CN112080279A

CN112080279A - Etching composition

Info

Publication number: CN112080279A
Application number: CN201910574759.3A
Authority: CN
Inventors: 吴柏衡; 李懿; 高桥秀树; 荻原绘里奈; 廖本男; 陈韵慈; 吕志鹏
Original assignee: KANTO-PPC Inc
Current assignee: KANTO-PPC Inc
Priority date: 2019-06-12
Filing date: 2019-06-28
Publication date: 2020-12-15
Also published as: TW202045685A; TWI795572B

Abstract

The invention discloses an etching composition. Specifically, the invention relates to an etching composition for selectively etching a titanium nitride hard mask, which comprises an alkaline compound, a chelating agent, a corrosion inhibitor and a solvent. The etching composition has excellent etching selectivity, can quickly remove titanium nitride (TiN) and dry etching residues, does not damage a low-k layer and a metal conductor layer, still has certain characteristics of oxidation capacity, etching selectivity, pH value and the like after being repeatedly used, and is suitable for being used in a recycling process.

Description

Etching composition

Technical Field

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

Background

Due to market demands, research continues to be conducted to develop microelectronic devices with higher performance and lower power consumption, and as the era progresses, microelectronic devices with smaller size are also demanded in the market, however, as the size of the microelectronic devices decreases, the reliability of Integrated Circuits (ICs) becomes an important issue in the field of IC assembly technology.

A dual damascene (dual damascene) structure process is a process of forming interconnection by back-end metallization of microelectronic device, in which a via hole and a metal wire are fabricated together in a damascene manner, a hard mask is formed on a low dielectric coefficient (low-k) material layer covering a metal conductor layer (such as cobalt or copper), the low-k layer is etched according to the hard mask to form a trench and a hole exposing a portion of the metal conductor layer, and finally the hard mask is removed and a diffusion barrier layer deposition and a metal deposition are performed. After etching the low-k layer to form trenches and holes, a wet chemical cleaning process may be performed to remove the metal hard mask, such as titanium nitride (TiN). The wet chemical cleaning process is a wet etching process and can also remove the residue of dry etching, which may be polymer or polymer combined with metal, and if the residue is not cleaned, the resistance of the conductive line will increase, especially in the hole portion. In addition, the exposed metal conductor layer and the low-k layer cannot be affected by the wet etching, so the chemical used in the wet etching must have high selectivity.

Conventionally, the post-dry etching cleaning solution used in the copper process is a fluorine-containing semi-aqueous solution, and the reaction of fluorine ions with the wafer surface microetching the oxide on the surface and removing the organic matter from the wafer surface to achieve the purpose of cleaning. The product is widely used in the copper making process of old generation. However, fluorine ions etch the low-k material, so that after the semiconductor process continues to shrink, the size of the trench and hole originally designed becomes larger due to the fluorine ion micro-etching, which causes misalignment of the copper wire (mismatch), and increases the chance of device failure, which does not meet the requirement of advanced semiconductor process.

The next generation of dry post-etching cleaning solution is semi-aqueous or aqueous solution containing hydrogen peroxide. The organic matter is oxidized by utilizing the oxidizing capacity of hydrogen peroxide to enable the organic matter to have hydrophilic functional groups so as to increase the solubility of the organic matter in water, in addition, the solvent can swell the organic matter so as to enable the organic matter to be separated from the surface of a wafer and to exist in the solution in a dissolving or suspending mode, and then, in a water washing stage, residues and cleaning liquid are cleaned together. The product does not contain fluorinion and can not corrode low-k materials, and a proper copper corrosion inhibitor is added for the copper material of the bottom metal conductor layer to protect the copper from being corroded. The cleaning solution containing hydrogen peroxide can be used for micro-etching TiN hard mask to enlarge the openings of the trenches and holes, so as to facilitate the subsequent diffusion barrier layer deposition and copper electroplating process. Chemical Mechanical Polishing (CMP) is then used to remove the copper and diffusion barrier metal from the surface, and the TiN hard mask is also removed during the CMP process.

However, in order to remove the TiN hard mask cleanly in a limited time in advanced semiconductor processes using novel metal materials as diffusion barrier layers, which further requires the removal of the TiN hard mask before the deposition of the diffusion barrier layers, a wet etching solution having high removal capability for the TiN hard mask and dry etching residues without corroding the bottom metal conductor copper or cobalt is urgently required to be developed.

Disclosure of Invention

In order to solve the above problems, the present invention provides an etching composition for selectively etching a titanium nitride hard mask, the composition comprising: an alkaline compound, a chelating agent, a corrosion inhibitor, and a solvent, wherein the alkaline compound is present in an amount of 1 to 25 wt%, the chelating agent is present in an amount of 0.1 to 2 wt%, and the corrosion inhibitor is present in an amount of 1 to 7 wt%, based on the total weight of the alkaline compound, the chelating agent, the corrosion inhibitor, and the solvent.

In some embodiments, the basic compound comprises 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 wt%, chelating agent can comprise 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2 wt%, and corrosion inhibitor can comprise 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7 wt%, based on the total weight of the basic compound, the chelating agent, the corrosion inhibitor, and the solvent.

The etching composition may further comprise an oxidizing agent, wherein the oxidizing agent includes, but is not limited to, hydrogen peroxide, ammonium persulfate, perbenzoic acid, FeCl₃、FeF₃、Fe(NO₃)₃、Sr(NO₃)₂、CoF₃、MnF₃Periodic acid, iodic acid, vanadia, 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, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium perchlorate, tetramethylammonium iodate, tetramethylammonium periodate, tetramethylammonium perborate, tetramethylammonium persulfate, tetrabutylammonium peroxymonosulfate, ferric nitrate, urea hydrogen peroxide, peracetic acid, 1, 4-benzoquinone, toluquinone, dimethyl-1, 4-benzoquinone, tetrachlorobenzoquinone, and alloxan. In one embodiment, the oxidizing agent is hydrogen peroxide, and the hydrogen peroxide solution comprises 10 to 20 wt%, 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 wt%, based on the weight of the etching composition.

The basic compounds include, but are not limited to, ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTMAH), AFR-240(4- (2-hydroxyethyl) -morpholine), 4-methylmorpholine N-oxide (NMMO), trimethylphenylammonium hydroxide (TMPAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide (TPAH), tetramethylammonium hydroxide (TMAH), benzyltriethylammonium hydroxide (BTEAH), potassium hydroxide, tetrabutylammonium hydroxide oxide (TBPH), (2-hydroxyethyl) trimethylammonium hydroxide, (2-hydroxyethyl) triethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, (2-hydroxypropyl) trimethylammonium hydroxide, diethyldimethylammonium hydroxide (DEDMAH), tris (2-hydroxyethyl) methylammonium hydroxide (THEMAH), Ammonium hydroxide, choline hydroxide, 1,3, 3-tetramethylguanidine, guanidine carbonate, arginine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and cysteine.

The etching composition may further comprise an organic acid compound, wherein the organic acid compound comprises 15 wt% or less, for example 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 wt% or less, based on the total weight of the etching composition.

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, asparagine, aspartic acid, glutamic acid, valine, lysine, and maleic acid.

The chelating agents include, but are not limited to, cyclohexanediaminetetraacetic acid (CDTA), hydroxyethylenediphosphonic acid (HEDP), aminoacetic acid, iminodiacetic acid, nitrilotriacetic acid, glutamic acid, pyridine-2-carboxylic acid, ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), ammonium bromide, ammonium chloride, phosphonic acid, diethylenetriaminepentaacetic acid (DTPA), diethylenetriaminepenta (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTMP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA), ethylenediamine, ethylenediaminedisuccinic acid, propylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) (EDTMPA), aminotri (methylenephosphonic acid), Pentamethyldiethylenetriamine (PMDETA), tetraethylene glycol dimethyl ether, boric acid, 2, 4-pentanedione, imidazole, and algaecypromide.

The corrosion inhibitor includes, but is not limited to, Benzotriazole (BTA), tolyltriazole (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, halobenzotriazoles (halo ═ F, Cl, Br, I), 5-nitrobenzotriazole, benzotriazole carboxylic acid, 1-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, 2-thiobenzothiazole, and the like, Benzimidazole, 2-aminobenzimidazole, imidazole, 1-methylimidazole, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, methyltetrazole, pentylenetetrazole, 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, diaminomethyltriazine, 2, 4-diamino-6-methyl-1, 3, 5-triazine, 2-amino-5-ethyl-1, 3, 4-thiadiazole, 5-amino-1, 3, 4-thiadiazole-2 thiol, 1, 3-dimethyl-2-imidazolidinone, 2-benzyl pyridine, imidazolinethione, sodium dodecyl sulfate, succinimide, adenine, adenylic acid, saccharin, uric acid, and benzoin oxime.

Such solvents include, but are not limited to, diethylene glycol butyl ether (BDG), dimethyl sulfoxide (DMSO), sulfolane, diethylene glycol Diethyl Ether (DEDG), dimethyl sulfone, 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, hexylene glycol, butylene carbonate, ethylene carbonate, propylene carbonate, choline bicarbonate, dipropylene glycol, tetramethylene sulfone, tetrahydrofuran methanol (THFA), 1, 2-butanediol, 1, 4-butanediol, tetramethylurea, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Dimethyl Ether (DEDG), dimethyl sulfone, dimethyl sulfide, N-methyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, triethylene glycol monobutyl 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, dipropylene 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, ethyl perfluorobutyl ether, methyl perfluorobutyl ether, alkyl carbonate, 4-methyl-2-pentanol, and water.

The etching composition may further include additives such as radical inhibitors and radical traps.

In one embodiment, the pH 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, and after the addition of the oxidizing agent, the pH 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 one embodiment, the etching composition etches titanium nitride at 60 ℃ at an etching rate of 12nm/min or more, copper at an etching rate of 0.3nm/min or less, and cobalt at an etching rate of 0.4nm/min or less.

In one embodiment, the etching composition has a ratio of an etching rate for titanium nitride to an etching rate for copper, i.e., an etching selectivity for titanium nitride relative to copper, of 85 or more, and an etching rate for titanium nitride to an etching rate for cobalt, i.e., an etching selectivity for titanium nitride relative to cobalt, of 100 or more.

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

In one embodiment, the etching composition can be used in a recycling process for recycling after selective etching of titanium nitride.

The etching composition provided by the invention has excellent etching selectivity, high etching rate to TiN and extremely low etching rate to copper and cobalt, can quickly and accurately remove TiN and dry etching residues during wet etching, and does not damage a low-k layer and a metal conductor layer. In addition, the etching composition has high stability, and tests show that the repeatedly used etching composition still has certain oxidation capacity, etching selectivity, pH value and other characteristics, and is very suitable for being applied to a recycling process.

Drawings

FIGS. 1A-1D show the results of stability tests for etching compositions of the invention, TiN etch rates, Cu and Co etch rates, H₂O₂The concentration and pH change with time.

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and those skilled in the art can easily understand the advantages and effects of the present invention from the disclosure of the present specification.

It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are only used for matching with the disclosure of the specification to understand and read by those skilled in the art, and are not used to limit the practical limit conditions of the present invention, so they have no technical significance, and any structural modification, ratio relationship change or size adjustment should still fall within the scope of the present invention without affecting the function and the achievable purpose of the present invention. In addition, the words such as "a" and "an" are used in this specification for clarity of description only and are not intended to limit the scope of the invention, and changes or modifications in the relative relationship may be made without substantial change in the technical content. Moreover, all ranges and values herein encompass edges and may be combined. Any number or point falling within the ranges set forth herein, e.g., any integer, may be considered a minimum or maximum value to derive a lower range, etc.

The etching composition of the present invention comprises an alkaline compound, a chelating agent, a corrosion inhibitor and a solvent, and may further comprise an organic acid compound, an oxidizing agent and an additive.

The chelating agent may complex free metal ions in the composition. The metal ions may come from the metal conductor layer, and the metal ions affect the oxidizing agent, so that the oxidizing agent is easily decomposed, and the oxidizing and etching capabilities of the etching composition are affected.

The corrosion inhibitor is a component containing chemical elements such as nitrogen, sulfur, oxygen and the like, and is generally a heterocyclic compound, and nitrogen, sulfur, oxygen and other atoms on the molecules of the corrosion inhibitor carry lone pair electrons and can form coordinate bonds with oxides on the surface of the metal, so that the corrosion inhibitor is adsorbed on the surface of the metal, and a passivation layer can be formed on the surface to prevent the metal from being corroded due to direct contact with a wet etching solution.

The etching composition of the 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, because of the high instability of the oxidizing agent over time, the concentrated composition may not contain an oxidizing agent, but the oxidizing agent is added together during dilution to complete the final composition. The oxidizing agent may be added to the diluent, introduced with the diluent to the concentrated composition, or may be added to the diluted composition.

In the following, the present invention is explained in detail by way of examples of embodiments. However, the interpretation of the present invention should not be limited to the description of the following examples.

The following components were selected for each of examples 1 to 17 of the present invention:

solvent: diethylene glycol butyl ether (BDG), dimethyl sulfoxide (DMSO), and diethylene glycol Diethyl Ether (DEDG).

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

Chelating agent: cyclohexanediaminetetraacetic acid (CDTA) and hydroxyethylidenediphosphonic acid (HEDP).

Organic acid compound (b): citric acid, glutaric acid, malic acid and maleic acid.

Basic compound (b): ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTMAH), 4- (2-hydroxyethyl) -morpholine (AFR-240), and 4-methylmorpholine N-oxide (NMMO).

The dosage ratios of the ingredients in the examples and the results of the tests are shown in Table 1 below.

Among them, the TiN etching rate was tested using a commercially available wafer coated with a TiN thin film by Physical Vapor Deposition (PVD). The thickness of the TiN film is 100nm, the TiN film is cut into the size of 2cm x 2cm, and the TiN film is etched by a soaking method. The beaker with the etching composition is placed in a water bath, and the etching test can be carried out after the temperature of the etching composition is raised to 60 ℃, and the etching time is 1 to 3 mins. And measuring the thickness difference of the TiN film before and after etching by a four-point probe measuring instrument, and dividing the thickness difference by the etching time to obtain the TiN etching rate.

The etching rates of Cu and Co were tested using a wafer plated with a Cu thin film by electrochemical plating (ECP) and a wafer plated with a Co thin film by PVD, respectively. The thickness of the Cu film is 2000nm, the thickness of the Co film is 40nm, the Cu film and the Co film are cut into the size of 2cm x 2cm, the Cu film and the Co film are etched by a soaking method after being pretreated by oxalic acid, and the etching time is 10 mins. The concentrations of Cu and Co ions in the etching composition before and after etching were measured by inductively coupled plasma mass spectrometry (ICP/MS) and converted into elution amounts to obtain the etching rates of Cu and Co, and the calculation formula is shown in the following formula I.

In formula I, C is a metal ion concentration (ppb) measured by ICP/MS, W is a weight (g) of the etching composition, D is a density of the metal: cu of 8.93g/cm³Co of 8.9gcm³And A is the area of the wafer (cm)²) And T is etching time (min).

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

As can be seen from Table 1, the etching composition of the present invention can rapidly remove TiN, has an etching rate of more than 12nm/min, has excellent etching selectivity, and the TiN/Cu etching selectivity has a level of at least 85, and the TiN/Co etching selectivity also has a level of at least 100.

Then, carrying out stability test on the etching composition, carrying out TiN etching test every 2.4hrs, wherein the TiN etching time is 1-3 mins each time, adding water at proper time to maintain the same weight of the etching composition, and carrying out the etching test for 24 hrs; the etching test of Cu and Co was performed every 4.8hrs with a Cu and Co etching time of 10mins, and water was added at appropriate times to maintain the same etching composition weight for 24 hrs. H of etching composition₂O₂And the pH value is also measured along with the time number.

The stability test results are shown in fig. 1A to 1D. FIG. 1A shows the change of TiN etching rate with time (etching times), the TiN etching rate gradually decreases with the increase of the etching times, and the etching rate after 24 hours is about 50% of the etching rate of the initial etching, and can still maintain the level above 12 nm/min; fig. 1B shows the Cu and Co etch rates as a function of time (number of etches), showing that the Cu and Co etch rates after the second etch are not significantly changed from the Cu and Co etch rates of the first etch, and are maintained at a lower etch rate level, wherein the Cu etch rate after 24 hours is below 0.2nm/min and the Co etch rate after 24 hours is below 0.1 nm/min. The results of FIG. 1A and FIG. 1B show that the etching composition of the present invention can maintain excellent TiN/Cu selectivity and TiN/Co selectivity after recycling.

FIG. 1C is H of an etching composition₂O₂Concentration change with time (number of etching times), H with increasing number of etching times₂O₂Concentration gradually decreased, H after 24 hours₂O₂Concentration of H about the first etch₂O₂Concentration 70%, the same trend as TiN etch rate; while fig. 1D shows the pH of the etching composition as a function of time (number of etching times), the pH decreased slowly as the number of etching times increased, and the pH was slightly different from that of the initial etching after 24 hours. As can be seen from the results of fig. 1A to 1D, the etching composition of the present invention has high stability, and the repeated use of the etching composition still maintains certain properties of oxidation ability, etching selectivity, pH, etc., and is very suitable for the recycling process.

Claims

1. An etching composition for selectively etching a titanium nitride hardmask, comprising:

a basic compound;

a chelating agent;

a corrosion inhibitor; and

a solvent, a water-soluble organic solvent,

characterized in that the alkaline compound comprises 1 to 25 wt.%, the chelating agent comprises 0.1 to 2 wt.%, and the corrosion inhibitor comprises 1 to 7 wt.%, based on the total weight of the alkaline compound, the chelating agent, the corrosion inhibitor, and the solvent.

2. The etching composition of claim 1, further comprising an oxidizing agent.

3. The etching composition of claim 2, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, ammonium persulfate, perbenzoic acid, FeCl₃、FeF₃、Fe(NO₃)₃、Sr(NO₃)₂、CoF₃、MnF₃Periodic 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, potassium nitrate, potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium perchlorate, tetramethylammonium iodate, tetramethylammonium periodate, tetramethylammonium perborate, tetramethylammonium persulfate, tetrabutylammonium peroxymonosulfate, ferric nitrate, urea hydrogen peroxide, peracetic acid, 1, 4-benzoquinone, toluquinone, dimethyl-1, 4-benzoquinone, tetrachlorobenzoquinone, and alloxan.

4. The etching composition of claim 3, wherein the oxidizing agent is hydrogen peroxide.

5. The etching composition of claim 4, wherein the hydrogen peroxide solution comprises 10 to 20 wt% based on the weight of the etching composition.

6. The etching composition of claim 1, wherein the basic compound is selected from ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTMAH), 4- (2-hydroxyethyl) -morpholine (AFR-240), 4-methylmorpholine N-oxide (NMMO), trimethylphenylammonium hydroxide (TMPAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide (TPAH), tetramethylammonium hydroxide (TMAH), benzyltriethylammonium hydroxide (BTEAH), potassium hydroxide, tetrabutylphosphine oxide (TBPH), (2-hydroxyethyl) trimethylammonium hydroxide, (2-hydroxyethyl) triethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, (2-hydroxypropyl) trimethylammonium hydroxide, and mixtures thereof, Diethyldimethylammonium hydroxide (DEDMAH), tris (2-hydroxyethyl) methylammonium hydroxide (THEMAH), ammonium hydroxide, choline hydroxide, 1,3, 3-tetramethylguanidine, guanidine carbonate, arginine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and cysteine.

7. The etching composition of claim 1, further comprising an organic acid compound, wherein the organic acid compound comprises less than 15 wt% of the total weight of the etching composition.

8. The etching composition of claim 7, wherein the organic acid compound is at least one selected from the group consisting of 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, asparagine, aspartic acid, glutamic acid, valine, lysine, and maleic acid.

9. The etching composition of claim 1, wherein the chelating agent is selected from the group consisting of cyclohexanediaminetetraacetic acid (CDTA), hydroxyethylenediphosphonic acid (HEDP), aminoacetic acid, iminodiacetic acid, nitrilotriacetic acid, glutamic acid, pyridine-2-carboxylic acid, ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), ammonium bromide, ammonium chloride, phosphonic acid, diethylenetriaminepentaacetic acid (DTPA), diethylenetriaminepenta (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTMP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA), ethylenediamine disuccinic acid, propylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) (EDTMPA), aminotris (methylenephosphonic acid), Pentamethyldiethylenetriamine (PMDETA), tetraethylenedimethyl ether, boric acid, 2, 4-pentanedione, Imidazole and algaecide.

10. The etching composition of claim 1, wherein the corrosion inhibitor is selected from Benzotriazole (BTA), tolyltriazole (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, halobenzotriazoles and halides F, Cl, Br or I, 5-nitrobenzotriazole, benzotriazole carboxylic acid, 1-amino-1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, benzotriazole derivatives thereof, and mixtures thereof, 3-amino-5-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, and the like, 2-aminobenzothiazole, 2-mercaptobenzothiazole, benzimidazole, 2-aminobenzimidazole, imidazole, 1-methylimidazole, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, methyltetrazole, pentylenetetrazole, 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, diaminemethyltriazine, dimethyltriazine, dimethylimidazole, dimethyltetrazole, and the like, 2, 4-diamino-6-methyl-1, 3, 5-triazine, 2-amino-5-ethyl-1, 3, 4-thiadiazole, 5-amino-1, 3, 4-thiadiazole-2 thiol, 1, 3-dimethyl-2-imidazolidinone, 2-benzylpyridine, imidazolinethione, sodium dodecyl sulfate, succinimide, adenine, adenylic acid, saccharin, uric acid, and benzoin oxime.

11. The etching composition of claim 1, wherein the solvent is selected from the group consisting of diethylene glycol butyl ether (BDG), dimethyl sulfoxide (DMSO), sulfolane, diethylene glycol Diethyl Ether (DEDG), dimethyl sulfone, 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, hexylene glycol, butylene carbonate, ethylene carbonate, propylene carbonate, choline bicarbonate, dipropylene glycol, tetramethylene sulfone, tetrahydrofuran methanol (THFA), 1, 2-butanediol, 1, 4-butanediol, tetramethylurea, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl 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, dipropylene 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, ethyl perfluorobutyl ether, methyl perfluorobutyl ether, alkyl carbonate, 4-methyl-2-pentanol, and water.

12. The etching composition of claim 1, further comprising at least one of a radical inhibitor, a radical scavenger.

13. The etching composition of claim 1, wherein the etching composition has a pH of between 6.5 and 9.5.

14. The etching composition of claim 2, wherein the etching composition has a pH of between 6 and 8.5.

15. The etching composition according to claims 1 to 14, wherein the etching rate of titanium nitride at 60 ℃ is 12nm/min or more.

16. The etching composition according to claims 1 to 14, which has an etching rate of 0.3nm/min or less for etching copper at 60 ℃.

17. The etching composition according to claims 1 to 14, which has an etching rate of 0.4nm/min or less at 60 ℃.

18. The etching composition as claimed in claims 1 to 14, wherein the ratio of the etching rate of titanium nitride to the etching rate of copper nitride is 85 or more.

19. The etching composition as claimed in claims 1 to 14, wherein the ratio of the etching rate for etching titanium nitride to the etching rate for etching cobalt is 100 or more.

20. An etching composition as claimed in claims 1 to 14 for use in a recycling process for recycling after selective etching of titanium nitride.