KR101695571B1 - Peroxide-based composition for etching metal - Google Patents
Peroxide-based composition for etching metal Download PDFInfo
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- KR101695571B1 KR101695571B1 KR1020150162229A KR20150162229A KR101695571B1 KR 101695571 B1 KR101695571 B1 KR 101695571B1 KR 1020150162229 A KR1020150162229 A KR 1020150162229A KR 20150162229 A KR20150162229 A KR 20150162229A KR 101695571 B1 KR101695571 B1 KR 101695571B1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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Abstract
The present invention relates to a composition for etching a hydrogen peroxide-based metal, and more particularly to a composition for etching a hydrogen peroxide-based metal which can prevent decomposition of hydrogen peroxide and modification of other components in a composition for etching a hydrogen peroxide-based metal.
Description
The present invention relates to a composition for etching a hydrogen peroxide-based metal, and more particularly, to a composition for etching a hydrogen peroxide-based metal which can prevent decomposition of hydrogen peroxide and modification of other components in the composition.
Semiconductor devices, display devices, printed boards, IC cards, and the like generally form metal thin film elements, electrode wiring elements and the like by patterning a metal thin film or the like on a substrate.
As a processing technique for patterning such a metal thin film into a fine structure such as a wiring, a photoresist pattern formed on the surface of the metal thin film by a photolithography technique is used as a mask, and a wet etching And dry etching such as ion etching or plasma etching.
Of these, the wet etching method is economically advantageous because it does not require an expensive apparatus and uses relatively inexpensive chemicals unlike the dry etching method. It also has the advantage of being able to provide a uniform etch to large area and / or substrates of various shapes. Due to the above advantages, wet etching is mainly used as a thin film pattern manufacturing method at present.
Description of the Related Art [0002] In recent years, materials such as copper, titanium, molybdenum, or alloys thereof, which have low electrical resistance and are easy to process in thin film patterns, are used as metal thin film elements used in semiconductor and liquid crystal display devices, Metals are preferred.
A metal etchant (or a composition for a metal etch) is essentially used for the above-described wet etching, and most metal etchants are widely used for hydrogen peroxide-based etchants which are excellent in cost and performance.
Hydrogen peroxide type etchant is produced by mixing hydrogen peroxide, chelating agent and other additives. The quality characteristics of etching result are changed by the chemical action between various components contained in the etchant. Especially, the aging characteristics (EPD degree of change, , The stability of the etchant, etc.).
Therefore, when combining the components having a specific functional group, it is essential to precisely control the kind and the ratio thereof, which requires considerable cost and effort.
As the etching of copper using hydrogen peroxide type etchant proceeds, excessive copper is dissolved into the etchant, and unstable hydrogen peroxide is decomposed to deteriorate the performance of the etchant.
Also, problems such as the chelating agent and etch inhibitor in the etchant are often lost due to the chemical denaturation of the components.
As a result, if the hydrogen peroxide in the etchant is decomposed or the other components are chemically denatured, the etching ability of the etchant must be reduced, which causes the replacement period of the etchant to be short.
Therefore, it is necessary to develop a hydrogen peroxide type etchant having improved stability in use as well as storage in an unused state.
An object of the present invention is to provide a composition for etching a hydrogen peroxide-based metal which is excellent in stability over time.
Specifically, it is an object of the present invention to provide a composition for etching a hydrogen peroxide-based metal which is capable of preventing decomposition of hydrogen peroxide in a composition for etching a hydrogen peroxide-based metal, thereby preventing the concentration of hydrogen peroxide from rapidly dropping.
It is another object of the present invention to provide a composition for etching a hydrogen peroxide based metal which can improve the stability of a composition for etching a hydrogen peroxide-based metal by reducing the chemical modification of other components in the composition for etching a hydrogen peroxide-based metal, .
According to one aspect of the present invention, there is provided a method for preparing a chelating agent comprising at least one main chelating agent selected from hydrogen peroxide, an acetic acid chelating agent and an amino acid chelating agent, a sulfuric acid-based chelating agent represented by the following general formula (1) There may be provided a composition for a hydrogen peroxide-based metal etching comprising a first sub chelating agent or a salt thereof, a phosphoric acid second sub chelating agent represented by the following Chemical Formula 3 or 4, or a salt thereof, an etching inhibitor and water.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
In the above Chemical Formulas 1 and 2,
R 1 to R 3 independently represent hydrogen, a hydroxyl group, a halogen group, an amino group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 haloalkyl group, a C 1 -C 10 aminoalkyl group , A phenyl group and a halogen-substituted phenyl group,
In Formula 3 and Formula 4,
R 4 to R 12 independently represent hydrogen, a hydroxy group, a halogen group, an amino group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 haloalkyl group, a C 1 -C 10 aminoalkyl group , A phenyl group and a halogen-substituted phenyl group.
When a functional group containing a nitrogen atom among R 1 to R 3 is present, it is preferable that the nitrogen atom is a 1,2 or 4-substituted nitrogen atom.
When a functional group containing a nitrogen atom among R 4 to R 12 is present, it is preferable that the nitrogen atom is a 1,2 or 4-substituted nitrogen atom.
In addition, when a functional group containing a carbon atom in R 4 to R 12 is present, at least one carbon atom may be substituted with a functional group selected from a carboxy group, an amino group, an amide group, a carbamoyl group, a nitro group and an acetyl group have.
The hydrogen peroxide-based metal etching composition according to the present invention is excellent in stability for long-term storage or use, and thus is less likely to decompose hydrogen peroxide in the composition.
In addition, the composition for etching a hydrogen peroxide-based metal according to the present invention can inhibit the chemical modification of the composition by preventing a side reaction between hydrogen peroxide and other components in the composition, and thus the etching ability of the composition for etching a hydrogen peroxide- have.
BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art to which the invention pertains. Only. Like reference numerals refer to like elements throughout the specification.
Hereinafter, the composition for etching a hydrogen peroxide-based metal according to the present invention will be described in detail.
The composition for etching a hydrogen peroxide type metal according to an aspect of the present invention may include hydrogen peroxide, a main chelating agent, a sub chelating agent, an etching inhibitor, and water as a hydrogen peroxide type etchant for wet etching of copper.
Here, the hydrogen peroxide (H 2 O 2 ) is a main oxidizing agent that allows the hydrogen peroxide-based metal etching composition to have an etching ability to a metal such as copper, titanium, or molybdenum, and a hydrogen peroxide- Thereby contributing to the stability of the composition.
For example, hydrogen peroxide can etch metals such as copper or molybdenum through mechanisms such as schemes 1 and 2 below.
[Reaction Scheme 1]
Cu + H 2 O 2 ↔ Cu 2 + + H 2 O + 1 / 2O 2 ↑
[Reaction Scheme 2]
Mo + 3H 2 O 2 ↔ Mo 6 + + 3H 2 O + 3 / 2O 2 ↑
As the main oxidizing agent, hydrogen peroxide may be contained in an amount of 5 to 40% by weight based on the total weight of the metal etching composition.
If the content of hydrogen peroxide contained in the metal etching composition is less than 5% by weight, the etching ability of the metal such as copper or molybdenum is insufficient, so that the etching may not be performed well or the etching rate may be excessively low.
On the other hand, if the content of hydrogen peroxide contained in the composition for metal etching exceeds 40% by weight, the etching rate is too fast to be difficult to control the etching, and an overeating angle may occur.
In addition, the composition for metal etching according to an embodiment of the present invention further includes a main chelating agent together with hydrogen peroxide.
The main chelating agent enhances the stability of the metal ion by supporting the etching of the metal and forming a chelate bond with the oxidized form of the metal (i.e., the metal ion), and the main chelating agent acts to increase the total weight of the metal etching composition 0.1 to 5% by weight.
If the content of the main chelating agent contained in the metal etching composition is less than 0.1 wt%, the chelate of metal ions such as copper or molybdenum dissolved in the metal etching composition is insufficient by the main oxidizing agent to precipitate or excessively dissolve metal ions There is a possibility that the etching ability of the metal etching composition is collapsed due to the decomposition of hydrogen peroxide by the metal ions.
On the other hand, if the content of the main chelating agent contained in the metal etching composition exceeds 5 wt%, etching control is not easily performed by the main chelating agent existing in excess, or the main chelating agent is precipitated There may be a problem.
In one embodiment, an acetic acid chelating agent and / or an amino acid chelating agent may be used as the main chelating agent.
More specifically, the acetic acid chelating agent may be at least one selected from iminodiacetic acid, methyliminodiacetic acid, iminostaric acid, and hydroxyethyliminodiacetic acid.
In addition, the amino acid chelating agent may be at least one selected from alanine, glutamic acid, aminobutyric acid, and glycine.
For example, iminodiacetic acid, which can be used as a main chelating agent, has a form in which two carboxyl groups are bonded to nitrogen as a central atom as shown in the following formula (5).
[Chemical Formula 5]
The metal (M, for example, divalent copper ion) after the acidic protons of the carboxy groups present at both terminals of iminodiacetic acid are removed is reacted with nitrogen of the central atom and oxygen of the two carboxyl groups Can be formed.
[Chemical Formula 6]
Referring to Formula (6), the metal (M) forms three bonds with one nitrogen atom and two oxygen atoms in one molecule of iminodiacetic acid, and the metal (M) By additionally forming one bond with acetic acid, a stable chelate bond can be maintained.
(7)
At this time, as the amount of metal ion dissolved in the metal etching composition increases, when iminodiacetic acid is exhausted as a cheating agent, the amount of copper forming the labile chelate bond represented by Chemical Formula 6 also increases.
The chelate bond of the structure represented by the general formula (6) can be precipitated as a metal-iminodiacetic acid type precipitate when the metal (M) is unstably chelated and left in this state for a long time.
In addition, since the solubility of the metal etching composition to the main chelating agent such as iminodiacetic acid is also limited, it is very difficult to increase the concentration of the main chelating agent in the metal etching composition in an infinite manner to form a chelate bond as shown in Chemical Formula 7 .
Although the above-mentioned problems have been exemplified by using iminodiacetic acid as the main chelating agent, it is not limited to iminodiacetic acid and is equally accompanied by other main chelating agents capable of forming an unstable chelate bond with the metal .
Therefore, according to one embodiment of the present invention, a sub chelating agent is further included in the metal etching composition so as to be able to form the stable chelate bond represented by the general formula (7) even when the amount of the metal ion dissolved in the metal etching composition is increased .
In addition, the sub-chelating agent contained in the metal etching composition not only assists the chelate bonding of the main chelating agent to the metal ion but also has a certain level of metal etching ability, and maintains pickling of the metal etching composition, The stability and the pH holding ability can be improved.
More specifically, the composition for metal etching according to one embodiment of the present invention comprises a sulfuric acid first sub chelating agent (or a salt thereof) represented by the following general formula (1) or (2) Phosphate secondary chelating agent (or a salt thereof).
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
Formula I and R 1 to R 3 are each independently hydrogen in the above formula (2), a hydroxyl group, a halogen group, an amino group, C 1 -C 10 alkyl, C 1 -C 10 alkoxy group, C 1 -C 10 haloalkyl group , A C 1 -C 10 aminoalkyl group, a phenyl group and a halogen-substituted phenyl group, and in the formula (3) and the formula (4), R 4 to R 12 independently represent hydrogen, a hydroxyl group, a halogen group, A C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 haloalkyl group, a C 1 -C 10 aminoalkyl group, a phenyl group and a halogen-substituted phenyl group.
In another example, when a functional group containing a carbon atom among R 4 to R 12 is present, at least one carbon atom is selected from a carboxy group, an amino group, an amide group, a carbamoyl group, a nitro group and an acetyl group Lt; / RTI >
The sulfuric acid-based sub-chelating agent (or salt thereof) represented by Chemical Formula 1 or Chemical Formula 2 and the phosphoric acid-based second sub-chelating agent (or salt thereof) represented by Chemical Formula 3 or Chemical Formula 4 shown below are reacted through oxygen or nitrogen atom It is possible to stably chelate the metal ion by providing an additional chelate bond to the metal ion forming the partial chelate bond with the main chelating agent.
At this time, when a functional group containing a nitrogen atom among R 1 to R 12 is present, the nitrogen atom is preferably a 1,2 or 4-substituted nitrogen atom.
The composition for metal etching according to an embodiment of the present invention includes hydrogen peroxide having strong oxidizing power, and hydrogen peroxide can cause an oxidation reaction with other compounds in the metal etching composition.
Particularly, a tertiary amine or a compound containing a tertiary amino group mainly used as a chelating agent (main chelating agent and sub chelating agent) can form N-oxide by reacting with hydrogen peroxide as shown in the following reaction formula 3.
[Reaction Scheme 3]
R 3 N: + H 2 O 2 ? R 3 N + -O - + H 2 O
When a compound containing a tertiary amine or a tertiary amino group is oxidized to form an N-oxide, the characteristics of a compound containing a tertiary amine or a tertiary amino group, especially pKa, are changed.
For example, in the case of aminotris (methylenephosphonic acid) as a chelating agent for a metal etching composition, it has six pKa values in the range of 0.3 to 12.2 since it has three phosphonic acid substituents.
Therefore, even if the metal ions are dissolved into the etching composition as the etching proceeds, the aminotris (methylenephosphonic acid) can supply the protons step by step, so that the pH of the etching composition can be stably maintained.
As described above, in the case of aminotris (methylenephosphonic acid), it has a large number of phosphonic acid substituent groups capable of supporting the chelate of the metal ion, and at the same time, the stepwise proton- Of chelating agents.
Aminotris (methylenephosphonic acid) is a tertiary amine compound, and can react with hydrogen peroxide to form N-oxide as shown in the following reaction formula (4).
[Reaction Scheme 4]
Of the N + of an N-oxide generated by the reaction formula 4 -O - bond is a coordination bond, a bond due to the donor of the outermost electron of the nitrogen atom.
In addition, due to the difference in electronegativity between the nitrogen atom (3.0) and the oxygen atom (3.5), the nitrogen atom and the oxygen atom are substantially separated from each other in charge.
The polarity of the coordinate bond is a characteristic of the phosphonic acid substituents bonded to the nitrogen atom, in particular pKa - by the charge separation of nitrogen and oxygen atoms, such as the N + -O - coordination bonds are to have a polar, N + -O .
Although the pH of the metal etching composition and / or the pKa of the chelating agent (the main chelating agent and / or sub chelating agent) during metal etching should be designed to be fairly elaborate to minimize changes in the quality characteristics of the etch result, A side reaction of the chelating agent with hydrogen peroxide such as 4 acts as a cause of changing the pH of the metal etching composition ultimately as well as the pKa of the chelating agent (main chelating agent and / or sub chelating agent).
Therefore, when a functional group containing a nitrogen atom among R 1 to R 12 is present, it is preferable that the nitrogen atom is not a tri-substituted nitrogen atom.
In addition, the first sub chelating agent and the second sub chelating agent included in the metal etching composition according to an embodiment of the present invention are preferably compounds other than a compound containing a tertiary amine or a tertiary amino group, It is also preferred that the compound is other than a compound containing a tertiary amine or a tertiary amino group.
As the main chelating agent satisfying the above-mentioned conditions, at least one compound selected from iminodiacetic acid, methyliminodiacetic acid, iminostaric acid, hydroxyethyliminodiacetic acid, alanine, glutamic acid, aminobutyric acid and glycine can be used .
Examples of the first sub chelating agent include sulfonic acid, methane sulfonic acid, methane disulfonic acid, ethane sulfonic acid, ethane disulfonic acid, propanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid, ethylbenzenesulfonic acid, potassium bisulfate, At least one compound selected from sulfates, sodium bisulfate, sodium sulfate, ammonium sulfate, ammonium persulfate, dimethyl sulfoxide and diethyl sulfoxide may be used. As the second sub chelating agent, aminoethylphosphonic acid, carboxyethyl At least one member selected from phosphonic acid, dimethyl phosphate, dimethyl phosphonate, hydroxyethylidenediphosphonic acid, methylenediphosphonic acid, hydroxyphosphonocarboxylic acid, methylenediphosphonocarboxylic acid and phosphonobutane-tris- Compounds may be used.
On the other hand, chelating agents (main chelating agents and sub chelating agents) which are not suitable for the metal etching composition according to an embodiment of the present invention include aminotris (methylenephosphonic acid), N, N-bis (phosphonomethyl) glycine, Diethylenetriaminepenta (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexamethylenediamine tetra (methylenephosphonic acid), N- (phosphonomethyl) iminodiacetic acid, tetramethylene diamine tetra Phosphonic acid).
According to one embodiment of the present invention, it is preferable that the first sub chelating agent and the second sub chelating agent in the metal etching composition are used together.
At this time, the content of the first sub chelating agent in the metal etching composition is preferably 0.5 to 2.0 wt%, and the content of the second sub chelating agent is preferably 0.1 to 1.6 wt%.
In particular, the weight ratio of the first sub chelating agent and the second sub chelate in the metal etching composition is preferably in the range of 6: 4 to 9: 1.
The first sub chelating agent which can be used according to one embodiment of the present invention is a sulfuric acid sub chelating agent having excellent stability over time, while the second sub chelating agent is a phosphate chelating agent, Excellent pickling retention.
When the weight ratio of the first sub chelating agent to the second sub chelating agent in the metal etching composition is less than 6: 4 (for example, 0.5: 9.5), the stability of the metal etching composition with time deteriorates, The EPD may be slowed down or the possibility that the components having etching ability in the metal etching composition are decomposed may increase.
On the other hand, when the weight ratio of the first sub chelating agent to the second sub chelating agent in the metal etching composition exceeds 9: 1 (for example, 9.5: 0.5), the etching ability of the metal may be insufficient, The pickling and holding power may be deteriorated and the pH stability of the metal etching composition may be reduced.
In addition, when the content of the first sub chelating agent and the second sub chelating agent in the metal etching composition is less than 0.5 wt% and 0.1 wt%, respectively, the chelate auxiliary function of the main chelating agent can not be sufficiently performed, The ability to stabilize the pH of the metal etching composition may be insufficient.
On the other hand, when the content of the first sub chelating agent and the second sub chelating agent contained in the metal etching composition exceeds 2 wt% and 1.6 wt%, respectively, etching control is facilitated by an excess amount of sub chelating agent Or the solubility of the sub chelating agent in the composition for metal etching may be excessively precipitated.
In addition, the composition for metal etching according to an embodiment of the present invention may further include an etching inhibitor to obtain a high quality etching result by controlling the etching rate of the metal.
The etching inhibitor may be included in an amount of 0.5 to 1.5% by weight based on the total weight of the metal etching composition.
If the content of the etching inhibitor contained in the metal etching composition is less than 0.5% by weight, there is a possibility that the etching speed of the metal is excessively fast and the quality of the etching result is lowered. On the other hand, when the content of the etching inhibitor contained in the metal etching composition is 1.5 If the weight% is exceeded, the etching rate may be lowered, and the productivity may deteriorate.
Also, for the same reason as the chelating agent, the etching inhibitor included in the metal etching composition according to an embodiment of the present invention is preferably a compound other than a compound containing a tertiary amine or a tertiary amino group.
Thus, the etch inhibitor may be selected from the group consisting of furan, thiophene, pyrrole, oxazole, imidazole, pyrazole, triazole, tetrazole, aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, At least one compound selected from pyrrolidine, alloxane, benzofuran, benzothiophene, indole, benzimidazole, benzpyrazole, tolutoriazole, hydrotolurriazole and hydroxytoluurriazole is used And pyridine-based compounds capable of reacting with hydrogen peroxide to form N-oxide are not suitable as the etching inhibitor used in the metal etching composition according to one embodiment of the present invention.
In addition to the above-mentioned components, the metal etching composition according to an embodiment of the present invention may further include additional components such as a corrosion inhibitor, a surfactant, a pH adjuster, an undercut inhibitor or a residue inhibitor.
Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.
Hydrogen peroxide-based metal For etching Composition of composition
The composition of the hydrogen peroxide-based metal etching composition according to Examples and Comparative Examples is shown in Table 1 below.
Content ratio
* Unit: Weight%
* A-1: iminodiacetic acid; A-2: glycine; A-3: nitrilotriacetic acid; B-1: Methanesulfonic acid; B-2: ammonium persulfate; C-1: hydroxyethylidenediphosphonic acid; C-2: methylene diphosphonic acid; C-3: Aminotris (methylenephosphonic acid); D-1: pyrrole; D-2: Pyridine.
In the case of Comparative Example 1 and Comparative Example 2, only the first sub chelating agent as the sulfuric acid-based sub chelating agent was included as the sub chelating agent, and in the case of Comparative Examples 3 to 5, the phosphoric acid sub- 2 sub chelating agent.
Particularly, in the case of Comparative Example 5, a second sub chelating agent containing a tertiary amino group was used.
In the case of Comparative Example 6, the first sub-chelating agent and the second sub-chelating agent of the same kind as in the Examples were used, but nitrilotriacetic acid was used as the main chelating agent.
In the case of Comparative Example 7, the first sub chelating agent and the second sub chelating agent were mixed at a weight ratio of 6: 4, and the second sub chelating agent used a compound containing a tertiary amino group.
In the case of Comparative Example 8, the first sub-chelating agent and the second sub-chelating agent of the same kind as in the Examples were used, but pyridine was used as the etching inhibitor.
Hydrogen peroxide-based metal For etching Evaluation of composition characteristics
Table 2 shows the degree to which the characteristics of the metal etching composition change over time according to the components of the hydrogen peroxide-based metal etching composition having the composition shown in Table 1.
The experimental temperature was room temperature and evaluated at 25 ℃ and 30 ℃, respectively, considering the seasonal characteristics. Further, since the metal etching composition is usually used within 30 days from the production date, a change in the characteristics up to 30 days is observed.
All measurements are expressed in days 0, that is, the degree of change in% based on the immediately measured value.
The degree of hydrolysis was a change relative to the initial concentration of hydrogen peroxide, which was measured by potassium permanganate (KmnO 4 ) titration method and calculated according to the following equation (1).
[Formula 1]
(Content of hydrogen peroxide (wt%) / content of initial hydrogen peroxide (wt%) on the 15th day or 30th day) x 100
The degree of component modification was a change relative to the concentration of the initial additives (the first sub-chelating agent and the second sub-chelating agent), and the contents of the first sub-chelating agent and the second sub-chelating agent were quantitatively analyzed by IC- (2) < / RTI >
[Formula 2]
(Content (wt%) of the first sub chelating agent and the second sub chelating agent / content (wt%) of the initial first sub chelating agent and second sub chelating agent on the 15th day or the 30th day) x 100
EPD (End Point Detection) refers to the time taken until the end of the etching. EPD change is the change relative to the initial EPD. The EPD is measured by observe the substrate and confirmed by SEM analysis. Lt; / RTI >
[Formula 2]
(EPD measurement value (sec) / initial EPD measurement value (sec) on the 15th day or 30th day) x 100
(° C)
* 15D: measured value at 15th day; 30D: 30 day measurement value.
Table 3 shows the degree to which the characteristics of the metal etching composition change with the passage of time using the hydrogen peroxide-based metal etching composition having the composition shown in Table 1. < tb > < TABLE >
The experimental temperature was 33 ° C., which is the general etching temperature, and all evaluation values were 0 ppm, ie, 2,500 ppm of copper powder was added into the composition for metal etching based on the measured value without addition of copper powder into the composition for metal etching And 5,000 ppm of copper powder were added.
(° C)
Referring to the evaluation values shown in Table 2 and Table 3, it can be confirmed that the aged characteristics vary depending on the kinds and contents of the main chelating agent, the first sub chelating agent and the second sub chelating agent contained in the metal etching composition.
As in Comparative Example 1 and Comparative Example 2, as in the case of Comparative Example 3 to Comparative Example 5, only the first sub chelating agent which is a sulfuric acid based sub chelating agent was used as the sub chelating agent, or the second sub chelate It was confirmed that both the hydrolysis degree, the degree of component modification and the EPD change were larger than those in Examples.
Particularly, in the case of Comparative Example 5, the hydrolysis degree, the degree of component modification and the EPD degree of change were significantly higher than those of Comparative Examples 1 to 4, which was the aminotris (methylene Phosphonic acid) reacts with hydrogen peroxide to form N-oxide.
In the case of Comparative Examples 6 to 8, nitrilotriacetic acid, aminotris (methylenephosphonic acid) and pyridine were used as materials capable of reacting with hydrogen peroxide to form N-oxide. In this case, 5, it was confirmed that the hydrolysis degree, the degree of component modification and the degree of EPD change were increased as the compound reacted with hydrogen peroxide to form N-oxide.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit of the invention as set forth in the appended claims. The present invention can be variously modified and changed by those skilled in the art, and it is also within the scope of the present invention.
Claims (11)
At least one main chelating agent selected from acetic acid chelating agents and amino acid chelating agents;
A first sulfur chelate chelating agent represented by the following general formula (1) or (2) or a salt thereof;
A second phosphate chelating agent represented by the following general formula (3) or (4) or a salt thereof;
Etch inhibitors; And
water;
/ RTI >
Composition for etching a hydrogen peroxide-based metal:
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
In the above Chemical Formulas 1 and 2,
R 1 to R 3 independently represent hydrogen, a hydroxyl group, a halogen group, an amino group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 haloalkyl group, a C 1 -C 10 aminoalkyl group , A phenyl group and a halogen-substituted phenyl group,
In Formula 3 and Formula 4,
R 4 to R 12 independently represent hydrogen, a hydroxy group, a halogen group, an amino group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 haloalkyl group, a C 1 -C 10 aminoalkyl group , A phenyl group and a halogen-substituted phenyl group,
When a functional group containing a nitrogen atom among R 4 to R 12 is present, the nitrogen atom is a 1,2 or 4-substituted nitrogen atom.
Wherein the weight ratio of the first sub chelating agent to the second sub chelate in the hydrogen peroxide-based metal etching composition is in the range of 6: 4 to 9: 1,
A composition for etching a hydrogen peroxide based metal.
When a functional group containing a nitrogen atom among R 1 to R 3 is present, the nitrogen atom is a 1,2 or 4-substituted nitrogen atom,
A composition for etching a hydrogen peroxide based metal.
The first sub chelating agent may be selected from the group consisting of sulfonic acid, methane sulfonic acid, methane disulfonic acid, ethanesulfonic acid, ethane disulfonic acid, propanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid, ethylbenzenesulfonic acid, potassium bisulfate, , At least one selected from sodium bisulfate, sodium sulfate, ammonium sulfate, ammonium persulfate, dimethylsulfoxide and diethylsulfoxide.
A composition for etching a hydrogen peroxide based metal.
Wherein the second sub-chelating agent is at least one selected from aminoethylphosphonic acid, carboxyethylphosphonic acid, dimethylphosphate, dimethylphosphonate, hydroxyethylidenediphosphonic acid and methylenediphosphonic acid,
A composition for etching a hydrogen peroxide based metal.
Wherein at least one carbon atom is substituted with a functional group selected from a carboxy group, an amino group, an amide group, a carbamoyl group, a nitro group and an acetyl group when a functional group containing a carbon atom among R 4 to R 12 is present,
A composition for etching a hydrogen peroxide based metal.
Wherein the second sub chelating agent is at least one selected from hydroxyphosphonocarboxylic acid, methylenediphosphonocarboxylic acid and phosphonobutane-tris-carboxylic acid,
A composition for etching a hydrogen peroxide based metal.
Wherein the acetic acid chelating agent is at least one selected from iminodiacetic acid, methyliminodiacetic acid, iminomalonic acid, and hydroxyethyliminodiacetic acid,
A composition for etching a hydrogen peroxide based metal.
Wherein the amino acid chelating agent is at least one selected from alanine, glutamic acid, aminobutyric acid and glycine,
A composition for etching a hydrogen peroxide based metal.
The etch inhibitor may be selected from the group consisting of furan, thiophene, pyrrole, oxazole, imidazole, pyrazole, triazole, tetrazole, aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, pyrrolidine At least one member selected from the group consisting of benzoic acid, fumaric acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid,
A composition for etching a hydrogen peroxide based metal.
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| KR1020150162229A KR101695571B1 (en) | 2015-11-19 | 2015-11-19 | Peroxide-based composition for etching metal |
| CN201680068003.6A CN108291314B (en) | 2015-11-19 | 2016-11-21 | Composition for etching copper and composition for etching hydrogen peroxide metal |
| PCT/KR2016/013412 WO2017086758A1 (en) | 2015-11-19 | 2016-11-21 | Composition for etching copper, and hydrogen peroxide-based composition for etching metal |
| JP2018526545A JP6670934B2 (en) | 2015-11-19 | 2016-11-21 | Composition for etching copper and composition for etching hydrogen peroxide-based metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200113458A (en) | 2019-03-25 | 2020-10-07 | 에스케이머티리얼즈 주식회사 | Compostion for etching titanium nitrate layer-tungsten layer containing laminate and methold for etching a semiconductor device using the same |
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| KR20020019422A (en) * | 2000-09-05 | 2002-03-12 | 다나까 칸코 | ECHING AGENT FOR Ti-BASED FILM AND METHOD OF ECHING BY USE OF SAME |
| KR20140045121A (en) * | 2012-10-08 | 2014-04-16 | 동우 화인켐 주식회사 | Etchant composition for copper-containing metal layer |
| KR20140093620A (en) * | 2013-01-14 | 2014-07-28 | 주식회사 이엔에프테크놀로지 | Etching composition for copper/molybdenum or copper/molybdenum alloy multilayers |
| KR20150039526A (en) * | 2013-10-02 | 2015-04-10 | 주식회사 이엔에프테크놀로지 | Etching composition for copper and molibdenum containing film |
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| KR20020019422A (en) * | 2000-09-05 | 2002-03-12 | 다나까 칸코 | ECHING AGENT FOR Ti-BASED FILM AND METHOD OF ECHING BY USE OF SAME |
| KR20140045121A (en) * | 2012-10-08 | 2014-04-16 | 동우 화인켐 주식회사 | Etchant composition for copper-containing metal layer |
| KR20140093620A (en) * | 2013-01-14 | 2014-07-28 | 주식회사 이엔에프테크놀로지 | Etching composition for copper/molybdenum or copper/molybdenum alloy multilayers |
| KR20150039526A (en) * | 2013-10-02 | 2015-04-10 | 주식회사 이엔에프테크놀로지 | Etching composition for copper and molibdenum containing film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200113458A (en) | 2019-03-25 | 2020-10-07 | 에스케이머티리얼즈 주식회사 | Compostion for etching titanium nitrate layer-tungsten layer containing laminate and methold for etching a semiconductor device using the same |
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