TWI795572B - 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 particularly, 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, the market also requires smaller-sized microelectronic devices. Size reduction and integrated circuit (IC) reliability have become extremely important issues in the field of IC assembly technology.

Dual damascene (dual damascene) structure process is the process of metallizing the back end of microelectronic devices to form interconnects. It is made in a damascene way together with through holes and metal wires. It is formed on the cover with a metal hard mask. On the low dielectric constant (low-k) material layer of the metal conductor layer (such as cobalt or copper), etch the low-k layer according to the metal hard mask to form trenches and holes that expose part of the metal conductor layer, and finally remove the Metal hard mask and diffusion barrier layer deposition and metal deposition. A metal hard 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 remove the residue of dry etching at the same time. The residue may be polymer or polymer combined with metal. If the residue is not removed, it will cause wire The resistance value increases, especially in the part of the hole. In addition, during wet etching, the exposed metal conductor layer and low-k layer below 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 semi-aqueous solution containing fluorine. Through the reaction of fluorine ions and the surface of the wafer, the oxides on the surface are micro-etched, and the organic matter is detached from the surface of the wafer to achieve the purpose of cleaning. This product has already been widely used in the old generation copper process on the market. However, because fluorine ions can etch low-k materials, after the semiconductor manufacturing process continues to shrink, fluorine ion micro-etching will increase the size of the originally designed trenches and holes, resulting in misalignment of copper wires, which will cause components to fail. The opportunity becomes larger, which does not meet the requirements of advanced semiconductor manufacturing processes, and the activity of fluorine ions is high, which makes it difficult to inhibit the corrosion of the underlying copper.

The next generation of dry post-etch cleaning solutions are semi-water or aqueous solutions containing hydrogen peroxide. It utilizes the oxidation ability of hydrogen peroxide to oxidize organic matter to make it have a hydrophilic functional group to increase the solubility of organic matter in water. In addition, the solvent can swell organic matter so that it is separated from the surface of the wafer and exists in the solution in a dissolved or suspended form. , and then in the water washing stage, the residue and cleaning solution 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 opening of the trenches and holes for the subsequent diffusion barrier layer deposition and copper electroplating process. Subsequent chemical mechanical polishing (CMP) is used to remove the copper and diffusion barrier layer metal on the surface, and the TiN hard mask is also removed during the CMP process.

However, the application of novel metal materials as diffusion barrier layers in advanced semiconductor processes creates 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 has a high removal ability for the TiN hard mask and dry etching residues, and at the same time does not corrode the bottom metal conductor copper or cobalt.

In order to solve the above problems, the present invention provides an etching composition for selectively etching a titanium nitride hard mask, which composition includes: an alkaline compound, a chelating agent, a corrosion inhibitor, and a solvent, wherein the alkali Based on the total weight of the chemical 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 accounts for 1 to 2% by weight. 7% by weight.

In some specific implementation aspects, 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, the chelating agent system 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 wt%, and the corrosion inhibitor system can account for 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7% by weight.

The etching composition may further include an oxidizing agent, wherein the oxidizing agent includes but 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, iodine Ammonium acid, 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 hydroperoxide, peracetic acid, 1,4-benzoquinone, toluoquinone, dimethyl-1,4-benzoquinone, tetrachlorobenzene quinones and alloxan. In a specific embodiment, the oxidizing agent is hydrogen peroxide, based on the weight of the etching composition, the hydrogen peroxide solution accounts for 10 to 20% by weight, 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 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), tetrapropylhydrogen Ammonium Oxide (TPAH), Tetramethylammonium Hydroxide (TMAH), Benzyltriethylammonium Hydroxide (BTEAH), Potassium Hydroxide, Tetrabutylphosphine Hydroxide (TBPH), (2-Hydroxyethyl)tri Methylammonium hydroxide, (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, (2-hydroxypropyl)trimethylammonium hydroxide, diethylammonium hydroxide Dimethylammonium Hydroxide (DEDMAH), Tris(2-Hydroxyethyl)methylammonium 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, 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), glycine, iminodiacetic acid, nitrilotriacetic acid, glutamic acid, pyridine- 2-Formic 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, ethylenediamine Disuccinic acid, propylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) (EDTMPA), aminotris(methylenephosphonic acid), pentamethyldiethylenetriamine (PMDETA), tetra Glyme, boric acid, 2,4-pentanedione, imidazole, and algicide.

The corrosion inhibitors include but are 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, halobenzotriazole and halo=F, Cl, Br or I, 5-nitrobenzotriazole, benzotriazole Azole 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-amine Base-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, methyl tetrazole, pentyl tetrazole, 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-2thiol, 1,3-dimethyl-2-imidazolidinone, 2-benzylpyridine, imidazolinthione, sodium lauryl sulfate, succinimide, adenine, adeno glycosides, saccharin, uric acid and benzoin oxime.

The solvent includes but not limited to diethylene glycol butyl ether (BDG), dimethylsulfoxide (DMSO), cyclobutylene, diethylene glycol diethyl ether (DEDG), dimethylsulfide, dimethylsulfide, 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, Tetrahydrothiophene Urea, tetrahydrofuran methanol (THFA), 1,2-butanediol, 1,4-butanediol, tetramethylurea, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol Alcohol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol 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 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 Fluorobutyl ether, alkyl carbonate, 4-methyl-2-pentanol and water.

The etch composition may further include additives such as free radical inhibitors and free radical scavengers.

In a specific embodiment, 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 oxidizing agent, 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 embodiment, the etching rate of the etching composition for etching titanium nitride at 60° C. is above 12 nm/min, the etching rate for copper is below 0.3 nm/min, and the etching rate for cobalt is 0.4 nm/min. below nm/min.

In a specific implementation aspect, the etching rate ratio of the etching composition for etching titanium nitride to the etching rate for etching copper, that is, the etching selectivity for titanium nitride relative to copper is above 85, and the etching composition for etching The ratio of the etching rate of titanium nitride to the etching rate of cobalt, that is, the etching selectivity of the etching composition for titanium nitride relative 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 can be more than 90, 95, 100, 110, 120, 130, 140, 150, 160, 170 or more, according to According to actual needs, the most suitable ratio of the etching rate of etching titanium nitride to the etching rate of etching copper is selected. 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, more preferably 110, 120, 130, 140, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, and above 650, select the most appropriate ratio of the etching rate of etching titanium nitride to the etching rate of cobalt according to actual needs.

In one embodiment, the etch composition can be used in a recycling process for recycling 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 etching composition can still maintain certain characteristics such as oxidation ability, etching selectivity and pH value after repeated use, and is very suitable for use in recycling processes.

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

The following describes the implementation of the present invention by means of specific implementations, 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 attached to this specification are only used to match the content disclosed in the specification, for the understanding and reading of those familiar with this technology, and are not used to limit the implementation of the present invention Therefore, it has no technical substantive meaning. Any modification of structure, change of proportional relationship or adjustment of size shall still fall within the scope of this invention without affecting the effect and purpose of the present invention. The technical content disclosed by the invention must be within the scope covered. At the same time, words such as "one" and other words quoted in this specification are only for the convenience of description, and are not used to limit the scope of the present invention. The change or adjustment of the relative relationship has no substantial change in the technical content. Below, it should also be regarded as the scope where the present invention can be implemented. Furthermore, all ranges and values herein are inclusive and combinable. Any numerical value or point, such as any integer, falling within a range stated herein may be used as a minimum or maximum value to derive lower ranges and the like.

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

Chelating agents 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, making it easy to decompose, resulting in the oxidation of the etching composition and affecting the etching ability.

Corrosion inhibitors are composed of chemical elements such as nitrogen, sulfur, and oxygen. They are generally heterocyclic compounds. The nitrogen, sulfur, and oxygen atoms on the corrosion inhibitor molecules have lone pairs of electrons, which can interact with the oxidation of metal surfaces. The substance forms a coordination bond, 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 being corroded by direct contact with the wet etching solution.

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 oxidizing agent is highly unstable over time, the concentrated composition may not contain the oxidizing agent, and the oxidizing agent may be added together during dilution to complete the final composition. The oxidizing agent can be added to the diluent, introduced with the diluent to the concentrated composition, or it can be added to the diluted composition.

Hereinafter, the present invention is described in detail through examples of embodiments. However, the interpretation of the present invention should not be limited to the description of the following examples.

Embodiments 1 to 17 of the present invention select the following ingredients for use respectively:

Solvents: diethylene glycol butyl ether (BDG), dimethylsulfoxide (DMSO) and diethylene glycol diethyl ether (DEDG).

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

Chelating agents: cyclohexanediaminetetraacetic acid (CDTA) and hydroxyethylenediphosphonic acid (HEDP).

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

Basic compounds: ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium 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.

Wherein, the TiN etch 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. Put the beaker containing the etching composition in a water bath, and perform the etching test after the temperature of the etching composition rises to 60° C., and the etching time is 1 to 3 minutes. The TiN etching rate can be obtained by measuring the difference in the thickness of the TiN film before and after etching with a four-point probe measuring instrument, and dividing it by the etching time.

The etch rates of Cu and Co were tested using a wafer coated with a Cu thin film by electrochemical plating (ECP) and a wafer coated with a Co thin film by PVD. The thickness of the Cu thin film is 2000nm, the thickness of the Co thin film is 40nm, cut into 2cm x 2cm size, pretreatment with oxalic acid and then etching of the Cu thin film and Co thin film by soaking method, 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, and 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 etch selectivity of TiN/Cu is calculated by TiN etch rate/Cu etch rate; the etch selectivity of TiN/Co is calculated by TiN etch rate/Co etch 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 more than 12nm/min, and has excellent etching selectivity. Its TiN/Cu etching selectivity has at least a level above 85, while TiN/Cu The Co etching selectivity also has a level of at least 100 or higher.

Then carry out the stability test of the etching composition of the present invention, conduct a TiN etching test every 2.4hrs, each TiN etching time is 1 to 3mins, and add water in time to maintain the same etching composition weight, etch test to 24hrs The etching test of Cu and cobalt is carried out every 4.8hrs, and the etching time of Cu and Co is 10mins each time, and water is added in time to maintain the same weight of the etching composition, and the etching test lasts to 24hrs. H ₂ O ₂ and pH of the etching composition were also measured over time.

Stability test results are shown in Figures 1A to 1D. Figure 1A is the change of TiN etching rate with time (etching times). As the etching times increase, 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 is the change of Cu and Co etching rate with time (etching times), and the results show that the Cu and Co etching rate after the second etching has no difference with respect to the Cu and Co etching rate of the first etching. Significant changes were maintained at a relatively low level of etching rate, wherein the etching rate of Cu after 24 hours was below 0.2 nm/min, and the etching rate of Co after 24 hours was below 0.1 nm/min. Combining the results of FIG. 1A and FIG. 1B, it shows that the etching composition of the present invention can still maintain excellent TiN/Cu selectivity and TiN/Co selectivity after recycling.

Figure 1C shows the change of the _H2O2 concentration of the etching composition with time (etching times). As the etching times increase _, the _{H2O2 concentration} gradually decreases. _{The H2O2 concentration} after 24 hours is about the same as the initial etching The concentration of H ₂ O ₂ is 70%, the trend is the same as the etching rate of TiN; and the pH value of the etching composition changes with time (etching times) in Figure 1D. As the etching times increase, the pH value decreases slowly. After 24 hours The pH is only slightly different from that of the initial etch. From the results in Figure 1A to Figure 1D, it can be seen that the etching composition of the present invention has high stability, and the etching composition still retains certain oxidation ability, etching selectivity, and pH value after repeated use, and is very suitable for recycling. In process.

Claims (13)

A concentrated etching composition for selectively etching a titanium nitride hard mask without adding an oxidant, comprising: an alkaline compound; a chelating agent; a corrosion inhibitor; an organic acid compound; and a solvent, wherein the concentrated etching composition Based on the total weight of the substance, the basic compound accounts for 1 to 25% by weight, the chelating agent accounts for 0.1 to 2% by weight, the organic acid compound accounts for more than 0.5 to 15% by weight, and the corrosion inhibitor accounts for 1% by weight. to 7% by weight, and the pH of the concentrated etching composition is between 6.5 and 9.5. Such as the concentrated etching composition of item 1 of the scope of the patent application, wherein the basic compound is selected from ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylhydrogen Ammonium oxide (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, tetrabutylammonium hydroxide Phosphine 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, hydrogen At least one of the group consisting of choline oxide, 1,1,3,3-tetramethylguanidine, guanidine carbonate, arginine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine and cysteine . Such as the concentrated etching composition of claim 1, wherein the organic acid compound is selected from 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, valamine At least one of the group consisting of acid and lysine. Such as the concentrated etching composition of item 1 of the scope of the patent application, wherein the chelating agent is selected from cyclohexanediamine tetraacetic acid (CDTA), hydroxyethylene diphosphonic acid (HEDP), aminoacetic acid, imino di Acetic acid, nitrilotriacetic acid, glutamic acid, pyridine-2-carboxylic acid, ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), ammonium bromide, ammonium chloride, phosphonic acid, di Ethylenetriaminepentaacetic 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), aminotris(methylenephosphonic acid) , at least one of the group consisting of pentamethyldiethylenetriamine (PMDETA), tetraglyme, boric acid, 2,4-pentanedione, imidazole and algicide. Such as the concentrated etching composition of item 1 of the scope of the patent application, 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, halobenzotriazole and halo=F, Cl, Br or 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 Azole, 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-methylbenzene And imidazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, methyl tetrazole, pentyl tetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole , 5-mercapto 1-methyltetrazole, 1,5-pentamethylene tetrazole, 1-phenyl-5-mercaptotetrazole, 1-phenyl-1H-tetrazole-thiol, 8-hydroxyquinoline phenoline, 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-2thiol, 1,3-dimethyl-2-imidazolidinone , 2-benzylpyridine, imidazoline thione, sodium lauryl sulfate, succinimide, adenine, adenylic acid, saccharin, uric acid and benzoin oxime at least one of the group. Such as the concentrated etching composition of item 1 of the scope of the patent application, wherein the solvent is selected from diethylene glycol butyl ether (BDG), dimethylsulfoxide (DMSO), cyclobutylene, diethylene glycol diethyl ether ( DEDG), dimethylsulfide, dimethylsulfide, 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 Esters, 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 mono Butyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propanediol Alcohol 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-propyl ether Butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, 2,3-dihydrodecafluoropentane, ethyl perfluorobutyl ether, methyl perfluorobutyl ether, alkyl carbonate, 4-methyl At least one of the group consisting of -2-pentanol and water. Such as the concentrated etching composition of claim 1, further comprising at least one of a free radical inhibitor and a free radical scavenger. The concentrated etching composition described in any one of items 1 to 7 of the scope of application, after being mixed with an oxidizing agent, the etching rate of etching titanium nitride is above 12nm/min under the condition of 60°C. The concentrated etching composition described in any one of items 1 to 7 of the patent claims, after being mixed with an oxidizing agent, can etch copper at a rate of 0.3nm/min or less at 60°C. For the concentrated etching composition described in any one of items 1 to 7 of the patent claims, after mixing with an oxidant, the etching rate for cobalt etching at 60°C is below 0.4nm/min. For the concentrated etching composition described in any one of items 1 to 7 of the patent claims, after mixing with an oxidizing agent, the ratio of the etching rate of etching titanium nitride to the etching rate of etching copper is more than 85. For the concentrated etching composition described in any one of items 1 to 7 of the patent claims, after it is mixed with an oxidizing agent, the ratio of the etching rate of etching titanium nitride to the etching rate of cobalt is more than 100. The concentrated etching composition as described in any one of items 1 to 7 of the patent claims can be used in a recycling process after being mixed with an oxidizing agent, so as to recover and reuse after selectively etching titanium nitride.

Images