KR102404226B1 - ETCHANT composition - Google Patents

Abstract

The present invention provides an etching composition used for etching a transition metal film used as an electrode of a TFT-LCD display, etc., and the etching composition according to the present invention effectively chelates metal ions generated during etching of the transition metal film. In addition to being able to stably maintain the improved treatment medium for a long period of time, it also effectively suppresses the self-decomposition reaction of the composition, thus exhibiting excellent stability without deterioration of the etching treatment medium despite long-term use or storage.

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 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 a fluoride ion. An etchant is disclosed. In addition, Patent Document 3 discloses an etchant in which five additives including a fluorine compound and organic molecules are added 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, in order to solve the problems of the prior art, the present inventor effectively chelates metal ions generated during the etching of the transition metal wiring and/or the transition metal layer, and decomposes organic materials that may occur due to the increased metal ions. The present invention was completed to provide an etching composition that can be minimized.

1)KR2000-0079355 2)KR2005-0000682 3)KR2006-0064881 4)KR2000-0032999

An object 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.

The etching composition for solving the above problems includes a mixed chelating agent including a first chelating agent represented by the following Chemical Formula 1 and a second chelating agent having two or more acid groups.

[Formula 1]

[In Formula 1,

R ₁ , R ₂ and R ₃ are each independently —C(=O)OM ₁ or —CH ₂ C(=O)OM ₂ , and M ₁ and M ₂ are each independently hydrogen or an alkali metal;

R ₄ is hydrogen, hydroxy(C1-C7)alkyl, -C(=O)OM ₃ or -CH ₂ C(=O)OM ₄ , M ₃ and M ₄ are each independently hydrogen or an alkali metal;

A is a direct bond, (C2-C7)alkylene or amino (C1-C7)alkylene.]

The etching composition according to an embodiment of the present invention may be a hydrogen peroxide-based etching composition. In this case, the hydrogen peroxide-based etching composition is effective for etching the transition metal layer. Specifically, according to the present invention, it is possible to form a tape profile excellent in straightness by imparting high selectivity to a transition metal film, particularly a metal film containing copper and/or molybdenum or molybdenum alloy film, and a mixed chelating agent of the above-mentioned combination By using the etchant, the number of etchants can be remarkably improved and the etching rate for the etchant can be maintained for a long time, showing superior properties than the conventionally used transition metal film etchant. In addition, even at a high concentration of copper ions, it reacts with hydrogen peroxide to form radicals, and effectively reduces the degree of decomposition of organic substances contained in the composition by the formed radicals, thereby maintaining the characteristics of the etchant for a long time.

Preferably, the etching composition according to an embodiment of the present invention may further include hexylamine as an fruit water stabilizer to express more stable etching characteristics.

More preferably, the etching composition according to an embodiment of the present invention includes iminodiacetic acid, iminodisuccinic acid, iminodisuccinic tetrasodium salt, ethylenediaminedisuccinic acid, ethylenediaminedisuccinic trisodium salt, and polyimi Two types of mixed chelating agents selected from nodisuccinic acid and the like are preferred.

The mixed chelating agent of the above-mentioned combination can realize excellent etching properties with a significantly improved etching treatment medium compared to the case of using a single chelating agent, respectively. In particular, it acts highly selectively on a metal film comprising copper and/or molybdenum or a molybdenum alloy film and thus takes precedence in the present invention. In this case, the number of treatments refers to an effective section in which etching characteristics are maintained as the concentration of etched metal ions in the etchant rapidly increases, and is usually expressed as the concentration of metal ions or the number of substrates that can be processed. This may mean a section in which the etching characteristics do not change even when the number of substrates to be processed is increased by inserting a substrate into the etchant composition itself once filled without replenishment of additional new liquid.

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 an etch inhibitor, an etch additive, a fluorine compound, and an undercut inhibitor. However, the present invention is not limited thereto.

The etching composition according to the present invention has the advantage of effectively chelating metal ions generated during the etching of the transition metal layer, thereby stably maintaining a remarkably improved number of treatments for a long period of time. Accordingly, when the transition metal film is etched, a tape profile with 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 exhibits 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 batch-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. , an excellent effect can be realized in the etching of a metal film including a copper and/or molybdenum or alloy film thereof having a low resistance.

In short, according to the present invention, the occurrence of problems such as electrical short, wiring defects, 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 a SEM photograph of a specimen using the etching composition of Example 1 according to the present invention.

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 has to be 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 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 cydilos 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 due to the high taper angle result in shortage defects.

Accordingly, in order to solve the above-mentioned problems, the present inventors have intensified research on an etching composition having a more improved number of treatment sheets. As a result, in the case of an etching composition containing a mixed chelating agent having a specific combination, it was confirmed that the number of etching treatment sheets was remarkably improved and at the same time its stability was increased to realize high etching properties despite long-term use. was completed.

The etching composition according to an embodiment of the present invention is characterized in that it includes a first chelating agent represented by the following Chemical Formula 1 and a second chelating agent having two or more acid groups.

[Formula 1]

[In Formula 1,

R ₁ , R ₂ and R ₃ are each independently —C(=O)OM ₁ or —CH ₂ C(=O)OM ₂ , and M ₁ and M ₂ are each independently hydrogen or an alkali metal;

R ₄ is hydrogen, hydroxy(C1-C7)alkyl, -C(=O)OM ₃ or -CH ₂ C(=O)OM ₄ , M ₃ and M ₄ are each independently hydrogen or an alkali metal;

A is a direct bond, (C2-C7)alkylene or amino (C1-C7)alkylene.]

Specifically, it was confirmed that when the mixed chelating agent of the above combination was used, a significant synergistic effect was exhibited compared to the case of using a single material in the chelating effect on metal ions generated during etching. Moreover, the etching composition according to the present invention has a significantly improved number of etching treatment sheets compared to the use of an IDA type compound used as a chelating agent in the conventional etching composition alone, and particularly shows remarkable long-term storage stability.

As used herein, the term “alkyl” includes both straight-chain and pulverized forms. Also, in the present invention, the term “alkylene” refers to a hydrocarbon in which one hydrogen atom has been removed from the alkyl.

In addition, in the present invention, the term "aminoalkylene" means "*-N(R _a )-alkylene-*", wherein R _a is hydrogen, (C1-C7)alkyl or (C6-C12 ) may be aryl, and R _a is preferably hydrogen or (C1-C4)alkyl, but is not limited thereto.

Also, in the present invention, the term "alkali metal" may be Na, K, etc., but is not limited thereto.

The etching composition according to an embodiment of the present invention may be a hydrogen peroxide-based etching composition containing hydrogen peroxide (fruit water, H ₂ O ₂ ) as a main component. This has an excellent effect in etching a transition metal film, particularly a metal film containing copper and/or molybdenum having low resistance. 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 excessive 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 particular, according to the present invention, in the metal film containing copper and/or molybdenum, it was confirmed that the number of treatment sheets can be improved to 700 sheets (copper ion concentration 7,000 ppm) or more compared to the existing 450 sheets (copper ion concentration 4,500 ppm) did 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 of the double metal film or the multi-metal film, thereby suppressing interfacial overetching. It enables highly selective etching.

Preferably, the etching composition according to an embodiment of the present invention may further use hexylamine as an fruit water stabilizer. Accordingly, it is good that hydrogen peroxide can be significantly stabilized during the etching process compared to the conventional etching composition, and etching characteristics can be exhibited with high stability. Specifically, the etching composition comprising a combination of the above-described mixed chelating agent and hexylamine, which is an fruit water stabilizer, according to the present invention shows an excellent effect in terms of the number of etching treatment sheets even after long-term storage for 30 days or more, so that storage stability is remarkably improved. can In this case, the fruit water stabilizer included in the etching composition according to the present invention may be, in particular, one or two or more selected from n-hexylamine, i-hexylamine, neo-hexylamine and cyclohexylamine.

More preferably, the etching composition according to an embodiment of the present invention includes iminodiacetic acid, iminodisuccinic acid, iminodisuccinic tetrasodium salt, ethylenediaminedisuccinic acid, ethylenediaminedisuccinic trisodium salt, and polyimi Two types of mixed chelating agents selected from nodisuccinic acid and the like are preferred.

The above-described etching composition is good because it solves the conventional problems and can realize excellent etching performance without changing etching characteristics such as etching rate and etching uniformity despite a long-term etching process.

In addition, the composition ratio (second chelating agent: first chelating agent, wt: wt) of the mixed chelating agent according to an embodiment of the present invention is not limited, but when it has a range of 1:1 to 8:1, It is preferable in terms of the performance of the etching characteristic.

The etching composition according to an embodiment of the present invention may be suitably controlled by the type and thickness of the desired transition metal layer, but also contains 10 to 30% by weight of hydrogen peroxide based on the total weight of the composition; 0.1 to 8% by weight of a mixed chelating agent; It is preferable to include 0.1 to 5% by weight of hexylamine and the balance of water. When the above-described range is satisfied, the properties of the etching composition are maintained for a long time, and a suitable etching rate and decomposition reaction during the etching process can be suppressed, and more preferably, 15 to 25 wt% of hydrogen peroxide based on the total weight of the composition; 1 to 5% by weight of a chelating agent; It may contain 0.1 to 3% by weight of hexylamine and the balance of water.

Of course, 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, an etch inhibitor, an etch additive, a fluorine compound, and an undercut inhibitor. doesn't happen In addition, the amount of each additive is not limited, and may be used in the range of 0.01 to 5% by weight based on the total weight of the composition.

Hereinafter, the etching composition according to an embodiment of the present invention will be described in more detail.

1) Mixed chelating agent

In the etching composition 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, to maintain the etching characteristics even in repeated etching processes do. 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 in that etching is not performed. can do. In addition, the mixed chelating agent according to the present invention can improve the stability of the composition by preventing the decomposition reaction of the etching composition itself. Moreover, according to the present invention, it is possible to realize significantly improved etching properties compared to the case of using the chelating agent alone, as well as to promote the decomposition reaction by the oxidized metal ions during the etching process to prevent exothermic and/or explosion phenomena can be significantly suppressed.

In the etching composition according to an embodiment of the present invention, the amount of the mixed chelating agent is not limited, but may be included in an amount of 0.1 to 8 wt%, preferably 1 to 8 wt%, more preferably 3 to 8 wt% 8% by weight.

2) hydrogen peroxide

In the etching composition of the present invention, hydrogen peroxide acts as a main oxidizing agent for a transition metal or a transition metal of a metal layer.

In the etching composition according to an embodiment of the present invention, the amount of hydrogen peroxide used is not limited, but may be included in an amount of 10 to 30% by weight based on the total weight of the composition. When the above-mentioned range is satisfied, sufficient etching is possible with excellent oxidizing power for transition metals, and a desirable etching rate can be realized, so that etching residues and/or etching defects can be prevented, and CD loss is reduced and Easy process control.

3) Etch inhibitor

In the etching composition of the present invention, the etch inhibitor controls the etching rate of the transition metal to reduce the CD loss of the pattern, increase the process margin, and to obtain an etch profile having an appropriate taper angle, intramolecular oxygen, It may be a heterocyclic compound including one or more heteroatoms selected from sulfur and nitrogen. 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 the etching composition according to an embodiment of the present invention, 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 based on the total weight of the composition for easy control of the etching rate and economical mass productivity. and preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight.

4) Etching additives

In the etching composition of the present invention, the etching additive serves as an auxiliary oxidizing agent for transition metals or metals and improves the taper profile. The etching additive may be one or more selected from inorganic acids, organic acids, inorganic acid salts, organic acid salts, and the like.

In a specific example, the inorganic acid may be sulfuric acid, nitric acid, phosphoric acid, etc., and the organic acid may be acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanoic acid, propionic acid, tartaric acid, gluconic acid, glycolic acid, succinic acid, etc. The present invention is not limited thereto. In addition, the inorganic acid salts include carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; Hydroxide salts, such as sodium hydroxide and potassium hydroxide; phosphates such as potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, potassium phosphate, potassium superphosphate, ammonium phosphate, and ammonium superphosphate; and borates such as sodium borate and potassium dispersed; The organic acid salt may be sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, calcium lactate, etc., but is not limited thereto.

In the etching composition according to an embodiment of the present invention, in terms of the effect of improving the etching properties, the etching additive may be one or more preferably selected from inorganic acids of phosphate, and more specifically, potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate. , but may be one or more selected from potassium phosphate, and the like, but is not limited thereto.

In the etching composition according to an embodiment of the present invention, the amount of the etching additive is not limited, but 0.01 to 5% by weight based on the total weight of the composition in terms of improving the taper profile and suppressing the deterioration of the etching properties. It may be included, preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight may be included.

5) Fluorine compounds

In the etching composition of the present invention, the fluorine compound reduces the tail length by improving the etching rate of the molybdenum film when the double metal film, for example, the copper / molybdenum film is simultaneously etched, and removes the molybdenum residue that is inevitably generated during etching works to The increase in the tail of molybdenum may reduce the luminance, and if residues remain on the substrate and the lower layer, electrical short, wiring defects and luminance are reduced, so it must be removed.

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 at least one 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 in a copper/molybdenum film In terms of effective removal of molybdenum residues and suppression of etching of the lower film such as a glass substrate, preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight may be included.

6) Fruit water stabilizer

In the etching composition according to an embodiment of the present invention, the peroxide stabilizer functions to control the hydrogen peroxide decomposition reaction when the metal ion content in the etching composition is high by repeating the etching process. Specifically, the fruit water stabilizer according to the present invention may be hexylamine, and additional fruit water stabilizers such as phosphates, glycols, amines, or mixtures thereof may be further included. The amount of hexylamine used as the peroxide stabilizer according to the present invention is not limited, but may be included in an amount of 0.1 to 3% by weight based on the total weight of the composition, and preferably 0.1 to 2% by weight in terms of excellent control effect on the hydrogen peroxide decomposition reaction %, more preferably 0.5 to 2% by weight.

7) water

In the etching composition of the present invention, water is not particularly limited, but deionized water may be preferable, and deionized water having a resistivity value of 18MQ/cm or more, which is the degree to which ions are removed in water, may be more preferable. In this case, the water may be included in an amount such that the total weight of the etching composition is 100% by weight.

The etching composition of the present invention having the above-mentioned composition can easily control the etching rate when the transition metal or metal film is etched, and has an excellent etch profile and excellent straightness of wiring. In addition, since residues can be completely removed, it can be very usefully used as an etching composition for a transition metal film used for TFT-LCD gates and source/drain electrodes, particularly a metal film containing copper/molybdenum.

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 7000 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 multi-layer 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 multi-layer is Cu It may include a /Mo(Mo-alloy) double layer, Cu/Mo(Mo-alloy)/Cu, or a triple layer of 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.

The etching method of the metal film using the etching composition of the present invention may be carried out according to a conventional method.

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 11)

Etching compositions of Examples 1 to 7 and Comparative Examples 1 to 11 according to the present invention were prepared by mixing each component at the component content shown in Table 1 below.

In order to evaluate the effect of the etching composition prepared by the above method, a molybdenum film was deposited to a thickness of 300 Å as a barrier metal on the TFT-LCD GLS, and a copper film to a thickness of 6,500 Å was deposited thereon, and then a photolithography process was performed to form a pattern to form a specimen. was prepared. To check the etching characteristics (CD skew, taper) of each etching composition, each specimen was subjected to 50% OE based on EPD using a mini-etcher equipment, and copper powder was added at 300pm and 5000ppm to observe the characteristics of the number of etchings. , 6000ppm, 7000ppm cumulative dissolution was evaluated specimens were observed using a scanning electron microscope (manufactured by Hitachi, SU8010).

In addition, whether or not precipitates are generated, which is a method of confirming the etching characteristics of the etching composition prepared by the above method, was confirmed whether 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.

As shown in Table 2, 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 to 5,000 ppm), the number of treatment sheets of the etchant composition according to the present invention was 700 (about 7,000 ppm to about 7,000 ppm). 7,500 ppm), which was confirmed to be an increase of 56% or more compared to the comparative example. 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 storage properties after storage for 30 days, and there is no degradation of the etching composition itself 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 treated etching compositions due to self-decomposition, such as changes occurring after storage for 7 days or changes occurring after storage for 30 days.

In addition, when hexylamine is used as the perwater stabilizer in the etching composition according to the present invention, the reaction between copper ions and hydrogen peroxide is effectively suppressed, thereby giving priority to the desired etching characteristics in the present invention.

In summary, the etching composition according to the present invention includes a combination chelating agent including two or more secondary amines, so that not only can the number of remarkably improved etching treatment agents be implemented, but also the decomposition of the etching composition is suppressed even when the concentration of metal ions is increased As a result, the etching characteristics are maintained for a long time, and excellent etching characteristics can be exhibited without lowering the etching rate and/or the number of etching treatment sheets even when the treatment time is increased due to high stability. In particular, the etching composition according to the present invention shows remarkable in the above-described etching properties even when a single chelating agent is used or a mixed chelating agent is used instead of a combination according to the present invention.

Claims (11)

with respect to the total weight of the composition,
10 to 30% by weight of hydrogen peroxide as a main oxidizing agent;
0.1 to 8 wt% of a chelating agent comprising iminodiacetic acid, which is a first chelating agent and a second chelating agent represented by the following Chemical Formula 1; and
remaining amount of water;
An etching composition comprising a.
[Formula 1]

[In Formula 1,
R ₁ , R ₂ and R ₃ are each independently —C(=O)OM ₁ or —CH ₂ C(=O)OM ₂ , and M ₁ and M ₂ are each independently hydrogen or an alkali metal;
R ₄ is hydrogen, hydroxy(C1-C7)alkyl, -C(=O)OM ₃ or -CH ₂ C(=O)OM ₄ , M ₃ and M ₄ are each independently hydrogen or an alkali metal;
A is a direct bond, (C2-C7)alkylene or amino (C1-C7)alkylene.] delete The method of claim 1,
An etching composition further comprising 0.1 to 5% by weight of hexylamine as an fruit water stabilizer based on the total weight of the composition. The method of claim 1,
The first chelating agent is at least one selected from iminodisuccinic acid, iminodisuccinic tetrasodium salt, ethylenediaminedisuccinic acid, ethylenediaminedisuccinic trisodium salt, and polyiminodisuccinic acid. The method of claim 1,
An etching composition further comprising at least one selected from an etch inhibitor, an etch additive, a fluorine compound, and an undercut inhibitor. 6. The method of claim 5,
The etching inhibitor is an etching composition comprising a heterocyclic compound containing one or more hetero atoms selected from oxygen, sulfur and nitrogen in the molecule. 7. The method of claim 6,
The heterocyclic compound is oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, 5-methyltetrazole, piperazine, methylpiperazine, hydroxylethylpiperazine, benzimidazole, At least one etching composition selected from benzpyrazole, tolutriazole, hydrotolutriazole, hydroxytolutriazole, indole, purine, pyridine, pyrimidine, pyrrole, and pyrroline. 6. The method of claim 5,
The etching additive is at least one etching composition selected from inorganic acids, organic acids, inorganic acid salts and organic acid salts. 9. The method of claim 8,
The inorganic acid is at least one selected from sulfuric acid, nitric acid, and phosphoric acid, and the organic acid is acetic acid, formic acid, butanoic acid, stric acid, glycolic acid, oxalic acid, malonic acid, pentanoic acid, propionic acid, tartaric acid, gluconic acid, glycolic acid and succinic acid. at least one selected from, the inorganic acid salt is at least one selected from carbonate, hydroxide, phosphate and borate, and the organic acid salt is sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate , potassium acetate, sodium lactate, potassium lactate, and at least one etching composition selected from calcium lactate. 6. The method of claim 5,
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 etching composition is an etching composition for a metal film including a copper, molybdenum or molybdenum alloy film.

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