TW201816186A - Hydrogen peroxide stabilizer and etching composition containing them - Google Patents

Abstract

The invention provides a hydrogen peroxide stabilizer and an etching composition containing the same The etching composition provided by the invention contains the hydrogen peroxide stabilizer., so that decomposition of hydrogen peroxide can be prevented when the etching process is carried out., and the over-etching of the metal interface is controlled so as to have excellent etching characteristics.

Description

   Hydrogen peroxide stabilizer and etching composition containing the same   

The present invention relates to a hydrogen peroxide stabilizer and an etching composition containing the same. More specifically, the present invention relates to the etching of a transition metal film containing a hydrogen peroxide stabilizer and its use as an electrode of a thin film transistor liquid crystal display (TFT-LCD). Etching composition.

Generally, a process of forming a metal wiring on a substrate in a semiconductor device includes a sputtering step for forming a metal film, and a photoresist based on a pattern required for an etching step of photoresist coating, exposure, and development. A forming step; an etching step for forming a wiring; and a stripping step for removing a photoresist unnecessary after forming the wiring.

In order to prepare substrates for semiconductor devices and thin-film transistor liquid crystal displays, aluminum or aluminum alloy layers are commonly used as the thin-film transistor (TFT) gate and data line electrode wiring materials. However, in order to achieve large-scale displays, it is necessary to reduce the number of electrode wiring. For this purpose, an attempt has been made to use copper, which is a low-resistance metal, for forming wiring.

Therefore, studies related to the etching composition used for copper film etching have also been performed. Generally, in order to etch a copper film of a wiring formed of such copper, hydrogen peroxide-based or potassium peroxymonosulfonate-based etching is mainly used. combination.

However, the potassium peroxymonosulfonate-based etching composition has the disadvantages of slow etching speed and instability based on time, and the hydrogen peroxide-based etching composition also has the fact that the etching composition itself is decomposed or is sharp due to time. The changes still have the disadvantage of being unstable.

In order to solve the above-mentioned problems, a hydrogen peroxide-based etching composition containing hydrogen peroxide, phosphoric acid, a phosphate, a chelating agent, and a cyclic amine compound is known in Korean Laid-Open Patent No. 2010-0040352.

However, a disproportionation reaction still occurs, and there is a disadvantage that the etching composition itself decomposes and is unstable. In particular, a cyclic amine compound is combined with copper ions generated when a copper film is etched. In the above case, it has the following problems: In the case of a chloride in the composition memory, when the chloride ion reacts with the conjugate, a hardly soluble precipitate or the like is generated.

On the other hand, the step of using a copper film to form a wiring has a problem that the adhesion with a silicon insulating film is reduced. To make up for the shortcomings of this copper film, titanium, molybdenum alloy, molybdenum, etc. are used as the lower barrier metal.

In the case where the barrier metal is titanium or molybdenum alloy, due to chemical properties, it has the disadvantage of requiring only etching using specific ions or specific conditions. When the barrier metal is molybdenum, it has a favorable copper / titanium, copper / molybdenum alloy film. In comparison, the etching step has a disadvantage that the adhesion with the copper film and the molybdenum film is reduced. In particular, the over-etching phenomenon due to the penetration of the etching composition is deepened in a portion where the adhesion between the copper film and the molybdenum film is reduced.

Therefore, there is still a need for an etching composition-related study that can be applied to both a variety of metal films and can effectively perform etching.

    [Prior technical literature]    

Patent document: Korean Published Patent No. 10-2010-0040352.

The present invention provides a hydrogen peroxide stabilizer that stabilizes hydrogen peroxide.

The present invention provides an etching composition containing the hydrogen peroxide stabilizer of the present invention, specifically an etching composition for a transition metal, and has excellent etching through a hydrogen peroxide stabilizer that stabilizes hydrogen peroxide and prevents decomposition of the etching composition itself. Performance, and has increased throughput and etching uniformity.

In addition, the present invention provides an etching composition capable of performing a highly selective etching including a single film or a double metal film such as copper through the hydrogen peroxide stabilizer of the present invention, and suppressing the decomposition reaction of hydrogen peroxide to stabilize it. Etch step.

The present invention provides a hydrogen peroxide stabilizer containing epoch-making hexylamine which stabilizes hydrogen peroxide.

In addition, the present invention provides an etching composition capable of performing high stability and high selective etching. The etching composition of the present invention contains hydrogen peroxide and the hydrogen peroxide stabilizer of the present invention.

An etching composition according to an embodiment of the present invention may further include an etching inhibitor and a chelating agent.

With respect to the total weight of the etching composition, the etching composition according to an embodiment of the present invention may include: 10 weight percent to 30 weight percent hydrogen peroxide; 0.01 weight percent to 5 weight percent of an etching inhibitor; 0.1 weight percent to 5 Chelating agent by weight; 0.1 to 5 weight percent of hexylamine; and water as the balance.

Preferably, the etching inhibitor according to an embodiment of the present invention may be a heterocyclic compound containing one or more heteroatoms selected from oxygen, sulfur, and nitrogen in the molecule. As a specific example of the heterocyclic compound, For oxazole, imidazole, pyrazole, triazole, tetrazole, aminotetrazole, methyltetrazole, xylazine, methylxazine, hydroxyethylxazine, benzimidazole, benzopyrazole, methylbenzene Tolutriazole, hydrotolutriazole, hydroxytolutriazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole or pyrroline.

Preferably, the chelating agent according to an embodiment of the present invention may include an amino group, a carboxylic acid group, or a phosphonic acid group in the molecule. Specifically, the chelating agent may be selected from the group consisting of iminodiacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid. , Diethylenetrinitrile pentaacetic acid, aminotri (methylenephosphonic acid), (1-hydroxyethane-1,1-diyl) bis (phosphonic acid), ethylenediaminetetra (methylenephosphonic acid), One or two or more of diethylenetriaminepenta (methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid, and glycine.

The etching composition according to an embodiment of the present invention may further include one or two or more kinds selected from an etching additive, a fluorine compound, and a side etching inhibitor.

Preferably, the etching additive according to an embodiment of the present invention may be an inorganic acid, an organic acid, an inorganic acid salt, an organic acid salt, or a mixture thereof. As a specific example, the inorganic acid may be sulfuric acid, nitric acid, or phosphoric acid, and the organic acid may be It is acetic acid, formic acid, butyric acid, glycolic acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, gluconic acid, glycolic acid or succinic acid, and the inorganic acid salt or organic acid salt may be hydrogen diphosphate. Potassium, sodium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, potassium superphosphate, ammonium phosphate or ammonium superphosphate.

The fluorine compound according to an embodiment of the present invention may be one or two or more 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 . The side corrosion inhibitor may be one or two or more selected from adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, isoguanine, and uric acid.

Preferably, the etching composition according to an embodiment of the present invention can be used to contain an alloy selected from copper, molybdenum, titanium, indium, zinc, tin, tungsten, silver, gold, chromium, manganese, iron, cobalt, nickel, and niobium. A transition metal film of one or two or more transition metals.

The hydrogen peroxide stabilizer of the present invention extremely stabilizes hydrogen peroxide by including hexylamine as a specific amine, thereby improving the stability of the etching composition containing the hydrogen peroxide.

The etching composition of the present invention suppresses the decomposition reaction of hydrogen peroxide as the metal ion concentration increases when the etching step is carried out via a hydrogen peroxide stabilizer containing the hexylamine of the present invention, thereby maintaining it for a long time. Etching characteristics.

That is, compared with the etching composition of the prior art, when the etching step is performed, the etching composition of the present invention has high stability of the etching composition by making hydrogen peroxide extremely stable, so that even if the processing amount and processing time increase, It also has no change in etching characteristics such as etching speed and etching uniformity, and thus has excellent etching performance.

In addition, when the etching step is performed, the etching composition of the present invention stabilizes hydrogen peroxide, and when the etching step of the double or multiple transition metal film is performed, the interface over-etching is suppressed by selectively protecting the interface between the metals. Therefore, a stable etching step can be performed, and as a result, the taper angle, critical dimension loss, and etching linearity are improved.

The present invention provides a hydrogen peroxide stabilizer containing hexylamine that stabilizes hydrogen peroxide.

The hydrogen peroxide stabilizer of the present invention stably stabilizes hydrogen peroxide via hexylamine and protects the interface of the multiple metal film to be etched.

As the hydrogen peroxide stabilizer of the present invention, hexylamine can be used independently, and it can be mixed with a solvent and other hydrogen peroxide stabilizers. Preferably, hexylamine can be used independently.

In addition, the present invention provides an etching composition, which can stabilize hydrogen peroxide through the hydrogen peroxide stabilizer of the present invention and protect the interface of a multiple metal film to significantly improve the etching characteristics. The etching composition of the present invention is characterized by containing Hydrogen peroxide and the hydrogen peroxide stabilizer of the present invention.

The inventors of the present invention recognize that by adding a hydrogen peroxide stabilizer containing hexylamine to the etching composition, when the etching step is performed, the decomposition of hydrogen peroxide is suppressed to stabilize the hydrogen peroxide, and the protection may be doubled or more through protection. The interface of the heavy metal film can be etched with high selectivity, thereby completing the present invention.

As an etching composition of the prior art, various studies have been conducted to solve the above-mentioned problems, as hydrogen peroxide decomposes with the concentration of metal ions generated when the etching step is performed, thereby significantly reducing the etching characteristics. When the etching composition is subjected to the etching step, if the concentration of the generated metal ions is 4000 ppm or more than 5000 ppm, hydrogen peroxide is decomposed to significantly reduce the etching performance.

In view of this, the present inventors conducted research from various angles. As a result, it was recognized that the concentration of metal ions that are still generated when the etching step is performed by including a hydrogen peroxide stabilizer containing hexylamine in the etching composition is conventional. The concentration of 4000 ppm or more is 5000 ppm or more, which suppresses the decomposition of hydrogen peroxide, and thus completed the present invention.

The hexylamine contained in the hydrogen peroxide stabilizer of the present invention is a chain amine having 6 carbons, that is, a linear or branched C6 alkylamine, and an alkane having 4, 5, or 7 carbons. Amines, that is, butylamine, pentylamine, or heptylamine, and 6 carbon atoms, but cyclohexylamines, which are cyclic amines, surprisingly significantly stabilize hydrogen peroxide, thereby increasing the Etching characteristics.

In addition, as the etching composition of the present invention containing a hydrogen peroxide and a hydrogen peroxide stabilizer containing the hexylamine of the present invention, hydrogen peroxide based on the concentration of metal ions generated when the etching step is performed suppresses decomposition while performing a double or During the etching step of the multiple transition metal film, the interface between the metals is selectively protected to suppress the interface from being over-etched, so that a stable etching step can be performed, thereby significantly improving the etching characteristics.

In other words, when the etching step is performed, the concentration of metal ions in the etching composition is increased, and this metal ion acts as a catalyst for decomposing hydrogen peroxide as an oxidant, thereby causing the entire etching step to change over time. The etching composition of the present invention surprisingly suppresses such decomposition of hydrogen peroxide via a hydrogen peroxide stabilizer containing hexylamine, thereby suppressing the temporal change of the overall etching step and improving the etching characteristics.

The hexylamine contained in the hydrogen peroxide stabilizer of the present invention may be a linear or branched hexylamine having 6 carbon atoms and having an amine group. As an example, the hexylamine is selected from the following compounds, but is not limited thereto.

In terms of having an excellent effect as a hydrogen peroxide stabilizer, preferably, the hexylamine of the present invention may be one or two or more kinds selected from n-hexylamine, isohexylamine, and neohexylamine.

An etching composition according to an embodiment of the present invention may further include an etching inhibitor and a chelating agent.

With respect to the total weight of the etching composition, the etching composition according to an embodiment of the present invention may include: 10 weight percent to 30 weight percent hydrogen peroxide; 0.01 weight percent to 5 weight percent of an etching inhibitor; 0.1 weight percent to 5 Chelating agent by weight; 0.1 to 5 weight percent of hexylamine and water as the balance can maintain the characteristics of the etching composition for a long time, and is used to suppress the decomposition reaction at an appropriate etching rate and when the etching step is performed On the aspect, preferably, relative to the total weight, it may include: 15 to 25 weight percent hydrogen peroxide; 0.05 to 1.50 weight percent of an etching inhibitor; and 1 to 5 weight percent of a chelating agent. ; 0.1 to 3% by weight of hexylamine and the balance of water.

Hereinafter, each constituent component of the transition metal etching composition according to an embodiment of the present invention will be described in detail.

a) Hydrogen peroxide

In the etching composition of the present invention, hydrogen peroxide functions as a transition metal or a primary oxidant of a metal of a transition metal or metal film.

Relative to the total weight of the etching composition, 10 to 30 weight percent of hydrogen peroxide according to an embodiment of the present invention may be included. In the case of containing less than 10% by weight of hydrogen peroxide, the oxidizing power of the transition metal is insufficient, so that etching may not be performed. In the case of containing more than 30% by weight of hydrogen peroxide, there is a problem that the etching rate is too fast. It is thus difficult to control the problem of steps. Since a better etching speed can be achieved, it is possible to prevent etching residues and poor etching, and in terms of reducing a critical dimension loss (CD loss) and easily adjusting a step, it may preferably include 15 to 25% by weight .

b) Etching inhibitor

In the etching composition of the present invention, by adjusting the etching speed of the transition metal, the etching inhibitor can reduce the critical loss of the pattern (CD loss), increase the profit of the step, and become a corrosion cross-sectional view with an appropriate taper angle. It is a heterocyclic compound containing one or two or more kinds of heteroatoms selected from oxygen, sulfur, and nitrogen in the molecule. The heterocyclic compound described in the present invention further includes a monocyclic heterocyclic compound and a monocyclic heterocyclic compound. A polycyclic heterocyclic compound with a condensed structure of a heterocyclic ring and a benzene ring.

As a specific example, the heterocyclic compound according to an embodiment of the present invention may be oxazole, imidazole, pyrazole, triazole, tetrazol, 5-aminotetrazole ( 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, benzimidazole, benzpyrazole, formazan Tolutriazole, hydrotolutriazole, or hydroxytolutriazole, preferably selected from tetrazole, 5-aminotetrazole, and methyl One or more of tetrazole.

Relative to the total weight of the etching composition, the etching inhibitor of the present invention may be included in an amount of 0.01 to 5 weight percent, and preferably, the etching inhibitor of the present invention may be included in an amount of 0.1 to 2 weight percent. In the case of containing less than 0.01% by weight of the etching inhibitor, there are problems that it is difficult to adjust the etching speed, reduce the ability to adjust the taper angle, and the step profit is small, thereby reducing mass productivity. In the case of an inhibitor, there is a problem of inefficiency in reducing the etching rate.

c) chelating agent

In the etching composition of the present invention, the chelating agent is activated by forming a chelate with metal ions generated during the etching, thereby preventing the reaction based on their metal ions, and finally maintaining the etching characteristics in repeated etching steps. . In particular, in the case of a copper layer, when a large amount of copper ions remain in the etching composition, there is a problem that a passivation film is formed and oxidized without etching. However, when a chelating agent is added, the formation of passivation of copper ions can be prevented. membrane. In addition, the chelating agent can increase the stability of the etching composition by preventing the decomposition reaction of hydrogen peroxide itself. Therefore, without adding a chelating agent to the etching composition, oxidized metal ions are activated during the etching process, so that the etching characteristics of the etching composition can be easily changed, and by promoting the decomposition reaction of hydrogen peroxide, Generates fever and eruption.

That is, the chelating agent of the embodiment of the present invention chelate with metal ions generated when the etching step is performed to suppress the decomposition of hydrogen peroxide. When the etching composition is stored, it also plays a role of improving stability, which is not particularly It is limited, but may include an amino group, a carboxylic acid group, or a phosphonic acid group in the molecule. Specifically, it may be selected from iminodiacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid. (ethylenediaminetetraacetic acid), diethylenetrinitrilacetic acid, amino tris (methylenephosphonic acid), (1-hydroxyethane-1,1-diyl) bis (Phosphonic acid) ((1-hydroxyethane-1,1-diyl) bis (phosphonic acid)), ethylenediamine tetra (methylene phosphonic acid), diethylenetriamine One or two or more of diethylenetriamine penta (methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid, and glycine , Preferably, can be selected from imino Diacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriamine-nitro-acetic acid one or two or more kinds.

With respect to the total weight of the etching composition, the chelating agent according to an embodiment of the present invention may be included in an amount of 0.1 to 5 weight percent, and may preferably be included in an amount of 0.1 to 3 weight percent. In the case of containing less than 0.1 weight percent of the chelating agent, the amount of non-startable metal ions is too small, thereby reducing the ability to inhibit the decomposition reaction of hydrogen peroxide. In the case of containing more than 5 weight percent of the chelating agent, Since a chelate is formed, the action of a metal cannot be expected, and it may become a problem of inefficiency.

The etching composition according to an embodiment of the present invention may further include one or two or more selected from the group consisting of an etching additive, a fluorine compound, and a side corrosion inhibitor according to the type of the transition metal or the metal film.

d) Etching additives

The above-mentioned etching additives function as auxiliary oxidants related to transition metals or metals and improve the cone shape. As the above-mentioned etching additives, inorganic acids, organic acids, inorganic acid salts, organic acid salts, or mixtures thereof can be used.

As a specific example, the inorganic acid may be sulfuric acid, nitric acid or phosphoric acid, and the organic acid may be acetic acid, formic acid, butyric acid, glycolic acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, Gluconic acid, glycolic acid or succinic acid, inorganic and organic acid salts may be sulfates or phosphates, and sulfates may be ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate or potassium persulfate, The sulfate can be potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, ammonium hydrogen sulfate, sodium phosphate, sodium superphosphate phosphates such as perphosphate, potassium phosphate, potassium perphosphate, ammonium phosphate, or ammonium perphosphate.

Preferably, in terms of the effect of improving the etching characteristics, the etching additive may be phosphate, and more specifically, it may be diammonium hydrogen phosphate, ammonium hydrogen sulfate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, ammonium phosphate, Potassium phosphate or a mixture thereof.

The etching additive of the present invention may be included in an amount of 0.1 to 5 weight percent with respect to the etching composition, and may preferably include 0.1 weight in terms of improving the effect of the sharp file based on the use of the etching additive and suppressing the reduction of the etching characteristics. Percent to 3 weight percent.

e) Fluorine compounds

As an example of the double metal film, the fluorine compound that can also be included in the etching composition of the present invention, when the copper / molybdenum film is etched at the same time, the tail length is reduced by increasing the etching speed of the molybdenum film, and the inevitably generated during etching is removed. The role of residues of molybdenum. Increasing the tail of molybdenum can reduce the brightness, and if the residue remains on the substrate and the lower film, it will cause electrical short circuit, poor wiring, and decrease the brightness, so it must be removed.

An embodiment of the present invention as long as the compound of Example fluorine dissociation may generate F ^- or HF ₂ ^- compound may be, as specific examples, it may be selected from _{HF, NaF, KF, AlF 3} , HBF 4, NH 4 F, NH One or two or more of ₄ HF ₂ , NaHF ₂ , KHF ₂ and NH ₄ BF ₄ may include 0.01% to 2% by weight relative to the total weight of the etching composition. Preferably, as an example of a metal residue, in copper The molybdenum film may contain 0.01% by weight to 1% by weight in order to effectively remove residues of molybdenum and suppress the etching of a lower film such as a glass substrate. The fluorine compound may be 0.01% by weight.

f) Side corrosion inhibitor

The etching composition according to an embodiment of the present invention may further include a side etch inhibitor. In order to control the etching of the side etching, the content of the fluorine compound and the etching inhibitor is adjusted. When this kind of adjustment can generate metal residue or reduce the etching rate, a side etching inhibitor can be added.

In particular, when the dual metal film is etched simultaneously, as an example, when the copper / molybdenum film is etched at the same time, generally, in order to control the side etching of the molybdenum film, the fluorine compound content in the etching composition can be reduced or an etching inhibitor can be increased. content.

However, when the content of the fluorine compound is reduced, there is a concern that residues of molybdenum may be generated. When the content of the etching inhibitor is increased, the etching rate of copper is significantly reduced, making it difficult to perform the etching step. In this regard, by applying a side etching inhibitor, it is possible to prevent the occurrence of residues of the molybdenum film or reduce the etching rate of copper.

The side corrosion inhibitor may be a compound containing one or more functional groups selected from the group consisting of an amino group, a hydroxyl group, a carbonyl group, and a methyl group in a condensation structure of pyrimidine and imidazole. As described above, the condensed structure of pyrimidine and imidazole contains more than one functional group selected from the group consisting of amino, hydroxyl, carbonyl, and methyl groups to exhibit excellent adsorption characteristics for molybdenum, and thus has a large side corrosion inhibition effect. As a result, an excellent effect of improving the etching characteristics can be exhibited.

Specifically, it can be adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, isoguanine, and Among purine bases such as uric acid, among them, adenine, guanine, or isoguanine is preferred.

Relative to the total weight of the etching composition, the above-mentioned side etch inhibitor may be included in an amount of 0.01 to 2% by weight. Preferably, it may include 0.05 in terms of improving effects based on the use of the side etch inhibitor and reducing the etching rate. Weight percent to 2 weight percent.

g) water

The etching composition of the present invention is not particularly limited to water, and may preferably be deionized water, and more preferably deionized water having a non-resistance value of 18 MQ / cm or more as a degree of removing ions in the water.

The water can be contained in an amount such that the total weight of the etching composition becomes 100% by weight.

h) Other additives

In order to improve the etching performance, the etching composition of the transition metal film of the present invention may further include any additives generally used in the etching composition. Examples of the additives include a hydrogen peroxide stabilizer, an etching stabilizer, and a glass etching inhibitor. These can be used alone or in combination of two or more.

When the etching step is repeated and the metal ion content in the etching composition is high, the hydrogen peroxide stabilizer plays a role of suppressing the decomposition reaction of hydrogen peroxide. Specifically, as the hydrogen peroxide stabilizer, phosphates, glycols, amines, or mixtures thereof can be used. In the case where the etching composition includes the above-mentioned hydrogen peroxide stabilizer, it may include 0.1 to 5 weight percent, preferably 0.5 to 3 weight percent with respect to the total weight of the etching composition. When the hydrogen peroxide stabilizer is contained in an amount of less than 0.1% by weight, the effect of controlling the decomposition reaction of hydrogen peroxide is very small. In the case where the hydrogen peroxide stabilizer is contained in an amount of more than 5% by weight, there is a concern that the etching function is reduced.

When the transition metal or the metal film is etched, the etching composition of the present invention having the above-mentioned composition is easy to adjust the etching rate, has an excellent etch profile, and has excellent linearity of wiring. In addition, the residue can be completely removed, and the film can be used as a transition metal film for a gate and a source / drain electrode of a thin film transistor liquid crystal display. In particular, it can be very useful as an etching composition for a film containing copper.

Furthermore, as a hydrogen peroxide stabilizer, the storage stability of the etching composition via hexylamine is very high. As the concentration of metal ions or transition metal ions generated in the etching step, decomposition of hydrogen peroxide does not occur even at 7000 ppm, and thus A stable etching step can be performed.

In addition, the etching composition of the present invention contains hexylamine so as not to etch an oxide semiconductor that is very fragile to pH and fluorine compounds, thereby maintaining the electrical characteristics of the oxide semiconductor and minimizing defects in steps, and does not need to be used. The insulating protective layer (etch stop) for protecting the semiconductor can also save the original cost as a result, thereby being economical.

In addition, the etching composition of the present invention uses hexylamine to utilize a double metal film, especially a copper / molybdenum film or a copper / titanium film etching step, thereby protecting the interface of the metal film together with the advantages mentioned above. In order to suppress the interface over-etching, a stable step can be realized.

As a result, etching characteristics such as taper angle, critical dimension loss, and etching linearity can be improved. Thus, when a double metal film or a multiple metal film is used as a metal material for a gate, source, or drain electrode of a thin film transistor constituting a liquid crystal display device, and especially a copper / molybdenum film, the above etching is performed. The composition is useful as an etching composition for forming a metal wiring pattern.

An etching composition according to an embodiment of the present invention is a composition that can be used for etching a metal film. The metal films described in the present invention all include a metal, a non-metal, or a transition metal. Preferably, the metal composition may be a transition metal and may independently include A metal or transition metal, or a mixture of metals or transition metals.

Specifically, it may be an independent metal film, a metal alloy film, or a metal oxide film. Examples of the metal oxide film include indium tin oxide (ITO), indium zinc oxide (IZO), and indium gallium zinc oxide (IGZO). .

The transition metal or metal film applicable to the etching composition according to an embodiment of the present invention may be selected from copper, molybdenum, titanium, indium, zinc, tin, tungsten, silver, gold, chromium, manganese, iron, cobalt, nickel, and A film of one or two or more metals or transition metals in niobium may be, as a specific example, a copper film, a copper / molybdenum film, a copper / titanium film, a copper / molybdenum alloy film, a copper / indium alloy film, Preferably, it may be a copper / molybdenum alloy film.

A copper / molybdenum film or a copper / molybdenum alloy film according to an embodiment of the present invention may be formed by laminating one or more copper (Cu) films and one or more molybdenum (Mo) films and / or mo-alloy films on each other. The multi-layer film can be composed of Cu / Mo (Mo-alloy) dual film, Cu / Mo (Mo-alloy) / Cu or Mo (Mo-alloy) / Cu / Mo (alloy) triple. For the film, the order of the films can be appropriately adjusted in accordance with the substance of the substrate and the adhesiveness.

The molybdenum alloy film according to an embodiment of the present invention may be made of molybdenum-tungsten (Mo-W), molybdenum-titanium (Mo-Ti), molybdenum-niobium (Mo-Nb), molybdenum-chromium (Mo-Cr), or molybdenum-tantalum ( Mo-Ta), the above molybdenum film or molybdenum alloy film is effectively etched in a non-residue manner, and can be vapor-deposited to a thickness of 100 Å to 500 Å, and the thickness of the copper film can be vaporized to 1000 Å to 10,000 Å.

The etching method of a metal film using the etching composition of the present invention can be performed according to a general method.

Specifically, the method may include the steps of etching a metal film, that is, the step of patterning after forming a photoresist film on the metal film; and using the etching composition of the present invention to form a patterned The metal film of the photoresist film is etched. In this case, the metal film formed on the substrate may be a single film, a double metal film, or a multiple metal film (multilayer metal film). In this case, the stacking order is not particularly limited.

And, the above-mentioned etching method is between the substrate and the transition metal film, that is, as an example between the substrate and the transition metal film, in the case of a copper / molybdenum film, it may be included between the substrate and the copper film or between the substrate and the molybdenum film. A step of forming a semiconductor structure therebetween.

The semiconductor structure may be a semiconductor structure for a display device such as a liquid crystal display device or a plasma display panel. Specifically, the semiconductor structure may include one or more films selected from the group consisting of a dielectric film, a conductive film, and an amorphous or polycrystalline silicon film, and these semiconductor structures may be prepared according to a general method.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

Examples 1 to 8 and Comparative Examples 1 to 23

An etching composition based on Examples 1 to 8 and Comparative Examples 1 to 23 of the present invention was prepared by mixing the components with the component contents described in Table 1 below.

HxA: n-hexylamine, BA: n-butylamine, PA: n-pentylamine, CHA: cyclohexylamine, HpA: n-heptylamine, IHA: isohexylamine, IBA: isobutylamine, IPA: isoamylamine, DeA: isoamyl Amine, ATZ: 5-aminotetrazole, IDA: iminodiacetic acid, AP: diammonium hydrogen phosphate, AS: ammonium hydrogen sulfate, MA: malonic acid, ABF: NH ₄ BF ₄ .

When the etching of each of the prepared etching compositions is performed, in order to know the stability of hydrogen peroxide according to the generated metal ion concentration, Examples 1 to 8 and Comparative Examples 1 to Comparative Examples prepared as described above are used. The etching composition of 23 was spray-tested over time.

As an elapsed time experiment, an etching composition (small etching) capable of performing spraying on an equipment having a concentration of amine used in Examples 1 to 8 and Comparative Examples 1 to 23 at 1.0% by weight was used. ME-001 (Mini-etcher ME-001)). After the copper powders of 1000 ppm, 2000 ppm, 3000 ppm, 4000 ppm, 5000 ppm, 5000 ppm, 6000 ppm, and 7000 ppm were dissolved in the etching solution, the spray was maintained at the same exhaust state at a temperature of 32 ° C, and changes in the hydrogen peroxide concentration were measured. In the case of spraying in a state where exhaust gas is present, if time passes, the water content decreases, and it is necessary to increase the hydrogen peroxide content. However, when the hydrogen peroxide is decomposed due to the reaction, the hydrogen peroxide content decreases. When the hydrogen peroxide content is reduced, the decomposition of hydrogen peroxide serves as an etching inhibitor and a chelating agent for organic matter, thereby causing changes in etching characteristics.

As shown in Table 2, the hydrogen peroxide solution stabilizer of the present invention prevents the decomposition of hydrogen peroxide, and the etching composition containing the hydrogen peroxide stabilizer has the following advantages even if the concentration of metal ions to be etched is increased, and the decomposition of hydrogen peroxide is suppressed. The etching characteristics are maintained for a long time, and the stability is high. Therefore, even if the processing amount and processing time are increased, the etching rate is not reduced, and the uniformity of the etching is not reduced.

Claims (14)

    A hydrogen peroxide stabilizer comprising hexylamine.         An etching composition containing hydrogen peroxide and the hydrogen peroxide stabilizer according to claim 1.         The etching composition according to claim 2, wherein the etching composition further includes an etching inhibitor and a chelating agent.         The etching composition according to claim 3, wherein the etching composition contains: 10% to 30% by weight of hydrogen peroxide relative to the total weight of the etching composition; 0.01% to 5% by weight of an etching inhibitor ; 0.1 to 5 weight percent of a chelating agent; 0.1 to 5 weight percent of hexylamine and water as the balance.         The etching composition according to claim 3, wherein the etching inhibitor is a heterocyclic compound containing one or two or more kinds of heteroatoms selected from oxygen, sulfur, and nitrogen in the molecule.         The etching composition according to claim 5, wherein the heterocyclic compound is oxazole, imidazole, pyrazole, triazole, tetrazole, aminotetrazole, methyltetrazole, xylazine, methylxazine, hydroxyethyl Methylpyrazine, benzimidazole, benzopyrazole, methylbenzotriazole, hydromethylbenzotriazole, hydroxymethylbenzotriazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole or Pyrroline.         The etching composition according to claim 3, wherein the chelating agent contains an amino group, a carboxylic acid group, or a phosphonic acid group in the molecule.         The etching composition according to claim 7, wherein the chelating agent is selected from the group consisting of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrile pentaacetic acid, and aminotris (methylenephosphonic acid) ), (1-hydroxyethane-1,1-diyl) bis (phosphonic acid), ethylenediamine tetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), propane One or two or more of amino acids, glutamic acid, aminobutyric acid, and glycine.         The etching composition according to claim 3, wherein the etching composition further comprises one or two or more selected from the group consisting of an etching additive, a fluorine compound, and a side etching inhibitor.         The etching composition according to claim 9, wherein the etching additive is an inorganic acid, an organic acid, an inorganic acid salt, an organic acid salt, or a mixture thereof.         The etching composition according to claim 10, wherein the inorganic acid is sulfuric acid, nitric acid, or phosphoric acid, and the organic acid is acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, and propionic acid. Tartaric acid, gluconic acid, glycolic acid or succinic acid, the inorganic or organic acid salt is dipotassium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, potassium superphosphate, ammonium phosphate or ammonium superphosphate .     The etching composition according to claim 9, wherein the fluorine compound is selected from the group consisting of HF, NaF, KF, AlF ₃ , HBF ₄ , NH ₄ F, NH ₄ HF ₂ , NaHF ₂ , KHF ₂ and NH ₄ BF ₄ One or two or more.     The etching composition according to claim 9, wherein the undercut inhibitor is one or two selected from the group consisting of adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, isoguanine, and uric acid the above.         The etching composition according to claim 2, wherein the etching composition comprises one or two or more selected from the group consisting of copper, molybdenum, titanium, indium, zinc, tin, and niobium, and is used for a metal film.