KR101157208B1 - Etchant Composition for Patterned Metal Layer and Method of Patterning Metal Layer Using Thereof - Google Patents

Abstract

The present invention relates to an etching composition of a copper-based metal wiring film and a method for patterning a metal wiring film using the same, wherein the etching composition comprises hydrogen peroxide; Oxidizing agents; Fluorine compounds; Chelating agents; Ammonium compounds; And deionized water such that the total weight of the total composition is 100% by weight, in detail, 3 to 35% by weight of hydrogen peroxide; 0.1-5% by weight of oxidizing agent; 0.001 to 2% by weight of a fluorine compound; 0.1 to 5 wt% chelating agent; 0.001-5% by weight of ammonium compound; And deionized water such that the total weight of the total composition is 100% by weight.

Description

Etching composition for patterned metal layer and method of patterning metal layer using thereof

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching composition of a copper-based metallization film, and more specifically, to a metallization film for a gate, a source, and a drain electrode constituting a thin film transistor (TFT) of a liquid crystal display. The present invention relates to an etching solution for obtaining a photoresist pattern by applying a resist to a photoresist and then developing the photoresist pattern to obtain a metal wiring of a desired pattern using the photoresist pattern as an etching mask.

In general, in order to form a metal wiring on a substrate in a semiconductor device, a metal film forming process by sputtering or the like, a photoresist forming process having a predetermined pattern on the metal film, and etching using the photoresist pattern as an etching mask are performed. Process (Republic of Korea Patent Publication 10-2006-0099089).

Among these, the etching process of the metal film is performed by dry etching using plasma or wet etching using an etching solution.

In the case of dry etching, the etching conditions are difficult, such as requiring high vacuum, and the etching requires a lot of time and expensive equipment, which is not suitable for quality maintenance, mass production, and large area processing. In the case of wet etching, the etching characteristics are relatively lower than those of dry etching, and an appropriate etching solution should be developed according to the material and composition of the object to be etched. However, research on etching solutions having improved etching characteristics is actively conducted due to the limitation of dry etching. It is becoming.

On the other hand, the resistance of the metallization film in the TFT-LCD device is a major factor causing the RC signal delay, and obtaining a low-resistance metallization film is a key to increasing the panel size and high resolution.

In the prior art, chromium (Cr, resistivity: 25x10 ^-6 Ωm), molybdenum (Mo, resistivity: 12x10 ^-6 Ωm), aluminum nidium (AlNd, resistivity: 5x10 ^-6 Ωm), which is used as a material of a metal wiring film in the prior art, and these Alloy has high resistance and is limited to use as gate and data wiring used in large size TFT-LCD.

In this regard, copper metals, which are significantly lower in resistance than aluminum or chromium and have no significant environmental problems, have attracted attention as low-resistance wiring film materials.

However, in the case of the copper film, many problems have been found in the selective etching using the photoresist pattern as a mask, and the problem of poor adhesion to the glass substrate or the silicon insulating film has been found.

Rather than using copper alone to solve this problem, a technique of using an intermediate metal film together to increase the adhesion between the copper film and the glass substrate or the silicon insulating film and to suppress the diffusion of copper into the silicon film has been proposed. The intermediate metal film may include titanium, titanium alloy, molybdenum or molybdenum alloy.

Related to the copper-based metal interconnect film etchant, Korean Patent Laid-Open Publication No. 2004-11041 discloses a copper / molybdenum film etching solution containing hydrogen peroxide, organic acids, sulfates, cyclic amine compounds, and deionized water. Although it is possible to obtain a linearity and a relatively satisfactory taper angle of, it is not preferable in terms of change over time because organic acid must be included as an essential component, and there is a problem that a residue of Mo is likely to remain. In particular, According to the research, the taper angle is 70-90 °, resulting in incomplete step coverage of the film, leading to data open defects, and the formation of residue due to partial passivation of molybdenum (Mo). There is a serious problem that a defect or the like occurs.

For etching of copper-based metallization film, peroxide-based etchant is used as in Korean Patent Laid-Open Publication No. 10-2006-0099089, where the amount of metal ions in the etchant increases more than a certain concentration, such as an increase in the number of treated sheets or a large area treatment. When this happens, CD loss of an etch profile increases.

An object of the present invention for solving the above problems is possible to collectively etch a copper film, or multiple films made of a copper film and another metal film, it is possible to prevent the change of CD loss according to the metal ion concentration in the etching solution , Large-area metal wiring film pattern and fine metal wiring film pattern can be formed, no molybdenum alloy residue remains after etching, excellent linearity of metal wiring film pattern, undercut prevention, excellent taper angle It is to provide an etching composition having a photoresist patterned on a metal wiring film for a gate, source or drain electrode constituting a TFT (Thin Film Transistor) of the TFT-LCD The present invention provides a method of forming metal wirings of a desired pattern by wet etching after forming.

The etching composition according to the present invention is a metal wiring film etching composition which is a copper single layer or a multilayer film in which a copper film and a molybdenum film are stacked, hydrogen peroxide 3 to 35% by weight; 0.1-5% by weight of oxidizing agent; 0.001 to 2% by weight of a fluorine compound; 0.1 to 5 wt% chelating agent; 0.001-5% by weight of ammonium compound; And deionized water such that the total weight of the total composition is 100% by weight.

The oxidant is at least one selected from the group consisting of potassium hydrogen sulfate, potassium sulfate, calcium sulfate, sodium nitrate, ammonium sulfate, sodium sulfate and sodium hydrogen sulfate, and the fluorine compound is acidic ammonium fluoride, silicate fluoride, ammonium difluoride, potassium hydrogen fluoride And hydrofluoric acid.

The chelating agent is an organic chelating agent containing an amino group and a carboxyl group, and the organic chelating agent is ethylenediamine tetraacetic acid (EDTA), iminodiacetic acid, nitrilotriacetic acid and di At least one selected from the group consisting of ethylene trinitrilo pentaacetic acid (DTPA; Diethylene Trinitrilo Pentaacetic Acid).

The ammonium compound is at least one selected from the group consisting of ammonium acetate, ammonium nitrate, ammonium citrate, ammonium chloride and ammonia water.

Preferably, the etching composition further contains 0.1 to 5% by weight of a copper etching inhibitor, the copper etching inhibitor is an azole compound of 5-aminotetrazole, 1,2,3-benzotriazole, methylbenzotriazole And imidazole.

The metal wiring film patterning method using the etching composition according to the present invention as described above a) a metal which is a copper film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film of these laminated on the substrate Forming a wiring film; b) applying a photoresist on the metallization film, exposing and developing the photoresist to form a photoresist pattern; c) etching the metallization layer using the etching composition according to the present invention using the photoresist pattern as an etching mask.

In the step a), the substrate is a glass substrate for a TFT-LCD, and the metal wiring layer formed thereon is a gate wiring layer or a data electrode (source) forming a gate electrode and a gate line for applying a signal to the gate electrode. A data wiring film forming a data line for applying a signal to a source electrode, a drain electrode, and a data electrode.

In the etching composition according to the present invention, multiple films including a copper film and a molybdenum film are collectively etched, thereby increasing a process margin during etching, preventing damage to the substrate, and forming a step between the copper film and the molybdenum film by etching. And prevent undercut formation, have a constant taper angle of 30 ° or more, and have excellent CD Loss of 0.5 μm ± 0.2 μm, resulting in excellent straightness of the metal pattern (patterned metal wiring film), and After forming the pattern, it is possible to suppress the occurrence of defects in subsequent processes, to prevent the formation of residues and tails of the molybdenum alloy, and to change the etching loss even when the metal ion concentration in the etching composition is 6000 ppm. Etching property is maintained even in repeated use of etching composition or etching of large area metal wiring film, so quality control is easy, large area processing and large quantity Effective for acid, the gate wiring (including gate electrode), data wiring (including source and drain electrode), and pixel wiring (including pixel electrode) of TFT-LCD can be manufactured using the same etching composition. have.

1 is a flowchart illustrating a method of patterning a metal interconnection film using an etching composition of the present invention.
FIG. 2 is a scanning electron microscope photograph of an etch profile of a laminated film of a copper film-molybdenum film etched using the etching composition of the present invention.
FIG. 3 is a scanning electron micrograph of an etching profile of a laminated film of a copper film-molybdenum film etched using the etching composition of the present invention containing 4000 ppm of copper ions.
4 is a scanning electron microscope photograph of the etching profile of the laminated film of the copper film-molybdenum film etched using the etching composition of the present invention containing 6000ppm copper ion,
5 is a scanning electron micrograph of the copper film-molybdenum film using the etching composition of the present invention after etching the laminated film, and then removing the photoresist.
FIG. 6 is a scanning electron micrograph of an etching profile of a laminated film of a copper film-molybdenum film etched using a Comparative Example 1 etching composition containing 4000 ppm of copper ions.

Hereinafter, the etching composition of the present invention will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided by way of example so that the spirit of the invention to those skilled in the art can fully convey. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms. Also, throughout the specification, like reference numerals designate like elements.

Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

An etching composition according to the present invention is an etching composition for manufacturing a patterned metal wiring film by wet etching a copper-based metal wiring film by using a patterned photoresist as an etching mask, wherein the copper-based metal wiring film is a single layer or a copper film of a copper film and It is a multilayer film in which a molybdenum film is laminated. In this case, the copper film includes a copper alloy film, and the molybdenum film includes a molybdenum alloy film.

The metal wiring film, which is a multilayer film including the copper film and the molybdenum film, includes a copper film (lower layer film) -molybdenum film (upper layer film) or a molybdenum film (lower layer film) -copper film (upper layer film), and at least two molybdenum films are copper It includes a triple layer of molybdenum film-copper film-molybdenum film stacked over the film, and includes a multilayer film in which two or more molybdenum films and two or more copper films are alternately stacked.

The object of the present invention described above is hydrogen peroxide 3 to 35% by weight; 0.1-5% by weight of oxidizing agent; 0.001 to 2% by weight of a fluorine compound; 0.1 to 5 wt% chelating agent; 0.001-5% by weight of ammonium compound; And deionized water such that the total weight of the total composition is 100% by weight.

In the etching composition according to the present invention, the hydrogen peroxide and the fluorine compound play a main role of etching the copper film and molybdenum film. The fluorine compound is at least one selected from the group consisting of acidic ammonium fluoride, ammonium difluoride, silicic acid fluoride, potassium hydrogen fluoride and hydrofluoric acid.

Preferably the fluorine compound is acidic ammonium fluoride, potassium hydrogen fluoride or mixtures thereof. By using acidic ammonium fluoride, potassium hydrogen fluoride or mixtures thereof, it is possible to reduce the residue of molybdenum alloy, to suppress the difference in etching rate with copper film, and to minimize the damage of the substrate including glass and silicon, which forms metal wiring film during etching. There is.

In addition, it is used together with the oxidizing agent, chelating agent, ammonium compound, and copper etch inhibitor described later to collectively view the copper film and the molybdenum film, and to control the etching profile of the multilayer film including the copper film and the molybdenum film, the etching loss control, and the tilt angle control. And the etching composition according to the present invention for preventing undercut contains 3 to 35% by weight of hydrogen peroxide, 0.001 to 2% by weight in order to prevent the effective etching of the molybdenum film, minimizing the substrate etching, the formation of residue or tail (tail) Contains a fluorine compound.

The oxidant dissolves the product produced by etching in an etching composition based on water, and plays a main role in controlling the etching rate of the metallization film. The oxidant is at least one selected from the group consisting of potassium hydrogen sulfate, potassium sulfate, calcium sulfate, sodium nitrate, ammonium sulfate, sodium sulfate and sodium hydrogen sulfate.

Preferably, the oxidant is potassium sulfate, ammonium sulfate, sodium nitrate or mixtures thereof. The potassium sulfate, ammonium sulfate, sodium nitrate or a mixture thereof controls the etching rate of hydrogen peroxide, controls the activity of fluorine contained in the fluorine compound, effectively dissolves the etching product, and does not change over time, so the etching characteristics of the chemical liquid This has a lasting effect.

The etching composition contains 0.1 to 5% by weight of an oxidizing agent for smooth etching of multiple films including a copper film and a molybdenum film, and minimization of substrate damage due to fluorine ions and prevention of undercut.

The chelating agent plays a main role of preventing the deterioration of the etching characteristics due to the increase in the metal ion concentration and maintaining the stability of the etching composition. The chelating agent is an organic chelating agent containing an amino group and a carboxyl group.

The organic chelating agent is Ethylene Diamine Tetraacetic Acid (EDTA), Iminodiacetic Acid, Nitrilotriacetic Acid, and Diethylene Trinitrilo Pentaacetic Acid (DTPA). One or more selected from the group consisting of:

Preferably, the organic chelating agent is ethylenediamine tetraacetic acid (EDTA), diethylene trinitrilo pentaacetic acid (DTPA), or a mixture thereof.

The preferred organic chelating agent increases in the etching composition as the area of the metal wiring film to be etched or the number of etching treatments (the number of substrates on which the metal wiring film is applied to perform etching for metal wiring) increases during the etching of the copper-based metal wiring film. In combination with metal ions (copper ions and molybdenum ions) to deactivate the metal ions, to prevent the self-decomposition of hydrogen peroxide, there is an effect of preventing the change in the CD-ROM according to the number of treatment.

In order to effectively inactivate metal ions while maintaining good etching loss characteristics and preventing precipitation of the chelating agent, the etching composition contains 0.1 to 5% by weight of chelating agent.

The ammonium compound serves to maintain the hydrogen ion concentration index of the etchant, the ammonium compound is one or more selected from the group consisting of ammonium acetate, ammonium nitrate, ammonium citrate, ammonium chloride and ammonia water, preferably ammonium chloride , Ammonium acetate, ammonia water or mixtures thereof. At this time, the ammonia water means 0.001 to 0.1% by weight of ammonia water.

The preferred ammonium compound not only effectively maintains the hydrogen ion concentration index in the etchant, but also has the effect of suppressing the residue of molybdenum and controlling the etching characteristics according to the number of treatments constantly.

In order to maintain a hydrogen ion concentration index to suppress the residue of molybdenum and to maintain the etching characteristics according to the number of treatments, the etching composition contains 0.001 to 5% by weight of an ammonium compound.

The copper etch inhibitor is used in combination with the above-described hydrogen peroxide, fluorine compound, oxidizing agent, chelating agent and ammonium compound to control the etching rate of the copper film. The copper etch inhibitor is at least one selected from the group consisting of azole compound 5-aminotetrazole, 1,2,3-benzotriazole, methylbenzotriazole and imidazole.

Preferably the copper etch inhibitor is 5-aminotetrazole, 1,2,3-benzotriazole or mixtures thereof, and the 5-aminotetrazole, 1,2,3-benzotriazole or mixtures thereof is copper In addition to suppressing the difference in etching rates between the film and the molybdenum film, there is an effect of controlling the sidiros.

The copper etch inhibitor is to suppress the etching rate difference between the copper film and the molybdenum film based on the hydrogen peroxide, the oxidizing agent, the fluorine-based compound, the chelating agent, the material of the ammonium compound and the amount of each material according to the present invention. In order to maintain the etch rate of the appropriate copper film and to maintain a constant taper tilt angle, the etching composition contains 0.1 to 5% by weight of copper etch inhibitor.

Hydrogen peroxide, oxidizing agent, fluorine-based compound, chelating agent, ammonium compound and copper etching inhibitor contained in the etching composition according to the present invention and the content of each material in the etching composition and the etching rate of the copper film, the etching rate of the molybdenum film, the copper film and molybdenum The difference in the etching rate of the film, the etching profile of the metallization film, the taper angle, the degree of CD loss and critical dimension loss, whether the molybdenum alloy residues are formed, and the amount of metal ions generated during etching. It affects the change of etching characteristics, margin of etching process design, calorific value during etching and composition change of etching composition during etching.

The etching composition according to the present invention contains 3 to 35% by weight of hydrogen peroxide, 0.001 to 2% by weight of the fluorine compound described above, and 0.1 to 5% by weight of the chelating agent described above to increase the process margin during etching of the metal wiring film, and the substrate It minimizes the damage, suppresses the exotherm, can suppress the rapid compositional change of the etching composition, and prevents the formation of molybdenum alloy residue.

In addition, the etching composition according to the present invention is 3 to 35% by weight of hydrogen peroxide and 0.001 to 2% by weight of the above-mentioned fluorine compound, 0.1 to 5% by weight of the oxidizing agent, 0.001 to 5% by weight of the ammonium compound and the above-mentioned copper etching 0.1 to 5% by weight of inhibitor to suppress the etching rate of the copper film and to increase the etching rate of the molybdenum film effectively reduce the etching rate difference between the copper film and molybdenum film to prevent damage to the substrate, and by etching the copper film and molybdenum It prevents step formation and undercut between layers, has a constant taper angle of 30 ° or more, and has excellent CD loss of 0.5 μm ± 0.2 μm, so that the metal pattern (patterned metal wiring film) It is excellent in straightness and suppresses the generation of a defect in a subsequent process after metal pattern formation.

In addition, the etching composition according to the present invention is 3 to 35% by weight of hydrogen peroxide, 0.001 to 2% by weight of the above-mentioned fluorine compound, 0.1 to 5% by weight of the oxidizing agent, 0.001 to 5% by weight of the ammonium compound and the above-mentioned copper etching inhibitor 0.1 It contains 0.1 to 5% by weight of the above-mentioned chelating agent together with ~ 5% by weight, while maintaining an excellent etching profile and preventing the formation of residues or tails, the change in etching loss is ± 0.2 even when the metal ion concentration in the etching composition is 6000 ppm. It is kept within μm, and the etching characteristics are kept constant even in the repeated use of the etching composition or the etching of the metal wiring film of a large area, so that the quality control is easy, and it is effective for the large area processing and mass production, and the gate of the TFT-LCD ) Wirings (including gate electrodes), data wirings (including source and drain electrodes), and pixel wirings (including pixel electrodes) may be manufactured using the same etching composition.

In addition, the etching composition according to the invention is hydrogen peroxide 3 to 35% by weight; 0.1 to 5% by weight of the oxidizing agent described above; 0.001 to 2% by weight of the above-mentioned fluorine compound; 0.1 to 5% by weight of the above chelating agent; By containing 0.001 ~ 5% by weight of the above-described ammonium compound; the metal ion concentration in the etching composition up to 6000ppm has the characteristic that the advantage of maintaining the exothermic and metal etching characteristics of the chemical solution is maintained.

In the method for patterning a metal wiring film using the etching composition according to the present invention described above, a copper film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, a molybdenum alloy film, or Forming a metal wiring film, which is a multilayer film of which they are stacked (s10), applying a photoresist (s20), irradiating light to the photoresist using a mask, and then developing the patterned photoresist (s30). ), Using the patterned photoresist as an etching mask, etching the metallization film using the etching composition according to the present invention (s40).

The substrate is a glass substrate for a TFT-LCD or a silicon substrate for a TFT-LCD, and the silicon substrate includes a silicon substrate loaded with locally intentional impurities (n or p-type impurities), and a heterogeneous material including an oxide film and a nitride film. And a silicon substrate on which a film is formed. The meaning of the upper part of the substrate includes both the case of contacting the surface of the substrate and the case of being spaced apart from the surface of the substrate by a predetermined distance without contacting the surface of the substrate.

The formation of the metallization layer, the application of the photoresist, the exposure and the development of the photoresist may be performed through a method commonly used in a semiconductor manufacturing process. For example, the metallization layer may be formed using a chemical precursor using a copper precursor or a molybdenum precursor. Deposition (CVD), plasma deposition or physical vapor deposition (PVD) using copper bulk, molybdenum bulk, and the application of the photoresist may be performed using spin coating, the exposure is a mark pattern Depending on the fineness of the may be performed using equipment such as ultraviolet, x-ray, ion beam and mask aligner, stepper.

The silicon substrate for TFT-LCD includes a plurality of gate lines and data lines orthogonal to each other with an insulating layer interposed therebetween, and the thin film transistors formed at the intersections of the gate lines and the data lines. It has a structure connected to the gate line, the source electrode is connected to the data line, the drain electrode is connected to the pixel electrode of the TFT-LCD liquid crystal cell.

By using the etching composition according to the present invention described above and the metal wiring layer patterning method described above, a data vessel including a source electrode, a drain electrode, and a data line is formed, and the same etching composition and the metal wiring layer patterning method according to the present invention. The gate wiring including the gate electrode and the gate line is formed by using the.

Preparation of Etch Composition

To prepare the etching composition according to the present invention (Examples 1 to 4) by mixing the materials of Table 1 in the following Table 2 (% means weight%).

(Table 1)

(Table 2)

As a comparative example, the materials of Table 3 below were mixed in the content of Table 4 (% means% by weight) below to prepare an etching composition (Comparative Examples 1 to 4) to be compared.

(Table 3)

(Table 4)

Etching of Metallization Film

After depositing 250 mol of molybdenum film on a glass substrate (100x100mm) using DC magnet sputter, a copper film of 3000 µm was deposited on the molybdenum film using DC magnet sputter to deposit a laminated film of copper (top) -molybdenum film (lower). Phosphorus metal interconnection film was prepared, and in order to evaluate whether molybdenum tail, residue and etching were produced, a metal interconnection film, which is a laminated film of molybdenum (top) -copper (bottom) layer, was prepared in a similar manner.

After applying the photoresist to the metal wiring film, using a mask having a pattern for forming the gate line and the gate electrode of the TFT-LCD, or using a mask having a pattern for forming the data line and the source and drain electrodes Exposure and development were performed to produce a photoresist pattern patterned with gate wirings or source and drain wirings.

Then, using the photoresist pattern as an etching mask, using the etching composition prepared in Examples 1 to 4 of Table 1 and Table 2 or each of the etching compositions prepared in Comparative Examples 1 to 4 of Table 3 and Table 4 Etching of the membrane was performed.

In the experiments of Examples to Comparative Examples, the etching of the metal wiring film was carried out at 30 ° C. using the same etching composition amount (10 kg) and a spray miniature (Techno Semichem Co., Ltd.).

The etching process using the etching composition was performed by giving an over etching rate of 60% or 100% from the end point detection (EPD), which is the point where the glass of the glass substrate is exposed. After completion of etching, After washing and drying, the lateral etching loss, taper angle, photoresist breakage, and etching residue of the etching profile were evaluated by scanning electron microscope.

In addition, to evaluate the etching characteristics according to the metal ion content of the etching composition, a copper powder corresponding to 4000ppm or 6000ppm was added to the etching solution (prepared etching composition) and stirred until the copper powder was completely dissolved. Subsequently, the etching characteristics of the etchant, in which the copper powder was dissolved in a spray method at 30 ° C., were analyzed using miniature (Techno Semichem Co., Ltd.).

Etch Characteristic Evaluation

After etching the metal wiring film (laminated film of molybdenum film-copper film), the etched side profile was observed using a scanning electron microscope (SEM, Hitachi, S-4700), and the distance between the photoresist end and the copper end CD loss was measured by measuring and the inclination angle (taper angle) was measured by measuring the inclination angle of the etched side.

In addition, by using a scanning electron microscope to observe the patterned metal wiring film before and after the strip (removed) of the patterned photoresist, photoresist breakage, molybdenum tail and residues during the etching of the metal wiring film, etching residues (including deposits) ) Was evaluated.

CD loss is excellent when 0.5 ㎛ ± 0.2 ㎛ or less, taper angle is excellent when 30˚ or more, the etching loss change rate (hereinafter CD change rate) is an evaluation index of the etching characteristics according to the metal ion content is copper powder It was evaluated that the etching loss was maintained at 0.5 μm ± 0.2 μm during the etching using the dissolved etchant, that is, the change of the etching loss within ± 0.2 μm at 4000 ppm or 6000 ppm copper ion concentration was excellent. The evaluation of etching characteristics according to the etching composition of ˜4 is shown in Table 5 below.

(Table 5)

Hereinafter, the results of etching characteristics of the etching composition of Example 1 will be described in detail, but the etching compositions of Examples 2 to 4 according to the present invention showed similar etching characteristics as in Example 1.

FIG. 2 is a scanning microscope photograph of the side surface of the metallization film etched using the etching composition of Example 1 of the present invention, and shows no damage of photoresist at 60% overetch rate, and the copper film (top) -molybdenum It can be seen that the multilayered film (lower layer) has a single inclined plane with an inclination angle of 48.15 ° and has an etching loss of 0.58 μm.

Figure 3 is a scanning microscope photograph of the side of the metal wiring film etched by dissolving 4000ppm copper powder in the etching composition of Example 1 of the present invention, there is no damage to the photoresist at 60% over-etch rate , Multilayered copper film (top) -molybdenum film (bottom) has a single inclined plane with an inclination angle of 60.38 °, and has an etching loss of 0.6 µm, resulting in little change in CD-Ros according to the number of treatments (within ± 0.2 µm) Can be seen.

Figure 4 is a scanning microscope photograph of the side of the metal wiring film etched using after dissolving 6000ppm copper powder in the etching composition of Example 1 of the present invention, there is no damage to the photoresist at 60% over-etch rate , Multilayered copper film (top) -molybdenum film (bottom) has a single inclined surface with an inclination angle of 63.77 °, and has an etching loss of 0.64㎛, so that the change in CD-Ros according to the number of treatments is small (within ± 0.2㎛) Can be seen.

FIG. 5 is a scanning electron micrograph of the metal wiring layer etched using the etching composition of Example 1 of the present invention and then removed by photoresist, wherein a copper film (bottom) -molybdenum film (top) is stacked in multiple layers It can be seen that the tail, residues and residues of the molybdenum are not formed upon etching of the film.

In Comparative Example 1, as the concentration of metal ions increases, as shown in FIG. 6, the change in CDiros was drastically changed. In Comparative Example 2, since the etching was not performed, patterning of the metal wiring film was impossible, and Comparative Example 3 In the case of etching, as the etching proceeds as soon as the substrate is input due to the excessive amount of the oxidizing agent, the etching loss is rapidly generated, and in the case of Comparative Example 4, precipitates were generated.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all of the equivalents or equivalents of the claims as well as the claims to be described later will belong to the scope of the present invention. .

Claims (9)

delete delete delete delete delete An etching composition of a metal wiring film in which a copper film and a molybdenum film are laminated, and hydrogen peroxide 3 to 35 wt%; 0.1 to 5% by weight of an oxidizing agent selected from the group consisting of potassium hydrogen sulfate, sodium nitrate, ammonium sulfate, sodium sulfate and sodium hydrogen sulfate; 0.001% to 2% by weight of a fluorine compound selected from the group consisting of acidic ammonium fluoride, silicic acid fluoride, potassium hydrogen fluoride and hydrofluoric acid; At least one from the group consisting of ethylenediamine tetraacetic acid (EDTA), iminodiacetic acid, nitrilotriacetic acid, and diethylene trinitrilo pentaacetic acid (DTPA); 0.1 to 5% by weight of the chelating agent selected; 0.001 to 5% by weight of an ammonium compound selected from the group consisting of ammonium acetate, ammonium nitrate, ammonium citrate, ammonium chloride and ammonia water; An etching composition comprising 0.1 to 5% by weight of a copper etch inhibitor and deionized water such that the total weight of the total composition is 100% by weight. The method according to claim 6,
The copper etching inhibitor is at least one selected from the group consisting of azole compound 5-aminotetrazole, 1,2,3-benzotriazole, methyl benzotriazole and imidazole. 8. The method of claim 7,
The etching composition maintains a change in etching loss (CD loss) within ± 0.2 ㎛ even if the metal ion concentration in the etching composition increases to 6000ppm. a) forming a copper wiring film, a copper alloy film, a titanium film, a titanium alloy film, a molybdenum film, a molybdenum alloy film, or a metal film formed of a multilayer film on the substrate;
b) applying a photoresist on the metallization film, exposing and developing the photoresist to form a photoresist pattern;
c) etching the metallization film using the etching composition according to any one of claims 6 to 8 using the photoresist pattern as an etching mask;
Patterning method of a metal wiring film comprising a.

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