TWI830877B - Metal layer etchant composition and etching method using the same - Google Patents

Abstract

The present invention relates to a metal film etching composition and an etching method using the same. The metal film etching composition according to the present invention contains hydrogen peroxide, organic acid, glycol polymer and water, has a pH range of 3.0 to 4.4, and has good resistance to copper, molybdenum and other lower films such as silicon films and transparent conductive films. Such as high selectivity or infinite selectivity of metal films, hydrogen peroxide stability is also excellent in a relatively high pH range, and even if etching is repeated and reused many times, the initial excellent characteristics can be maintained. In addition, it not only achieves a stripe profile with excellent linearity during etching, but also has the excellent effect of reducing CD loss and suppressing the generation of residues. In addition, since the composition has high stability, it is possible to obtain improved storage stability that can continuously maintain initial excellent characteristics before or after use, and has the effect of not generating precipitates during etching and suppressing heat generation.

Description

Metal film etching composition and etching method utilizing same

The present invention relates to a metal film etching composition.

Generally, a thin film transistor (TFT) display panel is used as a circuit substrate for independently driving each pixel in a liquid crystal display device or an organic EL (Electro Luminescence) display device. Scanning signal wiring or gate wiring for transmitting scanning signals and image signal lines or data wiring for transmitting image signals are formed in the TFT, including thin film transistors connected to the gate wiring and data wiring, and connected to the thin film transistors pixel electrodes, etc. The process of forming the wiring of such a TFT generally includes: a sputtering process for forming a metal film; a photoresist forming process based on photoresist coating, exposure and development to form the desired pattern; an etching process for forming the wiring; and A stripping process that removes unnecessary photoresist after wiring is formed.

In the past, in order to manufacture semiconductor devices and TFT-LCD substrates, aluminum or aluminum alloy layers were often used as wiring materials for TFT gate electrodes and data line electrodes. However, in order to realize a large display, it is necessary to reduce the resistance of the electrode wiring. , copper and/or molybdenum, which are low-resistance metals, are used for wiring formation. Therefore, research on etching compositions used for etching wiring containing copper and/or molybdenum is actively being conducted.

In order to etch wiring containing copper and/or molybdenum, an etching solution composition with strong oxidizing ability is required. For example, KR10-2018-0077610A discloses a metal film containing hydrogen peroxide, a fluorine-containing compound, a tetrazole compound, a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, a sulfate compound, and a polyol-type surfactant. Etching composition.

However, such conventional metal film etching compositions do not have a high selectivity for metal films such as copper and/or molybdenum. Therefore, there is a limitation in inducing corrosion of lower films such as silicon films and transparent conductive films located under the metal film. Therefore, it is difficult to form precise patterns, quality is reduced, economic efficiency is reduced, etc., which greatly limits the pattern formation of metal films.

Therefore, there is a need to study a metal film etching composition that can fundamentally and substantially block corrosion of lower films such as silicon films and transparent conductive films, and has high corrosion resistance to films of transition metals such as copper and molybdenum. Choose ratio.

existing technical documents

patent documents

(Patent Document 1) KR10-2018-0077610A (2018.07.09)

An object of the present invention is to provide a metal film etching composition that has a high selectivity or infinite selectivity for metal films such as copper and molybdenum with respect to lower films such as silicon films and transparent conductive films.

An object of the present invention is to provide a metal film etching composition excellent in stability of hydrogen peroxide in a relatively high pH range.

Another object of the present invention is to provide a metal film etching composition that can continue to maintain its initial excellent characteristics even if the etching is repeated and reused many times, and can maintain low performance even if the number of processed sheets increases. the cone angle.

Another object of the present invention is to provide a metal film etching composition that not only achieves a stripe profile with excellent linearity during etching but also has excellent characteristics of reducing CD loss and suppressing residue generation.

Another object of the present invention is to provide a metal film etching composition that has improved storage stability that can continuously maintain initial excellent characteristics before or after use because the composition has high stability.

Another object of the present invention is to provide a metal film etching composition that does not generate precipitates during etching and can suppress heat generation.

The metal film etching composition according to the present invention is characterized in that it contains hydrogen peroxide, organic acid, glycol polymer and water, and has a pH range of 3.0 to 4.4.

In one example of the present invention, the above-mentioned organic acid may include iminodisuccinic acid.

In an example of the present invention, the above-mentioned organic acid may further include any one selected from malonic acid, glycolic acid, acetic acid, formic acid, citric acid, oxalic acid, butyric acid, valeric acid, propionic acid, tartaric acid, gluconic acid, etc. , or two or more.

In one example of the present invention, the glycol polymer may include polyethylene glycol.

The metal film etching composition according to an example of the present invention may include 10 to 40 wt% hydrogen peroxide, 0.1 to 10 wt% organic acid, 0.1 to 5 wt% glycol-based polymer, and the balance water. .

The metal film etching composition according to an example of the present invention may further include any one, or two or more ammonium compounds selected from ammonium phosphate, ammonium hydrogenphosphate, ammonium superphosphate, ammonium fluoride, ammonium hydrogenfluoride, and the like.

The metal film etching composition according to an example of the present invention may further include an azole compound.

The metal film etching composition according to an example of the present invention may further include any one, or two or more hydrogen peroxide stabilizers selected from cyclohexylamine, n-hexylamine, isohexylamine, neohexylamine, etc.

The metal film etching composition according to an example of the present invention may further include any one or more pH adjusters selected from sodium hydroxide, potassium hydroxide, and the like.

The metal film etching composition according to an example of the present invention may include hydrogen peroxide, 5-aminotetrazole, cyclohexylamine, iminodisuccinic acid, iminodiacetic acid, ammonium phosphate, ammonium fluoride, and poly Ethylene glycol.

According to a metal film etching composition according to an example of the present invention, the metal film can be selectively etched with a high selectivity ratio or an infinite selectivity ratio relative to a silicon film or an indium-based oxide film, and the silicon film is selected from a silicon oxide film and an indium-based oxide film. Any one or more of silicon nitride films, etc., the indium-based oxide film is any one, or two or more types selected from the group consisting of indium zinc oxide film, indium tin oxide film, indium gallium zinc oxide film, etc., the metal The film is at least one selected from the group consisting of copper metal films, molybdenum metal films, and the like.

In an example of the present invention, the silicon film may include at least one selected from the group consisting of a silicon oxide film and a silicon nitride film, and the metal film may include at least one selected from the group consisting of a copper metal film, a molybdenum metal film, and the like.

The metal film etching method according to the present invention may include the step of etching the metal film using the metal film etching composition.

The metal film etching composition according to the present invention has the effect of having a high selectivity or infinite selectivity for metal films such as copper and molybdenum with respect to lower films such as silicon films and transparent conductive films.

The metal film etching composition according to the present invention has the effect of being excellent in hydrogen peroxide stability even in a relatively high pH range.

The metal film etching composition according to the present invention has the following effects: even if etching is repeated and reused many times, the initial excellent characteristics can be continuously maintained, and a low taper angle can be maintained even if the number of processed sheets increases.

The metal film etching composition according to the present invention not only achieves a stripe profile with excellent linearity during etching, but also has excellent effects of reducing CD loss and suppressing the generation of residue.

The metal film etching composition according to the present invention has the effect that since the composition has high stability, it has improved storage stability that can continuously maintain initial excellent characteristics even before or after use.

The metal film etching composition according to the present invention does not generate precipitates during etching and can suppress heat generation.

Even if there are no effects explicitly mentioned in the present invention, the effects described in the specification and their inherent effects expected from the technical features of the present invention are deemed to be equivalent to those described in the specification of the present invention.

The metal film etching composition according to the present invention and the etching method using the same will be described in detail below with reference to the accompanying drawings.

The drawings described in this specification are provided as examples in order to fully convey the idea of the present invention to those with ordinary knowledge in the art. Therefore, the present invention is not limited to the provided drawings and may be embodied in other forms. The drawings may be exaggerated to clarify the idea of the present invention.

Unless otherwise defined, the technical terms and scientific terms used in this specification have the meanings commonly understood by those with ordinary knowledge in the technical field to which the present invention belongs. In the following description and drawings, any words that may unnecessarily affect the present invention are omitted. Description of the conventional functions and composition of the subject matter of the invention.

Unless otherwise specified, the singular form of terms used in this specification may be construed to include the plural form.

Unless otherwise defined, the % unit used in this specification without special explanation refers to weight %.

The present invention provides a metal film etching composition that increases the etching speed of films of transition metals such as copper and molybdenum, and particularly significantly reduces the etching rate of films such as silicon films and transparent conductive films used as substrates or lower films. of etching, thereby having a very high selectivity ratio or essentially an infinite selectivity ratio.

As a result of the inventor's repeated efforts to minimize the etching of silicon films, transparent conductive films, and other films, it was found that when a specific composition is provided in a specific pH range, the etching speed of the film is significantly reduced, and the maximum reduction is 0 Å/s, which essentially prevents etching.

That is, even if the metal film etching composition according to the present invention satisfies the following specific pH range, if it does not satisfy the following specific composition, the etching rate for films such as silicon films and transparent conductive films greatly exceeds 0 Å/ s, and the corrosion of the film cannot be prevented to a significant extent. Furthermore, even if the composition meets the specific composition, it will not prevent corrosion of the film to a significant level if it does not meet the specific pH range.

Specifically, the metal film etching composition according to the present invention contains hydrogen peroxide, organic acid, glycol-based polymer and water, and has a pH range of 3.0 to 4.4, thereby having a High selectivity for copper, molybdenum and other metal films.

The organic acid preferably includes iminodisuccinic acid (IDS). When this condition is satisfied, that is, when the pH in the above-mentioned range and the composition containing iminodisuccinic acid are satisfied, a metal film such as copper or molybdenum is more sensitive to a film such as a transparent conductive film containing indium, gallium, zinc, etc. high selectivity ratio. Specifically, when an organic acid containing iminodisuccinic acid and a glycol-based polymer are used together, the adhesion of the composition to the lower film surface under the metal film becomes smooth, and the surface protection effect is maximized, thereby maximizing the surface protection effect. Compared with films such as silicon films and transparent conductive films, it can have an infinite selectivity for metal films such as copper and molybdenum. That is, it has the effect of being able to substantially prevent corrosion of films such as transparent conductive films containing indium, gallium, zinc, or the like. On the contrary, when iminodisuccinic acid is not included, even if it is used together with a glycol-based polymer, it is impossible to have an infinite selectivity for metal films such as copper and molybdenum with respect to films such as the transparent conductive film. For example, in organic acids and glycol-based polymers containing iminodisuccinic acid, when they are used individually (that is, when they are not used simultaneously), the infinite selectivity ratio effect is not shown, but only when they are used simultaneously. , in order to achieve the infinite selection ratio effect. The so-called "infinite selectivity ratio" means that the etching rate of films such as silicon films and transparent conductive films is 0 Å/s, which substantially prevents etching and at the same time allows the etching rate of metal films such as copper and molybdenum to be substantially etched. Significant value.

As mentioned above, the infinite selectivity effect exhibited by satisfying a specific pH range and a specific composition may be caused by the negative charge on the lower membrane surface in this pH range, and the cationic imino diamine groups. Succinic acid and glycol-based polymers can easily move to the surface and smoothly perform the role of etching inhibitors.

The glycol-based polymer is preferably polyethylene glycol (PEG), and more preferably has a hydroxyl group (-OH) at the terminal, which can further exhibit the above-mentioned effects, so it is even more preferable. As for the weight average molecular weight of the polyethylene glycol, it can be in liquid phase or solid phase at normal temperature (25°C). As an example, it can be 150 to 10000 g/mol, preferably 180 to 2000 g/mol. mol, when this condition is met, it can prevent the problem of reduced protective effect of the lower film caused by too low a weight average molecular weight, as well as uneven etching such as layer separation and reduced solubility of the etching composition caused by an excessively high weight average molecular weight. problem. When low-molecular glycol compounds such as ethylene glycol, propylene glycol, and diethylene glycol are used to replace the glycol polymer, the etching rate of films of transition metals such as copper and molybdenum is significantly reduced, and of course production may occur. Problems such as precipitates, heat generation, and reduced storage stability.

The metal film etching composition according to the present invention may also contain other kinds of organic acids besides iminodisuccinic acid. For example, the organic acid other than iminodisuccinic acid may include iminodiacetic acid, malonic acid, glycolic acid, acetic acid, formic acid, citric acid, oxalic acid, butyric acid, valeric acid, propionic acid, tartaric acid, and One, or two or more of gluconic acid, etc. As a specific example, as an organic acid other than iminodisuccinic acid, iminodiacetic acid is preferably used in terms of etching based on effective chelation and improving stability. In addition, in terms of efficient etching of metals such as copper and molybdenum, etching by chelation, and improving stability, it is preferred to further use at least one selected from the group consisting of malonic acid and glycolic acid. Organic acids. However, this is only described as a preferred example, and other organic acids may be used. Therefore, the present invention is not necessarily limited to this and is not necessarily interpreted.

The composition ratio of the metal film etching composition according to an example of the present invention can be appropriately adjusted as long as the above-mentioned effects can be achieved, and is therefore not particularly limited. But as an example, it preferably contains 10 to 40% by weight of hydrogen peroxide, 0.1 to 10% by weight of organic acid, 0.1 to 5% by weight of glycol polymer and the balance of water, and more preferably contains 15 to 10% by weight of organic acid. 35% by weight of hydrogen peroxide, 2 to 8% by weight of organic acid, 0.2 to 2% by weight of glycol polymer and the balance of water. However, this is only explained as a preferred example, and the present invention is not necessarily limited to this.

In terms of achieving the above effects well, in the composition according to the present invention, the organic acid containing iminodisuccinic acid in the organic acid is preferably used in 0.1 to 3% by weight, and more preferably in 0.2 to 2% by weight.

In addition, in the composition according to the present invention, when an organic acid other than iminodisuccinic acid is further used, the organic acid is preferably used in 0.5 to 8% by weight relative to the total weight of the composition, and more preferably 1 to 5% by weight. However, this is only explained as a preferred example, and the present invention is not necessarily limited to this.

As a better example, in the composition according to the present invention, the weight ratio of the organic acid containing iminodisuccinic acid to the glycol polymer can be 1:0.1~2, preferably 1:0.2~ 1.5.

The metal film etching composition according to an example of the present invention may further include any one, or two or more ammonium compounds selected from ammonium phosphate, ammonium hydrogenphosphate, ammonium superphosphate, ammonium fluoride, ammonium hydrogenfluoride, and the like. When the above conditions are met, the etching rate of metals such as copper, molybdenum, and molybdenum alloys can be increased, which is preferable. In addition, when ammonium-based compounds are further used, it is more preferable to use two or more types that are different from each other at the same time. When an ammonium-based compound is used, it is preferably 0.3 to 6% by weight, more preferably 0.5 to 4% by weight, based on the total weight of the composition. At this time, when phosphoric acid-based compounds such as ammonium phosphate, ammonium hydrogen phosphate, and ammonium superphosphate are used together with fluorine-based compounds such as ammonium fluoride and ammonium hydrogen fluoride, it is preferable to use 0.5 to 5% by weight of the phosphoric acid-based compound and 0.01 to 0.5% by weight. of fluorine compounds. However, this is only explained as a preferred example, and the present invention is not necessarily limited to this.

The metal film etching composition according to an example of the present invention may further include an azole compound. The azole compound suppresses the etching rate of the metal film to form a good etching profile, and is not particularly limited as long as it can improve the etching inhibition properties of films such as silicon films and transparent conductive films. For example, it can include imidazole, Pyrazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, tetrazole, oxazole, isoxazole, 1,2,3-oxadiazole, oxadiazole, furoxane , 1,3,4-oxadiazole, thiazole, isothiazole, thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole and Any one, or two or more types of their derivatives. Specifically, examples of the azole compound include 5-aminotetrazole, 5-methyltetrazole, tetrazole, pyrrole, imidazole, pyrazole, triazole, and pyrrolidine, and are more preferably selected from 5 -Tetrazole compounds such as aminotetrazole, 5-methyltetrazole, and tetrazole. When the azole compound is further included, the etching profile of the metal film is improved and the etching of the silicon film, transparent conductive film, etc. is prevented, and the initial etching prevention performance can be maintained more stably even if the composition is repeatedly used. good. The usage content of the azole compound is preferably 0.1 to 2% by weight, more preferably 0.2 to 1% by weight based on the total weight of the composition. However, this is only explained as a preferred example, and the present invention is not necessarily limited to this.

The metal film etching composition according to an example of the present invention may further include any one, or two or more hydrogen peroxide stabilizers selected from cyclohexylamine, n-hexylamine, isohexylamine, neohexylamine, etc. When the above conditions are met, it is preferable in that the hydrogen peroxide as the main component is stabilized, the initial etching prevention performance can be maintained more stably, and it is stable even when used for a long time. When using a hydrogen peroxide stabilizer, it is preferably 0.1 to 2 wt%, more preferably 0.2 to 1 wt%, relative to the total weight of the composition. However, this is only explained as a preferred example, and the present invention is not necessarily limited to this.

The metal film etching composition according to an example of the present invention may further include any one or more pH adjusters selected from the group consisting of sodium carbonate, ammonia, sodium hydroxide, potassium hydroxide, and the like. They are used to meet the above-mentioned pH range, as long as the content of the pH adjuster is appropriately adjusted so that it is within the above-mentioned pH range. As a specific embodiment, generally, the pH adjuster can be used in an amount of 0.01 to 5% by weight relative to the total weight of the composition, specifically, 0.1 to 2% by weight can be used, but the present invention is not limited thereto.

As described above, the metal film etching composition according to the present invention prevents etching of films such as silicon films, transparent conductive films, and the like, and is excellent in etching of metal films.

As a specific example, the etching speed of the metal film by the metal film etching composition according to the present invention may be 10 to 150 Å/sec. As a more specific example, the etching rate for copper can be 70 to 150 Å/sec, specifically 80 to 130 Å/sec, and the etching rate for molybdenum can be 10 to 40 Å/sec, specifically 12 to 120 Å/sec. 30Å/sec.

Examples of the silicon film include at least one selected from a silicon oxide film, a silicon nitride film, and the like. However, in addition to this, it can also exhibit an etching prevention effect on various silicon films.

The transparent conductive film refers to a transparent conductive film used in this technical field. Specifically, it can be exemplified by a film selected from the group consisting of indium zinc oxide (IZO) film, indium tin oxide (Indium Tin Oxide, ITO) film and Any one of indium gallium zinc oxide (IGZO) films, or two or more indium-based oxide films. However, in addition to this, the etching prevention effect on various transparent conductive films can also be exhibited.

Examples of the metal film include any one or two selected from the group consisting of copper, molybdenum, titanium, indium, zinc, tin, tungsten, silver, gold, chromium, manganese, iron, cobalt, nickel, niobium and alloys thereof. above. More specifically, it can be a copper film, a copper/molybdenum film, a copper/titanium film, a copper/molybdenum alloy film, a copper/indium alloy film, and more preferably, a copper/molybdenum film, a copper/molybdenum alloy film, etc. can be exemplified. . However, in addition, the effect of improving the etching characteristics of various transition metals can also be shown.

As a specific example, the copper/molybdenum film or the copper/molybdenum alloy film can be a multiple film in which more than one copper (Cu) film and more than one molybdenum (Mo) film and/or molybdenum alloy film (Mo-alloy) are laminated on each other. The multiple films may include a Cu/Mo(Mo-alloy) double film, a Cu/Mo(Mo-alloy)/Cu or a triple film of Mo(Mo-alloy)/Cu/Mo(alloy). The order of the films can be appropriately adjusted depending on the material and bonding properties of the substrate. However, this is only explained as a specific example, and the present invention is not necessarily limited to this.

As a specific example, the molybdenum alloy film may be composed of molybdenum-tungsten (Mo-W), molybdenum-titanium (Mo-Ti), molybdenum-niobium (Mo-Nb), molybdenum-chromium (Mo-Cr) or molybdenum-tantalum (Mo -Ta) composition, from the perspective of performing residue-free and efficient etching, the molybdenum film or molybdenum alloy film can be 100 to 500 Å, and the copper film can be evaporated to have a thickness of 1000 to 10000 Å. However, this is only explained as a preferred example, and the present invention is not necessarily limited to this.

The metal film according to the present invention can be used in an etching process, and the etching process can be a general etching process. For example, it can include the step of etching the metal film using the above-mentioned metal film etching composition.

Specifically, the etching process may include the following steps to etch the metal film: a step of evaporating a metal film on the substrate; a step of patterning after forming a photoresist film on the metal film; and using a photoresist film according to the present invention. A metal film etching composition is used to etch the metal film on which the patterned photoresist film is formed. The metal film formed on the substrate at this time may be a single film, a dual metal film, or a multiple metal film (multilayer metal film). In the case of a dual metal film or multiple metal films, the stacking sequence is not particularly limited.

As a more specific example, the etching process may include steps between the substrate and the metal film, that is, as an example, in the case of a copper/molybdenum film, between the substrate and the copper film or the substrate and the molybdenum film. The step of forming a semiconductor structure between films. The semiconductor structure may be a semiconductor structure for a display device such as a liquid crystal display device or a plasma display panel. Specifically, the semiconductor structure may include one or more films selected from a dielectric film, a conductive film, and an amorphous or polycrystalline silicon film, and these semiconductor structures may be manufactured by conventional methods.

The present invention will be described in detail below through examples. However, these are only to illustrate the present invention in more detail, and the patentable scope of the present invention is not limited to the following examples.

[Example 1]

Each component was mixed at the component content described in the following Table 1, and the etching composition of Example 1 was manufactured.

[Example 2 to Example 12]

Each component was mixed with the component content described in the following Table 1, and the etching composition of Example 2 to Example 12 was produced respectively.

[Comparative Example 1 to Comparative Example 11]

Each component was mixed with the component content described in the following Table 1, and the etching composition of Comparative Example 1 to Comparative Example 11 was manufactured respectively. [01] [Table 1] Ingredients (weight %) H ₂ O ₂ ATZ glycol compounds organic acid Ammonium compounds Hydrogen peroxide stabilizer pH regulator water pH PEG EG PG DEG IDS IDA MA GA AP AF AS CHA AHr NaOH KOH Example 1 20 0.5 0.5 - - - 0.5 3.0 1.0 - 1.8 0.06 - 0.6 - 0.50 - margin 3.5 Example 2 20 0.5 0.5 - - - 1.0 3.0 1.0 - 1.8 0.06 - 0.6 - 0.50 - margin 3.7 Example 3 20 0.5 1.0 - - - 0.5 3.0 1.0 - 1.8 0.06 - 0.6 - 0.50 - margin 3.5 Example 4 20 0.5 0.5 - - - 0.5 3.0 1.5 - 1.8 0.06 - 0.6 - 0.50 - margin 3.3 Example 5 20 0.5 0.5 - - - 0.5 2.5 1.0 - 1.8 0.06 - 0.6 - 0.50 - margin 3.7 Example 6 20 0.5 0.5 - - - 0.5 3.0 1.0 - 1.8 0.06 - 0.6 - 0.75 - margin 3.8 Example 7 20 0.5 0.5 - - - 0.5 3.0 1.0 - 1.8 0.06 - 0.6 - 0.30 - margin 3.2 Example 8 20 0.5 0.5 - - - 0.5 3.0 - 1 1.8 0.06 - 0.6 - 0.50 - margin 3.5 Example 9 20 0.5 0.5 - - - 0.5 3.0 1.0 - 1.8 0.06 - - 0.6 0.50 - margin 3.5 Example 10 20 0.5 0.5 - - - 0.5 3.0 1.0 - 1.8 0.06 - 0.6 - - 0.5 margin 3.6 Example 11 20 0.5 0.5 - - - - 3.0 1.0 - 1.8 0.06 - 0.6 - 0.80 - margin 3.5 Example 12 20 0.5 1.5 - - - - 3.0 1.0 - 1.8 0.06 - 0.6 - 0.50 - margin 3.5 Comparative example 1 20 0.5 - - - - - 3.0 1.0 - 1.8 0.06 - 0.6 - 0.80 - margin 3.5 Comparative example 2 20 0.5 - - - - 0.5 3.0 1.0 - 1.8 0.06 - 0.6 - 0.50 - margin 3.5 Comparative example 3 20 0.5 - - - - 1.5 3.0 1.0 - 1.8 0.06 - 0.6 - 0.20 - margin 3.5 Comparative example 4 20 0.5 0.5 - - - 0.5 3.0 1.0 - - 0.06 1.8 0.6 - 0.50 - margin 2.5 Comparative example 5 20 0.5 0.5 - - - 0.5 3.0 1.0 - - 0.06 2.5 0.6 - 0.50 - margin 2.5 Comparative example 6 20 0.5 0.5 - - - 0.5 3.0 - - 1.8 0.06 - 0.6 - 0.50 - margin 4.5 Comparative example 7 20 0.5 0.5 - - - 0.5 - 1.0 - 1.8 0.06 - 0.6 - 0.50 - margin 4.5 Comparative example 8 20 0.5 0.5 - - - 0.5 3.0 1.0 - 1.8 0.06 - 0.6 - - - margin 2.6 Comparative example 9 20 0.5 - 0.5 - - 0.5 - - - 1.8 0.06 - 0.6 - 0.50 - margin 5.0 Comparative example 10 20 0.5 - - 0.5 - 1.0 - - - 1.8 0.06 - 0.6 - 0.50 - margin 5.2 Comparative example 11 20 0.5 - - - 0.5 1.0 - - - 1.8 0.06 - 0.6 - 0.50 - margin 5.2 H ₂ O ₂ : Hydrogen peroxide ATZ: 5-aminotetrazole PEG: Polyethyleneglycol (81150, SIGMA-ALDRICH) EG: Ethylene glycol PG: Propylene glycol ( Propylene glycol) IDS: Iminodisuccinic acid IDA: iminodiacetic acid MA: malonic acid GA: Glycolic acid AP: ammonium phosphate dibasic AF: Ammonium fluoride AS: Ammonium sulfate CHA: Cyclohexylamine HxA: Hexylamine NaOH : Sodium hydroxide KOH: Potassium hydroxide

[Experimental example 1]

>Evaluation of whether precipitates are produced, whether heat is generated, etching performance, and changes over time during storage>

Whether the etching compositions produced in Examples 1 to 12 and Comparative Examples 1 to 10 produced precipitates, generated heat, and etching performance (critical dimension skew (CD skew), taper) were evaluated. , Preserve the characteristics that change over time.

Specifically, a molybdenum alloy film was evaporated to a thickness of 300Å on the lower films of the silicon oxide film, the indium zinc oxide film, the indium tin oxide film, and the indium gallium zinc oxide film, and on the molybdenum alloy film After the copper film is evaporated to a thickness of 6500Å, a photolithography process is performed to form a pattern and a test piece is produced. Furthermore, when the copper content of the etching composition was 3000, 4000, and 5000 ppm during etching, whether precipitates were generated, whether heat was generated, etching performance, and characteristics of changes over time during storage were evaluated.

Regarding the occurrence of precipitates, the occurrence of precipitates was evaluated as ○, and the case without occurrence was evaluated as Make an evaluation. Etching performance (critical dimension skew (CD skew), taper) was evaluated using a mini-etcher device and each test piece was evaluated based on the EPD (etch pit density) standard of 50% OE. Specifically, the critical dimension skew (CD skew) is evaluated as a good level when the skew is 0.60 μm to 1.00 μm, and the taper (taper) is evaluated as a good level when it is 30 degrees or more and less than 45 degrees. Regarding storage changes over time, in order to confirm the storage stability of the etching composition, a mini-etcher was used to evaluate changes in days, and the evaluation was based on good, poor, and very poor (confirmation of changes over time: 0~ 5 days).

The results of this are shown graphically in Table 2 and Table 3 below. [02] [Table 2] pH Cu content (ppm) Etching speed (Å/sec) Whether precipitates are produced Whether you have fever Etching performance Save changes over time Cu Mo Example 1 3.5 3000 86 15 × × good good 4000 86 15 × × good 5000 88 15 × × good Example 2 3.7 3000 84 14 × × good good 4000 83 14 × × good 5000 84 14 × × good Example 3 3.5 3000 86 15 × × good good 4000 87 15 × × good 5000 87 15 × × good Example 4 3.3 3000 92 15 × × good good 4000 92 15 × × good 5000 92 15 × × good Example 5 3.7 3000 90 16 × × good good 4000 90 16 × × good 5000 91 16 × × good Example 6 3.8 3000 82 17 × × good good 4000 82 17 × × good 5000 81 17 × × good Example 7 3.2 3000 92 14 × × good good 4000 92 14 × × good 5000 93 14 × × good Example 8 3.5 3000 85 15 × × good good 4000 85 15 × × good 5000 86 15 × × good Example 9 3.5 3000 85 13 × × good good 4000 85 13 × × good 5000 85 14 × × good Example 10 3.6 3000 86 15 × × good good 4000 86 15 × × good 5000 87 15 × × good Example 11 3.5 3000 90 15 × × good Difference 4000 91 15 × × good 5000 90 15 ○ ○ Difference Example 12 3.5 3000 90 15 × × good Difference 4000 92 15 × × good 5000 91 15 ○ ○ Difference [03] [Table 3] pH Cu content (ppm) Etching speed (Å/sec) Whether precipitates are produced Whether you have fever Etching performance Save changes over time Cu Mo Comparative example 1 3.5 3000 80 13 × × good very bad 4000 85 13 ○ ○ Difference 5000 92 13 ○ ○ very bad Comparative example 2 3.5 3000 83 12 × × good Difference 4000 82 12 × × good 5000 92 13 ○ ○ Difference Comparative example 3 3.5 3000 85 11 × × good Difference 4000 86 11 × × good 5000 96 10 ○ ○ Difference Comparative example 4 2.5 3000 84 13 × × good Difference 4000 84 13 × × good 5000 85 13 × × good Comparative example 5 2.5 3000 88 14 × × good Difference 4000 88 14 × × good 5000 88 15 × × good Comparative example 6 4.5 3000 71 13 ○ ○ Difference very bad 4000 68 13 ○ ○ Difference 5000 61 12 ○ ○ very bad Comparative example 7 4.5 3000 71 14 ○ ○ Difference very bad 4000 80 15 ○ ○ very bad 5000 88 16 ○ ○ very bad Comparative example 8 2.6 3000 96 10 × × Difference Difference 4000 96 10 × × Difference 5000 101 10 × × Difference Comparative example 9 5.0 3000 59 13 ○ ○ very bad very bad 4000 53 13 ○ ○ very bad 5000 48 13 ○ ○ very bad Comparative example 10 5.2 3000 55 12 ○ ○ very bad very bad 4000 50 12 ○ ○ very bad 5000 44 12 ○ ○ very bad Comparative example 11 5.2 3000 57 13 ○ ○ very bad very bad 4000 52 13 ○ ○ very bad 5000 47 13 ○ ○ very bad

As can be seen from the above-mentioned Table 2 and the above-mentioned Table 3, Examples 1 to 10 did not generate precipitates, did not generate heat, had good etching performance, and were also excellent in long-term storage stability. On the contrary, it was confirmed that the comparative examples produced precipitates, generated heat, had poor etching performance, decreased long-term storage stability, or had a combination of two or more of the above-mentioned problems. In particular, it was confirmed from Comparative Examples 9 to 11 that even if iminodisuccinic acid and a glycol-based compound are used, the glycol-based compound is ethylene glycol, propylene glycol, or diethylene glycol other than polyethylene glycol. No effect will be shown when using low molecular weight compounds such as diols.

[Experimental example 2]

>Evaluation of the etching selectivity of the metal film of the lower film>

The etching selectivity of the etching compositions produced in Examples 1 to 12 and Comparative Examples 1 to 8 with respect to the metal film of the lower film was evaluated. Furthermore, the presence of molybdenum alloy residue was evaluated.

Specifically, the thickness of the test piece before etching was measured using an ellipsometer (Ellipsometer, JA WOOLLAM, M-2000U) which is a film thickness measuring device. The etching process for the test piece was performed using each of the above etching compositions maintained at an etching temperature of 32°C in a quartz bath. The etching time is controlled to be the same. After the etching test piece was washed with ultrapure water, the remaining etching composition was completely dried using a drying device, the thickness was measured, and the etching rate was evaluated. In addition, the molybdenum alloy residue was analyzed by surface observation during SEM analysis. [04] [Table 4] pH Molybdenum alloy residue Etching speed (Å/s) SiO ₂ N _x IZO ITO IGZO Example 1 3.5 without 0 0 0 0 0 Example 2 3.7 without 0 0 0 0 0 Example 3 3.5 without 0 0 0 0 0 Example 4 3.3 without 0 0 0 0 0 Example 5 3.7 without 0 0 0 0 0 Example 6 3.8 without 0 0 0 0 0 Example 7 3.2 without 0 0 0 0 0 Example 8 3.5 without 0 0 0 0 0 Example 9 3.5 without 0 0 0 0 0 Example 10 3.6 without 0 0 0 0 0 Example 11 3.5 without 1.50 1.20 4.00 3.50 4.30 Example 12 3.5 without 1.00 0.80 3.30 2.80 3.85 Comparative example 1 3.5 without 3.00 2.50 5.00 4.00 5.00 Comparative example 2 3.5 without 2.50 2.30 3.00 2.50 4.50 Comparative example 3 3.5 have 2.30 2.00 2.70 2.20 4.10 Comparative example 4 2.5 have 2.00 1.50 1.50 1.30 1.60 Comparative example 5 2.5 have 2.00 1.50 1.50 1.30 1.60 Comparative example 8 2.6 have 1.80 1.30 1.30 1.10 1.40 IZO: Indium zinc oxide ITO: Indium tin oxide IGZO: Indium gallium zinc oxide

It can be seen from the above Table 4 that in Examples 1 to 8, the etching rate of the lower film of the silicon oxide film, silicon nitride film, indium zinc oxide film, indium tin oxide film and indium gallium zinc oxide film is 0Å/s, virtually no etching occurs. On the contrary, it was confirmed that the comparative example was accompanied by an etching rate of at least 1Å/s or more and could not completely block the etching of the lower film itself.

In particular, it was confirmed from Example 1, Example 11, Example 12, Comparative Example 2 and Comparative Example 3 that it is difficult to fundamentally prevent the lower film from being damaged when iminodisuccinic acid and polyethylene glycol are used alone. Etching, only by using them together can the etching of the lower film be fundamentally prevented.

In addition, it was confirmed from Comparative Examples 4 to 6 and 8 that even if iminodisuccinic acid and polyethylene glycol are used together, when the pH range does not satisfy 3.0 to 4.4, it is impossible to fundamentally prevent the lower membrane from being damaged. etching. It is thought that the reason for this is that in this pH range, along with the positive charge on the film surface, imino disuccinic acid and polyethylene glycol having cations can move to the surface, thereby effectively performing an etching inhibitor (inhibitor). )effect.

without

Figure 1 is a scanning electron microscope picture of a test piece etched using the etching composition according to Example 1 of the present invention.

Claims (10)

A metal film etching composition, characterized in that it contains hydrogen peroxide, organic acid, glycol polymer and water, wherein the metal film etching composition contains 10 to 40% by weight of hydrogen peroxide, 0.1 to 10 % by weight of organic acid, 0.1 to 5% by weight of glycol polymer and the balance of water, and the pH range is from 3.0 to 4.4. The metal film etching composition of claim 1, wherein the organic acid includes iminodisuccinic acid. The metal film etching composition of claim 2, wherein the organic acid further includes malonic acid, glycolic acid, acetic acid, formic acid, citric acid, oxalic acid, butyric acid, valeric acid, propionic acid, tartaric acid and gluconic acid. Any one, or two or more. The metal film etching composition of claim 1, wherein the glycol polymer contains polyethylene glycol. The metal film etching composition of claim 1, wherein the metal film etching composition further includes any one, or two or more kinds of ammonium phosphate, ammonium hydrogen phosphate, ammonium superphosphate, ammonium fluoride and ammonium hydrogen fluoride. Ammonium compounds. The metal film etching composition of claim 1, wherein the metal film etching composition further contains an azole compound. The metal film etching composition of claim 1, wherein the metal film etching composition further includes any one, or two or more hydrogen peroxide stabilizers selected from the group consisting of cyclohexylamine, n-hexylamine, isohexylamine and neohexylamine. The metal film etching composition of claim 1, wherein the metal film etching composition further includes any one or more pH adjusters selected from sodium hydroxide and potassium hydroxide. The metal film etching composition of claim 2, wherein the metal film etching composition selectively etches the metal film with an infinite selectivity ratio relative to the silicon film or the indium-based oxide film, and the silicon film is selected from the group consisting of silicon oxide films and silicon nitride film, the indium-based oxide film is any one, or two or more types selected from the group consisting of indium zinc oxide film, indium tin oxide film and indium gallium zinc oxide film, and the metal The film is at least one selected from the group consisting of copper metal films and molybdenum metal films. A metal film etching method, which includes the step of etching a metal film using the metal film etching composition of any one of claims 1 to 9.