Cleaning composition, corrosion composition, kit, corrosion process, and device

Abstract

The invention provides the cleaning composition, the corrosion composition, the kit, the corrosion process and the device, the problem that the corrosion selectivity of AlN relative to AlOx is relatively low is solved, and metal materials such as copper and high-quality cobalt in a metal interconnection circuit are not damaged when a hard mask is removed; the cleaning composition comprises a metal protective agent and a nitrogen-containing heterocyclic compound, the nitrogen-containing heterocyclic compound is selected from at least one of nitrogen-containing heterocyclic compounds and nitrogen-containing heterocyclic compounds; the definition of each group is described in the specification.

Description

Technical Field

[0001] This application belongs to the field of electronic device cleaning agents, specifically relating to a cleaning composition, a etching composition, a reagent kit, an etching process, and a device. Background Technology

[0002] Hard masks are widely used materials in the manufacturing of electronic devices, primarily to prevent the pattern on a patterned composition from being destroyed due to pattern miniaturization. They provide higher selective etching and better contour control in the early stages of thin film structure. Titanium nitride is a commonly used hard mask in electronic device fabrication, and it is not only used as a sacrificial layer but also widely used in multi-layer lithography processes.

[0003] Meanwhile, stop layers in electronic devices, such as AlN and AlOx layers, ensure that the structure to be protected is not excessively corroded. However, AlN layers may contain charge traps, and retaining too much of them can introduce electrical instability risks, leading to a surge in dynamic resistance and deterioration of switching characteristics. Therefore, they must be selectively removed. In contrast, chemically and electrically stable alumina can be retained to continue to perform passivation and protection functions, thereby improving device performance and reliability. Summary of the Invention

[0004] This application discloses a cleaning composition, etching composition, kit, etching process, and device to solve the problem of low selectivity of AlN relative to AlOx etching during the removal of hard masks in the manufacturing process of electronic devices.

[0005] In a first aspect, this application provides a cleaning composition. The cleaning composition comprises: a metal protectant and a nitrogen-containing heterocyclic compound.

[0006] The nitrogen-containing heterocyclic compound is selected from , , and At least one of them; R1 and R4 are each independently hydrogenated or substituted or unsubstituted C1-C6 alkyl groups. R2, R3, and R5 are each independently substituted or unsubstituted C1-C6 alkyl groups. At least one of R4 and R5 is a hydroxyl-substituted C1-C6 alkyl group. Y is N or CR. a R a It is hydrogen or a substituted or unsubstituted C1-C6 alkyl group. Ring A is a substituted or unsubstituted 4- or 10-membered cycloalkyl group or a substituted or unsubstituted 4- or 10-membered heterocyclic alkyl group. Ring B is a substituted or unsubstituted 4- or 10-membered heterocyclic alkyl group. m and x are integers from 0 to 4. n is an integer from 1 to 5. k is an integer from 0 to 3.

[0007] Through the above technical solution, the cleaning composition of this application achieves selective corrosion between AlN and AlOx, thereby increasing the corrosion rate of AlN.

[0008] In one possible implementation, R1 is hydrogen or a substituted or unsubstituted C1-C4 alkyl group.

[0009] In one possible implementation, R1 is hydrogen or methyl.

[0010] In one possible implementation, R2 is a substituted or unsubstituted C1-C4 alkyl group.

[0011] In one possible implementation, R2 is a C1-C4 alkyl group.

[0012] In one possible implementation, m is an integer of 0, 1, 2, or 3.

[0013] In one possible implementation, m is 0.

[0014] In one possible implementation, Y is N.

[0015] In one possible implementation, R3 is a substituted or unsubstituted C1-C4 alkyl group.

[0016] In one possible implementation, R3 is a C1-C4 alkyl group.

[0017] In one possible implementation, x is an integer of 0, 1, 2, or 3.

[0018] In one possible implementation, x is 0.

[0019] In one possible implementation, n is an integer of 1, 2, 3, or 4.

[0020] In one possible implementation, n is 1.

[0021] In one possible implementation, ring A is a substituted or unsubstituted 6- to 8-membered cycloalkyl or a substituted or unsubstituted 6- to 8-membered heterocycloalkyl.

[0022] In one possible implementation, ring A is a substituted or unsubstituted 6- to 8-membered heterocyclic alkyl group.

[0023] In one possible implementation, ring A is a 6- to 8-membered heterocyclic alkyl group.

[0024] In one possible implementation, ring A is a nitrogen-containing heptyl group.

[0025] In one possible implementation, ring B is an unsubstituted 5- to 8-membered heterocyclic alkyl group.

[0026] In one possible implementation, ring B is a substituted or unsubstituted 5- to 8-membered cycloalkyl group.

[0027] In one possible implementation, ring B is a azircyclohexyl group.

[0028] In one possible implementation, R4 is a substituted or unsubstituted C1-C6 alkyl group.

[0029] In one possible implementation, R4 is a hydroxyl-substituted C1-C6 alkyl group.

[0030] In one possible implementation, R4 is a hydroxyl-substituted ethyl group.

[0031] In one possible implementation, R5 is a substituted or unsubstituted C1-C4 alkyl group.

[0032] In one possible implementation, R5 is a C1-C4 alkyl group.

[0033] In one possible implementation, k is an integer of 0, 1, 2, or 3.

[0034] In one possible implementation, k is 0.

[0035] In one possible implementation, the nitrogen-containing heterocyclic compound is selected from... , , , and At least one of them.

[0036] In one possible implementation, the metal protectant is selected from substituted or unsubstituted monoheterocyclic aromatic compounds containing at least two adjacent nitrogen atoms, substituted or unsubstituted fused-ring aromatic compounds containing at least two adjacent nitrogen atoms fused with a benzene ring, or combinations thereof.

[0037] Through the above technical solution, metal protective agent molecules can be spread evenly on the surface of low-k materials, forming a hydrophobic, physical barrier that can effectively block water molecules and OH groups. - Ions and other corrosive species penetrate into the porous structure of low-K materials, enabling the effective removal of titanium nitride hard masks without damaging the low-K materials or metals such as Cu and Co.

[0038] In one possible implementation, the term "substituted or unsubstituted" refers to a substance selected from halogen, hydroxyl, amino, cyano, nitro, ester, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 alkyl, C4-C6 alkyl, C5-C6 alkyl, C6-C6 alkyl, C6-C6 alkyl, C7 ... 10 carbonyl group, C2-C 10 Heterocyclic group, C6-C 10 Aryl and C1-C 10One or more substituents in the heteroaryl group are substituted or unsubstituted.

[0039] In one possible implementation, the term "substituted or unsubstituted" refers to something that is substituted or unsubstituted by one or more substituents selected from halogens and C1-C6 alkyl groups.

[0040] In one possible implementation, the term "substituted or unsubstituted" refers to something that is substituted or unsubstituted by one or more substituents selected from C1-C6 alkyl groups.

[0041] In one possible implementation, the term "substituted or unsubstituted" refers to being substituted or unsubstituted by one or more substituents selected from methyl, ethyl, propyl, and butyl.

[0042] In one possible implementation, the substituted or unsubstituted monoheterocyclic aromatic compound containing at least two adjacent nitrogen atoms is selected from the substituted or unsubstituted compounds of the following: pyrazole, 1,2,3-triazole or 1,2,4-triazole.

[0043] In one possible implementation, the fused-ring aromatic compound, which is a monoheterocyclic compound containing at least two adjacent nitrogen atoms and fused with an aromatic ring, whether substituted or unsubstituted, is selected from substituted or unsubstituted benzotriazole (1H-Benzotriazole, BTA).

[0044] In one possible implementation, the substituted or unsubstituted monoheterocyclic aromatic compound comprising at least two adjacent nitrogen atoms is selected from the following compounds optionally substituted with one or more C1-C6 alkyl groups: pyrazole, 1,2,3-triazole, or 1,2,4-triazole.

[0045] In one possible implementation, the metal protectant is selected from at least one of pyrazole, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, and 5-methyl-1H-benzotriazole (5mBTA).

[0046] In one possible implementation, the ratio of the mass of the metal protectant to the mass of the nitrogen-containing heterocyclic compound ranges from 0.15 to 4.

[0047] In one possible implementation, the ratio of the mass of the metal protectant to the mass of the nitrogen-containing heterocyclic compound ranges from 0.2 to 3.4.

[0048] In one possible implementation, the ratio of the mass of the metal protectant to the mass of the nitrogen-containing heterocyclic compound ranges from 1.8 to 2.4.

[0049] In one possible implementation, the cleaning composition further comprises: an organic acid.

[0050] Through the above technical solution, organic acids can chelate metal ions, stabilize the composition of the corrosion composition, and create a stable and efficient reaction environment, allowing nitrogen-containing heterocyclic compounds to further corrode AlN. Furthermore, organic acids are homogeneous catalysts (free ions in solution), while metal protectants are heterogeneous catalysts / corrosion problems (atoms on the material surface). The combined effect of the two ensures the precision of the process and further improves the selective corrosion of AlN.

[0051] In one possible implementation, the organic acid is selected from at least one of N-β-hydroxyethylethylenediaminetriacetic acid and ethylenediaminetetraacetic acid.

[0052] In one possible implementation, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid ranges from 2.5 to 24.

[0053] In one possible implementation, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid ranges from 2.5 to 20.

[0054] In one possible implementation, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid ranges from 3.3 to 5.5.

[0055] In one possible implementation, the cleaning composition further comprises a solvent. The solvent includes water and organic solvents.

[0056] In one possible implementation, based on the total mass of the solvent, the solvent comprises: water with a mass fraction ranging from 60% to 70%, and the remainder being organic solvents.

[0057] In one possible implementation, the cleaning composition further comprises a pH adjuster.

[0058] The above technical solution can keep the pH of the cleaning composition relatively stable during use, which is conducive to the function of the corrosion composition and improves the corrosion efficiency of hard masks.

[0059] In one possible implementation, the pH range of the cleaning composition is 6 to 8.

[0060] In one possible implementation, the pH range of the cleaning composition is 7 to 7.5.

[0061] In one possible implementation, the pH of the cleaning composition is 7.2.

[0062] In one possible implementation, the metal protectant is 0.9% to 2% by mass, based on the total mass of the cleaning composition.

[0063] In one possible implementation, the metal protectant is 1.2% to 2% by mass, based on the total mass of the cleaning composition.

[0064] In one possible implementation, the metal protectant is 1.2% by mass, based on the total mass of the cleaning composition.

[0065] In one possible implementation, the mass percentage of the nitrogen-containing heterocyclic compound is 0.3% to 6% based on the total mass of the cleaning composition.

[0066] In one possible implementation, the mass percentage of the nitrogen-containing heterocyclic compound is 0.5% to 6% based on the total mass of the cleaning composition.

[0067] In one possible implementation, the mass percentage of the nitrogen-containing heterocyclic compound is 6% based on the total mass of the cleaning composition.

[0068] In one possible implementation, the organic acid is present in a mass percentage of 0.1% to 0.3% based on the total mass of the cleaning composition.

[0069] In one possible implementation, the organic acid is present in a mass percentage of 0.2% to 0.3% based on the total mass of the cleaning composition.

[0070] In one possible implementation, the organic acid is 0.3% by mass based on the total mass of the cleaning composition.

[0071] In one possible implementation, the solvent is 55% to 66% by mass, based on the total mass of the cleaning composition.

[0072] In one possible implementation, the solvent is 60% to 61% by mass, based on the total mass of the cleaning composition.

[0073] In one possible implementation, the solvent is 60.2% by mass, based on the total mass of the cleaning composition.

[0074] In one possible implementation, the pH adjuster is 0.75% to 7% by mass, based on the total mass of the cleaning composition.

[0075] In one possible implementation, the pH adjuster is 1.3% to 1.5% by mass, based on the total mass of the cleaning composition.

[0076] In one possible implementation, the pH adjuster is 1.3% by mass, based on the total mass of the cleaning composition.

[0077] Secondly, this application provides a corrosion composition. The corrosion composition comprises an oxidizing agent and the cleaning composition described above in this disclosure.

[0078] In one possible implementation, the ratio of the mass of the cleaning composition to the mass of the oxidant is in the range of 10 to 30.

[0079] The above technical solution can reduce the decomposition of oxidant and the interference of metal ions during the corrosion process by the assistance of the cleaning composition, thus ensuring that the oxidant can give full play to its corrosion effect and achieve a high corrosion selectivity and corrosion rate.

[0080] In one possible implementation, the ratio of the mass of the cleaning composition to the mass of the oxidant ranges from 15 to 27.

[0081] In one possible implementation, the ratio of the mass of the cleaning composition to the mass of the oxidant ranges from 13 to 26.

[0082] In one possible implementation, the oxidant is selected from hydrogen peroxide.

[0083] In one possible implementation, the corrosion rate of the corrosion composition on the AlN compound is greater than the corrosion rate on AlOx.

[0084] In one possible implementation, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx is greater than 1.

[0085] In one possible implementation, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx is greater than or equal to 3.5.

[0086] In one possible implementation, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx is 5.6.

[0087] Thirdly, this application provides a kit. The kit comprises: the cleaning composition described above in this disclosure, and an oxidizing agent.

[0088] Fourthly, this application provides an etching process comprising: providing a patterned substrate comprising an aluminum oxide layer and a nitrogen oxide layer; and treating the patterned substrate with the etching composition disclosed herein or a diluent thereof.

[0089] Fifthly, this application provides a device. The device comprises a patterned substrate prepared by the etching process described above in this disclosure. Attached Figure Description

[0090] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0091] Figure 1 Corrosion rate graphs of TiN by the corrosion compositions of Example 7 and Comparative Example 3 of this application under continuous hydrogen peroxide replenishment mode; Figure 2 Corrosion rate graphs of Co by the corrosion compositions of Example 7 and Comparative Example 3 of this application under continuous hydrogen peroxide replenishment mode; Figure 3 Corrosion rate graphs of Cu by the corrosion compositions of Example 7 and Comparative Example 3 of this application under continuous hydrogen peroxide replenishment mode; Figure 4 The corrosion rate graphs of the corrosion compositions of Example 7 and Comparative Example 3 of this application on TiN without the addition of hydrogen peroxide are shown. Figure 5 The corrosion rate graphs of the corrosion compositions of Example 7 and Comparative Example 3 of this application on Co are shown without the addition of hydrogen peroxide. Figure 6 Corrosion rate graphs of Cu for the corrosion compositions of Example 7 and Comparative Example 3 of this application without the addition of hydrogen peroxide; Figure 7 The graph shows the hydrogen peroxide content in the corrosion compositions of Example 7 and Comparative Example 3 of this application without the addition of hydrogen peroxide. Figure 8 This is a graph showing the pH changes of the cleaning compositions of Example 7 and Comparative Example 3 of this application; Figure 9 This is a comparison graph showing the corrosion rate and corrosion selectivity of the corrosion compositions of Example 7 and Comparative Example 3 of this application; Figure 10 This is a comparison graph showing the corrosion rate and selectivity for AlN corrosion of the corrosion compositions of Examples 8 to 11 and Comparative Example 4 of this application. Detailed Implementation

[0092] The terms “comprises” or “comprising” as used herein should be interpreted as having a non-exhaustive meaning and allowing for the addition or reference to further elements, such as adding features or method steps or members or components to anything that includes the listed elements. “Comprises” may be replaced with “including” if the practice of a given language variant requires it, or may be limited to “consistently consisting of” if other elements besides those listed are not essential to the practice of this application, or may be limited to “consisting of” in the absence of any other elements.

[0093] As used herein, the term "patterning" refers to photolithography, a crucial step in electronic device manufacturing. This step involves etching a patterned structure onto a material to be patterned (i.e., a patterning composition) through exposure and development processes. The pattern on the photomask is then transferred to a substrate using an etching process. This substrate can include not only silicon wafers but also other metal layers, dielectric layers, and the aforementioned substrates with surface modifications or added supporting layers.

[0094] As used herein, the term "patterned composition" refers to a corrosion-resistant material whose solubility in a developing solution changes after being irradiated or exposed to light such as ultraviolet light, deep ultraviolet light, X-rays, electron beams, or ion beams.

[0095] As used in this paper, the term "mask" refers to a mask that acts as an optical element in the optical path during the patterning process. The mask carries the design pattern, and light selectively transmits the design pattern onto the patterned material film through its transmission or reflection.

[0096] The numerical range for the number of carbon atoms in this article refers to the integers within a given range, for example, "C1-C1". 20 "or "C1- 20 "" means that the group may have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.

[0097] As used herein, the terms “optional” or “optionally” mean that the event or situation described below may or may not occur, including both the occurrence and non-occurrence of the event or situation.

[0098] The term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. Examples of alkyl groups include, but are not limited to, C1-C1 alkyl groups. 20 Alkyl, C1-C 10Alkyl, C1-C6 alkyl, C1-C4 alkyl, C4-C 12 Alkyl, C6-C 12 Alkyl groups, such as methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, s-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), etc.; for example, the term "C1-C6 alkyl" refers to alkyl groups containing 1 to 6 (e.g., 1, 2, 3, 4, 5, 6) carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-methylpentyl, etc.).

[0099] As used herein, the term "alkenyl" refers to a straight-chain or branched hydrocarbon group with at least one carbon-carbon double bond, which can be C 2-4 alkenyl, C 2-6 alkenyl, C 2-8 alkenyl, C 2-10 Alkenyl groups, such as vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, etc. For example, the term "C..." 2-6 "Alkenyl" refers to an alkenyl group containing 2 to 6 (e.g., 2, 3, 4, 5, 6) carbon atoms (e.g., vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, pentenyl, 1-methylbutenyl, 2-methylbutenyl, 3-methylbutenyl, hexenyl, 2-methylpentenyl, etc.).

[0100] As used herein, the term "alkynyl" refers to a straight-chain or branched hydrocarbon group with at least one carbon-carbon triple bond, which can be C 2-4 alkynyl group, C 2-6 alkynyl group, C 2-8 alkynyl group, C 2-10 Alkyne groups, such as ethynyl, enynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1,3-butadiynyl, etc. For example, the term "C..." 2-6 "Alkenyl" refers to an alkyne group containing 2 to 6 (e.g., 2, 3, 4, 5, 6) carbon atoms (e.g., ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1,3-butadiynyl, penynyl, 1-methylbutynyl, 2-methylbutynyl, 3-methylbutynyl, hexynyl, 2-methylpentynyl, etc.).

[0101] The term "alkoxy" refers to -O-alkyl, where "alkyl" is defined as above, and examples of "alkoxy" include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, and isopentoxy. "Optionally substituted alkoxy" means that the alkyl group is substituted or unsubstituted.

[0102] As used herein, the term "fused ring (or fused cyclic group)" refers to an organic compound structure in which two or more rings are coupled together by sharing two adjacent atoms (e.g., two adjacent carbon atoms) and a covalent bond. For example, a fused ring can refer to a group formed by the fusion of multiple benzene rings, such as naphthalene, anthracene, or phenanthrene. It can also refer to a macrocyclic system formed by the fusion of multiple heterocyclic rings, such as porphyrin rings.

[0103] As used herein, the term "carbocyclic group" refers to a non-aromatic cyclic group consisting of carbon and hydrogen atoms and having at least one saturated or unsaturated cyclic structure. Such carbocyclic groups include, but are not limited to, monocyclic, fused polycyclic, bridged, or spirocyclic structures. Non-limiting examples of carbocyclic groups include, but are not limited to, C1. 3-20 carbonyl group, C 3-18 carbonyl group, C 3-16 carbonyl group, C 3-12 carbonyl group, C 3-10 carbonyl group, C 3-8 carbonyl group, C 3-7 carbonyl group, C 3-6 Carbocyclic groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexenyl, norbornel, adamantyl, bicyclo[2.2.2]octyl, etc.

[0104] As used herein, the term "heterocyclic group" or "heterocycle" refers to a saturated, partially unsaturated, or unsaturated non-aromatic cyclic group consisting of a carbon atom and at least one heteroatom, and may exist as a monocyclic, fused polycyclic, bridged, or spirocyclic group. Unless otherwise indicated, the heterocycle is typically a ring containing 1 to 5 (e.g., 1, 2, 3, 4, 5) heteroatoms independently selected from sulfur, oxygen, and / or nitrogen. Non-limiting examples of heterocyclic groups include, but are not limited to, C1-C1. 20 Heterocyclic groups, C1-C 15 Heterocyclic group, C 1- C 12 Heterocyclic group, C 1- C 10 Heterocyclic group, C 1- C8 heterocyclic group, C 1-C5 heterocyclic groups, such as aziridine, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothiophenyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,1-dioxo-thiomorpholinyl, homopiperazinyl, oxacyclopentyl, azirspiro[3.3]heptyl, 8-azibicyclo[3.2.1]octyl.

[0105] The term "C1-C" as used in this article 20 A "heterocyclic group" refers to a heterocyclic group that has, in addition to 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms), at least one heteroatom selected from N, O, and S as a cyclic atom (e.g., 1, 2, 3, 4, 5 heteroatoms).

[0106] As used herein, the term "aryl" refers to a monocyclic or fused polycyclic system consisting solely of carbon atoms as cyclic atoms, and having at least one aromatic ring or all of its rings being aromatic rings. The term "C6-C" is also used. 18 "Aryl" or "aromatic ring" refers to an aryl group or aromatic ring as defined above, having 6 to 18 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms). The aryl group includes a ring system formed by the fusion of aromatic rings with other aromatic rings, or by the fusion of an aromatic ring with a non-aromatic carbon ring (e.g., cycloalkanes, cycloalkenes, or cycloalkynes). Furthermore, in the aforementioned fused aryl group, the connection site between the aryl group and the remaining portion of the molecule can be on the aromatic ring or on other rings fused with the aromatic ring. Non-limiting examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracene, 1,2,3,4-tetrahydronaphthyl, indenyl, etc.

[0107] As used herein, the term "heteroaryl" refers to a monocyclic or fused polycyclic system containing at least one (e.g., 1 to 5, such as 1, 2, 3, 4, or 5) ring atoms selected from N, O, and S, with the remaining ring atoms being carbon, and having at least one aromatic ring, or all rings in a heteroaryl group being aromatic rings. The cyclic carbon atoms and heteroatoms may be substituted with oxo or thio groups. The term "C1-C" is also used. 10"Heteroaryl" refers to a heteroaryl group as defined above that has 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms. The heteroaryl includes ring systems formed by the fusion of a heteroaryl ring with an aromatic carbon ring, a heteroaryl ring with another heteroaryl ring, or a heteroaryl ring with a non-aromatic carbon ring (e.g., cycloalkanes, cycloalkenes, or cycloalkynes) or a heterocycle (e.g., heterocyclic alkanes, heterocyclic alkenes, or heterocyclic alkynes), and in the aforementioned fused heteroaryl, the connection site between the heteroaryl and the remaining portion of the molecule can be on the heteroaryl ring or on other rings fused with the heteroaryl ring. Non-limiting examples of heteroaryl include, but are not limited to, pyrroleyl, furanyl, thiopheneyl, imidazolyl, oxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, tetrazolyl, triazolyl, triazinyl, benzofuranyl, benzothiopheneyl, indoleyl, isoindoleyl, etc. , , , and wait.

[0108] The term "amino" as used in this article refers to -NH2.

[0109] As used herein, the term "ester group" refers to a group having -OCOR m or -COOR m The structural group. The R in the ester group. m The following groups, whether substituted or unsubstituted, represent alkyl, alkenyl, ynyl, carbocyclic, heterocyclic, aryl, or heteroaryl groups, wherein the alkyl, alkenyl, ynyl, carbocyclic, heterocyclic, aryl, or heteroaryl groups are as defined above.

[0110] The term "cyano" refers to a group having a -CN structure.

[0111] The term "nitro" refers to a group with a -NO2 structure.

[0112] As used herein, the term "substituted or unsubstituted" means that a group is substituted or unsubstituted by one or more substituents (e.g., 1 to 10, 1 to 5, or 1 to 2), and when substituted, the substituent is independently selected from one or more of the following groups: halogen, hydroxyl, amino, C1-C6 alkylamino, di(C1-C6 alkyl)amino, cyano, nitro, ester, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C3-C10 carbocyclic, C2-C10 heterocyclic, C6-C10 aryl, and C1-C10 heteroaryl, etc. Whenever a substituent is described as "substituted," the substituent can be substituted by one of the substituents listed above.

[0113] Generally, existing cleaning compositions are mainly used to assist the main etchant in removing hard mask titanium nitride, while taking into account the selectivity between titanium nitride and AlOx to improve the titanium nitride corrosion rate. However, in the fabrication of electronic devices, the presence of an AlN corrosion stop layer may affect the performance of the electronic devices, and existing cleaning compositions are difficult to meet the requirements of selectively corroding AlN.

[0114] Based on this, embodiments of this application provide a cleaning composition. The cleaning composition comprises: a metal protectant and a nitrogen-containing heterocyclic compound.

[0115] Among them, nitrogen-containing heterocyclic compounds are selected from , , and At least one of them; R1 and R4 are each independently hydrogenated or substituted or unsubstituted C1-C6 alkyl groups. R2, R3, and R5 are each independently substituted or unsubstituted C1-C6 alkyl groups. At least one of R4 and R5 is a hydroxyl-substituted C1-C6 alkyl group. Y is N or CR. a R a It is hydrogen or a substituted or unsubstituted C1-C6 alkyl group. Ring A is a substituted or unsubstituted 4- or 10-membered cycloalkyl group or a substituted or unsubstituted 4- or 10-membered heterocyclic alkyl group. Ring B is a substituted or unsubstituted 4- or 10-membered heterocyclic alkyl group. m and x are integers from 0 to 4. n is an integer from 1 to 5. k is an integer from 0 to 3.

[0116] As an example, m can be 0, 1, 2, 3, or 4.

[0117] For example, n can be 0, 1, 2, 3, 4, or 5.

[0118] As an example, k can be 0, 1, 2, or 3.

[0119] With the development of the electronics industry, more and more metallic materials are being introduced into the production and manufacturing of electronic devices. In the field of electronic devices, copper is mainly used to manufacture interconnect circuits.

[0120] The cleaning composition of this application, when applied during patterning in the manufacturing process of electronic devices, allows the metal protectant to remove hard masks without damaging the metal materials in the metal interconnects. For example, it can effectively control the corrosion rate of metal materials such as copper and high-quality cobalt. The metal protectant, in conjunction with nitrogen-containing heterocyclic compounds, provides stable corrosion performance and can improve the selectivity of AlN corrosion relative to AlOx.

[0121] To address the aforementioned problems, this application provides a solution by adding [the following to the cleaning composition] , , and At least one of them was used to achieve selective corrosion between AlN and AlOx, thereby increasing the corrosion rate of AlN.

[0122] In one possible implementation, R1 is hydrogen or a substituted or unsubstituted C1-C4 alkyl group.

[0123] In one possible implementation, R1 is hydrogen or methyl.

[0124] In one possible implementation, R2 is a substituted or unsubstituted C1-C4 alkyl group.

[0125] In one possible implementation, R2 is a C1-C4 alkyl group.

[0126] In one possible implementation, m is an integer of 0, 1, 2, or 3.

[0127] In one possible implementation, m is 0.

[0128] In one possible implementation, Y is N.

[0129] In one possible implementation, R3 is a substituted or unsubstituted C1-C4 alkyl group.

[0130] In one possible implementation, R3 is a C1-C4 alkyl group.

[0131] In one possible implementation, x is an integer of 0, 1, 2, or 3.

[0132] In one possible implementation, x is 0.

[0133] In one possible implementation, n is an integer of 1, 2, 3, or 4.

[0134] In one possible implementation, n is 1.

[0135] In one possible implementation, ring A is a substituted or unsubstituted 6- to 8-membered cycloalkyl or a substituted or unsubstituted 6- to 8-membered heterocycloalkyl.

[0136] In one possible implementation, ring A is a substituted or unsubstituted 6- to 8-membered heterocyclic alkyl group.

[0137] In one possible implementation, ring A is a 6- to 8-membered heterocyclic alkyl group.

[0138] In one possible implementation, ring A is a nitrogen-containing heptyl group.

[0139] In one possible implementation, ring B is an unsubstituted 5- to 8-membered heterocyclic alkyl group.

[0140] In one possible implementation, ring B is a substituted or unsubstituted 5- to 8-membered cycloalkyl group.

[0141] In one possible implementation, ring B is a azircyclohexyl group.

[0142] In one possible implementation, R4 is a substituted or unsubstituted C1-C6 alkyl group.

[0143] In one possible implementation, R4 is a hydroxyl-substituted C1-C6 alkyl group.

[0144] In one possible implementation, R4 is a hydroxyl-substituted ethyl group.

[0145] In one possible implementation, R5 is a substituted or unsubstituted C1-C4 alkyl group.

[0146] In one possible implementation, R5 is a C1-C4 alkyl group.

[0147] In one possible implementation, k is an integer of 0, 1, 2, or 3.

[0148] In one possible implementation, k is 0.

[0149] In one possible implementation, the nitrogen-containing heterocyclic compound is selected from... , , , and At least one of them.

[0150] Generally, among existing materials, copper wires have lower resistance and better conductivity compared to other materials, meaning they can transmit information and signals faster. For many years, dual-damascene copper interconnect technology was a mainstream technology with high usage. However, due to the increasing complexity of integrated circuit manufacturing processes, traditional copper interconnects are no longer sufficient. In recent years, electronic device manufacturing processes have moved towards 10nm and below, placing increasingly higher demands on materials. Compared to copper, cobalt's advantages lie in improved conductivity, reduced power consumption, and smaller size. Cobalt has low crystallinity, fewer grain boundaries, low resistance, and weak diffusion during deposition. Furthermore, cobalt has low chemical reactivity and weak electromigration. These characteristics help manufacturers continuously develop advanced fabrication processes. As linewidths continue to decrease and patterns become increasingly complex, removing hard masks without damaging the contacting low-k materials better preserves pattern information.

[0151] Therefore, in one possible embodiment of this application, the metal protectant is selected from substituted or unsubstituted monoheterocyclic aromatic compounds containing at least two adjacent nitrogen atoms, substituted or unsubstituted fused-ring aromatic compounds containing at least two adjacent nitrogen atoms with a monoheterocyclic aromatic ring, or combinations thereof.

[0152] Understandably, the two nitrogen atoms of the aforementioned metal protectant can coordinate with the metal atoms to form an extremely stable and dense monomolecular adsorption layer. The surface of low-k materials is rich in Si-OH (silanol) and Si-H groups. The nitrogen atoms on the aforementioned metal protectant molecules can act as hydrogen bond acceptors, forming hydrogen bonds with the Si-OH groups on the surface. This allows the metal protectant molecules to spread evenly across the surface of the low-k material, forming a hydrophobic, physical barrier that effectively blocks water molecules and OH groups. - Ions and other corrosive species penetrate into the porous structure of low-K materials, enabling the effective removal of titanium nitride hard masks without damaging the low-K materials or metals such as Cu and Co.

[0153] In one possible implementation, the term "substituted or unsubstituted" refers to a substance selected from halogen, hydroxyl, amino, cyano, nitro, ester, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 alkyl, C4-C6 alkyl, C5-C6 alkyl, C6-C6 alkyl, C6-C6 alkyl, C7 ... 10 carbonyl group, C2-C 10 Heterocyclic group, C6-C 10 Aryl and C1-C 10 One or more substituents in the heteroaryl group are substituted or unsubstituted.

[0154] In one possible implementation, the term "substituted or unsubstituted" refers to something that is substituted or unsubstituted by one or more substituents selected from halogens and C1-C6 alkyl groups.

[0155] In one possible implementation, the term "substituted or unsubstituted" refers to something that is substituted or unsubstituted by one or more substituents selected from C1-C6 alkyl groups.

[0156] In one possible implementation, the term "substituted or unsubstituted" refers to being substituted or unsubstituted by one or more substituents selected from methyl, ethyl, propyl, and butyl.

[0157] In one possible implementation, the substituted or unsubstituted monoheterocyclic aromatic compound containing at least two adjacent nitrogen atoms is selected from the substituted or unsubstituted compounds of the following: pyrazole, 1,2,3-triazole or 1,2,4-triazole.

[0158] In one possible implementation, the fused-ring aromatic compound, consisting of a substituted or unsubstituted monoheterocycle containing at least two adjacent nitrogen atoms and an aromatic ring, is a substituted or unsubstituted monoheterocycle containing at least two adjacent nitrogen atoms and a C6-C ... 12 Fused aromatic compounds with fused aromatic rings, or fused aromatic compounds with a monoheterocyclic ring containing at least two adjacent nitrogen atoms fused to a benzene ring, whether substituted or unsubstituted.

[0159] In one possible implementation, the fused-ring aromatic compound, which is a monoheterocyclic compound containing at least two adjacent nitrogen atoms and fused with an aromatic ring, is selected from substituted or unsubstituted benzotriazoles.

[0160] In one possible implementation, the substituted or unsubstituted monoheterocyclic aromatic compound comprising at least two adjacent nitrogen atoms is selected from the following compounds optionally substituted with one or more C1-C6 alkyl groups: pyrazole, 1,2,3-triazole, or 1,2,4-triazole.

[0161] In one possible implementation, the fused-ring aromatic compound, either substituted or unsubstituted and comprising at least two adjacent nitrogen atoms, is selected from benzotriazoles optionally substituted with one or more C1-C6 alkyl groups.

[0162] In one possible implementation, the metal protectant is selected from at least one of pyrazole, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, and 5-methyl-1H-benzotriazole.

[0163] In one possible implementation, the ratio of the mass of the metal protectant to the mass of the nitrogen-containing heterocyclic compound ranges from 0.15 to 4.

[0164] As an example, the mass ratio of the metal protectant to the nitrogen-containing heterocyclic compound can be 0.15, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or 4, or any number between any two of the above values.

[0165] In one possible implementation, the ratio of the mass of the metal protectant to the mass of the nitrogen-containing heterocyclic compound ranges from 0.2 to 3.4.

[0166] As an example, the ratio of the mass of the metal protectant to the mass of the nitrogen-containing heterocyclic compound can be 0.2, 0.4, 0.8, 1.2, 1.8, 2.2, 2.6, 3, or 3.4, or any number between any two of the above values.

[0167] In one possible implementation, the ratio of the mass of the metal protectant to the mass of the nitrogen-containing heterocyclic compound is in the range of 1.8 to 2.4.

[0168] As an example, the ratio of the mass of the metal protectant to the mass of the nitrogen-containing heterocyclic compound can be 1.8, 1.9, 2, 2.1, 2.2, 2.3, or 2.4, or any number between any two of the above values.

[0169] In one possible implementation, the cleaning composition further comprises: an organic acid.

[0170] Understandably, free metal ions can trigger the decomposition of corrosive components (such as hydrogen peroxide). By using organic acids, which have multiple oxygen atoms as coordinating atoms, metal ions can be chelated to form stable, water-soluble cyclic complexes, thus slowing down the decomposition of corrosive components.

[0171] In other words, organic acids can chelate metal ions, stabilize the composition of the corrosion compound, and create a stable and efficient reaction environment, allowing nitrogen-containing heterocyclic compounds to further corrode AlN. Furthermore, organic acids are homogeneous catalysts (free ions in solution), while metal protectants are heterogeneous catalysts / corrosion problems (atoms on the material surface). The combined effect of these two factors ensures the precision of the process and further improves the selective corrosion of AlN.

[0172] In one possible embodiment, the organic acid is selected from at least one of trans-1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, azirmonatriacetic acid, diethylenetriaminepentaacetic acid (DTPA), 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaceticacid (DOTA), N-β-hydroxyethylethylenediaminetriacetic acid, alanine, glycolic acid, aspartic acid, and succinic acid.

[0173] In one possible implementation, the organic acid is selected from at least one of trans-1,2-cyclohexanediaminetetraacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, diethylenetriaminepentaacetic acid, N-β-hydroxyethylethylenediaminetriacetic acid, and ethylenediaminetetraacetic acid.

[0174] In one possible implementation, the organic acid is selected from at least one of N-β-hydroxyethylethylenediaminetriacetic acid and ethylenediaminetetraacetic acid.

[0175] In one possible implementation, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid ranges from 2.5 to 24.

[0176] As an example, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid can be 2.5, 5, 7.5, 10, 12.5, 15, 17.5, 20, 22.5 or 24, or any number between any two of the above values.

[0177] In one possible implementation, the ratio of the mass of the nitrogen-containing heterocyclic compound to the mass of the organic acid ranges from 2.5 to 20.

[0178] As an example, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid can be 2.5, 4.5, 6.5, 8.5, 10.5, 12.5, 14.5, 16.5, 18.5, or 20, or any number between any two of the above values.

[0179] In one possible implementation, the ratio of the mass of the nitrogen-containing heterocyclic compound to the mass of the organic acid ranges from 3.3 to 5.5.

[0180] As an example, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid can be 3.5, 3.75, 4, 4.25, 4.5, 4.75, 5, 5.25, or 5.5, or any number between any two of the above values.

[0181] In one possible implementation, the cleaning composition further comprises a solvent.

[0182] Understandably, the solvent is mainly used to enhance the dissolution of patterned compositions and polymer ashing residues, while its low surface tension helps in the cleaning of some high aspect ratio structures.

[0183] In one possible implementation, the solvent comprises water and an organic solvent.

[0184] In one possible implementation, based on the total mass of the solvent, the solvent comprises: water with a mass fraction ranging from 60% to 70%, and the remainder being organic solvents.

[0185] As an example, the water content can be 60%, 62%, 64%, 66%, 68%, or 70%, or any number between any two of the above values.

[0186] In one possible embodiment, the organic solvent is selected from at least one of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, ethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol monobutyl ether (BDG), propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol phenyl ether, tripropylene glycol methyl ether, tripropylene glycol butyl ether, dipropylene glycol butyl ether, dipropylene glycol dimethyl ether, dimethyl sulfoxide (DMSO), sulfolane, and dimethyl sulfone.

[0187] In one possible implementation, the organic solvent is selected from at least one of sulfolane, diethylene glycol butyl ether, dimethyl sulfoxide, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, dimethyl sulfone, and propylene glycol ethyl ether.

[0188] In one possible implementation, the organic solvent is selected from dimethyl sulfoxide and ethylene glycol dimethyl ether.

[0189] In one possible implementation, the cleaning composition further comprises a pH adjuster.

[0190] Understandably, maintaining a relatively stable pH in the cleaning composition during use is beneficial for the corrosion composition to function and improve the corrosion efficiency on hard masks.

[0191] In one possible implementation, the pH range of the cleaning composition is 6 to 8.

[0192] As an example, the pH of the cleaning composition can be 6, 6.5, 7, 7.5, or 8, or any number between any two of the above values.

[0193] In one possible implementation, the pH range of the cleaning composition is 7 to 7.5.

[0194] As an example, the pH of the cleaning composition can be 7, 7.1, 7.2, 7.3, 7.4 or 7.5, or any number between any two of the above values.

[0195] In one possible implementation, the pH of the cleaning composition is 7.2.

[0196] In one possible implementation, the pH adjuster is selected from at least one of 1,8-diazabicyclo[5.4.0]undec-7-ene, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, phosphoric acid, tartaric acid, citric acid, phthalic acid, succinic acid, salicylic acid, N-methylmorpholine-N-oxide, trimethylamine oxide, ethanolamine, diethanolamine, and triethanolamine (TEA).

[0197] In one possible implementation, the pH adjuster is selected from at least one of phosphoric acid, ammonia, succinic acid, 1,8-diazobisspirocyclic[5.4.0]undecyl-7-ene, succinic acid, N-methylmorpholine-N-oxide, tetraethylammonium hydroxide, and triethanolamine.

[0198] In one possible implementation, the pH adjuster is selected from at least one of phosphoric acid, ammonia, and tetraethylammonium hydroxide.

[0199] In one possible implementation, the metal protectant is 0.9% to 2% by mass, based on the total mass of the cleaning composition.

[0200] As an example, the mass percentage of the metal protectant can be 0.9%, 1.2%, 1.4%, 1.6%, 1.8%, or 2%, or any number between any two of the above values.

[0201] In one possible implementation, the metal protectant is 1.2% to 2% by mass, based on the total mass of the cleaning composition.

[0202] As an example, the mass percentage of the metal protectant can be 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%, or any number between any two of the above values.

[0203] In one possible implementation, the metal protectant is 1.2% by mass, based on the total mass of the cleaning composition.

[0204] In one possible implementation, the mass percentage of the nitrogen-containing heterocyclic compound is 0.3% to 6% based on the total mass of the cleaning composition.

[0205] As an example, the mass percentage of nitrogen-containing heterocyclic compounds can be 0.3%, 1.2%, 2.4%, 3.6%, 4.8%, or 6%, or any number between any two of the above values.

[0206] In one possible implementation, the mass percentage of the nitrogen-containing heterocyclic compound is 0.5% to 6% based on the total mass of the cleaning composition.

[0207] As an example, the mass percentage of nitrogen-containing heterocyclic compounds can be 0.5%, 1.5%, 2.5%, 3.5%, 4.5%, 5.5%, or 6%, or any number between any two of the above values.

[0208] In one possible implementation, the mass percentage of the nitrogen-containing heterocyclic compound is 6% based on the total mass of the cleaning composition.

[0209] In one possible implementation, the organic acid is present in a mass percentage of 0.1% to 0.3% based on the total mass of the cleaning composition.

[0210] As an example, the mass percentage of organic acid can be 0.1%, 0.15%, 0.2%, 0.25%, or 0.3%, or any number between any two of the above values.

[0211] In one possible implementation, the organic acid is present in a mass percentage of 0.2% to 0.3% based on the total mass of the cleaning composition.

[0212] As an example, the mass percentage of organic acid can be 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, or 0.3%, or any number between any two of the above values.

[0213] In one possible implementation, the organic acid is 0.3% by mass based on the total mass of the cleaning composition.

[0214] In one possible implementation, the solvent is 55% to 66% by mass, based on the total mass of the cleaning composition.

[0215] As an example, the mass percentage of the solvent can be 55%, 57%, 59%, 61%, 63%, 65%, or 66%, or any number between any two of the above values.

[0216] In one possible implementation, the solvent mass percentage is 60% to 61% based on the total mass of the cleaning composition.

[0217] As an example, the mass percentage of the solvent can be 60%, 60.2%, 60.4%, 60.6%, 60.8%, or 61%, or any number between any two of the above values.

[0218] In one possible implementation, the solvent is 60.2% by mass, based on the total mass of the cleaning composition.

[0219] In one possible implementation, the pH adjuster is 0.75% to 7% by mass, based on the total mass of the cleaning composition.

[0220] As an example, the mass percentage of the pH adjuster can be 0.75%, 1%, 2%, 3%, 4%, 5%, 6%, or 7%, or any number between any two of the above values.

[0221] In one possible implementation, the pH adjuster is 1.3% to 1.5% by mass, based on the total mass of the cleaning composition.

[0222] As an example, the mass percentage of the pH adjuster can be 1.3%, 1.35%, 1.4%, 1.45%, or 1.5%, or any number between any two of the above values.

[0223] In one possible implementation, the pH adjuster is 1.3% by mass, based on the total mass of the cleaning composition.

[0224] Embodiments of this application provide a corrosion composition. The corrosion composition comprises an oxidant and a cleaning composition. The cleaning composition is any of the cleaning compositions described above in any possible implementation.

[0225] It is understood that the beneficial effects of the corrosion composition provided in the embodiments of this application can be referred to the beneficial effects of the electronic devices mentioned above, and will not be repeated here.

[0226] In one possible implementation, the ratio of the mass of the cleaning composition to the mass of the oxidant is in the range of 10 to 30.

[0227] As an example, the ratio of the mass of the cleaning composition to the mass of the oxidant can be 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 or 30, and any number between any two of the above values.

[0228] Understandably, setting the ratio of the mass of the cleaning composition to the mass of the oxidant in the range of 10 to 30 can reduce the decomposition of the oxidant and the interference of metal ions during the corrosion process with the assistance of the cleaning composition, ensuring that the oxidant can fully exert its corrosion effect, thereby achieving a higher corrosion selectivity and corrosion rate.

[0229] In one possible implementation, the ratio of the mass of the cleaning composition to the mass of the oxidant ranges from 15 to 27.

[0230] As an example, the ratio of the mass of the cleaning composition to the mass of the oxidant can be 15, 17, 19, 21, 23, 25, or 27, or any number between any two of the above values.

[0231] In one possible implementation, the ratio of the mass of the cleaning composition to the mass of the oxidant ranges from 13 to 26.

[0232] As an example, the ratio of the mass of the cleaning composition to the mass of the oxidant can be 13, 14.5, 16, 17.5, 19, 21.5, 23, 24.5 or 26, or any number between any two of the above values.

[0233] In one possible implementation, the oxidant is selected from at least one of hydrogen peroxide, urea peroxide, persulfate, ammonium persulfate, persulfate, pyrosulfate, and ozone.

[0234] In one possible implementation, the oxidant is hydrogen peroxide.

[0235] In one possible implementation, the corrosion rate of the corrosion composition on the AlN compound is greater than the corrosion rate on AlOx.

[0236] In one possible implementation, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx is greater than 1.

[0237] As an example, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx can be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5, or any number between any two of the above values.

[0238] In one possible implementation, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx is greater than or equal to 3.5.

[0239] As an example, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx can be 3.5, 5, 6.5, 8 or 8.5, or any number between any two of the above values.

[0240] In one possible implementation, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx is 5.6.

[0241] As an example, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on AlOx can be 5.6, 6, 6.5, 7, 7.5 or 8, or any number between any two of the above values.

[0242] In one possible implementation, the ratio of the mass of the oxidant to the mass of the nitrogen-containing heterocyclic compound ranges from 0.5 to 20.

[0243] As an example, the ratio of the mass of the oxidant to the mass of the nitrogen-containing heterocyclic compound can be 0.5, 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20, or any number between any two of the above values.

[0244] In one possible implementation, the ratio of the mass of the oxidant to the mass of the nitrogen-containing heterocyclic compound ranges from 0.6 to 16.7.

[0245] As an example, the ratio of the mass of the oxidant to the mass of the nitrogen-containing heterocyclic compound can be 0.6, 3, 5, 7, 9, 11, 13, 15, or 16.7, or any number between any two of the above values.

[0246] In one possible implementation, the mass ratio of the oxidant to the nitrogen-containing heterocyclic compound is 0.65.

[0247] An embodiment of this application provides a kit. The kit includes: the cleaning composition described above in this disclosure, and an oxidizing agent.

[0248] In one possible implementation, the cleaning composition and oxidant are present in a single formulation within the kit.

[0249] In one possible implementation, the cleaning composition and the oxidant are present as separate formulations in the kit.

[0250] In one possible implementation, the oxidant is selected from at least one of hydrogen peroxide, urea peroxide, persulfate, ammonium persulfate, persulfate, pyrosulfate, and ozone.

[0251] In one possible implementation, the oxidant is hydrogen peroxide.

[0252] An embodiment of this application provides an etching process, which includes steps (1) and (2).

[0253] Step (1): Provide a patterned substrate, which includes an aluminum oxide layer and a nitrogen oxide layer.

[0254] Step (2): Treat the patterned substrate with the above-described etching composition or diluent thereof disclosed herein.

[0255] As an example, for the need for selective removal of hard masks in copper damascus processes, especially in process nodes of 28nm and below, the etching process of this application can efficiently and selectively etch hard masks without damaging the sidewalls and bottom metal or non-metal materials of trench and via structures.

[0256] Furthermore, the etching process described in this application is suitable for selectively opening the AlN etching stop layer in certain three-layer stacked structures, is compatible with the sidewall and bottom materials of trench and through-hole structures, and exhibits good process compatibility with the alumina layer, while effectively removing plasma ashing residues from the sidewalls and bottom.

[0257] An embodiment of this application provides a device. The device includes a patterned substrate prepared by the etching process described above in this disclosure.

[0258] The following will further describe the scheme of this application through specific examples.

[0259] Unless otherwise stated, all percentages in the examples are mass percentages.

[0260] Examples and comparative examples provide a cleaning composition, which is prepared by dissolving an organic acid in a solvent consisting of water and an organic solvent, then adding other components except for a pH adjuster, and finally adding a pH adjuster to adjust the pH.

[0261] The components and amounts of the cleaning compositions in the examples and comparative examples are shown in Table 1 below.

[0262] Table 1. Components and dosages of the cleaning compositions in the examples and comparative examples.

[0263] Performance testing Test 1: The cleaning compositions of Examples 1 to 6, Comparative Examples 1, 2 and 5 were mixed with hydrogen peroxide at a volume ratio of 26:1 to obtain corrosion compositions, and tested at 60°C. For metals, the film thickness change was characterized by measuring the resistance difference using a four-probe test. By measuring the resistance difference before and after corrosion, the change in film thickness was obtained using the inverse relationship between resistance and film thickness. For non-metals, the film thickness change was characterized by using an ellipsometer. The results are shown in Table 2.

[0264] Table 2 Corrosion rate of the corrosive composition (Å / min)

[0265] Table 2 shows that the cleaning compositions of Examples 1-6 exhibit a higher corrosion rate for AlN than for AlOx, demonstrating the advantage of selective corrosion. The TiN corrosion rate of the cleaning compositions of Examples 1-6 is also higher than that of Co and Cu metals, showing selective corrosion of Co / Cu interconnect materials by TiN. In Comparative Example 1, which does not contain the nitrogen-containing heterocyclic compound described in this application, the corrosion rates of AlN and AlOx are similar, with no significant selective corrosion. In Comparative Example 2, after removing the metal protectant, the corrosion rates of Co / Cu both show a significant upward trend, indicating that the metal protectant can effectively reduce the corrosion rate of interconnect materials and also improve the corrosion selectivity of TiN for interconnect materials. Comparing Example 1 and Comparative Example 5, it can be seen that the addition of NMMO inhibits the TiN corrosion rate but has virtually no effect on the Co / Cu corrosion rate, thereby reducing the selectivity.

[0266] Test 2: The cleaning compositions of Example 7 and Comparative Example 3 were mixed with hydrogen peroxide at a volume ratio of 13:1 to obtain corrosion compositions, and tested at 60°C. During the test, the hydrogen peroxide content was monitored, and the consumed hydrogen peroxide was continuously replenished to the initial level (spiking mode). The corrosion rate change of the important metal film during the lifetime was tested, and the results are as follows: Figures 1-3 As shown.

[0267] The corrosion rate changes of the corrosion compositions in Examples 7 and 3 above under a continuous hydrogen peroxide replenishment mode are as follows: Figures 1-3 As shown, Figure 1 The graph shows the corrosion rate of TiN by the corrosion compositions of Example 7 and Comparative Example 3 under continuous hydrogen peroxide replenishment mode. The horizontal axis represents the corrosion time in h, and the vertical axis represents the corrosion rate in Å / min. Figure 2 The graph shows the corrosion rate of Co by the corrosion compositions of Example 7 and Comparative Example 3 under continuous hydrogen peroxide replenishment mode. The horizontal axis represents the corrosion time in h, and the vertical axis represents the corrosion rate in Å / min. Figure 3The graph shows the corrosion rate of Cu by the corrosion compositions of Example 7 and Comparative Example 3 under continuous hydrogen peroxide replenishment mode. The horizontal axis represents the corrosion time in hours, and the vertical axis represents the corrosion rate in Å / min.

[0268] It can be seen that the cleaning composition of Example 7 can maintain a relatively stable TiN corrosion rate, while the cleaning composition of Comparative Example 3 shows a decreasing trend in TiN corrosion rate over time. During this process, the Co and Cu corrosion rates of both are basically stable. Therefore, the cleaning composition of Example 7 can ensure a better selectivity compared to the cleaning composition of Comparative Example 3.

[0269] The corrosion rate changes of the corrosion compositions in Examples 7 and 3 above, under the mode of no hydrogen peroxide replenishment, are as follows: Figures 4-7 As shown, Figure 4 The graph shows the corrosion rate of TiN by the corrosion compositions of Example 7 and Comparative Example 3 without the addition of hydrogen peroxide. The horizontal axis represents the corrosion time in hours, and the vertical axis represents the corrosion rate in Å / min. Figure 5 The graph shows the corrosion rate of Co by the corrosion compositions of Example 7 and Comparative Example 3 without the addition of hydrogen peroxide. The horizontal axis represents the corrosion time in h, and the vertical axis represents the corrosion rate in Å / min. Figure 6 The graph shows the corrosion rate of Cu by the corrosion compositions of Example 7 and Comparative Example 3 without the addition of hydrogen peroxide. The horizontal axis represents the corrosion time in hours, and the vertical axis represents the corrosion rate in Å / min. Figure 7 The graph shows the hydrogen peroxide content in the corrosion compositions of Example 7 and Comparative Example 3 without replenishment of hydrogen peroxide. The horizontal axis represents the corrosion time in hours, and the vertical axis represents the hydrogen peroxide content in minutes.

[0270] It can be seen that the cleaning compositions of Example 7 and Comparative Example 3 both showed varying degrees of decrease in the TiN corrosion rate. However, the TiN corrosion rate stability of the cleaning composition of Example 7 was still higher than that of the cleaning composition of Comparative Example 3, while the TiN corrosion rate of the cleaning composition of Comparative Example 3 decreased more significantly over time. Since the Co / Cu corrosion rate was relatively stable, the selectivity of the cleaning composition of Comparative Example 3 changed more significantly. The trend of hydrogen peroxide degradation shows that the hydrogen peroxide degradation in the corrosion composition of Example 7 was significantly slower than that in the corrosion composition of Comparative Example 3.

[0271] During the corrosion process, the pH value of the cleaning compositions of Example 7 and Comparative Example 3 was measured, and the results are as follows: Figure 8 As shown, Figure 8 The graph shows the pH changes of the cleaning compositions of Example 7 and Comparative Example 3. The horizontal axis represents the corrosion time in hours, and the vertical axis represents the pH value.

[0272] As can be seen from the pH change trend, the cleaning composition of Example 7 contains nitrogen-containing heterocyclic compounds. Regardless of whether hydrogen peroxide is added, the pH stability is better than that of Comparative Example 3, indicating that nitrogen-containing heterocyclic compounds can also stabilize the system environment, slow down the decomposition of hydrogen peroxide, and thus achieve the effect of stabilizing corrosion.

[0273] like Figure 9 As shown, Figure 9 The graph shows a comparison of the corrosion rate and corrosion selectivity of the corrosion compositions of Example 7 and Comparative Example 3. The horizontal axis represents the corrosion time in hours, and the vertical axis represents the corrosion rate and the selectivity of AlN relative to AlOx. The corrosion rate is expressed in Å / min. It can be seen that the corrosion composition of Example 7 has a higher AlN / AlOx corrosion selectivity, and the corrosion of aluminum compounds is affected by pH to some extent. Example 7, which has better pH stability, has a more stable AlN / AlOx corrosion selectivity, while the corrosion selectivity of Comparative Example 3 fluctuates relatively more.

[0274] Test 3: The cleaning compositions of Examples 8-11 and Comparative Example 4 were mixed with hydrogen peroxide at a volume ratio of 20:1 to obtain corrosion compositions. The mixtures were heated to 55°C, and the thickness of the non-metallic film was measured using an ellipsometry. The results are as follows: Figure 10 As shown.

[0275] Figure 10 This is a comparison graph of the corrosion rate and selectivity for AlN corrosion of the corrosion compositions of Examples 8 to 11 and Comparative Example 4. The horizontal axis represents the content of nitrogen-containing heterocyclic compounds in %, and the vertical axis represents the corrosion rate and the selectivity of AlN relative to AlOx. The corrosion rate is in Å / min. It can be seen that the nitrogen-containing heterocyclic compounds of this application can increase the corrosion rate of AlN, but have no significant effect on the corrosion rate of AlOx, thereby achieving the purpose of improving the selectivity.

[0276] The above-described preferred embodiments have further detailed the purpose, technical solutions, and advantages of this application. It should be understood that the above description is only a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A cleaning composition, characterized in that, include: Metal protectants and nitrogen-containing heterocyclic compounds; The nitrogen-containing heterocyclic compound is selected from , , and At least one of them; R1 and R4 are each independently hydrogen or substituted or unsubstituted C1-C6 alkyl groups; R2, R3 and R5 are each independently a substituted or unsubstituted C1-C6 alkyl group; at least one of R4 and R5 is a hydroxyl-substituted C1-C6 alkyl group; Y is N or CR a R a It is hydrogen or a substituted or unsubstituted C1-C6 alkyl group; Ring A is a substituted or unsubstituted 4- to 10-membered cycloalkyl or a substituted or unsubstituted 4- to 10-membered heterocycloalkyl; Ring B is a substituted or unsubstituted 4- to 10-membered heterocyclic alkyl group; m and x are integers from 0 to 4; n is an integer from 1 to 5; k is an integer from 0 to 3.

2. The cleaning composition according to claim 1, characterized in that, R1 is hydrogen or a substituted or unsubstituted C1-C4 alkyl group; or, R1 is hydrogen or methyl. And / or, R2 is a substituted or unsubstituted C1-C4 alkyl group; or, R2 is a C1-C4 alkyl group; And / or, m is an integer of 0, 1, 2 or 3; or, m is 0.

3. The cleaning composition according to claim 1, characterized in that, The Y is N; and / or, the R3 is a substituted or unsubstituted C1-C4 alkyl; or, the R3 is a C1-C4 alkyl. And / or, x is an integer of 0, 1, 2 or 3; or, x is 0; And / or, n is an integer of 1, 2, 3 or 4; or, n is 1; And / or, the ring A is a substituted or unsubstituted 6- or 8-membered cycloalkyl or a substituted or unsubstituted 6- or 8-membered heterocycloalkyl; Alternatively, ring A may be a substituted or unsubstituted 6- to 8-membered heterocyclic alkyl group; Alternatively, ring A may be a 6- or 8-membered heterocyclic alkyl group; Alternatively, ring A may be a nitrogen-containing heptyl alkyl group.

4. The cleaning composition according to claim 1, characterized in that, The ring B is a substituted or unsubstituted 5- to 8-membered heterocyclic alkyl group; Alternatively, ring B can be a 5- or 8-membered heterocyclic alkyl group; Alternatively, ring B may be an azacyclohexyl group; And / or, R4 is a substituted or unsubstituted C1-C6 alkyl; or, R4 is a hydroxylated C1-C6 alkyl; or, R4 is a hydroxylated ethyl. And / or, R5 is a substituted or unsubstituted C1-C4 alkyl; or, R5 is a C1-C4 alkyl. And / or, the k is an integer of 0, 1, 2 or 3; or, the k is 1.

5. The cleaning composition according to claim 1, characterized in that, The nitrogen-containing heterocyclic compound is selected from , , , and At least one of them.

6. The cleaning composition according to claim 1, characterized in that, The metal protectant is selected from substituted or unsubstituted monoheterocyclic aromatic compounds containing at least two adjacent nitrogen atoms, substituted or unsubstituted fused-ring aromatic compounds containing at least two adjacent nitrogen atoms with a monoheterocyclic aromatic ring, or combinations thereof.

7. The cleaning composition according to claim 1, characterized in that, The term "substituted or unsubstituted" refers to substances selected from halogens, hydroxyl groups, amino groups, cyano groups, nitro groups, ester groups, C1-C6 alkyl groups, C1-C6 alkoxy groups, and C3-C6 alkyl groups. 10 Carbocyclic group, C2-C 10 Heterocyclic group, C6-C 10 Aryl and C1-C 10 One or more substituents in the heteroaryl group are substituted or unsubstituted; Alternatively, the term "substituted or unsubstituted" refers to something that is substituted or unsubstituted by one or more substituents selected from halogens and C1-C6 alkyl groups; Alternatively, the term "substituted or unsubstituted" refers to something that is substituted or unsubstituted by one or more substituents selected from C1-C6 alkyl groups; Alternatively, the term "substituted or unsubstituted" refers to something that is substituted or unsubstituted by one or more substituents selected from methyl, ethyl, propyl, and butyl.

8. The cleaning composition according to claim 6, characterized in that, The substituted or unsubstituted monoheterocyclic aromatic compound containing at least two adjacent nitrogen atoms is selected from the following substituted or unsubstituted compounds: pyrazole, 1,2,3-triazole or 1,2,4-triazole; Alternatively, the substituted or unsubstituted monoheterocyclic aromatic compound containing at least two adjacent nitrogen atoms and fused with an aromatic ring is selected from substituted or unsubstituted benzotriazoles; Alternatively, the metal protectant may be selected from at least one of pyrazole, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, and 5-methyl-1H-benzotriazole.

9. The cleaning composition according to claim 1, characterized in that, The ratio of the mass of the metal protective agent to the mass of the nitrogen-containing heterocyclic compound is in the range of 0.15 to 4. Alternatively, the ratio of the mass of the metal protective agent to the mass of the nitrogen-containing heterocyclic compound is in the range of 0.2 to 3.4; Alternatively, the mass ratio of the metal protective agent to the nitrogen-containing heterocyclic compound is 1.8:2.

4.

10. The cleaning composition according to claim 1, characterized in that, It also contains: organic acids.

11. The cleaning composition according to claim 10, characterized in that, The mass ratio of the nitrogen-containing heterocyclic compound to the organic acid ranges from 2.5 to 24. Alternatively, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid ranges from 2.5 to 20. Alternatively, the mass ratio of the nitrogen-containing heterocyclic compound to the organic acid may be in the range of 3.3:5.

5.

12. The cleaning composition according to claim 1, characterized in that, It also contains solvents; the solvents include water and organic solvents; Alternatively, based on the total mass of the solvent, the solvent comprises: 60% to 70% water by mass, with the remainder being organic solvents.

13. The cleaning composition according to claim 1, characterized in that, It also includes: a pH adjuster; the pH range of the cleaning composition is 6 to 8; Alternatively, the pH range of the cleaning composition is 7 to 7.5; Alternatively, the pH of the cleaning composition is 7.

2.

14. The cleaning composition according to any one of claims 1 to 13, characterized in that, The cleaning composition further comprises: an organic acid, a solvent, and a pH adjuster; the metal protectant is 0.9% to 2% by mass based on the total mass of the cleaning composition; or, the metal protectant is 1.2% to 2% by mass; or, the metal protectant is 1.2% by mass. And / or, the mass percentage of the nitrogen-containing heterocyclic compound is 0.3% to 6%; or, the mass percentage of the nitrogen-containing heterocyclic compound is 0.5% to 6%; or, the mass percentage of the nitrogen-containing heterocyclic compound is 6%. And / or, the organic acid has a mass percentage of 0.1% to 0.3%; or, the organic acid has a mass percentage of 0.2% to 0.3%; or, the organic acid has a mass percentage of 0.3%. And / or, the solvent has a mass percentage of 55% to 66%; or, the solvent has a mass percentage of 60% to 61%; or, the solvent has a mass percentage of 60.2%. And / or, the pH adjuster has a mass percentage of 0.75% to 7%; or, the pH adjuster has a mass percentage of 1.3% to 1.5%; or, the pH adjuster has a mass percentage of 1.3%.

15. A corrosive composition, characterized in that, include: Oxidizing agents and cleaning compositions as described in any one of claims 1 to 14.

16. The corrosion composition according to claim 15, characterized in that, The ratio of the mass of the cleaning composition to the mass of the oxidant is in the range of 10 to 30; Alternatively, the ratio of the mass of the cleaning composition to the mass of the oxidant is in the range of 15 to 27; Alternatively, the ratio of the mass of the cleaning composition to the mass of the oxidant is in the range of 13 to 26.

17. The corrosion composition according to claim 15, characterized in that, The corrosion rate of the corrosion composition on AlN compounds is greater than that on AlOx; the ratio of the corrosion rate of the corrosion composition on AlN compounds to the corrosion rate of the corrosion composition on AlOx is greater than 1. Alternatively, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on the AlOx is greater than or equal to 3.

5. Alternatively, the ratio of the corrosion rate of the corrosion composition on the AlN compound to the corrosion rate of the corrosion composition on the AlOx is 5.

6.

18. A reagent kit, characterized in that, It comprises: the cleaning composition as described in any one of claims 1 to 14; and an oxidizing agent.

19. An etching process, characterized in that, include: A patterned substrate is provided, the patterned substrate comprising an aluminum oxide layer and a nitrogen oxide layer; The patterned substrate is treated with the etching composition or diluent of any one of claims 15 to 17.

20. A device, characterized in that, include: The patterned substrate prepared by the etching process as described in claim 19.

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