Etching liquid composition for titanium-based metal film, titanium-based metal wiring and semiconductor element

Abstract

The present invention provides a titanium metal film etching liquid composition, a titanium metal wiring, and a semiconductor element, wherein the titanium metal film etching liquid composition contains an inorganic acid, a fluorine-containing compound, and a sulfate compound, and does not contain hydrogen peroxide and chloride, and the Y1 value and the Y2 value defined by specific mathematical formulas 1 and 2 are within specific ranges. The titanium metal film etching liquid composition of the present invention can minimize undercutting and residue generation.

Description

Technical Field

[0001] The present invention relates to a titanium-based metal film etching liquid composition, and more particularly to a titanium-based metal film etching liquid composition which minimizes undercut and residue generation, has a high etching rate, and is excellent in the cumulative number of sheets processed and copper corrosion resistance. Background Art

[0002] In recent years, as semiconductors have become more highly integrated, smaller, and lighter, flip chip bonding has become more commonly used as a semiconductor chip packaging method.

[0003] The flip chip bonding method is a packaging method in which bumps are formed on a wafer to form solder bumps that function as lead frames, and then the wafer is directly packaged or connected to a printed circuit board (PCB).

[0004] The flip chip bonding method is specifically carried out through the wafer bump processing process, which is generally composed of the under bump metallurgy (UBM) manufacturing process and the solder bump processing process. As solder bumps, tin-silver (Sn-Ag) alloy is mostly used, but there are also many cases where gold (Gold) bumps are used. The technology used in UBM manufacturing is a dry plating method using sputtering or a wet plating method using electroless plating. UBM is to form a titanium-based metal film from titanium or a titanium alloy on a substrate, and then form a copper-based metal film from copper or a copper alloy on the above-mentioned titanium-based metal film, and then make a photoresist layer thereon, and after exposing and developing to form a specific pattern, the upper copper-based metal film and the lower titanium-based metal film are etched in sequence for manufacturing.

[0005] In such a UBM formation process, it is necessary to selectively etch the titanium-based metal film to minimize the titanium residual film.

[0006] Korean Patent Publication No. 10-2016-0029094 discloses an etching solution composition for titanium-based metal films, which includes hydrogen peroxide, a phosphonic acid chelating agent having a nitrogen atom in its structure, an alkali metal hydroxide, and an organic acid having at least one hydroxyl group and at least three carboxyl groups.

[0007] However, the titanium-based metal film etching solution composition described above may induce undercutting due to hydrogen peroxide, which may cause a signal failure problem on a semiconductor wafer.

[0008] Therefore, it is necessary to develop an etching solution composition for a titanium-based metal film that can minimize undercut and residue generation.

[0009] In addition, there is a need to develop an etching liquid composition for a titanium-based metal film that has a high etching rate, improves the number of sheets processed and can improve the process margin, and is also excellent in corrosion resistance of a copper-based metal film. Summary of the invention

[0010] Issues to be solved

[0011] An object of the present invention is to provide a titanium-based metal film etching liquid composition which minimizes undercut and residue generation, has a high etching rate, and is excellent in the cumulative number of sheets processed and copper corrosion resistance.

[0012] Another object of the present invention is to provide a titanium-based metal wiring formed using the above-mentioned titanium-based metal film etching solution composition.

[0013] Still another object of the present invention is to provide a semiconductor element including the titanium-based metal wiring.

[0014] Solution to the problem

[0015] On the one hand, the present invention provides an etching solution composition for titanium-based metal films, which comprises an inorganic acid, a fluorine-containing compound and a sulfate compound, wherein the Y1 value defined by the following mathematical formula 1 is 0.14 to 0.25, the Y2 value defined by the following mathematical formula 2 is 70 to 105, and does not contain hydrogen peroxide and chloride.

[0016] [Mathematical formula 1]

[0017] Y1=0.007X1+0.22X2+0.008X3

[0018] [Mathematical formula 2]

[0019] Y2=7.2X1-143.2X2+8.1X3+11.3X1X2-0.51X1X3+11.9X2X3

[0020] In the above formula,

[0021] X1 is the content of inorganic acid,

[0022] X2 is the content of fluorine-containing compounds,

[0023] X3 is the content of sulfate compounds.

[0024] In one embodiment of the present invention, the titanium-based metal film may include one or more films selected from a titanium film and a titanium alloy film.

[0025] In one embodiment of the present invention, the inorganic acid may include one or more selected from the group consisting of nitric acid and sulfuric acid.

[0026] In one embodiment of the present invention, the fluorine-containing compound may include at least one selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride.

[0027] In one embodiment of the present invention, the sulfate compound may include at least one selected from the group consisting of sodium sulfate, ammonium sulfate, potassium sulfate, copper sulfate, titanium sulfate, glucosamine sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate and ammonium hydrogen sulfate.

[0028] The titanium-based metal film etching solution composition according to one embodiment of the present invention may further contain an azole compound.

[0029] In one embodiment of the present invention, the azole compound may include one or more selected from the group consisting of 5-aminotetrazole, imidazole, benzimidazole, benzotriazole (BTA), tolyltriazole, adenine, guanine, 5-phenyltetrazole and 5-mercapto-1-methyltetrazole.

[0030] The titanium metal film etching liquid composition according to one embodiment of the present invention may contain 0.5 to 20 wt % of an inorganic acid, 0.05 to 2.0 wt % of a fluorine-containing compound, and 0.5 to 15 wt % of a sulfate compound relative to the total weight of the composition, and may contain water in an amount that makes the total weight of the composition 100 wt %.

[0031] The etching solution composition for titanium-based metal films according to one embodiment of the present invention may contain 0.5 to 20 wt % of an inorganic acid, 0.05 to 2.0 wt % of a fluorine-containing compound, 0.5 to 15 wt % of a sulfate compound and 0.1 to 2.0 wt % of an azole compound relative to the total weight of the composition, and may contain a remainder of water so that the total weight of the composition becomes 100 wt %.

[0032] In another aspect, the present invention provides titanium-based metal wiring formed using the above-mentioned titanium-based metal film etching solution composition.

[0033] In still another aspect, the present invention provides a semiconductor device including the titanium-based metal wiring.

[0034] In one embodiment of the present invention, the titanium-based metal wiring may form an under bump metallurgy layer.

[0035] Effects of the Invention

[0036] The titanium-based metal film etching liquid composition of the present invention can minimize undercutting and residue generation. In addition, the titanium-based metal film etching liquid composition of the present invention has a high etching rate, can improve the processing number characteristics and improve the process margin, and has excellent corrosion resistance of copper-based metal films. DETAILED DESCRIPTION

[0037] Hereinafter, the present invention will be described in more detail.

[0038] One embodiment of the present invention relates to an etching solution composition for titanium-based metal films, which comprises an inorganic acid (A), a fluorine-containing compound (B) and a sulfate compound (C), wherein the Y1 value defined by the following mathematical formula 1 is 0.14 to 0.25, the Y2 value defined by the following mathematical formula 2 is 70 to 105, and does not contain hydrogen peroxide and chloride.

[0039] [Mathematical formula 1]

[0040] Y1=0.007X1+0.22X2+0.008X3

[0041] [Mathematical formula 2]

[0042] Y2=7.2X1-143.2X2+8.1X3+11.3X1X2-0.51X1X3+11.9X2X3

[0043] In the above formula,

[0044] X1 is the content of inorganic acid,

[0045] X2 is the content of fluorine-containing compounds,

[0046] X3 is the content of sulfate compounds.

[0047] The titanium metal film etching solution composition according to one embodiment of the present invention can minimize undercut and residue generation because the Y1 value defined by the above formula 1 is 0.14 to 0.25 and the Y2 value defined by the above formula 2 is 70 to 105.

[0048] If the Y1 value defined by the above formula 1 is less than 0.14, the titanium-based metal film may be difficult to etch or the etching rate may be reduced, and residue may be generated. If it is greater than 0.25, undercut may be aggravated and pattern loss may occur.

[0049] If the Y2 value defined by the above-mentioned Mathematical Formula 2 is less than 70, residue may be generated, and if it is greater than 105, the etching rate of the titanium-based metal film may be slowed down, and undercut may be increased.

[0050] In addition, the titanium-based metal film etching liquid composition according to one embodiment of the present invention does not contain hydrogen peroxide and chloride, so undercutting can be minimized. In addition, the titanium-based metal film etching liquid composition according to one embodiment of the present invention does not contain a basic compound, so undercutting can be minimized.

[0051] Examples of the chloride include ammonium chloride and sodium chloride, and examples of the alkaline compound include potassium hydroxide and tetramethylammonium hydroxide.

[0052] In one embodiment of the present invention, the titanium-based metal film includes titanium as a constituent component of the film, and may include one or more films selected from a titanium film and a titanium alloy film.

[0053] The above-mentioned titanium alloy refers to an alloy of one or more metals selected from titanium, titanium silicide, titanium nitride and titanium oxide and one or more metals selected from aluminum (Al), magnesium (Mg), calcium (Ca), cobalt (Co), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W).

[0054] Hereinafter, the constituent components of the etching solution composition according to one embodiment of the present invention will be described in more detail.

[0055] Inorganic acid (A)

[0056] In one embodiment of the present invention, the inorganic acid (A) acts as an oxidant that helps the titanium metal film to be easily etched. In addition, the inorganic acid (A) acts to increase the solubility of titanium in the etching solution and increase the number of sheets that can be processed.

[0057] Examples of the inorganic acid include nitric acid and sulfuric acid, which may be used alone or in combination of two or more. Nitric acid and / or sulfuric acid are preferred because they minimize undercutting and residue generation.

[0058] The content of the inorganic acid may be 0.5 to 20% by weight, preferably 1 to 10% by weight, relative to the total weight of the composition. If the content of the inorganic acid is less than 0.5% by weight, the etching rate of the titanium metal film may be reduced, and the number of sheets processed may also be reduced. If the content of the inorganic acid is greater than 20% by weight, there is no advantage that matches the increase in content, which is not preferred from an economic point of view.

[0059] Fluorinated compounds (B)

[0060] In one embodiment of the present invention, the fluorine-containing compound (B) is a main component for etching the titanium-based metal film and plays a role in increasing the etching rate.

[0061] As the fluorine-containing compound, a compound that dissociates into fluorine ions or polyatomic fluorine ions in a solution can be used, for example, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, etc. These can be used alone or in a mixture of two or more.

[0062] The content of the fluorine-containing compound may be 0.05 to 2.0 weight %, preferably 0.1 to 1.0 weight %, relative to the total weight of the composition. If the content of the fluorine-containing compound is less than 0.05 weight %, the etching rate of the titanium metal film may be reduced, and if it is greater than 2.0 weight %, wiring loss may occur due to the increase in undercut, and silicon forming the metal wiring may be damaged.

[0063] Sulfate compounds (C)

[0064] In one embodiment of the present invention, the sulfate compound (C) serves to increase the removal rate of a natural oxide film formed on the surface of the titanium-based metal film and an oxide film that may be formed during etching.

[0065] As the sulfate compound, metal sulfate, ammonium sulfate, organic sulfate or hydrogen sulfate can be used, for example, sodium sulfate, ammonium sulfate, potassium sulfate, copper sulfate, titanium sulfate, glucosamine sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, ammonium hydrogen sulfate, etc. These can be used alone or in a mixture of two or more.

[0066] The content of the sulfate compound may be 0.5 to 15% by weight, preferably 1 to 10% by weight, relative to the total weight of the composition. When the content of the sulfate compound satisfies the above range, the oxide film removal effect can be reflected. If the content of the sulfate compound is less than 0.5% by weight, the oxide film removal is insufficient and titanium residue may be generated. If the content of the sulfate compound is greater than 15% by weight, the etching speed of the titanium-based metal film is slowed down, and the oxide film removal effect matching the increment will not be increased, so it is not preferred from an economic point of view.

[0067] Azole compound (D)

[0068] The titanium-based metal film etching solution composition according to one embodiment of the present invention may further contain an azole compound (D).

[0069] In one embodiment of the present invention, the azole compound (D) can be added according to the stacked structure of the metal film forming the metal wiring. When a wiring containing copper or a copper alloy is formed on the titanium-based metal film to be etched, the azole compound plays a role in preventing the wiring from being damaged.

[0070] Examples of the azole compound include 5-aminotetrazole, imidazole, benzimidazole, benzotriazole (BTA), tolyltriazole, adenine, guanine, 5-phenyltetrazole, 5-mercapto-1-methyltetrazole, etc. These may be used alone or in combination of two or more.

[0071] The content of the azole compound may be 0.1 to 2.0% by weight relative to the total weight of the composition. If the content of the azole compound is less than 0.1% by weight, the wiring containing copper or copper alloy may be damaged, and if it is greater than 2.0% by weight, there is no corrosion resistance improvement effect that matches the increase in weight, so it is not preferred from an economical point of view.

[0072] Water (E)

[0073] In addition, the etching solution composition of one embodiment of the present invention may contain water in an amount that makes the total weight of the composition 100% by weight. In the present invention, the water is not particularly limited, but is preferably deionized water used in semiconductor processes, and more preferably deionized water having a resistivity of 18 MΩ·cm or more, which reflects the degree of ion removal in water.

[0074] The "balance" of the present invention means the balance that makes the total weight of the composition of the present invention including the essential components and other additional components reach 100 weight%, and the meaning of the above "balance" does not limit the composition of the present invention to not containing additional components.

[0075] The titanium metal film etching liquid composition according to one embodiment of the present invention may contain 0.5 to 20 wt % of an inorganic acid, 0.05 to 2.0 wt % of a fluorine-containing compound, and 0.5 to 15 wt % of a sulfate compound relative to the total weight of the composition, and may contain water in an amount that makes the total weight of the composition 100 wt %.

[0076] The etching solution composition for titanium-based metal films according to one embodiment of the present invention may contain 0.5 to 20 wt % of an inorganic acid, 0.05 to 2.0 wt % of a fluorine-containing compound, 0.5 to 15 wt % of a sulfate compound and 0.1 to 2.0 wt % of an azole compound relative to the total weight of the composition, and may contain a remainder of water so that the total weight of the composition becomes 100 wt %.

[0077] The etching solution composition according to one embodiment of the present invention may further contain additives generally used in the art, such as metal ion chelating agents, corrosion inhibitors, and the like, in addition to the above-mentioned components.

[0078] The above-mentioned components used in the etching solution composition according to one embodiment of the present invention can be produced by a generally known method, and preferably have a purity that can be used in semiconductor processes.

[0079] The etching liquid composition according to one embodiment of the present invention can minimize undercut and residue generation in the process of forming metal wiring by etching a titanium-based metal film in a semiconductor manufacturing process.

[0080] Therefore, one embodiment of the present invention relates to a titanium-based metal wiring formed using the above-mentioned titanium-based metal film etchant composition.

[0081] The titanium-based metal wiring according to one embodiment of the present invention can be produced by using the above-mentioned etching solution composition and performing an etching process generally known in the art.

[0082] For example, the titanium metal wiring according to one embodiment of the present invention can be manufactured by performing an etching process including the following steps: forming a titanium metal film on a substrate; forming a photoresist film on the titanium metal film and then patterning the film; and etching the titanium metal film using the etching solution composition. Optionally, the process may further include forming a copper metal film on the titanium metal film.

[0083] One embodiment of the present invention relates to a semiconductor element including the titanium-based metal wiring.

[0084] The titanium-based metal wiring may form an under bump metallurgy (UBM) layer.

[0085] The semiconductor element of one embodiment of the present invention can be manufactured by a common process in the art, which includes, for example, a) a step of stacking titanium or a titanium alloy on a semiconductor wafer to form a titanium-based metal film; b) a step of stacking copper or a copper alloy to form a copper-based metal film; c) a step of applying a photosensitive substance; d) a step of exposing using a mask for bump formation; e) a step of selectively removing the photosensitive substance using a developer to form a predetermined pattern; f) a step of forming a solder bump on the formed pattern; g) a step of selectively etching the above-mentioned copper-based metal film to form a copper-based UBM layer; h) a step of selectively etching the above-mentioned titanium-based metal film to form a titanium-based UBM layer, and the titanium-based metal film etching liquid composition of the present invention is used in the above-mentioned step h).

[0086] The solder bumps may be formed by filling the formed pattern with copper (Cu) / tin-silver (Sn—Ag) by electroplating and then removing the remaining photosensitive material.

[0087] The etching may be performed using a wet etching method generally known in the art, such as a method using immersion, spraying, or both.

[0088] The present invention will be described in more detail below by way of examples, comparative examples and experimental examples. It is obvious to those skilled in the art that these examples, comparative examples and experimental examples are only used to illustrate the present invention, and the scope of the present invention is not limited thereto.

[0089] Examples 1 to 13 and Comparative Examples 1 to 10:

[0090] The components shown in the following Table 1 were mixed, and deionized water was added as the remainder so that the total amount was 100% by weight to prepare an etching solution composition (unit: % by weight).

[0091] At this time, the Y1 value defined by the following mathematical formula 1 and the Y2 value defined by the following mathematical formula 2 were calculated and shown in the following Table 1.

[0092] [Mathematical formula 1]

[0093] Y1=0.007X1+0.22X2+0.008X3

[0094] [Mathematical formula 2]

[0095] Y2=7.2X1-143.2X2+8.1X3+11.3X1X2-0.51X1X3+11.9X2X3

[0096] In the above formula,

[0097] X1 is the content of inorganic acid,

[0098] X2 is the content of the fluorine-containing compound, and X3 is the content of the sulfate compound.

[0099] [Table 1]

[0100]

[0101] A-1: Nitric acid

[0102] A-2: Sulfuric acid

[0103] B-1: Ammonium fluoride

[0104] B-2: Ammonium bifluoride

[0105] Chloride: Ammonium Chloride

[0106] Alkaline compound: Potassium hydroxide

[0107] C-1: Ammonium sulfate

[0108] C-2: Ammonium hydrogen sulfate

[0109] D-1: Benzotriazole

[0110] Experimental Example 1:

[0111] The etching rate, undercut, residual film removal ability, cumulative number of sheets processed, and copper corrosion resistance of the etching solution compositions of the examples and comparative examples prepared above were evaluated by the following method. The results are shown in Table 2 below.

[0112] (1) Titanium etching speed

[0113] A titanium film is deposited on a wafer substrate with a thickness of 50 nm, and a copper film is deposited on the titanium film with a thickness of 100 nm, and then a photoresist having a pattern of lines (Line): space (Space) = 2μm: 2μm is formed on the substrate by a photolithography process. Afterwards, only the copper film is etched to form a pattern without damaging the titanium film. The etching liquid compositions of the above-mentioned embodiments and comparative examples are respectively used to perform an etching process on the substrate having the above-mentioned pattern. During the etching process, the prepared substrate is immersed in a constant temperature bath, and the etching liquid composition is stirred at 400RPM, and the temperature of the etching liquid composition is set to about 30°C. The above-mentioned etching temperature can be changed as needed according to other process conditions and other factors.

[0114] After etching the substrate at 10 second intervals, the etched surface was confirmed using SEM (Hitachi, model: S-4700). The moment when there was no titanium on the wafer surface was determined as the etching time. It can be considered that the shorter the etching time, the faster the etching speed.

[0115] (2) Titanium undercut

[0116] After the substrate was immersed and etched for twice the etching time determined when evaluating the titanium etching rate and using the same evaluation method as when evaluating the titanium etching rate, the cross-sections of the titanium film and the copper film were confirmed using SEM (manufactured by Hitachi, Ltd., model name: S-4700).

[0117] The undercut (the extent to which the titanium film is etched laterally from the copper film) was confirmed in the cross-sectional SEM analysis results and evaluated based on the following evaluation criteria.

[0118] <Evaluation Criteria>

[0119] ◎: Almost no undercut (less than 0.2 μm)

[0120] ○: Slight undercut but no effect on pattern (greater than 0.2 μm and less than 0.25 μm)

[0121] △: There is undercut and the pattern is affected (greater than 0.25μm and less than 0.5μm)

[0122] ×: Pattern disappears (larger than 0.5 μm)

[0123] (3) Titanium residual film removal capability

[0124] After the substrate was immersed and etched for 1.2 times the etching time determined when evaluating the above-mentioned titanium etching rate and using the same evaluation method as when evaluating the above-mentioned titanium etching rate, the surface of the chip exposed by etching of titanium was observed using SEM (product of Hitachi, model name: S-4700) to confirm the titanium residual film.

[0125] The degree of removal of the titanium residual film on the wafer surface was evaluated according to the following evaluation criteria.

[0126] <Evaluation Criteria>

[0127] ◎: No residual film

[0128] ○: There is a little residual film but it is negligible

[0129] △: There is residual film and it may cause problems in subsequent processes

[0130] ×: Severe residual film and causing problems in subsequent processes

[0131] (4) Cumulative number of processed sheets

[0132] In order to evaluate the cumulative number of processed sheets, titanium powder (Sigma-Aldrich, size: <45 μm) was dissolved in the etching solution composition of the embodiment and the comparative example at a concentration of 50 ppm, 100 ppm, 150 ppm, and 200 ppm, respectively, and the titanium etching rate was evaluated in the same manner as when evaluating the above titanium etching rate. The maximum titanium powder dissolution concentration at which the etching time satisfies the etching time of the etching solution composition without dissolving titanium powder (the same result as when evaluating the above titanium etching rate) was obtained. It can be considered that as the concentration increases, more substrates can be processed.

[0133] (5) Copper corrosion resistance

[0134] In order to evaluate the degree of corrosion of copper wiring, a substrate was prepared in the same manner as when evaluating the titanium etching rate, and an etching process was performed using the etching solution compositions of the embodiment and the comparative example, respectively. During the etching process, the prepared substrate was immersed in a thermostatic bath, the etching solution composition was stirred at 400 RPM, and the treatment was performed at 50° C. for 10 minutes.

[0135] After etching, the copper surface was observed using SEM (manufactured by Hitachi, Ltd., model name: S-4700), and the copper corrosion resistance was evaluated according to the following evaluation criteria.

[0136] <Evaluation Criteria>

[0137] ◎: Copper has no corrosion

[0138] ○: Slight corrosion, but negligible

[0139] △: Corrosion may cause problems in subsequent processes

[0140] ×: Severe corrosion and causes problems for subsequent processes

[0141] [Table 2]

[0142]

[0143] As shown in Table 2, the etching liquid compositions of Examples 1 to 13, which contain an inorganic acid, a fluorine-containing compound, and a sulfate compound, have a Y1 value of 0.14 to 0.25 as defined by Mathematical Formula 1, and a Y2 value of 70 to 105 as defined by Mathematical Formula 2, and do not contain hydrogen peroxide and chloride, can minimize undercutting and residue generation. In addition, the etching liquid compositions of Examples 1 to 13 show a high etching rate, and are excellent in the cumulative number of sheets processed and copper corrosion resistance.

[0144] On the other hand, the etching solution compositions of Comparative Examples 1 to 3 which do not contain any of the inorganic acid, fluorine-containing compound and sulfate compound, Comparative Examples 4 to 6 which contain hydrogen peroxide or chloride, and Comparative Examples 7 to 10 in which the values ​​of Mathematical Formulas 1 and 2 are out of the specific ranges, make it difficult to etch the titanium-based metal film, or cause undercutting and residue generation.

[0145] Furthermore, the etching liquid composition of Comparative Example 5 containing hydrogen peroxide and a basic compound as main etching components had lower etching performance for titanium-based metal films than the etching liquid compositions of Examples 1 to 13, resulting in a decrease in the number of sheets processed.

[0146] In addition, the etching solution composition of Comparative Example 6 containing an inorganic acid and hydrogen peroxide as main etching components showed poor copper corrosion resistance.

[0147] The etching solution composition of Comparative Example 8 prolonged the etching completion time of the titanium-based metal film and also caused undercutting.

[0148] The above describes in detail the specific parts of the present invention. It is obvious to those skilled in the art that such specific technologies are only preferred embodiments, and the scope of the present invention is not limited thereto. Those skilled in the art should be able to make various applications and modifications within the scope of the present invention based on the above contents.

[0149] Therefore, the actual scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A titanium-based metal film etching liquid composition, comprising an inorganic acid, a fluorine-containing compound, a sulfate compound and an azole compound, wherein the Y1 value defined by the following mathematical formula 1 is 0.14 to 0.25, the Y2 value defined by the following mathematical formula 2 is 70 to 105, and the composition does not contain hydrogen peroxide, chloride and alkaline compounds, The inorganic acid comprises one or more selected from the group consisting of nitric acid and sulfuric acid, Mathematical formula 1 Y1=0.007X1+0.22X2+0.008X3 Mathematical formula 2 Y2=7.2X1-143.2X2+8.1X3+11.3X1X2-0.51X1X3+11.9X2X3 In the mathematical formulas 1 and 2, X1 is the content of the inorganic acid expressed in % by weight relative to the total weight of the composition, X2 is the content of the fluorine-containing compound expressed in % by weight relative to the total weight of the composition, X3 is the content of the sulfate compound expressed in % by weight relative to the total weight of the composition. 2 . The titanium-based metal film etching liquid composition according to claim 1 , wherein the fluorine-containing compound comprises at least one selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, sodium hydrogen fluoride and potassium hydrogen fluoride.

3. The titanium-based metal film etching liquid composition according to claim 1, wherein the sulfate compound comprises at least one selected from the group consisting of sodium sulfate, ammonium sulfate, potassium sulfate, copper sulfate, titanium sulfate, glucosamine sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate and ammonium hydrogen sulfate.

4. The titanium-based metal film etching liquid composition according to claim 1, wherein the azole compound comprises one or more selected from the group consisting of 5-aminotetrazole, imidazole, benzimidazole, benzotriazole BTA, tolyltriazole, adenine, guanine, 5-phenyltetrazole and 5-mercapto-1-methyltetrazole.

5. The titanium-based metal film etching liquid composition according to claim 1, comprising 0.5 to 20 wt% of an inorganic acid, 0.05 to 2.0 wt% of a fluorine-containing compound, 0.5 to 15 wt% of a sulfate compound, and 0.1 to 2.0 wt% of an azole compound, relative to the total weight of the composition, and comprising a balance of water such that the total weight of the composition becomes 100 wt%. 6 . A titanium-based metal wiring formed using the titanium-based metal film etching liquid composition according to claim 1 . 7 . A semiconductor element comprising the titanium-based metal wiring according to claim 6 . 8 . The semiconductor device according to claim 7 , wherein the titanium-based metal wiring forms an under bump metallization layer.

Images