KR20230113150A - Etchant composition for titanium-containing metal layer and etching method of titanium-containg metal layer using the same - Google Patents

Abstract

The present disclosure relates to an etchant composition for a metal film containing titanium and a method using the same, and it is possible to selectively etch a titanium-containing metal film without affecting other film qualities during a process of manufacturing semiconductors and display devices, thereby enabling a semiconductor manufacturing process. It is possible to increase productivity and reliability with improved etching characteristics.

Description

Metal film etchant composition containing titanium and etching method using the same

The present disclosure relates to an etchant composition for a metal film containing titanium and an etching method using the same, which can selectively etch a metal film containing titanium without affecting other film qualities in a process of manufacturing semiconductors and display devices It relates to an etchant composition and a method using the same.

The development of IT technology is accelerating the high performance and miniaturization of portable devices such as mobile phones, digital cameras, MP3 players, and USB memories. Moreover, the currently emerging smartphone is evolving toward a PC in the palm of your hand. These products require capabilities equal to those of existing personal computers (PCs), and to implement them, technology development for semiconductor devices satisfying ultra-high speed, large capacity, low power consumption, excellent performance and reliability is required.

A general semiconductor device is manufactured using one transistor and one capacitor as a unit cell, and the transistor of the semiconductor device generally has a MOS structure. A transistor having such a MOS structure includes a source electrode, a gate electrode, and a drain electrode structure, and a source electrode and a drain electrode terminal are formed on a silicon substrate, and current flows through these terminals. A voltage can be applied to the gate electrode terminal, and Al is mainly used as a metal in the uppermost layer, and silicon oxide is usually used as an oxide film under this metal layer. At this time, a titanium silicide (TiSi) film is generally used as a wiring to connect the above-described source electrode, gate electrode, and drain electrode for smooth flow of current between the electrodes.

The aforementioned titanium silicide film is formed by forming a titanium film on a substrate on which a source electrode, a gate electrode, and a drain electrode are formed, and annealing the formed titanium film. At this time, since the substrate is exposed to the atmosphere during the annealing process, the titanium film may react with oxygen or water vapor to form a titanium oxide film. The titanium oxide film thus formed may cause problems in the formation of the titanium silicide film due to strong bonding force, which may cause a short circuit. In addition, as semiconductor processes become more complicated and miniaturized, the problem of reliability deterioration due to such defects is becoming more serious.

Therefore, in order to prevent defects in the titanium silicide film, a process of etching the titanium film after the process of forming the titanium silicide film is essential. As a prior art, Patent Document 1 discloses an etching agent composition composed of hydrofluoric acid, periodic acid and sulfuric acid, and Patent Document 2 discloses hydrogen peroxide, a fluorine-containing compound, a compound containing an amino group and a carboxyl group at the same time, a nitrate compound, and a cyclic amine compound And it discloses an etchant composition composed of water. However, although these prior art attempts to efficiently etch a titanium film using fluorine, the effect is not sufficient, and metals other than titanium are simultaneously etched to cause damage to other film materials. In addition, an etchant composition using a buffer or high concentration of hydrogen peroxide has been proposed as a composition for selectively etching the titanium film, but damage to other film properties and over-etching of the titanium film still remain as homework.

Korean Patent Publication No. KR 10-2000-0028870 A Korean Patent Publication No. KR 10-2011-0019604 A

An object of the present disclosure is to provide a titanium-containing metal film etchant composition that etches a titanium-containing metal film at a high etching rate and at the same time has an anti-corrosion effect on other film materials stacked together.

An object of the present disclosure is to provide an etchant composition capable of stably etching a titanium-containing metal film without causing over-etching of the titanium-containing metal film and titanium residue during an etching process.

An object of the present disclosure is to provide a method of etching a titanium-containing metal film and a method of manufacturing a semiconductor device having improved productivity and reliability due to excellent etching characteristics of the titanium-containing metal film and anti-corrosion effect on other film materials.

In order to solve the above problems, the present disclosure may provide a metal film etchant composition containing titanium, including polyvalent phosphonic acid or a salt thereof, an inorganic base, a sulfonic acid-based polymer compound, hydrogen peroxide, and a residual amount of water.

In one embodiment of the present disclosure, the molecular weight of the sulfonic acid-based polymer compound may be 10,000 to 50,000 g/mol.

In one embodiment of the present disclosure, the sulfonic acid-based polymer compound may be included in an amount of 0.001 to 0.1% by weight.

In one embodiment of the present disclosure, the polyvalent phosphonic acid or salt thereof may be included in an amount of 0.01 to 5% by weight based on the total weight of the composition.

In one embodiment of the present disclosure, the inorganic base may be included in an amount of 0.1 to 3% by weight based on the total weight of the composition.

In one embodiment of the present disclosure, the sulfonic acid-based polymer compound may be represented by Formula 1 below.

[Formula 1]

(In Formula 1, R ¹ to R ³ are each independently selected from hydrogen, a C1-C7 linear or branched alkyl group, and a halogen element, L is a direct bond or C1-C10 alkylene, and -CH ₂ - may be replaced by C6-C12 aryl, -C(=O)-, -NR'-, or a combination thereof, wherein R' is hydrogen or C1-C7 alkyl, and n is 30 to 1000 is an integer of).

In one embodiment of the present disclosure, based on the total weight of the etchant composition, the polyvalent phosphonic acid or salt thereof is 0.01 to 3% by weight; 0.5 to 3% by weight of inorganic base; 0.001 to 0.1% by weight of the sulfonic acid-based polymer compound; 15 to 25% by weight of hydrogen peroxide; and a residual amount of water.

The etchant composition according to one embodiment of the present disclosure may further include a phosphate-based compound.

In one embodiment of the present disclosure, the phosphate-based compound may be included in an amount of 0.01 to 2% by weight based on the total weight of the etchant composition.

In one embodiment of the present disclosure, the weight ratio of the phosphate-based compound and the inorganic base may be 1:3 to 1:15.

The etchant composition according to one embodiment of the present disclosure may not include a quaternary ammonium salt.

The etchant composition according to one embodiment of the present disclosure may have a pH of 7 to 11.

In addition, the present disclosure may provide an etching method comprising the step of contacting the above-described etchant composition to a metal film containing titanium.

In addition, the present disclosure includes forming a metal film containing 　 titanium on a substrate on which a source electrode, a gate electrode and a drain electrode are formed; It is possible to provide a method for manufacturing a semiconductor device including; and etching the metal film with the etchant composition described above.

In the method of manufacturing a semiconductor device according to an embodiment of the present disclosure, after the step of forming the metal film containing titanium, one single film or two or more multilayer films selected from a silicon insulating film and a second metal film is formed on a portion of the metal film. Forming a; may further include.

In one embodiment of the present disclosure, the second metal film is a single film or a multilayer film including one or more metals selected from copper, molybdenum, tungsten, titanium, tantalum, chromium, neodymium, niobium, nickel, indium, and tin. can be

The method of manufacturing a semiconductor device according to one embodiment of the present disclosure may further include annealing the metal film containing titanium after the etching step.

According to the present disclosure, it is possible to selectively and quickly etch a metal film containing titanium, and to implement an anti-corrosion effect on another metal film including a silicon insulating film or a copper-based metal film.

According to the present disclosure, the pH change in the chemical solution is small and the problem of bubble generation due to decomposition of hydrogen peroxide can be solved by implementing stable etching characteristics. In addition, since it may not contain quaternary ammonium salts that may cause over-etching or residue on the metal film containing titanium by reaction with hydrogen peroxide, the metal film containing titanium may be etched more stably.

According to the present disclosure, by minimizing damage to an upper layer and a lower layer such as a silicon wafer, a silicon insulating layer, a copper-based metal layer, etc., subsequent processes can be stably performed.

In particular, according to the present disclosure, it is possible to provide a precisely controlled titanium film without damage to the above-described upper and lower films. Accordingly, it is possible to prevent defects in electrical device characteristics, which may be exemplified by short circuits, wiring defects, and luminance reduction that may occur during subsequent processes.

The etchant composition according to the present disclosure can be usefully used as an etching process through selective etching of a titanium film and a method of manufacturing a semiconductor device including such an etching process.

1 shows a scanning electron microscope (SEM) image of a copper film etched through the etchant composition of Comparative Example 1 according to the present disclosure.
2 shows a scanning electron microscope (SEM) image of a copper film in which etching has not occurred through the etchant composition of Example 1 according to the present disclosure.

Hereinafter, an etchant composition for etching a metal film containing titanium without affecting other metal films during the manufacturing process of semiconductors and display devices, an etching method using the same, and a semiconductor device manufacturing method will be described.

At this time, unless there is another definition in the technical terms and scientific terms used, they have meanings commonly understood by those of ordinary skill in the art to which this disclosure belongs, and the gist of the present disclosure in the following description and accompanying drawings Descriptions of well-known functions and configurations that may be unnecessarily obscure are omitted.

The singular form used herein may be intended to include the plural form as well, unless the context dictates otherwise.

In addition, units used in this specification without special mention are based on weight, and as an example, the unit of % or ratio means weight% or weight ratio, and unless otherwise defined, weight% is any one component of the entire composition It means the weight percent occupied in the composition.

Further, as used herein, numerical ranges include lower and upper limits and all values within that range, increments logically derived from the shape and breadth of the defined range, all values defined therebetween, and the upper limit of the numerical range defined in a different form. and all possible combinations of lower bounds. Unless otherwise specifically defined in the specification of the present disclosure, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

In addition, the term "includes" in this specification is an open description having the same meaning as the expression "includes", "includes", "has" or "characterized by", and is not further listed. It does not exclude any element, material or process.

In addition, as used herein, the term "substantially does not include" means that other elements, materials, or processes that are not listed together with a specified element, material, or process will allow for at least one basic and novel technical idea of the disclosure. It means that it can be present in an amount or degree that does not have an inconceivably significant effect.

Hereinafter, the present disclosure will be described in detail.

A metal film etchant composition containing titanium according to an embodiment of the present disclosure may include polyvalent phosphonic acid or a salt thereof, an inorganic base, a sulfonic acid-based polymer compound, hydrogen peroxide, and a residual amount of water.

Hereinafter, polyvalent phosphonic acid in the present specification may mean polyvalent phosphonic acid and/or polyvalent phosphonic acid salt. Specifically, the polyvalent phosphonic acid salt may be an alkali metal salt, an alkaline earth metal salt, or an ammonium salt of polyvalent phosphonic acid. Specific examples of the alkali metal salt or alkaline earth metal salt may be a sodium salt, potassium salt, calcium salt, or magnesium salt. In one embodiment of the present disclosure, the polyvalent phosphonic acid may include a polyvalent phosphonic acid sodium salt or a polyvalent phosphonic acid potassium salt.

In the titanium film etchant composition according to an embodiment of the present disclosure, the polyvalent phosphonic acid may be included in an amount of 0.005 to 5% by weight based on the total weight of the composition. Specifically, it may be 0.005 to 3% by weight, 0.01 to 3% by weight, 0.01 to 2.5% by weight, or 0.01 to 2% by weight. At this time, as it is included within the above content range, it is possible to provide an effect of improved etching rate of the titanium film and etching residue cleaning performance.

In the present disclosure, polyvalent phosphonic acid may suppress the activity of titanium ions by chelating titanium ions so that titanium ions dissolved in an etchant are not re-adsorbed to the substrate surface during etching. As polyvalent phosphonic acid is used, it is possible to minimize etching of other metal films that may occur when an excessive amount of organic acid is used for etching. The polyvalent phosphonic acid may be diphosphonic acid, triphosphonic acid, or tetraphosphonic acid. Specifically, for example of diphosphonic acid, it may be hydroxyethylidene diphosphonic acid.

In this case, the polyvalent phosphonic acid may include an alkali metal salt of polyvalent phosphonic acid.

In the etchant composition according to an embodiment of the present disclosure, the inorganic base may serve as a pH adjuster, and non-limiting examples of the inorganic base may be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and the like, Specifically, a hydroxide salt may be preferable.

The inorganic base may be included in 0.1 to 3.0% by weight, 0.5 to 2.8% by weight, 1.0 to 2.8% by weight, or 1.5 to 2.7% by weight based on the total weight of the metal film etchant composition. As it is used within the above-mentioned range, the generation of titanium residue is prevented and the effect of suppressing the etching of other metals is excellent.

The amount used may be adjusted depending on the pH, but if added in excess of the above-mentioned range relative to the total weight of the composition, it may not be appropriate because the etching rate and surface uniformity may decrease.

The sulfonic acid-based polymer compound may provide an effect of suppressing etching defects by preventing over-etching of the titanium film. The sulfonic acid-based polymer compound is a combination of repeating units including a sulfonic acid group, and may be a polymer of the same repeating unit or a copolymer of different repeating units. Forms of the copolymerization may include irregular copolymers, alternating copolymers, block copolymers, graft copolymers, and the like. The irregular copolymer has an irregular arrangement in which the arrangement order of the monomers, such as the first monomer and the second monomer, is not determined, and the alternating copolymer has a form in which each monomer is alternately arranged, and the block copolymer is Each monomer forms a block, and the graft copolymer is a type in which one type of monomer has a skeletal chain structure and another type of monomer is bonded in a branched form.

The molecular weight of the sulfonic acid-based polymer compound may be 10,000 to 80,000 g/mol, 10,000 to 50,000 g/mol, 15,000 to 40,000 g/mol, or 20,000 to 30,000 g/mol. Here, the molecular weight is based on the number average molecular weight (Mn) unless otherwise specified. In this case, the polymer compound can be well dissolved in the etchant, and over-etching can be effectively suppressed to exhibit uniform etching characteristics. If the molecular weight is less than 10,000 g / mol, it is difficult to suppress over-etching of the titanium film, and if the molecular weight exceeds the above-mentioned range, the polymer compound does not dissolve well in the etching solution and is widely adsorbed to the substrate, resulting in defects due to residue generation. may or may not be suitable.

The sulfonic acid-based polymer compound may be included in an amount of 0.001 to 0.1% by weight, specifically 0.01 to 0.1% by weight, based on the total weight of the composition. In this case, the sulfonic acid functional group chelates titanium ions, thereby suppressing the generation of titanium residues and being advantageous in protecting other metal films. When the sulfonic acid-based polymer compound is included in an amount of more than 0.1% by weight, stability of the etchant may deteriorate, which is not suitable.

A sulfonic acid-based polymer compound according to a preferred embodiment of the present disclosure is a homopolymer and may be represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1, R ¹ to R ³ are each independently selected from hydrogen, a C1-C7 linear or branched alkyl group, and a halogen element, L is a direct bond or C1-C10 alkylene, and of the alkylene - CH ₂ - may be replaced by C6-C12 aryl, -C(=O)-, -NR'-, or a combination thereof, where R' is hydrogen or C1-C7 alkyl, and n is from 30 to 1000 is an integer

More specifically, in the sulfonic acid-based polymer compound, in Formula 1, R ¹ to R ³ are each independently hydrogen, L is a direct bond or C1-C7 alkylene, and -CH ₂ - of the alkylene is C6-C12 aryl. , -C(=O)-, -NR'-, or a combination thereof, where R' is hydrogen and n is an integer from 40 to 600.

Another form of the sulfonic acid-based polymer compound is a copolymer, specifically, for example, poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) acrylonitrile or poly (4-styrenesulfonic acid-co-maleic acid), but is not limited thereto.

Examples of preferred homopolymer types of the sulfonic acid-based polymer compound include poly(4-styrenesulfonic acid) (PSS), poly(anetholesulfonic acid) (PAS), and polyvinyl sulfonic acid (poly(4-styrenesulfonic acid)). vinylsulfonic acid), PVS), or polyacrylamido-2-methyl-1-propanesulfonic acid (poly(2-acrylamido2-methyl-1-propanesulfonic acid), PAMPS), but is not limited thereto.

The water included in the etchant composition is not particularly limited, but may specifically be deionized water, and more specifically, deionized water for a semiconductor process, and may have a specific resistance value of 18 MΩ cm or more.

As the etchant composition according to an embodiment of the present disclosure has stable etching characteristics, the change in pH of the chemical solution may be small even during repetitive etching processes. Specifically, the pH of the titanium film etchant composition according to an embodiment of the present disclosure may be 7 to 11, more specifically 8 to 10.

An etchant composition according to an embodiment of the present disclosure may simultaneously satisfy the following content range. Specifically, based on the total weight, the polyvalent phosphonic acid is 0.005 to 3% by weight, the inorganic base is 0.5 to 3% by weight, the sulfonic acid-based polymer compound is 0.001 to 0.1% by weight, the hydrogen peroxide is 15 to 25% by weight, and the remaining amount of water may include

More specifically, the etchant composition according to the present disclosure contains 0.01 to 2% by weight of polyvalent phosphonic acid, 1.5 to 3% by weight of an inorganic base, 0.01 to 0.1% by weight of a sulfonic acid-based polymer compound, 15 to 23% by weight of hydrogen peroxide, and the remaining amount of water. may include

The etchant composition according to an embodiment of the present disclosure may further include a phosphate-based compound. Specifically, the phosphate-based compound may be included in an amount of 0.01 to 1% by weight or 0.05 to 0.5% by weight based on the total composition. Phosphate-based compounds include monobasic sodium phosphate (NaH ₂ PO ₄ ), dibasic sodium phosphate (Na ₂ HPO ₄ ), tribasic sodium phosphate (Na ₃ PO 4 ), monobasic potassium phosphate (KH 2 PO ₄ ), and secondary sodium phosphate (KH ₂ PO ₄ ). Potassium phosphate (K ₂ HPO ₄ ), monobasic ammonium phosphate ((NH ₄ )H ₂ PO ₄ ), dibasic ammonium phosphate ((NH ₄ ) ₂ HPO ₄ ), tribasic ammonium phosphate ((NH ₄ ) ₃ PO ₄ ) or a combination of two or more thereof. Preferably, it may be monobasic potassium phosphate (KH ₂ PO ₄ ), dibasic potassium phosphate (K ₂ HPO ₄ ), or a combination thereof. In this case, the etching rate may be adjusted so that uniform etching may be performed.

In the etchant composition according to an embodiment of the present disclosure, the content ratio of the phosphate-based compound and the inorganic base may be specifically 1:3 to 1:15, more specifically 1:5 to 1:12, based on weight.

More specifically, the etchant composition according to the present disclosure contains 0.01 to 2% by weight of polyvalent phosphonic acid, 1.5 to 3% by weight of an inorganic base, 0.01 to 0.1% by weight of a sulfonic acid-based polymer compound, 15 to 23% by weight of hydrogen peroxide, and 0.1 to 1% by weight of a phosphate-based compound. It may include weight percent and a residual amount of water. The present disclosure can provide excellent etching selectivity by not causing over-etching of the titanium film while maximally suppressing etching of other metal films by combining the above-described appropriate mixing ratio.

In addition, the etchant composition according to an embodiment of the present disclosure may not substantially include a quaternary ammonium salt. When the etchant composition includes a quaternary ammonium salt, the etching rate of the titanium film is rapidly increased, which may cause over-etching, which is undesirable. For example, the quaternary ammonium salt may be tetraalkylammonium hydroxide, trialkylarylammonium hydroxide, and the like, specifically tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide , tetraoctylammonium hydroxide, benzyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, or methyltributylammonium hydroxide, but is not limited as long as it has the aspect of a quaternary ammonium salt. Here, the alkyl may be C1-C8 alkyl, and the aryl may be C6-C12 aryl.

In the etchant composition according to an embodiment of the present disclosure, the etchant of the etchant composition is a pure titanium film. According to the present disclosure, etching or damage to an upper or lower layer represented by a silicon insulating layer or a copper-based metal layer other than the titanium layer does not occur. Therefore, it is possible to effectively prevent defects in electrical device characteristics, which may be exemplified by short circuits, wiring defects, and luminance reduction that may occur during subsequent processes.

The silicon insulating film may be one or a combination of two or more selected from a silicon nitride film and a silicon oxide film.

For example, the silicon nitride may be a SiNx layer, a SiON layer, or a doped SiN layer.

For example, the silicon oxide is a SOD (Spin On Dielectric) film, HDP (High Density Plasma) film, thermal oxide film, BPSG (Borophosphate Silicate Glass) film, PSG (Phospho Silicate Glass) film, BSG (Boro Silicate Glass) Glass) film, PSZ (Polysilazane) film, FSG (Fluorinated Silicate Glass) film, LP-TEOS (Low Pressure Tetra Ethyl Ortho Silicate) film, PETEOS (Plasma Enhanced Tetra Ethyl Ortho Silicate) film, HTO (High Temperature Oxide) film, MTO (Medium Temperature Oxide) film, USG (Undopped Silicate Glass) film, SOG (Spin On Glass) film, APL (Advanced Planarization Layer) film, ALD (Atomic Layer Deposition) film, PE-oxide film (plasma enhanced oxide) or O ₃ -TEOS (O ₃ -Tetra Ethyl Ortho Silicate) and the like.

The copper-based metal film may be a single film made of copper or copper alloy; Or a multi-layer film in which two or more of the single films are stacked.

For example, the copper alloy may be used without limitation as long as it is a metal that can be used for an electrode of a semiconductor device, and non-limiting examples thereof include molybdenum, tungsten, titanium, tantalum, chromium, neodymium, niobium, nickel, and indium. And it may be one or two or more selected from comments and the like.

In addition, the present disclosure describes the use of the metal film etchant composition containing titanium described above.

One aspect of the present disclosure includes contacting the etchant composition to a metal film containing titanium; It may be a method of etching a metal film containing titanium.

In addition, one aspect of the present disclosure includes forming a metal film containing titanium on a substrate on which a source electrode, a gate electrode, and a drain electrode are formed; and etching the metal film using the etchant composition described above.

According to the present disclosure, in selectively etching a titanium film used as a metal film for preventing diffusion of a semiconductor device, the etching of an upper or lower film, which can be exemplified by a silicon wafer, a silicon insulating film, or a copper-based metal film, is effectively prevented. and selectively etch only the titanium film. In addition, re-adsorption of titanium ions that may occur during the etching process can be prevented, and titanium residues that can be generated from this can be stably dissolved in the chemical solution to efficiently remove titanium residues, resulting in damage to the upper or lower film. can be minimized. Accordingly, according to the present disclosure, electrical and physical defects that may occur in an etching process may be minimized, and stable device characteristics may be implemented. Also, it is very advantageous commercially.

In the method of manufacturing a semiconductor device according to an embodiment of the present disclosure, after the step of forming the metal film containing titanium, one single film or two or more films selected from a silicon insulating film and a second metal film are formed on a portion of the metal film. Forming a multilayer film; may further include.

The second metal film may be a copper-based metal film, and the copper-based metal film may be a single film made of copper or a copper alloy or a multi-layer film in which two or more of the single films are stacked, and the copper alloy may include molybdenum, tungsten, titanium, It may contain one or two or more selected from tantalum, chromium, neodymium, niobium, nickel, indium, and tin.

The method of manufacturing a semiconductor device according to an embodiment of the present disclosure may further include annealing the metal film containing titanium after the etching step. Through the above steps, a titanium silicide film may be formed, and cracks that may occur in the annealing step by performing the etching step according to the present disclosure may not be caused. That is, according to the present disclosure, a titanium silicide film having more improved performance can be provided.

The etchant composition for a metal film containing titanium according to the present disclosure will be described in more detail through the following examples. However, the following examples are only references for explaining the present disclosure in detail, and the present disclosure is not limited thereto, and may be implemented in various forms.

[Examples 1 to 10 and Comparative Examples 1 to 5]

An etchant composition (8 kg) was prepared with the components and contents shown in Table 1 below.

[Table 1]

(Assessment Methods)

1. Etch Characteristics

A substrate was prepared on which a titanium film (600 Å), a silicon oxide film (600 Å), and a copper film (600 Å) were respectively deposited as single films on a silicon wafer (600 Å). A photoresist process of a certain pattern was applied thereon to prepare a specimen by cutting the patterned glass into 5X5 cm using a diamond knife.

An etchant composition according to the content combinations described in Examples and Comparative Examples of Table 1 was prepared to be 8 kg. After putting the prepared etchant composition into the experimental equipment of the spray type 　etching method and warming it by setting the temperature to 32 ℃, the 　etching process was performed when the temperature reached. For the total etching time, overetching was performed at 100% based on end point detection (EPD). After etching was completed, after washing with distilled water three times, each film thickness change was confirmed through an ellipsometer (SE-MG-1000), and the etching characteristics were evaluated.

2. Titanium residue level

The titanium residue level of the specimen obtained through the etching characteristic evaluation method was evaluated according to the following criteria.

[Criterion 1] Titanium residue level

- No residue : ○

- 1 to 10 residues: △

- More than 10 residues/bundle: Ⅹ

3. Whether the metal film (copper film) is etched

For the specimens obtained through the etching characteristic evaluation method, whether other metal films (copper films) were etched was evaluated according to the following criteria.

[Criterion 2] Other metal film (copper film) = Etch rate

- No etching : ○

- Range of 1Å/min to 20Å/min: △

- Exceeding 20Å/min : X

[Table 2]

[Table 3]

Referring to Table 2, according to the present disclosure, 0.01 to 3% by weight of a polyvalent phosphonic acid, 0.5 to 3% by weight of an inorganic base, 0.01 to 0.1% by weight of a sulfonic acid-based polymer compound, 15 to 25% by weight of hydrogen peroxide, and the remaining amount of water Looking at the examples in which the containing etchant composition was used, overetching of the titanium film did not occur even though overetching was performed at 100% in all cases. In addition, there was no titanium residue, and as shown in FIG. 2 , the copper film was not etched, so it was confirmed that the protective effect against other metal films was excellent and the selectivity was excellent.

On the other hand, in the case of the etchant composition of Comparative Example described in Table 3, overetching was induced in all cases except for Comparative Example 4 when the overetch was performed at 100%. Etching did not occur in Comparative Example 4 in which no inorganic base was added. In addition, a large number of titanium residues remain during etching according to the comparative example, and as shown in FIG. 1, the titanium film as well as the copper film deposited therewith are etched, confirming that it is not suitable for protecting other metal films such as copper films. .

As described above, the present disclosure has been described with specific details, limited examples, and comparative examples, but these are only provided to help a more general understanding of the present disclosure, and the present disclosure is not limited to the above examples. Those skilled in the art can make various modifications and variations from these descriptions. Therefore, the spirit of the present disclosure should not be limited to the described embodiments and should not be determined, and all things equivalent or equivalent to the claims as well as the following claims belong to the scope of the present disclosure.

Claims (17)

A metal film etchant composition containing titanium, comprising polyvalent phosphonic acid or a salt thereof, an inorganic base, a sulfonic acid-based polymer compound, hydrogen peroxide, and a residual amount of water. According to claim 1,
The molecular weight of the sulfonic acid-based polymer compound is 10,000 to 50,000 g / mol, a metal film etchant composition containing titanium. According to claim 1,
The sulfonic acid-based polymer compound is contained in 0.001 to 0.1% by weight, a metal film etchant composition containing titanium. According to claim 1,
The polyvalent phosphonic acid or a salt thereof is contained in 0.01 to 5% by weight based on the total weight of the composition, a metal film etchant composition containing titanium. According to claim 1,
The inorganic base is contained in 0.1 to 3% by weight relative to the total weight of the composition, a metal film etchant composition containing titanium. According to claim 1,
The sulfonic acid-based polymer compound is represented by Formula 1 below, a metal film etchant composition containing titanium
[Formula 1]

(In Formula 1, R ¹ to R ³ are each independently selected from hydrogen, a C1-C7 linear or branched alkyl group, and a halogen element, L is a direct bond or C1-C10 alkylene, and -CH ₂ - may be replaced by C6-C12 aryl, -C(=O)-, -NR'-, or a combination thereof, wherein R' is hydrogen or C1-C7 alkyl, and n is 30 to 1000 is an integer of). According to claim 1,
Based on the total weight of the etchant composition, the polyvalent phosphonic acid or salt thereof is 0.01 to 3% by weight; 0.5 to 3% by weight of an inorganic base and 0.001 to 0.1% by weight of a sulfonic acid-based polymer compound; 15 to 25% by weight of hydrogen peroxide; And a metal film etchant composition containing titanium, comprising a residual amount of water. According to claim 1,
A metal film etchant composition containing titanium, further comprising a phosphate-based compound. According to claim 8,
Based on the total weight of the etchant composition, the phosphate-based compound is included in 0.01 to 2% by weight, a metal film etchant composition containing titanium. According to claim 8,
The weight ratio of the phosphate-based compound and the inorganic base is 1: 3 to 1: 15, a metal film etchant composition containing titanium. According to claim 1,
A metal film etchant composition containing titanium that does not contain a quaternary ammonium salt. According to claim 1,
A metal film etchant composition containing titanium, having a pH of 7 to 11. A method of etching a metal film containing titanium, comprising: contacting the etchant composition according to any one of claims 1 to 12 with a metal film containing titanium. forming a metal film containing titanium on a substrate on which a source electrode, a gate electrode, and a drain electrode are formed; and
Etching the metal film with the etchant composition according to any one of claims 1 to 12; Method of manufacturing a semiconductor device comprising the. According to claim 14,
After forming the metal film containing titanium,
Forming one single film or two or more multi-layered films selected from a silicon insulating film and a second metal film on a portion of the metal film. According to claim 14,
The second metal film is a single film or a multilayer film containing one or more metals selected from copper, molybdenum, tungsten, titanium, tantalum, chromium, neodymium, niobium, nickel, indium, and tin. According to claim 14,
After the etching step,
Method of manufacturing a semiconductor device further comprising the step of annealing the metal film containing the titanium.