TW202045685A - Etching composition - Google Patents

Abstract

The present invention provides an etching composition for selectively etching a titanium nitride hard mask, comprising basic compound, chelating agent, corrosion inhibitor and solvent. The etching composition provided by the present invention has excellent etching selectivity, which is able to quickly remove titanium nitride (TiN) and residues after dry etching but does not damage a low-k layer and a metal conductor layer. The etching composition retains certain oxidizing power, etching selectivity and pH value after repeated use, and is suitable for use in a recycle mode process.

Description

Etching composition

The present invention relates to an etching composition, and more specifically, to an etching composition for selectively etching titanium nitride (TiN) hard masks and residues.

Due to market demand, the industry continues to invest in research to develop microelectronic devices with higher performance and lower energy consumption. With the evolution of the times, there is also a demand for smaller size microelectronic devices in the market. However, with the development of microelectronic devices The size reduction and the reliability of integrated circuits (IC) have become extremely important issues in the field of IC assembly technology.

The dual damascene structure process is a process of metallization at the back of the microelectronic device to form an interconnection body. The through hole and the metal wire are made in a damascene manner. The metal hard mask is formed on the cover. On the low-k material layer of the metal conductor layer (such as cobalt or copper), the low-k layer is etched according to the metal hard mask to form trenches and holes that expose part of the metal conductor layer, and finally the Metal hard mask and carry out diffusion barrier layer deposition and metal deposition. A hard metal mask such as titanium nitride (TiN) can be removed by a wet chemical cleaning process after etching the low-k layer to form trenches and holes. The wet chemical cleaning process is a kind of wet etching, and can also remove dry etching residues. The residues may be polymers or polymers combined with metals. If the residues are not removed, it will lead to wires. The increase in resistance value, especially in the part of the hole is more significant. In addition, during wet etching, the exposed metal conductor layer and low-k layer cannot be affected. Therefore, the chemical substances used in wet etching must be highly selective.

Traditionally, the post-dry etching cleaning solution used in the copper process is a fluorine-containing semi-aqueous solution. Through the reaction of fluoride ions with the wafer surface, the oxides on the surface are microetched to remove organic matter from the wafer surface for cleaning purposes. This product has been widely used in the copper process of the old generation in the market. However, because fluoride ions will etch low-k materials, after the semiconductor process continues to shrink, fluoride ion microetching will increase the size of the originally designed trenches and holes, causing misalignment of the copper wires and making the components fail. The opportunity becomes larger, which does not meet the requirements of advanced semiconductor manufacturing processes, and the activity of fluoride ions is large, which makes it difficult to inhibit the corrosion of the underlying copper.

The next generation of dry etching cleaning solution is semi-aqueous or aqueous solution containing hydrogen peroxide. It uses the oxidizing power of hydrogen peroxide to oxidize organics and make them have hydrophilic functional groups to increase the solubility of organics in water. In addition, the solvent can swell the organics to separate the surface of the wafer and exist in the solution in a dissolved or suspended manner. , And then in the water washing stage, the residue and cleaning fluid are cleaned together. This product does not contain fluoride ions and will not corrode low-k materials. For the copper material of the bottom metal conductor layer, an appropriate copper corrosion inhibitor is added to protect the copper from corrosion. The cleaning solution containing hydrogen peroxide can micro-etch the TiN hard mask to enlarge the openings of the trenches and holes to facilitate the subsequent diffusion barrier layer deposition and copper electroplating process. Subsequent chemical mechanical polishing (CMP) is used to remove the copper and diffusion barrier metal on the surface, and the TiN hard mask is also removed in the CMP process.

However, in advanced semiconductor manufacturing processes, novel metal materials are used as the diffusion barrier layer, resulting in the need to remove the TiN hard mask before depositing the diffusion barrier layer. The TiN hard mask can be removed within a short period of time. Therefore, it is urgent to develop a wet etching solution that can remove TiN hard masks and dry etching residues without corroding the copper or cobalt of the bottom metal conductor.

In order to solve the above problems, the present invention provides an etching composition for selective etching of titanium nitride hard masks. The composition includes: a basic compound, a chelating agent, a corrosion inhibitor and a solvent, wherein the alkali Based on the total weight of the organic compound, the organic acid compound, the chelating agent, the corrosion inhibitor, and the solvent, the basic compound accounts for 1 to 25% by weight, the chelating agent accounts for 0.1 to 2% by weight, and the corrosion inhibitor The agent system accounts for 1 to 7% by weight.

In some embodiments, based on the total weight of the basic compound, the chelating agent, the corrosion inhibitor, and the solvent, the basic compound accounts for 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25% by weight, chelating agent can account for 0.1, 0.2, 0.3, 0.4 , 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2% by weight, and corrosion inhibitors can account for 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7 wt%.

The etching composition may further include an oxidizing agent, where the oxidizing agent includes, but is not limited to, hydrogen peroxide, ammonium persulfate, perbenzoic acid, FeCl ₃ , FeF ₃ , Fe(NO ₃ ) ₃ , Sr(NO ₃ ) ₂ , CoF _3. MnF ₃ , periodic acid, iodic acid, vanadium oxide, ammonium vanadate, ammonium peroxymonosulfate, ammonium hypochlorite, ammonium chlorite, ammonium chlorate, ammonium perchlorate, ammonium iodate, periodic iodine Ammonium nitrate, ammonium nitrate, ammonium perborate, ammonium hypobromite, ammonium tungstate, sodium persulfate, sodium hypochlorite, sodium perborate, sodium hypobromite, potassium iodate, potassium permanganate, potassium persulfate, potassium nitrate, Potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium perchlorate, tetramethylammonium iodate, tetramethylammonium periodate, tetramethylammonium perborate, tetramethylammonium persulfate Ammonium, tetrabutylammonium peroxymonosulfate, peroxymonosulfuric acid, ferric nitrate, urea hydrogen peroxide, peracetic acid, 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, tetrachlorobenzene Quinone and alloxan. In a specific embodiment, the oxidant is hydrogen peroxide, and the hydrogen peroxide solution accounts for 10 to 20% by weight based on the weight of the etching composition, such as 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20% by weight.

The basic compound includes, but is not limited to, ethyl trimethyl ammonium hydroxide (ETMAH), tetraethyl ammonium hydroxide (TEAH), benzyl trimethyl ammonium hydroxide (BTMAH), AFR-240 (4-(2 -Hydroxyethyl)-morpholine), 4-methylmorpholine N-oxide (NMMO), trimethylphenylammonium hydroxide (TMPAH), tetrabutylammonium hydroxide (TBAH), tetrapropyl hydrogen Ammonium oxide (TPAH), tetramethylammonium hydroxide (TMAH), benzyltriethylammonium hydroxide (BTEAH), potassium hydroxide, tetrabutylphosphine hydroxide (TBPH), (2-hydroxyethyl) three Methyl ammonium hydroxide, (2-hydroxyethyl) triethyl ammonium hydroxide, (2-hydroxyethyl) tripropyl ammonium hydroxide, (2-hydroxypropyl) trimethyl ammonium hydroxide, diethyl Dimethyl ammonium hydroxide (DEDMAH), tris (2-hydroxyethyl) methyl ammonium hydroxide (THEMAH), ammonium hydroxide, choline hydroxide, 1,1,3,3-tetramethylguanidine, Guanidine carbonate, arginine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine and cysteine.

The etching composition may further include an organic acid compound, wherein, based on the total weight of the etching composition, the organic acid compound accounts for less than 15% by weight, such as 15, 14.5, 14, 13.5, 13, 12.5, 12, 11.5 , 11, 10.5, 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5% by weight or less.

The organic acid compounds include, but are not limited to, citric acid, ammonium citrate, malic acid, glutaric acid, maleic acid, malonic acid, adipic acid, acetic acid, iminodiacetic acid, lactic acid, oxalic acid, succinic acid, Glycine, serine, proline, leucine, alanine, aspartic acid, aspartic acid, glutamic acid, valine, lysine, and maleic acid.

The chelating agent includes, but is not limited to, cyclohexanediaminetetraacetic acid (CDTA), hydroxyethylene diphosphonic acid (HEDP), aminoacetic acid, iminodiacetic acid, nitrilotriacetic acid, glutamine acid, pyridine- 2-Formic acid, ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), ammonium bromide, ammonium chloride, phosphonic acid, diethylenetriaminepentaacetic acid (DTPA), diethylenetriamine penta (Methylene phosphonic acid), nitrilotri(methylene phosphonic acid) (NTMP), 2-phosphoranebutane-1,2,4-tricarboxylic acid (PBTCA), ethylenediamine, ethylenediamine Disuccinic acid, propylene diamine tetraacetic acid, ethylene diamine tetra (methylene phosphonic acid) (EDTMPA), amino tris (methylene phosphonic acid), pentamethyl ethylene triamine (PMDETA), tetra Glyme, boric acid, 2,4-pentanedione, imidazole and algaecide.

The corrosion inhibitor includes, but is not limited to, benzotriazole (BTA), tolutriazole (TTA), 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino -1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, methyl-1H- Benzotriazole, 5-phenylbenzotriazole, hydroxybenzotriazole, halobenzotriazole (halo=F, Cl, Br, I), 5-nitrobenzotriazole, benzotriazole Triazole carboxylic acid, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole , 3-Mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 4-methyl-4H-1,2,4-triazole-thiol, 4- Amino-4H-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, 2-(5-aminopentyl)benzotriazole , 5-phenylthiol-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, naphthotriazole , Thiazole, carbazole, benzothiazole, 2-aminobenzothiazole, 2-mercaptobenzothiazole, benzimidazole, 2-aminobenzimidazole, imidazole, 1-methylimidazole, 2-mercaptobenzothiazole Imidazole, 2-mercapto-5-methylbenzimidazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, methyltetrazole, pentylenetetrazole, 5-phenyl-1H-tetrazole Azole, 5-benzyl-1H-tetrazole, 5-mercapto-1-methyltetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, 1-phenyl-1H -Tetrazole-thiol, 8-hydroxyquinoline, 1-thioglycerol, ascorbic acid, pyrazole, indazole, triazine, diaminomethyl triazine, 2,4-diamino-6-methyl- 1,3,5-triazine, 2-amino-5-ethyl-1,3,4-thiadiazole, 5-amino-1,3,4- Thiadiazole-2 mercaptan, 1,3-dimethyl-2-imidazolidinone, 2-benzylpyridine, imidazoline thione, sodium lauryl sulfate, succinimide, adenine, adenine Uric acid, saccharin, uric acid and benzoin oxime.

The solvent includes but not limited to diethylene glycol butyl ether (BDG), dimethyl sulfide (DMSO), cyclobutyl sulfide, diethylene glycol diethyl ether (DEDG), dimethyl sulfide, dimethyl sulfide, N -Methylpyrrolidone (NMP), dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), methanol, ethanol, isopropanol, butanol, pentanol, hexanol, 2-ethyl-1- Hexanol, heptanol, octanol, ethylene glycol, propylene glycol, butanediol, hexanediol, butylene carbonate, ethylene carbonate, propylene carbonate, choline bicarbonate, dipropylene glycol, tetrahydrothiophene Sulfur, tetrahydrofuran methanol (THFA), 1,2-butanediol, 1,4-butanediol, tetramethylurea, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene two Alcohol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene two Alcohol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propylene Base ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, 2,3-dihydrodecafluoropentane, ethyl perfluorobutyl ether, methyl all Fluorobutyl ether, alkyl carbonate, 4-methyl-2-pentanol and water.

The etching composition may further include additives such as a radical inhibitor and a radical trap.

In a specific implementation aspect, the pH value of the etching composition is between 6.5 and 9.5, such as 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5. After adding an oxidant, the pH value of the etching composition is Between 6 and 8.5, such as 6.0, 6.5, 7.0, 7.5, 8.0, 8.5.

In a specific implementation aspect, the etching rate of the etching composition for etching titanium nitride at 60°C is 12nm/min or more, the etching rate of copper is 0.3nm/min or less, and the etching rate of cobalt is 0.4 Below nm/min.

In a specific embodiment, the etching rate of the etching composition for etching titanium nitride to the etching rate for etching copper, that is, the etching selectivity for titanium nitride to copper is 85 or more, and the etching composition is etched The ratio of the etching rate of titanium nitride to the etching rate of cobalt, that is, the etching selectivity of the etching composition to titanium nitride to cobalt is 100 or more.

The ratio of the etching rate of the etching composition of the present invention for etching titanium nitride to the etching rate for etching copper is at least 85 or more, and may be 90, 95, 100, 110, 120, 130, 140, 150, 160, 170 or more, according to Choose the most suitable ratio of the etching rate for etching titanium nitride to the etching rate for etching copper according to actual needs. On the other hand, the ratio of the etching rate of the etching composition of the present invention for etching titanium nitride to the etching rate for etching cobalt is at least 100, and may be 110, 120, 130, 140, 150, 200, 250, 300, 350, Above 400, 450, 500, 550, 600, 650, choose the most appropriate ratio of the etching rate for etching titanium nitride to the etching rate for cobalt according to actual needs.

In a specific implementation aspect, the etching composition can be used in a recycling process, so as to be recycled and reused after selective etching of titanium nitride.

The etching composition provided by the present invention has excellent etching selectivity, high etching rate for TiN, and extremely low etching rate for copper and cobalt, and can quickly and accurately remove TiN and dry etching residues during wet etching , Will not damage the low-k layer and the metal conductor layer. In addition, the etching composition of the present invention has high stability. Tests have shown that the repeated use of the etching composition still retains certain characteristics such as oxidation ability, etching selectivity, and pH value, and is extremely suitable for use in recycling processes.

Figures 1A to 1D show the results of the stability test of the etching composition of the present invention, which are the TiN etching rate, Cu and Co etching rate, H ₂ O ₂ concentration and pH change over time, respectively.

The following is a description of the implementation of the present invention through specific specific implementation modes, and those skilled in the art can easily understand the advantages and effects of the present invention from the content disclosed in this specification.

It should be noted that the structures, proportions, sizes, etc. shown in the drawings in this manual are only used to match the contents disclosed in the manual for the understanding and reading of those familiar with the art, and are not intended to limit the implementation of the present invention Therefore, it does not have any technical significance. Any structural modification, proportional relationship change, or size adjustment should still fall within the scope of the present invention without affecting the effects and objectives that can be achieved. The technical content disclosed by the invention can be covered. At the same time, the words such as "一" quoted in this specification are only for ease of description and are not used to limit the scope of implementation of the present invention. The change or adjustment of the relative relationship does not substantially change the technical content. Below, it should also be regarded as the scope of the present invention. In addition, all ranges and values herein are inclusive and combinable. Any value or point falling within the range described herein, for example, any integer can be used as the minimum or maximum value to derive the lower range and so on.

The etching composition of the present invention includes basic compounds, chelating agents, corrosion inhibitors and solvents, and may further include organic acid compounds, oxidants and additives.

The chelating agent can complex free metal ions in the composition. The metal ions may come from the metal conductor layer, and the metal ions will affect the oxidant and make it easy to decompose, which will affect the oxidation and etching ability of the etching composition.

Corrosion inhibitors are components containing chemical elements such as nitrogen, sulfur, and oxygen. They are generally heterocyclic compounds. The nitrogen, sulfur, and oxygen atoms on the corrosion inhibitor molecule have lone pairs of electrons, which can be oxidized on the metal surface. The compound forms coordination bonds, so that the corrosion inhibitor is adsorbed on the metal surface, and a passivation layer can be formed on the surface to prevent the metal from directly contacting the wet etching solution and being corroded.

The etching composition of the present invention is a concentrated composition, which can be diluted before use, and the ratio of the diluent to the concentrated composition is 0.1:1 to 100:1. In addition, since the oxidant is highly unstable over time, the concentrated composition may not contain the oxidant, and the oxidant may be added at the time of dilution to complete the final composition. The oxidizing agent can be added to the diluent, introduced into the concentrated composition along with the diluent, or can also be added to the diluted composition.

Hereinafter, the present invention will illustrate the details through examples of embodiments. However, the interpretation of the present invention should not be limited to the description of the following embodiments.

The following ingredients are selected for each of Examples 1 to 17 of the present invention:

Solvent: Diethylene glycol butyl ether (BDG), dimethyl sulfide (DMSO) and diethylene glycol diethyl ether (DEDG).

Corrosion inhibitors: benzotriazole (BTA) and tolutriazole (TTA).

Chelating agents: cyclohexanediaminetetraacetic acid (CDTA) and hydroxyethylene diphosphonic acid (HEDP).

Organic acid compounds: citric acid, glutaric acid, malic acid and maleic acid.

Basic compounds: ethyl trimethyl ammonium hydroxide (ETMAH), tetraethyl ammonium hydroxide (TEAH), benzyl trimethyl ammonium hydroxide (BTMAH), 4-(2-hydroxyethyl)-morpholine (AFR-240) and 4-methylmorpholine N-oxide (NMMO).

The dosage ratio of the ingredients in each embodiment and the test results are shown in Table 1 below.

Among them, the TiN etching rate is tested using a commercially available wafer coated with a TiN film by physical vapor deposition (PVD). The thickness of the TiN film is 100nm, cut into a size of 2cm x 2cm, and the TiN film is etched by soaking. The beaker containing the etching composition is placed in a water bath, and the etching test can be performed after the temperature of the etching composition is raised to 60°C. The etching time is 1 to 3 minutes. The TiN film thickness difference before and after etching is measured with a four-point probe measuring instrument, and the TiN etching rate can be obtained by dividing by the etching time.

The etch rates of Cu and Co were tested using electrochemical plating (ECP) coated Cu thin film wafers and PVD coated Co thin film wafers. The thickness of the Cu film is 2000nm, and the thickness of the Co film is 40nm, cut into a size of 2cm x 2cm, pretreated with oxalic acid and then immersed to etch the Cu and Co films. The etching time is 10mins. Measure the concentration of Cu and Co ions in the etching composition before and after etching with an inductively coupled plasma mass spectrometer (ICP/MS), convert it into the amount of dissolution, and obtain the etching rate of Cu and Co. The calculation formula is as follows I show.

In formula I, C is the metal ion concentration (ppb) measured by ICP/MS, W is the weight (g) of the etching composition, D is the density of the metal: Cu is 8.93g/cm ³ , Co is 8.9g /cm ³ , A is the wafer area (cm ² ), and T is the etching time (min).

In Table 1, the etching selectivity of TiN/Cu is calculated from TiN etching rate/Cu etching rate; the etching selectivity of TiN/Co is calculated from TiN etching rate/Co etching rate.

It can be seen from Table 1 that the etching composition of the present invention can quickly remove TiN, the etching rate can reach 12nm/min or more, and it has excellent etching selectivity. Its TiN/Cu etching selectivity is at least 85 or above, and TiN/ The Co etching selectivity also has at least 100 levels.

The etching composition of the present invention is then subjected to a stability test. The TiN etching test is performed every 2.4hrs. The TiN etching time is 1 to 3mins each time. Water is added in time to maintain the same etching composition weight. The etching test is performed to 24hrs. ; Cu and cobalt etching test is performed once every 4.8hrs, each Cu and Co etching time is 10mins, and water is added in time to maintain the same etching composition weight, etching test to 24hrs. The H ₂ O ₂ and pH value of the etching composition are also measured with time.

The stability test results are shown in Figure 1A to Figure 1D. Figure 1A shows the change of TiN etching rate with time (etching times). As the number of etchings increases, the TiN etching rate gradually decreases. After 24 hours, the etching rate is about 50% of the initial etching rate, and it can still maintain 12nm/ The level above min; Figure 1B shows the change of Cu and Co etching rate with time (etching times). The result shows that the Cu and Co etching rate after the second etching is not compared with the Cu and Co etching rate in the first etching. Significant changes are maintained at a relatively low level of etching rate. Among them, the Cu etching rate after 24 hours is below 0.2nm/min, and the Co etching rate after 24 hours is below 0.1nm/min. Combining the results of Fig. 1A and Fig. 1B, it is shown that the etching composition of the present invention can maintain excellent TiN/Cu selectivity and TiN/Co selectivity after being recycled and reused.

Figure 1C shows the change of the H ₂ O ₂ concentration of the etching composition with time (number of etchings). As the number of etchings increases, the H ₂ O ₂ concentration gradually decreases. After 24 hours, the H ₂ O ₂ concentration is about that of the initial etching. 70% of the H ₂ O ₂ concentration, the trend is the same as the TiN etching rate; and the firstD picture shows the change of the pH value of the etching composition with time (the number of etchings). As the number of etchings increases, the pH value slowly decreases. After 24 hours The pH value is only slightly different from the pH value of the initial etching. From the results of Figures 1A to 1D, it can be seen that the etching composition of the present invention has high stability, and the repeated use of the etching composition still retains certain characteristics such as oxidation ability, etching selectivity and pH value, and is very suitable for recirculation In the process.

Claims (20)

An etching composition for selective etching of a titanium nitride hard mask includes: a basic compound; a chelating agent; a corrosion inhibitor; and a solvent, wherein the basic compound, the organic acid compound, and the chelating agent , Based on the total weight of the corrosion inhibitor and the solvent, the basic compound accounts for 1 to 25% by weight, the chelating agent accounts for 0.1 to 2% by weight, and the corrosion inhibitor accounts for 1 to 7% by weight. For example, the etching composition of item 1 in the scope of patent application includes an oxidizing agent. For example, the etching composition of item 2 of the scope of patent application, wherein the oxidant is selected from hydrogen peroxide, ammonium persulfate, perbenzoic acid, FeCl ₃ , FeF ₃ , Fe(NO ₃ ) ₃ , Sr(NO ₃ ) ₂ , CoF ₃ , MnF ₃ , periodic acid, iodic acid, vanadium oxide, ammonium vanadate, ammonium peroxymonosulfate, ammonium hypochlorite, ammonium chlorite, ammonium chlorate, ammonium perchlorate, ammonium iodate, Ammonium periodate, ammonium nitrate, ammonium perborate, ammonium hypobromite, ammonium tungstate, sodium persulfate, sodium hypochlorite, sodium perborate, sodium hypobromite, potassium iodate, potassium permanganate, potassium persulfate, nitric acid Potassium, potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium perchlorate, tetramethylammonium iodate, tetramethylammonium periodate, tetramethylammonium perborate, persulfuric acid Tetramethylammonium, tetrabutylammonium peroxymonosulfate, peroxymonosulfuric acid, ferric nitrate, urea hydrogen peroxide, peracetic acid, 1,4-benzoquinone, toluoquinone, dimethyl-1,4-benzoquinone, four At least one of the group consisting of chloranil and alloxan. For example, the etching composition of item 3 in the scope of patent application, wherein the oxidizing agent is hydrogen peroxide. For example, the etching composition of item 4 of the scope of patent application, wherein, based on the weight of the etching composition, the hydrogen peroxide solution accounts for 10 to 20% by weight. For example, the etching composition of item 1 in the scope of patent application, wherein the basic compound is selected from ethyl trimethyl ammonium hydroxide (ETMAH), tetraethyl ammonium hydroxide (TEAH), and benzyl trimethyl ammonium hydroxide Ammonium (BTMAH), 4-(2-hydroxyethyl)-morpholine (AFR-240), 4-methylmorpholine N-oxide (NMMO), trimethylphenylammonium hydroxide (TMPAH), four Butylammonium hydroxide (TBAH), tetrapropylammonium hydroxide (TPAH), tetramethylammonium hydroxide (TMAH), benzyltriethylammonium hydroxide (BTEAH), potassium hydroxide, tetrabutylammonium hydroxide Phosphine (TBPH), (2-hydroxyethyl) trimethyl ammonium hydroxide, (2-hydroxyethyl) triethyl ammonium hydroxide, (2-hydroxyethyl) tripropyl ammonium hydroxide, (2- Hydroxypropyl) trimethylammonium hydroxide, diethyldimethylammonium hydroxide (DEDMAH), tris(2-hydroxyethyl)methylammonium hydroxide (THEMAH), ammonium hydroxide, choline hydroxide, At least one of 1,1,3,3-tetramethylguanidine, guanidine carbonate, arginine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and cysteine. For example, the etching composition of item 1 in the scope of the patent application includes an organic acid compound, and based on the total weight of the etching composition, the organic acid compound accounts for less than 15% by weight. For example, the etching composition of item 7 of the patent application, wherein the organic acid compound is selected from citric acid, ammonium citrate, malic acid, glutaric acid, maleic acid, malonic acid, adipic acid, acetic acid, Aminodiacetic acid, lactic acid, oxalic acid, succinic acid, glycine, serine, proline, leucine, alanine, aspartic acid, aspartic acid, glutamine, valine , Lysine and at least one of the group consisting of maleic acid. For example, the etching composition of item 1 in the scope of patent application, wherein the chelating agent is selected from cyclohexanediaminetetraacetic acid (CDTA), hydroxyethylene diphosphonic acid (HEDP), aminoacetic acid, iminodiacetic acid , Nitrilotriacetic acid, glutamic acid, pyridine-2-carboxylic acid, ethylenediaminetetraacetic acid (EDTA), ethylenediamine disuccinic acid (EDDS), ammonium bromide, ammonium chloride, phosphonic acid, diethylenetriaminepentaacetic acid (DTPA), diethylenetriaminepenta(methylenephosphonic acid), Nitrotris (methylene phosphonic acid) (NTMP), 2-phosphoranebutane-1,2,4-tricarboxylic acid (PBTCA), ethylenediamine, ethylenediamine disuccinic acid, propylenediamine tetra Acetic acid, ethylene diamine tetra (methylene phosphonic acid) (EDTMPA), amino tris (methylene phosphonic acid), pentamethyl ethylene triamine (PMDETA), tetraglyme, boric acid, 2 , At least one of the group consisting of 4-pentanedione, imidazole and alginamide. For example, the etching composition of item 1 in the scope of patent application, wherein the corrosion inhibitor is selected from benzotriazole (BTA), tolutriazole (TTA), 1,2,4-triazole, 3-amino- 1,2,4-triazole, 5-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3,5-diamino-1 , 2,4-triazole, methyl-1H-benzotriazole, 5-phenylbenzotriazole, hydroxybenzotriazole, halobenzotriazole (halo=F, Cl, Br, I ), 5-nitrobenzotriazole, benzotriazole carboxylic acid, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 3-amino -5-Mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 4-methyl-4H-1 ,2,4-Triazole-thiol, 4-amino-4H-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, 2 -(5-Aminopentyl)benzotriazole, 5-phenylthiol-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl- 1,2,3-triazole, naphthotriazole, thiazole, carbazole, benzothiazole, 2-aminobenzothiazole, 2-mercaptobenzothiazole, benzimidazole, 2-aminobenzimidazole, Imidazole, 1-methylimidazole, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, methyltetrazole, Pentyltetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-mercapto 1-methyltetrazole, 1,5-pentamethylenetetrazole, 1-phenyl -5-Mercaptotetrazole, 1-phenyl-1H-tetrazole-thiol, 8-hydroxyquinoline, 1-thioglycerol, ascorbic acid, pyrazole, indazole, triazine, diaminomethyl triazine, 2,4-Diamino-6-methyl-1,3,5-triazine, 2-amino-5-ethyl-1,3,4-thiadiazole, 5-amino-1,3 ,4-thiadiazole-2 mercaptan, 1,3-dimethyl-2-imidazolidinium At least one of the group consisting of ketone, 2-benzylpyridine, imidazoline thione, sodium lauryl sulfate, succinimide, adenine, adenylic acid, saccharin, uric acid, and benzoin oxime. For example, the etching composition of item 1 in the scope of the patent application, wherein the solvent is selected from the group consisting of diethylene glycol butyl ether (BDG), dimethyl sulfide (DMSO), cyclobutyl sulfide, and diethylene glycol diethyl ether (DEDG) ), dimethyl sulfide, dimethyl sulfide, N-methylpyrrolidone (NMP), dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), methanol, ethanol, isopropanol, butanol, Pentanol, hexanol, 2-ethyl-1-hexanol, heptanol, octanol, ethylene glycol, propylene glycol, butylene glycol, hexanediol, butylene carbonate, ethylene carbonate, propylene carbonate , Choline bicarbonate, dipropylene glycol, tetrahydrothiophene, tetrahydrofuran methanol (THFA), 1,2-butanediol, 1,4-butanediol, tetramethylurea, diethylene glycol monomethyl ether , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl Base ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, two Propylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, 2,3-dihydrodecafluoropentane At least one of alkane, ethyl perfluorobutyl ether, methyl perfluorobutyl ether, alkyl carbonate, 4-methyl-2-pentanol and water. For example, the etching composition in item 1 of the scope of patent application includes at least one of a radical inhibitor and a radical trap. For example, the etching composition of item 1 in the scope of patent application, wherein the pH value of the etching composition is between 6.5 and 9.5. For example, the etching composition of item 2 of the scope of patent application, wherein the pH of the etching composition is between 6 and 8.5. For example, the etching composition of items 1 to 14 in the scope of patent application has an etching rate of 12nm/min or more for etching titanium nitride at 60°C. For example, the etching composition of items 1 to 14 in the scope of patent application has an etching rate of 0.3nm/min or less for etching copper at 60°C. For example, the etching composition of items 1 to 14 in the scope of patent application has an etching rate of 0.4nm/min or less for etching cobalt at 60°C. For example, the etching composition of items 1 to 14 in the scope of patent application has a ratio of the etching rate of etching titanium nitride to the etching rate of etching copper is 85 or more. For example, the etching composition of items 1 to 14 in the scope of patent application has a ratio of the etching rate of etching titanium nitride to the etching rate of etching cobalt of 100 or more. For example, the etching composition of items 1 to 14 in the scope of the patent application is used in a recycling process to be recycled and reused after selective etching of titanium nitride.

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