KR20220139260A - Etchant composition - Google Patents

Abstract

The present invention provides an etchant composition used for etching a transition metal film used as an electrode of a TFT-LCD display, etc. With a significantly increased number of films to be treated, the etchant composition of the present invention has excellent etching properties, such as etch bias, taper angle, and tail length, and thus can be useful for manufacturing TFT-LCD display, OLED electrodes, etc. The etchant composition of the present invention comprises an etching inhibitor selected from monocyclic or polycyclic heterocyclic compounds containing at least one heteroatom selected from oxygen, sulfur and nitrogen in the molecule; chelating agents; an etch control agent selected from sulfates and phosphates; hydrogen peroxide; and a residual amount of water.

Description

etching composition {ETCHANT COMPOSITION}

The present invention relates to an etching composition, and more particularly, to an etching composition used for etching a transition metal film used as an electrode of a TFT-LCD display, in particular a copper and/or molybdenum-containing metal film.

In general, a thin film transistor (TFT) is used as a circuit board for independently driving each pixel in a liquid crystal display device or an organic EL (Elec3tro Luminescence) display device. The TFT has a scan signal line or gate line that transmits a scan signal and an image signal line or data line that transmits an image signal, and a thin film transistor connected to the gate line and data line, a pixel electrode connected to the thin film transistor, etc. consists of The process of forming the wiring of such a TFT is generally a sputtering process for forming a metal film, a photoresist application, a photoresist formation process of a desired pattern by exposure and development, an etching process for wiring formation, and a photoresist unnecessary after the wiring is formed. It consists of a peeling process to remove

Conventionally, aluminum or aluminum alloy layers have been commonly used as wiring materials for TFT gate and data line electrodes to manufacture semiconductor devices and TFT-LCD substrates. To this end, attempts are being made to use copper and/or molybdenum, which are metals having low resistance, for wiring formation. Accordingly, research on an etching composition used for etching a wiring including copper and/or molybdenum is being actively conducted.

In order to etch the copper and molybdenum-containing wirings, a composition of an etchant having a strong oxidizing power is required. Accordingly, Patent Document 1 discloses a mixture of hydrogen peroxide (H ₂ O ₂ ) and an inorganic acid or a neutral salt as an etchant for a copper film, and Patent Document 2 includes hydrogen peroxide, a copper reaction inhibitor, a perwater stabilizer and fluoride ions. An etchant is disclosed. In addition, Patent Document 3 discloses an etchant obtained by adding five additives including a fluorine compound and organic molecules to hydrogen peroxide, and Patent Document 4 discloses a mixture of iron (III) hexahydrate and hydrofluoric acid (HF). . However, the conventionally known etchant has a problem in that the etching rate for the copper film and other metal films is too fast, or the taper angle of the etched metal pattern exceeds about 90°, that is, has a reverse taper shape. In addition, when the concentration of copper ions is increased, copper ions react with hydrogen peroxide to form radicals, and the formed radicals decompose organic materials contained in the composition to change the characteristics of the etchant, thereby increasing the defect rate.

Accordingly, the present inventors solve the problems of the prior art and at the same time provide an etching composition having excellent etching characteristics such as taper angle, CD loss and etching straightness even when the metal ion content in the etchant is high with a significantly improved treatment medium. The present invention was completed to provide.

KR2000-0079355 KR2005-0000682 KR2006-0064881 KR2000-0032999

The problem to be solved by the present invention is to provide an etching composition effective for etching a transition metal film used as an electrode of a TFT-LCD display, etc. It is an object of the present invention to provide an etching composition exhibiting excellent etching properties for a metal film and an etching method using the same.

An etching composition for solving the above problems includes an etch inhibitor selected from monocyclic or polycyclic heterocyclic compounds containing one or more heteroatoms selected from intramolecular oxygen, sulfur and nitrogen; chelating agents; and an etch control agent selected from sulfate and phosphate.

The etching composition according to an embodiment of the present invention is characterized in that it contains 20 to 60 parts by weight of a chelating agent and 5 to 12 parts by weight of an etch control agent based on 1 part by weight of the etch inhibitor, and the following Relations 1 and 2 Satisfies.

(Relation 1)

△T _a ＜ 10°

(In Relation 1, ΔT _a means the absolute value of the taper angle change width.)

(Relation 2)

ΔE _bias ＜ 0.05 ㎛

(In Relation 2, ΔE _bias means the absolute value of the etch bias change width.)

The etching composition according to an embodiment of the present invention is used for etching copper, molybdenum, or an alloy film thereof.

In particular, the etching composition according to an embodiment of the present invention can provide high selectivity to a metal film including copper and/or molybdenum or a molybdenum alloy film and remarkably improve the number of etching treatment sheets at the same time. In addition, despite the high concentration of metal ions in the etchant, desired etching characteristics may be more stably expressed.

In addition, the etching composition according to an embodiment of the present invention may further include commonly known additives, and non-limiting examples thereof include, but are not limited to, a fluorine compound, an undercut inhibitor, and the like. .

The present invention provides an etching method using an etching composition satisfying the above conditions. In this case, the etching composition is characterized in that the copper, molybdenum, or an alloy film thereof is selectively etched.

The etching composition according to the present invention has the advantage of being able to stably maintain a remarkably improved number of treatments for a long period of time. Accordingly, when the transition metal layer is etched, a tape profile having excellent linearity can be realized, and CD loss can be remarkably reduced, thereby effectively suppressing the generation of residues. In addition, the etching composition according to the present invention has significantly improved storage stability, and shows stability without deterioration in the number of etching treatment sheets despite long-term use or storage.

In addition, the etching composition according to the present invention can not only greatly simplify the process, but also greatly simplify the process because the etching composition according to the present invention can simultaneously etch the gate wiring and the source/drain wiring when manufacturing a substrate such as a liquid crystal display device or an organic EL (Electro Luminescence) display device. , it is possible to implement an excellent effect in the etching of a metal film including a copper and/or molybdenum or alloy film having a low resistance.

In short, according to the present invention, the occurrence of problems such as electrical short, defective wiring, and decrease in luminance is minimized, and the amount of etchant used is relatively reduced while a large-area, high-brightness liquid crystal display device or organic EL (Electro Luminescence) A display device or the like can be provided in a very economical way.

1 is an SEM photograph analyzed after etching in 30 treated sheets (copper ion concentration 300 ppm) using the etching composition (Example 1) presented in the present invention.
2 is an SEM photograph analyzed after etching using the etching composition (Example 1) presented in the present invention in the number of 700 sheets (copper ion concentration: 7,000 ppm). It can be seen that the etching characteristics are maintained without changes in CD loss and taper angle from 30 to 700 sheets processed.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be embodied in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims. Hereinafter, the etching composition according to the present invention will be described in detail.

Recently, high image quality and/or enlargement required for display substrates require an increase in the thickness of a metal film used for wiring. Specifically, the size of the pixel decreases due to the high image quality, the wiring width gradually decreases, and the wiring resistance must be decreased due to the large size. To this end, the thickness of the metal film used as the wiring is inevitably increased. For the reasons as described above, the process time for the desired etching is lengthened, and the concentration of metal ions in the etchant solution is rapidly increased, so it is necessary to make an effort to improve the effective period in which the etching characteristics are maintained, that is, the number of treatment sheets.

Although the conventional etching composition has an excellent etching rate, when the concentration of metal ions during etching is increased, there are problems such as an increase in sidiloss and an increase in taper angle. The increase in the CD loss causes a change in the resistance value of the metal film, and cracks in the PAS insulating film occur due to the high taper angle, thereby causing shortage defects.

Accordingly, the present inventors have solved the above-mentioned problems and have intensified research on an etching composition having a more improved number of treatment sheets. As a result, in the case of a specific etching composition, it was confirmed that it was possible to realize high etching characteristics despite long-term use by remarkably improving the number of etching treatment sheets and increasing the stability thereof, thereby completing the present invention. At this time, according to an embodiment of the present invention, it was confirmed that excellent in etching characteristics, such as etch 　 bias, taper angle, tail length, etc., but is not limited thereto.

The etching composition according to an embodiment of the present invention includes an etch inhibitor selected from monocyclic or polycyclic heterocyclic compounds containing at least one hetero atom selected from oxygen, sulfur and nitrogen in a molecule; chelating agents; and an etch control agent selected from sulfate and phosphate.

Specifically, the etching composition according to the present invention is characterized in that it contains 20 to 60 parts by weight of the chelating agent and 5 to 12 parts by weight of the etch control agent based on 1 part by weight of the etch inhibitor in the composition described above. At this time, according to the present invention, the etching composition has a high content of the chelating agent relative to the total weight of the composition. This is different from that in the conventional etching composition, including the same amount of an etch inhibitor, a chelating agent, an etch control agent, and the like.

The etching composition according to an embodiment of the present invention is remarkable in etching characteristics such as _a taper angle (Ta) and an etch bias (E _bias ) when etching a transition metal film, particularly a copper and/or molybdenum or copper-molybdenum alloy film. looks like

The etching composition according to an embodiment of the present invention satisfies the following Relations 1 and 2 as it has the above-described combination.

(Relation 1)

△T _a ＜ 10°

(In Relation 1, ΔT _a means the absolute value of the taper angle change width.)

(Relation 2)

ΔE _bias ＜ 0.05 ㎛

(In Relation 2, ΔE _bias means the absolute value of the etch bias change width.)

Furthermore, the etching composition according to an embodiment of the present invention provides a high content of the chelating agent relative to the total weight of the composition and an appropriate ratio between the chelating agent, the etch inhibitor, and the etch control agent, thereby providing a high chelating effect with metal ions generated during etching. It was found that it can be implemented and has an unexpected synergistic effect in the number of etching treatments according to having the above-described combination.

Specifically, as the etching proceeds due to the high content of the chelating agent, the degree of decomposition can be reduced by chelating the copper ions even when the copper metal ions in the composition continuously increase to effectively suppress the radical reaction of hydrogen peroxide. In addition, even when the number of treatments is increased at an appropriate ratio between the proposed chelating agent, etch inhibitor, and etch control agent, the range of change in CD loss and taper angle is significantly reduced compared to the conventional etching composition, confirming that up to 700 sheets of treatment can be applied. did.

The etching composition according to an embodiment of the present invention may further include a fluorine compound. At this time, the fluorine compound reduces the tail length by improving the etching rate of the molybdenum or molybdenum alloy film when simultaneously etching the double metal film, for example, a copper / molybdenum or copper / molybdenum alloy film, and molybdenum or molybdenum which is inevitably generated during etching It acts to remove the residue of the molybdenum alloy film.

According to the present invention, it is possible to provide excellent luminance characteristics by effectively suppressing the tail length of the molybdenum or molybdenum alloy film generated during etching, as well as etching characteristics such as taper angle and etch bias, and no residue of molybdenum or molybdenum alloy film is generated. It is good because it is possible to effectively suppress problems such as electrical shorts and wiring defects that may occur in the substrate and/or the lower layer.

The fluorine compound according to an embodiment of the present invention is a compound capable of dissociating to generate F ^- or HF ₂ ^- , but specific examples include HF, NaF, KF, A 1F ₃ , HBF ₄ , NH ₄ F, It may be one or more selected from NH ₄ HF ₂ , NaHF ₂ , KHF ₂ and NH ₄ BF ₄ . At this time, in the etching composition according to an embodiment of the present invention, the amount of the fluorine compound used is not limited, but may be included in an amount of 0.01 to 5% by weight based on the total weight of the composition, and as an example of a metal residue, copper/molybdenum or copper In terms of effectively removing the molybdenum or molybdenum alloy film residue from the / molybdenum alloy film and suppressing the etching of the lower film such as a glass substrate, it may be preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight.

In the etching composition according to an embodiment of the present invention, the etch inhibitor controls the etch rate of the transition metal to reduce the CD loss of the pattern, increase the process margin, and an etch profile having an appropriate taper angle. , may be a heterocyclic compound containing one or more heteroatoms selected from oxygen, sulfur and nitrogen in the molecule. In this case, the heterocyclic compound according to the present invention may include a monocyclic heterocyclic compound and a polycyclic heterocyclic compound having a condensed structure of a monocyclic heterocycle and a benzene ring.

Specific examples of the heterocyclic compound include oxazole, imidazole, pyrazole, triazole, tetrazole , 5-aminotetrazole, 5 -Methyltetrazole , piperazine, methylpiperazine, hydroxylethylpiperazine, benzimidazole, benzpyrazole , tolutriazole ), hydrotolutriazole, hydroxytolutriazole, indole, purine, pyridine, pyrimidine, pyrrole and pyrroline (pyrroline) and the like, and preferably one or two or more selected from tetrazole, 5-aminotetrazole and 5-methyltetrazole.

In this case, the amount of the etch inhibitor used is not limited, but it may be included in an amount of 0.01 to 5% by weight, preferably 0.05 to 5% by weight, more preferably 0.05 to 5% by weight, for easy adjustment of the etch rate and economical mass productivity. 3% by weight.

In addition, in the etching composition according to an embodiment of the present invention, the etch control agent may be one or more selected from sulfate and phosphate. At this time, the etching composition according to the present invention is characterized in that the pH is in the range of 1 to 5.

The etch control agent serves as a secondary oxidizing agent for a transition metal or metal and improves the taper profile, and includes potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, and sodium persulfate ( sodium persulfate), potassium sulfate, potassium persulfate, ammonium sulfate, sulfate selected from ammonium persulfate; ammonium phosphate monobasic, ammonium phosphate dibasic, sodium phosphate monobasic, sodium phosphate dibasic, potassium phosphate monobasic and a phosphate selected from potassium phosphate dibasic and the like; and the like, and in terms of the effect of improving the etching properties, the etching control agent is preferably a mixture of one or more selected from the sulfate salts and one or more selected from the phosphate salts, but is not limited thereto.

In the etching composition according to an embodiment of the present invention, the chelating agent forms a chelate with metal ions generated during etching to inactivate them, thereby preventing the occurrence of side reactions by these metal ions, and as a result, etching is performed even in repeated etching processes. to keep the characteristics. In particular, in the case of a copper layer, when a large amount of copper ions remain in the etching composition, a passivation film is formed and oxidized, and there is a problem that the etching is not performed. It was confirmed that the stability of the composition can be improved by effectively preventing and simultaneously preventing the decomposition reaction of the etching composition itself.

Furthermore, according to the present invention, by using a chelating agent 10 times or more of the amount of the etch inhibitor, not the combination of the etch inhibitor, the etch control agent, and the chelating agent used at the same level in the conventional etch composition, it is possible to realize significantly improved etching properties. In addition, it was found that the decomposition reaction caused by the oxidized metal ions during the etching process can be promoted to significantly suppress heat generation and/or explosion. In addition, it was found that, as described above, a surprising synergistic effect was exhibited in etching properties such as etch 　 bias, taper angle, and tail length due to the combination of an excessive amount of the chelating agent, the etch inhibitor, and the etch control agent in an appropriate ratio.

The chelating agent in the etching composition according to an embodiment of the present invention is not limited, but preferably iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrilepentaacetic acid, aminotris(methylenephosphonic acid), ( One selected from 1-hydroxyethane-1,1-diyl)bis(phosphonic acid), ethylenediamine tetra(methylenephosphonic acid), diethylenetriamine penta(methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid and glycine More preferably, it may be one or more having two or more acid groups such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and diethylenetrinitrilepentaacetic acid. In particular, when two or more acetic acid groups are used, the above-mentioned effect takes precedence.

The etching composition according to an embodiment of the present invention is a hydrogen peroxide-based etching composition containing hydrogen peroxide (fruit water, H ₂ O ₂ ) as a main component, which is a transition metal film, particularly a metal film including a copper and molybdenum or molybdenum alloy film having low resistance. It has an excellent effect on etching. In general, in a hydrogen peroxide-based etching composition, a metal ion formed by etching reacts with hydrogen peroxide to form a radical, and the radical formed in this way decomposes an organic component contained in the composition, thereby lowering the etching characteristics, and the differential pressure due to the precipitation of an excessive amount of decomposition products cause problems such as However, according to the present invention, by effectively chelating metal ions, it is possible to remarkably improve the problem. In this case, the amount of hydrogen peroxide used is not limited, and is preferably included in an amount of 10 to 30% by weight, preferably 15 to 30% by weight, and more preferably 20 to 30% by weight based on the total weight of the composition.

In particular, according to the present invention, in the metal film containing copper and/or molybdenum, the number of treated sheets, which was only 450 sheets (copper ion concentration 4,500 ~ 5,000 ppm), is at least 700 sheets (copper ion concentration 7,000 ~ 7,500 ppm) or more It has been confirmed that it can be improved with a maximum of 2,000 sheets. In addition, according to the present invention, it is possible to dramatically improve etching characteristics such as taper angle, CD loss, and etch straightness, as well as protect the interface between the double metal film or the multi-metal film, thereby suppressing interfacial overetching. It enables highly selective etching.

In addition, it goes without saying that the etching composition according to an embodiment of the present invention may further include an additive such as an fruit water stabilizer. This stabilizes hydrogen peroxide during the etching process, thereby helping to exhibit etching properties with high stability. The fruit water stabilizer has an alcohol group and an amine group or has them at the same time, and is not limited as long as it is commonly used in the art, but specific examples thereof include methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, triethanol amine, dimethylethanolamine, N-methylethanolamine, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, and the like, but is not limited thereto. The etching composition according to an embodiment of the present invention can be suitably controlled by the type and thickness of the desired transition metal layer, but, based on 1 part by weight of the etch inhibitor, the etch control agent and the chelating agent are 1:10 to Mixing in a weight ratio in the range of 1:30 is preferred for the desired effect in the present invention, but is not limited thereto.

The etching composition according to the present invention provides easy control of the etching rate during etching of a transition metal or metal film, excellent etch profile, and excellent straightness of wiring. In addition, it is possible to completely remove molybdenum or molybdenum alloy film residues that may occur during etching, so transition metal films used for TFT-LCD gates and source/drain electrodes, especially copper/molybdenum or molybdenum alloy films, are etched. It can be very usefully used as a composition.

Furthermore, it not only has significantly improved storage stability compared to the conventional etching composition, but also does not decompose hydrogen peroxide even at a concentration of 7,000 ppm of metal ions generated in the etching process, and can be etched stably.

The etching composition according to an embodiment of the present invention may be used to etch a metal film, and the metal film described in the present invention includes all of a metal, a non-metal, or a transition metal. Preferably, the metal film may be a single metal film, a metal alloy film, or a metal oxide film, and as a specific example thereof, copper and/or molybdenum as a main component, titanium, indium, zinc, tin, tungsten, silver, gold, chromium , manganese, iron, cobalt, nickel, and may be a metal film further comprising one or more metals or transition metals selected from niobium, preferably a copper film, a copper / molybdenum film, a copper / titanium film, a copper / molybdenum alloy The film may be a copper/indium alloy film, and more preferably a copper/molybdenum film or a copper/molybdenum alloy film, but is not limited thereto.

The copper/molybdenum film or copper/molybdenum alloy film may be a multilayer in which one or more copper (Cu) films and one or more molybdenum (Mo) films and/or molybdenum alloy films (Mo-alloy) are stacked on each other, and the multilayer is Cu. It may include a /Mo(Mo-alloy) double layer, a triple layer of Cu/Mo(Mo-alloy)/Cu or Mo(Mo-alloy)/Cu/Mo(alloy). The order of the layers may be appropriately adjusted according to the material and bonding properties of the substrate.

Molybdenum alloy film according to an embodiment of the present invention is molybdenum-tungsten (Mo-W), molybdenum-titanium (Mo-Ti), molybdenum-niobinium (Mo-Nb), molybdenum-chromium (Mo-Cr) or molybdenum - It may be made of tantalum (Mo-Ta), and the molybdenum film or molybdenum alloy film may be deposited to have a thickness of 100 to 500 Å and the copper film to have a thickness of 1000 to 10,000 Å in terms of efficient etching without residue.

In addition, the present invention provides a method of etching a metal film using the above-described etching composition. Of course, the etching method of the metal film according to the present invention can be performed according to a conventional method, and by using the etching composition of a specific composition according to the present invention, it is excellent in etching characteristics, that is, etch 　 bias, taper angle, tail length, etc. see.

Specifically, depositing a metal film on the substrate; patterning after forming a photoresist film on the metal film; and etching the metal layer on which the patterned photoresist layer is formed using the etching composition of the present invention. In this case, the metal film formed on the substrate may be a single film, a double metal film, or a multi-metal film (multi-layer metal film), and in the case of a double metal film or a multi-metal film, the stacking order is not particularly limited.

In addition, the etching method of the metal film may include; forming a semiconductor structure between the substrate and the metal film, that is, between the substrate and the copper film or between the substrate and the molybdenum film in the case of, for example, a copper/molybdenum film. 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 layers selected from a dielectric film, a conductive film, and a silicon film such as an amorphous or polycrystalline film, and these semiconductor structures may be manufactured according to a conventional method.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. Of course, the following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

In the present invention, unless otherwise stated, all temperatures are in °C, and the amount of the composition used is in units of weight %.

(Examples 1 to 7 and Comparative Examples 1 to 6)

Etching compositions of Examples 1 to 7 and Comparative Examples 1 to 6 according to the present invention were prepared by mixing each component at the component content shown in Table 1 below.

(Table 1)

In order to evaluate the effect of the etching composition prepared by the above method, a molybdenum film is deposited to a thickness of 100 Å as a barrier metal on the TFT-LCD GLS, and a copper film is deposited to a thickness of 5,000 Å on the TFT-LCD GLS, and then a photolithography process is performed to form a pattern to form a specimen. was prepared. To check the etching characteristics (taper angle, etch bias) of each etching composition, each specimen was processed with respect to 50% of the EPD standard using a mini-etcher equipment, and copper powder was added at 300 ppm and 5,000 to observe the characteristics of the number of etching treatments. Specimens evaluated by cumulative dissolution up to ppm and 7,000 ppm were observed using a scanning electron microscope (manufactured by Hitachi, SU8010) (see FIGS. 1 to 2).

In addition, the occurrence of precipitates, which is a method of confirming the etching characteristics of the etching composition prepared by the above method, was confirmed whether or not precipitates were generated by adding 7,000 ppm of copper powder to the etching compositions of Examples and Comparative Examples under a constant temperature condition of 32°C.

In addition, in order to confirm the storage stability of the etching composition prepared by the above method, the mini-etcher was evaluated for each time period (confirmation of change over time: 0 to 30 days).

The results of Examples and Comparative Examples according to the above evaluation are shown in Table 2 below.

(Table 2)

As shown in Table 2, according to the present invention, even when the metal ion content in the etchant is high by repeating the etching process according to the present invention, not only can the etching characteristics be maintained, but also the taper angle change width and the etching bias change width are significantly improved. By implementing a tape profile with excellent performance and remarkably reducing CD loss, the generation of residues can be effectively suppressed.

In addition, in the case of the etchant composition shown as a comparative example, if the number of its treatment sheets was 450 (about 4,500 ppm ~ 5,000 ppm), the number of sheets of the etchant composition according to the present invention was 700 sheets (about 7,000 ppm ~ 7,500 ppm) compared to the comparative example It was confirmed that the level was increased by more than 56%. As such, the remarkable improvement effect of the number of treatments is that when the concentration of copper ions, which is a chronic problem of the conventional etchant composition, increases (when the number of sheets is increased), the copper ions react with hydrogen peroxide to form radicals, and the formed radicals are in the composition. By decomposing the contained organic matter, it was possible to solve problems such as lowering the characteristics of the etchant and showing a high defect rate.

In addition, it can be seen that the etching composition according to the present invention has excellent properties over time after storage for 30 days, so that the etching composition itself does not decompose over time. On the other hand, in the case of the comparative example, it was found that there were problems such as a significant decrease in the number of etching compositions treated due to self-decomposition, such as changes occurred after storage for 7 days or changes after storage for 30 days.

In short, the etching composition of a specific combination according to the present invention can not only realize a significantly improved number of etching treatment sheets, but also suppress the decomposition of the etching composition even when the concentration of metal ions increases, so that the etching properties are maintained for a long time, and the processing stability is high Even with an increase in time, excellent etching characteristics may be exhibited without deterioration of the etching rate and the number of etching treatment sheets. Therefore, according to the present invention, the occurrence of problems such as electrical short, wiring defects, and reduction in luminance is minimized, and the amount of etchant used is relatively reduced while a large-area, high-brightness liquid crystal display or organic EL (Electro Luminescence) It is possible to provide a high-quality transition metal film used as an electrode of a display device, in particular, a metal film containing copper and/or molybdenum or molybdenum alloy film in a very economical way.

Claims (9)

an etching inhibitor selected from monocyclic or polycyclic heterocyclic compounds containing at least one hetero atom selected from intramolecular oxygen, sulfur and nitrogen; chelating agents; an etch modifier selected from sulfate and phosphate; hydrogen peroxide; and an etching composition comprising the remaining amount of water,
An etching composition that satisfies the following Relations 1 and 2.
(Relation 1)
β _a ＜ 10°
(In Relation 1, β _a means the absolute value of the change width of the taper angle.)
(Relation 2)
β _bias ＜ 0.05 ㎛
(In Relation 2, β _bias means the absolute value of the etch bias change width.) The method of claim 1,
The etching composition is an etching composition for a metal layer including copper, molybdenum, a copper/molybdenum double layer, or a copper/molybdenum alloy double layer. The method of claim 1,
An etching composition in which the treatment number is in the range of 5,000 to 7,000 ppm. The method of claim 1,
Etching composition further comprising a fluorine compound. 5. The method of claim 4,
The fluorine compound is at least one selected from HF, NaF, KF, AlF ₃ , HBF ₄ , NH ₄ F, NH ₄ HF ₂ , NaHF ₂ , KHF ₂ and NH ₄ BF ₄ Etching composition. The method of claim 1,
The etch inhibitor is oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, 5-methyltetrazole, piperazine, methylpiperazine, hydroxylethylpiperazine, benzimidazole, benz At least one etching composition selected from pyrazole, tolutriazole, hydrotolutriazole, hydroxytolutriazole, indole, purine, pyridine, pyrimidine, pyrrole and pyrroline. The method of claim 1,
The etching control agent is potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, sodium persulfate, potassium sulfate, potassium persulfate, ammonium sulfate, ammonium persulfate, monobasic ammonium phosphate, dibasic ammonium phosphate, monobasic sodium phosphate, dibasic sodium phosphate , at least one etching composition selected from the first potassium phosphate and the second potassium phosphate. The method of claim 1,
The chelating agent is iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrilepentaacetic acid, aminotris(methylenephosphonic acid), (1-hydroxyethane-1,1-diyl)bis(phosphonic acid) , ethylenediamine tetra(methylenephosphonic acid), diethylenetriamine penta(methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid, and at least one etching composition selected from glycine. An etching method using the etching composition of any one of claims 1 to 8.

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