Composition, method for treating a metal-containing film using the same, and method for manufacturing a semiconductor device using the same.
A hydrofluoric acid-based composition with an etching regulator effectively controls the etching rate of metal-containing films, addressing reliability issues in semiconductor manufacturing by enhancing cleaning and etching processes.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2025-09-02
- Publication Date
- 2026-03-16
AI Technical Summary
Existing semiconductor manufacturing processes face challenges in effectively controlling the etching rate of metal-containing films, particularly metal oxides, which can lead to damage and reliability issues in semiconductor devices.
A composition comprising hydrofluoric acid and an etching regulator, represented by Chemical Formula 1, is used to treat metal-containing films, allowing for precise control of the etching rate and enhancing cleaning abilities without hydrogen peroxide.
The composition enables effective etching, cleaning, and polishing of metal-containing films, resulting in high-quality semiconductor devices with reduced residue and improved reliability.
Smart Images
Figure 2026048055000001_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a composition, a method for treating a metal-containing film using the same, and a method for manufacturing a semiconductor device using the same.
Background Art
[0002] In order to meet the excellent performance and low price required by consumers, an increase in the integration degree and an improvement in the reliability of semiconductor devices are required. As the integration degree of semiconductor devices increases, damage to the components of semiconductor devices in the manufacturing process of semiconductor devices has a greater impact on the reliability and electrical characteristics of semiconductor memory devices. In particular, in the manufacturing process of semiconductor devices, various processing steps, such as etching, cleaning, and polishing steps, can be performed on a predetermined film (for example, a metal-containing film). However, there is a continuous need for a composition having an appropriate etching rate and the like for performing an effective metal-containing film processing step.
Summary of the Invention
Problems to be Solved by the Invention
[0003] The problem to be solved by the present invention is to provide a composition capable of effectively controlling the etching rate for various metal-containing films, such as a metal-containing film containing a metal oxide, a method for treating a metal-containing film using the same, and a method for manufacturing a semiconductor device using the same.
Means for Solving the Problems
[0004] According to one aspect, it contains hydrofluoric acid and an etching regulator, the etching regulator contains at least one compound represented by the following Chemical Formula 1, and a composition that does not contain hydrogen peroxide is provided:
[0005]
Chemical Formula
[0006] In the above Chemical Formula 1, L1 is a single bond, *-O-*, *-S-*, or a C1-C , , alkylene group, R1 is *-OH, *-C(=O)-OH, *-P(=O)(OH)2, or *-N(L 11 -R 11 )(L 12 -R 12 ), L 11 and L 12 are each independently a single bond or a C1-C 10 alkylene group, R 11 and R 12 are each independently hydrogen, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, or *-NH2, Among the C1-C 11 alkylene groups of the above L1, L 12 and L 10 at least one hydrogen of the alkylene group is selectively substituted with a C1-C 10 alkyl group, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, or *-NH2, * and *' are each a bonding site with an adjacent atom, In the above Chemical Formula 1, the number of groups represented by *-P(=O)(OH)2 is 1, 2, or 3.
[0007] According to another aspect, a step of preparing a substrate provided with a metal-containing film, and a step of bringing the metal-containing film into contact with the composition are included, and a method for treating a metal-containing film is provided.
[0008] According to still another aspect, a step of preparing a substrate provided with a metal-containing film, a step of bringing the metal-containing film into contact with the composition, and a step of performing subsequent manufacturing process(es) to fabricate a semiconductor device are included, and a method for manufacturing a semiconductor device is provided. [Effects of the Invention]
[0009] The aforementioned composition allows for easy control of the etching rate of various metal-containing films, such as metal oxide films, and has excellent cleaning ability. It can be effectively used in various processing steps for the metal-containing films, such as etching, cleaning, and polishing. By processing metal-containing films using the aforementioned composition, high-quality semiconductor devices can be manufactured. [Brief explanation of the drawing]
[0010] [Figure 1] This is a flowchart of one embodiment of a method for fabricating semiconductor devices. [Modes for carrying out the invention]
[0011] metal-containing film The metals contained in the aforementioned metal-containing film include alkali metals (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), lanthanide metals (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), and transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr)). This may include, for example, hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), etc., post-transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.
[0012] According to one embodiment, the metal contained in the metal-containing film may include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof. The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.
[0013] According to one embodiment, the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metal contained in each of the metal, metal nitride, metal oxide, and metal oxynitride may include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.
[0014] According to other embodiments, the metal-containing film comprises a metal oxide, the metal oxide may comprise i) indium, gallium, zinc, or any combination thereof, or ii) aluminum.
[0015] In further embodiments, the metal-containing film may include IGZO (Indium Gallium Zinc Oxide), aluminum oxide (e.g., Al2O3), or a combination thereof. The atomic or weight ratios of indium, gallium, and zinc in the aforementioned IGZO can be varied in many ways. For example, the zinc content in the IGZO can be 20 wt% to 40 wt%, for example, 30 wt%.
[0016] In further embodiments, the metal-containing film may contain a metal. For example, the metal-containing film may contain aluminum. In yet another embodiment, the metal-containing film may include a metal nitride. The metal contained in the metal nitride may include indium, titanium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof. For example, the metal-containing film may include titanium nitride. The titanium nitride may further include indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, tungsten, silicon, or any combination thereof. Further examples include titanium nitride (TiN), titanium nitride further containing aluminum (e.g., titanium / aluminum nitride (TiAlN)), titanium nitride further containing lanthanum, titanium nitride further containing silicon (TiSiN), and so on.
[0017] As yet another example, the metal-containing film may include the metal nitride and the metal oxide.
[0018] As yet another example, the metal-containing film may further include, in addition to metals, metalloids (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), nonmetals (e.g., nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.) and any combination thereof. For example, the metal-containing film may further contain silicon oxide. The metal-containing film may have a single-layer structure containing one or more substances, or a multilayer structure or three-dimensional pattern structure containing different substances.
[0019] composition The aforementioned composition, Hydrofluoric acid It contains (HF) and an etching controller, but does not contain hydrogen peroxide. A description of the etching controller will be provided later. The above composition can be used in a variety of processing steps for metal-containing films as described herein, such as etching, cleaning, and polishing steps. The composition may further contain water. While not intended to be limited by any particular theory, hydrogen peroxide can impair the stability of the composition and the effectiveness of the etching modifier.
[0020] Hydrofluoric acid The hydrofluoric acid serves to remove residues from the surface of the metal-containing film and, if necessary, to etch a portion of the metal-containing film. The aforementioned Hydrofluoric acid The content (weight) is, for example, per 100 wt% of the composition: 0.01 wt% to 2 wt%, 0.01 wt% to 1.5 wt%, 0.01 wt% to 1.0 wt%, 0.01 wt% to 0.5 wt%, 0.01 wt% to 0.2 wt%, 0.01 wt% to 0.1 wt%, 0.01 wt% to 0.09 wt%, 0.01 wt% to 0.08 wt%, 0.01 wt% to 0.07 wt%, 0.01 wt% to 0.05 wt%, 0.03 wt% to 2 wt%, 0.03 wt% to 1.5 wt%, 0.03 wt% to 1.0 wt%, 0.03 wt% to 0.5 wt%, 0.03 wt% to 0.2 wt%, 0 .03wt%~0.1wt%, 0.03wt%~0.09wt%, 0.03wt%~0.08wt%, 0.03wt%~0.07wt%, 0 .03wt%~0.05wt%, 0.05wt%~0.07wt%, 0.04wt%~2wt%, 0.04wt%~1.5wt%, 0.04 wt%~1.0wt%, 0.04wt%~0.5wt%, 0.04wt%~0.2wt%, 0.04wt%~0.1wt%, 0.04wt%~0.09wt%, 0.04wt%~0.08wt%, 0.04wt%~0.07wt%, or 0.04wt%~0.06wt%. When the content of the hydrofluoric acid satisfies the range described above, residues on the surface of the metal-containing film can be effectively removed without substantial damage to the metal-containing film.
[0021] Etching modifier The etching modifier interacts with various metal atoms in the metal-containing film that is to be treated, and plays a role in regulating the etching rate and other parameters. For example, if the metal-containing film contains a metal oxide, the etching modifier plays a role in suppressing the etching of the metal oxide. The etching modifier may contain at least one compound represented by the following chemical formula 1:
[0022] [ka]
[0023] In the above chemical formula 1, L1 is a single bond, *-O-*', *-S-*', or C1-C 10 It is an alkylene group, R1 is either *-OH, *-C(=O)-OH, *-P(=O)(OH)2, or *-N(L 11 -R 11 )(L 12 -R 12 ) and L 11 and L 12 These are independent of each other, and are single bonds or C1-C 10 It is an alkylene group, R 11 and R 12 These are, independently of each other, hydrogen, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, or *-NH2. The aforementioned L1, L 11 and L 12 C1-C 10 At least one hydrogen atom in the alkylene group is selectively C1-C 10 Substituted with alkyl groups, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, or *-NH2, * and *' are bonding sites with adjacent atoms, In the above chemical formula 1, the number of groups represented by *-P(=O)(OH)2 is 1, 2, or 3.
[0024] According to one embodiment, in the chemical formula 1, L1 is Single bond, *-O-*', or C1-C6 alkylene group; or C1-C 10 It is also a C1-C6 alkylene group substituted with at least one of the following: alkyl group, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, and *-NH2.
[0025] According to other embodiments, in the chemical formula 1, L1 is A single bond, *-O-*', or a methylene group; or C1-C 10 It is also a methylene group substituted with at least one of the following: alkyl group, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, and *-NH2. In further embodiments, in the chemical formula 1, R1 is also *-OH, *-C(=O)-OH, or *-P(=O)(OH)2. Furthermore, according to another embodiment, in the chemical formula 1, R1 is *-N(L 11 -R 11 )(L 12 -R 12 ) and L 11 and L 12 They are independent of each other, A single bond or a C1-C6 alkylene group; or C1-C 10 A C1-C6 alkylene group substituted with at least one of an alkyl group, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, and *-NH2; R 11 is hydrogen or *-P(=O)(OH)2, R 12 It can also be hydrogen, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, or *-NH2.
[0026] Furthermore, according to another embodiment, in the chemical formula 1, R1 is *-N(L 11 -R 11 )(L 12 -R 12 ) and L 11 and L 12Each is a single bond, R 11 and R 12 Each of them is also hydrogen.
[0027] Furthermore, according to another embodiment, in the chemical formula 1, R1 is *-N(L 11 -R 11 )(L 12 -R 12 ) and L 11 is a methylene group, R 11 This is also *-P(=O)(OH)2.
[0028] Furthermore, according to another embodiment, in the chemical formula 1, R1 is *-N(L 11 -R 11 )(L 12 -R 12 ) and L 11 and L 12 Each is a methylene group, R 11 This is *-P(=O)(OH)2, and R 12 This is also *-C(=O)-OH or *-P(=O)(OH)2.
[0029] Furthermore, according to another embodiment, in the chemical formula 1, R1 is *-N(L 11 -R 11 )(L 12 -R 12 ) and L 11 It is a methylene group, R 11 This is *-P(=O)(OH)2, L 12 teeth, A single bond or a C1-C6 alkylene group; or C1-C 10 A C1-C6 alkylene group substituted with at least one of an alkyl group, *-OH, *-C(=O)-OH, *-P(=O)(OH)2, and *-NH2; R 12 It is either hydrogen or an *-OH group.
[0030] In further embodiments, the etching modifier may comprise at least one of the following compounds 1 to 13:
[0031] [ka]
[0032] In the aforementioned chemical formula 1, the number of groups represented by *-P(=O)(OH)2 is 1, 2, or 3, and in the aforementioned chemical formula 1, R1 is *-OH, *-C(=O)-OH, *-P(=O)(OH)2, or *-N(L 11 -R 11 )(L 12 -R 12 ) is a hydrophilic group. Here, for example, if the metal-containing film contains a metal oxide, the compound of chemical formula 1 can effectively protect the metal oxide and substantially suppress etching of the metal-containing film. The content (by weight) of the etching modifier may be, for example, 0.001wt% to 10wt%, 0.001wt% to 7wt%, 0.001wt% to 5wt%, 0.005wt% to 10wt%, 0.005wt% to 7wt%, 0.005wt% to 5wt%, 0.01wt% to 10wt%, 0.01wt% to 7wt%, or 0.01wt% to 5wt% per 100wt% of the composition. The compositions mentioned above include those with values of 5.0 or less, 4.0 or less, 3.0 or less, 2.4 or less, 2.0 or less, 1.0 or less, -2.0 to 5.0, -2.0 to 4.0, -2.0 to 3.0, -2.0 to 2.4, -2.0 to 2.0, -2.0 to 1.0, -1.0 to 5.0, -1.0 to 4.0, -1.0 to 3.0, -1.0 to 2.4, -1.0 to 2.0, -1.0 to 1.0, 0.01 to 5.0, 0.01 to 4.0, 0.01 to 3.0, and 0. The composition may have a pH of 0.1-2.4, 0.01-2.0, 0.01-1.0, 0.1-5.0, 0.1-4.0, 0.1-3.0, 0.1-2.4, 0.1-2.0, 0.1-1.0, 0.5-5.0, 0.5-4.0, 0.5-3.0, 0.5-2.4, 0.5-2.0, 0.5-1.0, 0.96-5.0, 0.96-4.0, 0.96-3.0, 0.96-2.4, 0.96-2.0, or 0.96-1.0. Having a pH within the aforementioned range allows for smoother interaction between the etching modifier and the metal atoms in the metal-containing film.
[0033] According to one embodiment, the composition may be used in metal-containing film processing steps, such as etching, cleaning, and polishing steps for a metal-containing film. A description relating to the metal-containing film is provided herein.
[0034] Alternatively, the composition may also be used as an etching by-product remover, a post-etch by-product remover, an ashing by-product remover, a cleaning composition, a photoresist (PR) remover, an etching composition for the packaging process, a cleaning agent for the packaging process, a wafer adhesive remover, an etching solution (Etchant), a post-etch residue stripper, an ashing residue cleaner, a photoresist residue stripper, a CMP cleaner, or a post-CMP cleaner.
[0035] Method for treating metal-containing films and method for manufacturing semiconductor devices The metal-containing film can be effectively treated using the compositions described above. For example, a contact step between the metal-containing film and the composition may cause a portion or more of the metal-containing film to be etched, cleaned, or polished. Referring to Figure 1, one embodiment of the metal-containing film treatment method may include the steps of: preparing a substrate to which a metal-containing film is provided (S100); and contacting the metal-containing film with a composition as described herein (S110). For further details regarding the aforementioned metal-containing film, please refer to the provisions of this specification. According to one embodiment, the metal contained in the metal-containing film may include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof. The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.
[0036] According to one embodiment, the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, and the metal contained in each of the metal, metal nitride, metal oxide, and metal oxynitride may include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.
[0037] According to other embodiments, the metal-containing film comprises a metal oxide, the metal oxide may comprise i) indium, gallium, zinc, or any combination thereof, or ii) aluminum.
[0038] In further embodiments, the metal-containing film may include IGZO (Indium Gallium Zinc Oxide), aluminum oxide (e.g., Al2O3), or a combination thereof. The atomic or weight ratios of indium, gallium, and zinc in the aforementioned IGZO can be varied in many ways.
[0039] In further embodiments, the metal-containing film may contain a metal. For example, the metal-containing film may contain aluminum.
[0040] In further embodiments, the metal-containing film comprises IGZO (Indium Gallium Zinc Oxide), aluminum oxide, or a combination thereof, and a portion or more of the metal-containing film can be cleaned by removing residues from the surface of the metal-containing film during the contact step between the metal-containing film and the composition. The aforementioned residue is a substance that remains on the surface of the metal-containing film and / or metal-containing film pattern as a by-product generated during the deposition and / or patterning of the metal-containing film, causing increased electrical resistance and / or electrical short circuits between electrical wiring. The aforementioned residue is also etching residue generated as a result of etching, and may include, for example, etching gas residue, polymer residue, metal-containing residue, or any combination thereof. The etching gas residue is also a residue derived from the etching gas used in dry etching. The etching gas is, for example, carbon fluoride gas. For example, the etching gas may include CHF3, C2F6, CF4, C4F8, C2HF5, etc. The etching gas residue may include the etching gas itself and / or the reaction products with any substance that came into contact with the etching gas during the etching process using the etching gas. The polymer residue is also a polymer derived from various organic materials contained in the photoresist, dielectric layer, buffer layer, diffusion barrier layer, etc., used during the fabrication and / or patterning of the metal-containing film. For example, the polymer residue may also be a polymer containing carbon, silicon, fluorine, or any combination thereof. The aforementioned metal-containing residue is also any residue containing metal that was separated from the metal-containing film during the production and / or patterning of the metal-containing film. Since the aforementioned composition contains an etching modifier comprising the compound represented by chemical formula 1 as described above, the etching rate for various metal-containing films can be easily controlled.
[0041] On the other hand, referring to Figure 1, a semiconductor device manufacturing method according to one embodiment may include the steps of: preparing a substrate provided with a metal-containing film (S100); bringing the metal-containing film into contact with the composition (S110); and carrying out subsequent steps to manufacture a semiconductor device (S120).
[0042] According to one embodiment, the substrate is provided with a transistor including a channel, and the metal-containing film may be included in the channel of the transistor. Here, the metal-containing film comprises IGZO (Indium Gallium Zinc Oxide), and a portion or more of the metal-containing film can be cleaned by removing residue from the surface of the metal-containing film during the contact step between the metal-containing film and the composition.
[0043] Examples 1 to 4 and Comparative Examples C1 to C3 Compositions for Examples 1 to 4 and Comparative Examples C1 to C3 were prepared by mixing hydrofluoric acid in the amounts listed in Table 1 with the substances and etching modifiers listed in Table 1. The remainder of each composition is water (deionized water).
[0044] Evaluation Example 1 The composition of Example 1 was placed in two separate beakers. i) A 2cm x 2cm IGZO film specimen was immersed in the first beaker at 25°C for 20 seconds. ii) A 2cm x 2cm Al2O3 film specimen was immersed in the second beaker at 25°C for 3 minutes. The thickness of each IGZO and Al2O3 film was then measured using an ellipsometer (M-2000, JAWoolam), a four-point resistance meter, and an XRF to evaluate the etching rate (Å / min) of the composition of Example 1 for the IGZO and Al2O3 films. The results, along with the pH of the composition of Example 1 as evaluated by a pH meter, are summarized in Table 1. Next, the surfaces of the immersed IGZO and Al2O3 films were observed using a TEM (transmission electron microscope) to evaluate whether any residues had been removed. The results are summarized in Table 1. The above tests were repeated using the compositions of Examples 2 to 4 and Comparative Examples C1 to C3, and the results are summarized in Table 1.
[0045] [Table 1]
[0046] [ka]
[0047] Table 1 confirms that the compositions of Examples 1 to 4 simultaneously possess superior etching suppression and cleaning capabilities for IGZO films and Al2O3 films compared to the compositions of Comparative Examples C1 to C3.
[0048] Examples 5 and 6 and Comparative Examples C4 and C5 Compositions for Examples 5 and 6 and Comparative Examples C4 and C5 were prepared by mixing hydrofluoric acid in the amounts listed in Table 2 with the substances and etching modifiers listed in Table 2. The remainder of each composition is water (deionized water).
[0049] Evaluation Example 2 Using the same method as in Evaluation Example 1, the pH, etching rate of the IGZO film, and etching rate of the Al2O3 film for the compositions of Examples 5 and 6 and Comparative Examples C4 and C5 were evaluated, and the results are summarized in Table 2.
[0050] [Table 2]
[0051] [ka]
[0052] Table 2 confirms that the compositions of Examples 5 and 6 have superior etching suppression capabilities against IGZO films and Al2O3 films compared to the compositions of Comparative Examples C4 and C5.
[0053] Examples 7 to 13 and Comparative Example C6 The compositions of Examples 7 to 13 and Comparative Example C6 were prepared by mixing hydrofluoric acid in the amounts listed in Table 3 with the substances and etching modifiers listed in Table 3. The remainder of each composition is water (deionized water).
[0054] Evaluation Example 3 The pH, etching rate of the IGZO film, and etching rate of the Al2O3 film for the compositions of Examples 7 to 13 and Comparative Example C6 were evaluated using the same method as in Evaluation Example 1, and the results are summarized in Table 3. For comparison, the data for Example 4 is also included in Table 3.
[0055] [Table 3]
[0056] [ka]
[0057] Table 3 confirms that the compositions of Examples 4 and 7 to 13 exhibit superior etching suppression ability against IGZO and Al2O3 films compared to the composition of Comparative Example C6.
[0058] Comparative Examples C7 and C8 Compositions C7 and C8 were prepared by mixing hydrogen peroxide and hydrofluoric acid in the amounts listed in Table 4 with etching modifiers in the amounts listed in Table 4. The remainder of each composition is water (deionized water).
[0059] Evaluation Example 4 The pH, etching rate of the IGZO film, and etching rate of the Al2O3 film for the compositions of Comparative Examples C7 and C8 were evaluated using the same method as in Evaluation Example 1, and the results are summarized in Table 4. For comparison, the data for Example 4 is also included in Table 4.
[0060] [Table 4]
[0061] [ka] Table 4 confirms that the composition of Example 4 has superior etching suppression ability against IGZO films and Al2O3 films compared to the compositions of Comparative Examples C7 and C8.
[0062] Example 14 The composition of Example 14 was prepared by mixing hydrofluoric acid in the amounts listed in Table 5 with the substances and etching modifiers listed in Table 5. The remainder of each composition corresponds to water (deionized water).
[0063] Comparative Examples C9 and C10 Compositions for Comparative Examples C9 and C10 were prepared by mixing ammonium difluoride in the amounts listed in Table 5 with the substances and etching modifiers listed in Table 5. The remainder of each composition is water (deionized water).
[0064] Evaluation Example 5 Using the same method as in Evaluation Example 1, the pH, etching rate of the IGZO film, and etching rate of the Al2O3 film for the compositions of Example 14 and Comparative Examples C9 and C10 were evaluated, and the results are summarized in Table 5. For comparison, the data for Example 4 is also shown in Table 4.
[0065] [Table 5]
[0066] [ka]
[0067] Table 5 shows that the composition of Example 4 has superior etching suppression ability against IGZO films and Al2O3 films compared to the composition of Comparative Example C9, and the composition of Example 14 has superior etching suppression ability against IGZO films and Al2O3 films compared to the composition of Comparative Example C10.
Claims
1. It contains hydrofluoric acid and etching modifiers, The etching modifier comprises at least one compound represented by the following chemical formula 1, Compositions that do not contain hydrogen peroxide: 【Chemistry 1】 In the aforementioned chemical formula 1, L １ These are single bonds, *-O-*', *-S-*', or C １ -C １０ It is an alkylene group, R １ is *-OH, *-C(=O)-OH, *-P(=O)(OH) ２ , or *-N(L １１ -R １１ )(L １２ -R １２ ), and L １１ and L １２ These are independent of each other, and are single bonds or C １ -C １０ It is an alkylene group, R １１ and R １２ These are, independently of each other, hydrogen, *-OH, *-C(=O)-OH, and *-P(=O)(OH) ２ , or *-NH ２ And, Said L １ , L １１ and L １２ C １ -C １０ At least one hydrogen atom of the alkylene group is selectively C １ -C １０ Alkyl group, *-OH, *-C(=O)-OH, *-P(=O)(OH) ２ , or *-NH ２ Replaced by, * and *' are bonding sites with adjacent atoms, In the chemical formula 1, *-P(=O)(OH) ２ The number of bases represented is 1, 2, or 3.
2. The composition according to claim 1, wherein the content of the hydrofluoric acid is 0.01 wt% to 2 wt% per 100 wt% of the composition.
3. The composition according to claim 1, wherein the content of the hydrofluoric acid is 0.01 wt% to 0.1 wt% per 100 wt% of the composition.
4. In the above chemical formula 1, L １ but, Single bond, *-O-*', or C １ -C ６ Alkylene group, or C １ -C １０ Alkyl group, *-OH, *-C(=O)-OH, *-P(=O)(OH) ２ and *-NH ２ C is replaced with at least one of the following １ -C ６ The composition according to claim 1, wherein the group is alkylene.
5. In the above chemical formula 1, R １ *-OH, *-C(=O)-OH, or *-P(=O)(OH) ２ The composition according to claim 1.
6. In the above chemical formula 1, R １ *-N(L １１ -R １１ ) (L １２ -R １２ ) and L １１ and L １２ They are independent of each other, Single bond or C １ -C ６ Alkylene group, or C １ -C １０ Alkyl group, *-OH, *-C(=O)-OH, *-P(=O)(OH) ２ and *-NH ２ C is replaced with at least one of the following １ -C ６ It is an alkylene group, R １１ is hydrogen or *-P(=O)(OH) ２ And, R １２ is hydrogen, *-OH, *-C(=O)-OH, *-P(=O)(OH) ２ , or *-NH ２ The composition according to claim 1.
7. The composition according to claim 1, wherein the etching modifier comprises at least one of the following compounds 1 to 13: 【Chemistry 2】
8. The composition according to claim 1, wherein the content of the etching modifier is 0.001 wt% to 10 wt% per 100 wt% of the composition.
9. The content of the hydrofluoric acid is 0.03 wt% to 0.07 wt% per 100 wt% of the composition. The composition according to claim 1, wherein the content of the etching modifier is 0.01 wt% to 5 wt% per 100 wt% of the composition.
10. The composition according to claim 1, wherein the pH of the composition is 3.0 or less.
11. The steps include preparing a substrate to which a metal-containing film is provided, A method for treating a metal-containing film, comprising the step of bringing the metal-containing film into contact with the composition described in any one of claims 1 to 10.
12. The metal-containing film processing method according to claim 11, wherein, in the contact step between the metal-containing film and the composition, a portion or more of the metal-containing film is etched, cleaned, or polished.
13. The metal-containing film treatment method according to claim 11, wherein the metal contained in the metal-containing film includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.
14. The metal-containing film treatment method according to claim 11, wherein the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.
15. The metal-containing film includes a metal oxide, The aforementioned metal oxide i) containing indium, gallium, zinc, or any combination thereof, ii) The metal-containing film treatment method according to claim 11, comprising aluminum.
16. The metal-containing film treatment method according to claim 11, wherein the metal-containing film comprises IGZO (Indium Gallium Zinc Oxide), aluminum oxide, or a combination thereof.
17. The metal-containing film treatment method according to claim 11, wherein the metal-containing film contains aluminum.
18. The metal-containing film comprises IGZO (Indium Gallium Zinc Oxide), aluminum oxide, or a combination thereof. The metal-containing film treatment method according to claim 11, wherein a portion or more of the metal-containing film is cleaned by removing residue from the surface of the metal-containing film during the contact step between the metal-containing film and the composition.
19. The steps include preparing a substrate to which a metal-containing film is provided, The steps include bringing the metal-containing film into contact with the composition according to any one of claims 1 to 10, A method for manufacturing a semiconductor device, comprising the step of carrying out subsequent manufacturing processes to produce a semiconductor device.
20. A transistor including a channel is provided on the substrate, The metal-containing film is included in the channel of the transistor. The aforementioned metal-containing film includes IGZO (Indium Gallium Zinc Oxide), The semiconductor device manufacturing method according to claim 19, wherein a portion or more of the metal-containing film is cleaned by removing residue from the surface of the metal-containing film during the contact step between the metal-containing film and the composition.