimethyl sulfoxide and sulfolane mixture with a mass ratio of 1:1), 30% of the ether alcohol solvent (specifically BDG), and the balance being water.

[0086] Example 6

[0087] A composition consists of the following components by mass content: 1.25% of a first protective agent (specifically 1,2,3-triazole), 0.05% of a second protective agent (specifically phthalic acid), 0.05% of a chelating agent (specifically CDTA), 8% of a solubilizer (specifically N-methylmorpholine-N-oxide), 0.1% of a buffer (specifically TMAH), 10% of an aprotic solvent (specifically dimethyl sulfoxide), 25% of an ether alcohol solvent (specifically BDG), and the balance being water.

[0088] Example 7

[0089] A composition consists of the following components by mass content: 1% of a first protective agent (specifically 1,2,4-triazole), 0.05% of a second protective agent (specifically benzoic acid), 0.05% of a chelating agent (specifically CDTA), 8% of a solubilizer (specifically N-methylmorpholine-N-oxide), 0.1% of a buffer (specifically TMAH), 10% of an aprotic solvent (specifically dimethyl sulfoxide), 25% of an ether alcohol solvent (specifically BDG), and the balance being water.

[0090] To highlight the beneficial effects of the embodiments of the present application, the following comparative examples are set.

[0091] Comparative Example 1

[0092] A composition consists of the following components by mass content: 0.1% of EDTA, 8% of N-methylmorpholine-N-oxide, 30% of BDG, 5% of DMSO, 5% of sulfolane, 0.5% of TMAH, 0.1% of phosphoric acid, and the balance being water.

[0093] Comparative Example 2

[0094] A composition consists of the following components by mass content: 0.1% of EDTA, 8% of N-methylmorpholine-N-oxide, 1.25% of 1,2,3-triazole, 30% of BDG, 5% of DMSO, 5% of sulfolane, 0.5% of TMAH, 0.1% of phosphoric acid, and the balance being water.

[0095] Comparative Example 3

[0096] A composition consists of the following components by mass content: 0.1% of EDTA, 8% of N-methylmorpholine-N-oxide, 0.3% of phthalic acid, 30% of BDG, 5% of DMSO, 5% of sulfolane, 0.5% of TMAH, and the balance being water.

[0097] For convenient reading, the parameters of the compositions of the above embodiments and comparative examples are summarized in Table 1.

[0098] Table 1

[0099]

[0100] pH Stability Test of the Composition

[0101] Monitor the change of the pH value of the composition in Example 1 over time at 60°C. The results are shown in Figure 1 . It can be seen from Figure 1 that the composition provided in the embodiment of the present application has high pH value stability within 48 hours.

[0102] Etching Test

[0103] Mix the above Examples 1 to 6 and Comparative Examples 1 to 3 with an oxidant (specifically hydrogen peroxide) at a mass ratio of 25:1 to obtain the cleaning agents for each example and comparative example; use the cleaning agents for each example and comparative example to clean the workpiece to be cleaned, and summarize the etching rates of the cleaning agents on different materials in Table 2.

[0104] Table 2

[0105]

[0106] In Table 2, ULK refers to ultra low k (ultra-low dielectric constant material) with a dielectric constant < 2.5; BD2 (black diamond), specifically refers to a porous low k material, and its main component is porous silicon oxide.

[0107] It can be seen from the data in Table 2 that the cleaning agent obtained by compounding the composition provided in the embodiment of the present application with an oxidant can achieve a relatively high selective etching of AlN to AlO x and has good compatibility with Co.

[0108] Cleaning Agent Stability Test

[0109] Taking Example 1 as a sample, mix the composition of Example 1 with hydrogen peroxide at a mass ratio of 25:1 to obtain the cleaning agent of Example 1, and monitor the etching rates of the cleaning agent on various substances within 48 hours. The results are respectively summarized in FIG. 2A to FIG. 2H ; Figure 2A is the curve of the etching rate of the cleaning agent on AlN changing with time; Figure 2B is the curve of the etching rate of the cleaning agent on AlO x changing with time, Figure 2C is the curve of the etching rate of the cleaning agent on Co changing with time, Figure 2D is the curve of the etching rate of the cleaning agent on NDC changing with time, Figure 2E is the curve of the etching rate of the cleaning agent on NFDARC changing with time, Figure 2FThe etching rate of the cleaning agent on ODC versus time curve Figure 2G The etching rate of the cleaning agent on TEOS versus time curve Figure 2H The etching rate of the cleaning agent on DLK versus time curve. From FIG. 2A to FIG. 2H It can be seen that the cleaning agent provided by the embodiments of the present application can achieve selective etching of AlN on AlO x , AlN on Co, and the etching rate is stable within 48 hours, and the etching rate on other film layers is also relatively stable.

[0110] To further explore the influence of the dosages of the first protective agent and the second protective agent on the etching rate of cobalt metal, Examples 8 to 11 are set, and the component parameters of the compositions of each example are summarized in Table 3.

[0111] Table 3

[0112]

[0113]

[0114] Mix the compositions of Examples 8 to 11 above with hydrogen peroxide in a mass ratio of 25:1 to obtain the cleaning agents of Examples 8 to 11, and test that the etching rate of the cleaning agent of Example 8 on Co is The etching rate of the cleaning agent of Example 9 on Co is The etching rate of the cleaning agent of Example 10 on Co is The etching rate of the cleaning agent of Example 11 on Co is From the above data and combined with the data of Examples 4 and 6, it can be seen that when the mass ratio of the first protective agent to the second protective agent is within the more recommended range of the present application, it is more conducive to taking into account the selective etching of AlN on AlO x , AlN on Co.

[0115] Composition and oxidant dosage test

[0116] Prepare a composition for providing a cleaning agent, including the following components by mass percentage: 62.25% water, 0.15% EDTA, 8.0% NMMO, 1.2% 1,2,3-triazole, 0.4% phthalic acid, and 25% BDG.

[0117] Mix the above composition with hydrogen peroxide in different mass ratios to obtain the cleaning agents of Examples 12 to 15; use the cleaning agents of the above examples to clean the workpieces, and the etching rates on different materials are summarized in Table 4.

[0118] Table 4

[0119]

[0120] As can be seen from the data in Table 4, as the amount of hydrogen peroxide used increases, the etching rate of AlN increases significantly, and the etching rate of AlO x increases slowly, and the etching selectivity between the two also changes accordingly.

[0121] Effect of the pH value of the cleaning agent on the etching rate

[0122] Prepare a composition for providing a cleaning agent, including the following components by mass ratio: 6% sulfolane, 9% NMMO, 30% BDG, 1.5% 1,2,3-triazole, 0.5% phthalic acid. Adjust the pH value of the composition in different examples with phosphoric acid and choline, and the balance is water. Test the effect of the pH value of the composition on the etching rate of the cleaning agent.

[0123] Prepare cleaning agents of the composition with different pH values and hydrogen peroxide according to a mass ratio of 25:1. The etching rates for different materials are summarized in Table 5.

[0124] Table 5

[0125]

[0126] As can be seen from the data in Table 5, an increase or decrease in the pH value will affect the etching rate of AlN because the etching of AlN is accompanied by hydrolysis, and Al is an amphoteric element, and both acidic and alkaline conditions will enhance the hydrolysis of AlN.

[0127] It should be understood that the first, second, and various numerical numbers involved in this article are only for the convenience of description and are not used to limit the scope of this application.

[0128] In this application, "and / or" describes the association relationship of associated objects and indicates that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone, where A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after.

[0129] In this application, "at least one" means one or more, and "a plurality" means two or more. "At least one of the following (items)" or its similar expressions refer to any combination of these items, including any combination of single items (items) or plural items (items). For example, "at least one of a, b, or c", or, "at least one of a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0130] In this application, "-" represents a range value, including the endpoint values at both ends. For example, the value of a can be 0.5 - 15, which means the value of a can be between 0.5 and 15, and includes the endpoint values 0.5 and 15.

[0131] It should be understood that in various embodiments of this application, the magnitude of the serial numbers of the above processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The order of execution of each process should be determined by its function and internal logic, and should not constitute any limitation to the implementation process of the embodiments of this application.

Claims

1. A composition, characterized in that comprising a first protective agent, a second protective agent and a solvent; The first protecting agent includes substituted or unsubstituted 1,2,3-triazole and / or substituted or unsubstituted pyrazole, and the second protecting agent includes substituted or unsubstituted benzoic acid and / or substituted or unsubstituted phthalic acid; In the composition, the mass content of the first protective agent is greater than or equal to the mass content of the second protective agent.

2. The composition according to claim 1, characterized in that The mass ratio of the first protective agent to the second protective agent is 1:1 to 20:

1.

3. The composition according to claim 1 or 2, characterized in that The first protective agent accounts for 1%-5% of the mass of the composition.

4. The composition according to any one of claims 1 to 3, characterized in that The substituted 1,2,3-triazoles include The R 11 , R 12 Each is independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, wherein the aryl group includes a phenyl group and a benzyl group; and the R 11 , R 12 Not all hydrogen atoms at the same time; and / or, the substituted pyrazole comprises The R 21 , R 22 , R 23 Each is independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, wherein the aryl group includes a phenyl group and a benzyl group; and the R 21 , R 22 , R 23 Not all are hydrogen atoms.

5. The composition according to any one of claims 1 to 4, characterized in that The substituted benzoic acid includes The R 31 , R 32 , R 33 , R 34 Each is independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, wherein the aryl group includes a phenyl group and a benzyl group; and the R 31 , R 32 , R 33 , R 34 Not all hydrogen atoms at the same time; And / or, the substituted phthalic acid comprises The R 41 , R 42 , R 43 , R 44 Each is independently selected from any one of a hydrogen atom, a C1-C4 alkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a mercapto group, and an aryl group, wherein the aryl group includes a phenyl group and a benzyl group; and the R 41 , R 42 , R 43 , R 44 Not all are hydrogen atoms.

6. The composition according to any one of claims 1 to 5, characterized in that The composition also includes a chelating agent; the chelating agent includes one or more of trans-1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminetriacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, and diethylenetriaminepentaacetic acid; the mass proportion of the chelating agent in the composition is 0.001%-1%.

7. The composition according to any one of claims 1 to 6, characterized in that The composition further includes a solubilizer; the solubilizer includes one or more of N-methylmorpholine-N-oxide and N-ethylmorpholine-N-oxide; the mass proportion of the solubilizer in the composition is 1%-30%.

8. The composition according to any one of claims 1 to 7, characterized in that The composition further comprises a buffer; the buffer comprises one or more of 1,8-diazabicyclo[5.4.0]undec-7-ene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and phosphoric acid.

9. The composition according to any one of claims 1 to 8, characterized in that The pH value of the composition is 6-8.

10. The composition according to any one of claims 1 to 9, characterized in that The solvent includes water and / or an organic solvent; The organic solvent includes an aprotic solvent and / or an ether alcohol solvent, wherein the aprotic solvent includes one or more of dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone; the ether alcohol solvent includes one or more of diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, glycerol, ethylene glycol, and propylene glycol; The mass proportion of the organic solvent in the composition is 0.1%-50%, and the mass proportion of the water in the composition is 1%-99%.

11. Use of the composition according to any one of claims 1 to 10 in the field of cleaning agents.

12. A cleaning agent, characterized in that: The method comprises a composition as claimed in any one of claims 1 to 10 and an oxidant; wherein the oxidant comprises hydrogen peroxide.

13. The cleaning agent according to claim 12, characterized in that The mass ratio of the oxidant to the composition is 1:1 to 1:

30.

14. The cleaning agent according to claim 12 or 13, characterized in that: The cleaning agent has an etching selectivity ratio for AlN and AlO x of ≥ 4.5:1, where 0 < x ≤ 1.5; the cleaning agent has an etching selectivity ratio for AlN and Co of ≥ 1.67:

1.

15. A cleaning method, characterized in that: include: Using the cleaning agent as described in any one of claims 12 to 14 to contact the workpiece to be cleaned; Or, the composition according to any one of claims 1 to 10 is mixed with an oxidant and then contacted with the workpiece to be cleaned.

16. A method for preparing a semiconductor device, characterized in that: include: Forming a patterned film layer on a substrate containing a hard mask, transferring the pattern of the patterned film layer to the hard mask, and etching the substrate to obtain a patterned substrate; The patterned substrate is cleaned using the cleaning agent described in any one of claims 12 to 14, or the patterned substrate is cleaned using a mixture of the composition described in any one of claims 1 to 10 and an oxidant.

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