KR20150089792A - Cleaning agent for electonic materials composed of various substrates - Google Patents
Cleaning agent for electonic materials composed of various substrates Download PDFInfo
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- KR20150089792A KR20150089792A KR1020140010800A KR20140010800A KR20150089792A KR 20150089792 A KR20150089792 A KR 20150089792A KR 1020140010800 A KR1020140010800 A KR 1020140010800A KR 20140010800 A KR20140010800 A KR 20140010800A KR 20150089792 A KR20150089792 A KR 20150089792A
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- ether
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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Abstract
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent for use in electronic parts, and more particularly, to a cleaning agent for use in an electronic component, which is capable of suppressing erosion of wiring while suppressing fine impurities, The present invention relates to a detergent which can effectively clean the detergent composition.
According to the present invention, it is possible to provide a cleaning agent that is excellent in cleaning power and can suppress corrosion of wiring included in the surface of an electronic substrate.
Description
The present invention relates to a cleaning agent for cleaning electronic components, and more particularly, to a cleaning agent for cleaning electronic components, and more particularly, to a cleaning agent for cleaning various electronic components, The present invention relates to a detergent for electronic components of various substrates which can effectively clean a substrate.
As the demand for larger and more solidified displays increases, the number of wirings included in displays is also increasing. Here, copper and aluminum, which are low-resistance materials, are used as the material of the wiring constituting the gate electrode or the source / drain electrode. However, wiring using copper (hereinafter referred to as " wiring " Copper wiring) is more preferred as a material for wiring in the fields of liquid crystal display (LCD) devices and flat panel displays. Thus, copper wiring is used to form the array line, and copper wiring is also utilized to prevent the flow delay between the resistor and the capacitor in the semiconductor wiring line.
On the other hand, foreign substances such as organic contaminants and particles may be included in the surface of the substrate and around the wiring in various processes of manufacturing the display, and it is necessary to remove them. In order to remove such foreign substances, conventionally, . Among them, ammonium hydroxide, tetramethylammonium hydroxide and the like have been extensively used as they do not contain ingredients such as sodium and potassium which can cause malfunction of electronic parts. However, the metallic wiring line formed of aluminum or copper for the wiring of the display is easily corroded by the solvent contained in the conventional cleaning agent, that is, the wiring constituting the gate electrode or the source / drain electrode provided on the substrate There was a problem that it could easily be corroded. To overcome this problem, Korean Patent Laid-Open No. 10-2010-0107003 In US Pat. No. 6,958,312 discloses a cleaning agent for an electronic material containing an anionic surfactant, an organic solvent, an alkali and a polymer dispersant, a chelating agent, and a cleaning agent containing an amine, a glycol ether and a solvent. And a method of cleaning by using the method.
However, since there is a limitation in preventing corrosion of the wiring while maintaining the cleaning power by the cleaning agent previously used or proposed by the prior art, the present invention proposes a cleaning agent for improving this.
It is an object of the present invention to provide a cleaning agent having excellent cleaning power and capable of suppressing corrosion of wiring included in the surface of an electronic substrate.
According to an aspect of the present invention, there is provided a cleaning agent for electronic components of various substrates,
A cleaning liquid used in various substrate manufacturing processes, wherein the cleaning liquid is composed of an alkaline compound, a surfactant, an ether compound, an anti-rust agent and a chelating agent.
The alkali compound may be 0.01 to 5% by weight.
The surfactant may be 0.01 to 0.5% by weight.
The glycol or glycol ether compound may be 0.3 to 20% by weight.
The rust preventive may be 0.001 to 3% by weight.
The chelating agent may be 0.01 to 0.5% by weight.
The alkali compound may be selected from ammonium hydroxide, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, and a mixture of one or more of these.
The glycol or glycol ether compound may be selected from the group consisting of diethylene glycol butyl ether (DEGBE), diethylene glycol ethyl ether (DEGEE), diethylene glycol methyl ether (DEGME), diethylene glycol propyl ether (DEGPE), ethylene glycol ethyl ether, ethylene Glycol ether compounds such as glycol methyl ether and ethylene glycol butyl ether, and ethylene compounds such as ethylene glycol may be selected and mixed.
The chelating agent includes an aminopolycarboxylic acid system and a hydroxycarboxylic acid system, and the aminopolycarboxylic acid system includes ethylenediaminetetraacetic acid (salt) (EDTA) and diethylenetriaminepentaacetic acid (salt) (DTPA) And the hydroxycarboxylic acid system includes citric acid (salt), hydroxyacetic acid (salt), and any one of them may be selected and used.
The nonionic surfactant is a polyethylene glycol type nonionic surfactant which is an ethylene oxide adduct of a higher alcohol and an alkylphenol. The nonionic surfactant is a nonionic surfactant such as polyoxyethylene alkylphenyl ether, ethoxylated alcohol, 14), and polyoxyethylene butylphenyl ether can be selected and used.
The rust inhibitor includes a triazole-based compound, an imidazole-based compound, and a thiazole-based compound, and the triazole-based compound includes benzotriazole and tolyltriazole. Examples of the imidazole-based compound include benzoimidazole, 2- Benzothiazole, and 2-mercaptobenzothiazole, and any one of these derivatives may be selected and used.
According to the present invention, it is possible to provide a cleaning agent that is excellent in cleaning power and can suppress corrosion of wiring included in the surface of an electronic substrate.
FIG. 1 is a view showing a state in which a metal glass on which copper (Cu) is vapor-deposited on a glass is observed by a scanning electron microscope (SEM)
2 is a view showing a state observed with a scanning electron microscope (SEM) after immersion in a cleaning agent using an antirust agent in a metal glass in which copper is deposited on a glass
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.
Various types of substrates such as a substrate for a flat panel display (a glass substrate for a liquid crystal panel, a color filter substrate, an array substrate, a substrate for a plasma display and an organic EL substrate), a semiconductor container plate (a semiconductor device and a silicon wafer) In the electronic substrate manufacturing process, foreign substances such as organic contaminants and particles may be contained on the surface of the substrate or around the wiring, and it is necessary to remove them. In this case, the cleaning agent is used to remove the foreign material. The role of the cleaning agent used herein is not limited to the flatness of the surface of the substrate, and the organic matter, metal ions, strongly attached fine particles, From the substrate surface. In addition, by dispersing the desorbed particles stably using a detergent, it is possible to realize excellent particle removing ability, to generate few bubbles, to provide excellent stability over time, to enable cleaning in a short time during the manufacture of a display So that it is possible to efficiently clean high altitude contributing to the improvement of the production rate.
To this end, the present invention proposes a cleaning agent containing an alkali component and a nonionic surfactant excellent in cleansing power, a chelating agent, and a rust inhibitor for suppressing the occurrence of corrosion, thereby preventing corrosion of wiring made of copper or aluminum . In other words, the present invention relates to a cleaning agent containing a corrosion inhibitor, a specific ether compound, an alkali, a nonionic surfactant, a chelating agent and the like, which suppress corrosion of metal, So that it can be cleaned and removed effectively. Thus, the cleaning agent according to the present invention can be suitably used for cleaning various types of electronic substrates having not only a display substrate but also a glass substrate or a surface on which a metal wiring formed on the substrate is exposed. That is, a cleaning agent capable of suppressing erosion on the glass substrate and the display panel, including strong cleaning power, is provided below.
Examples of the substance included in the cleaning agent according to the present invention include an alkali compound, a glycol ether compound, a chelate, a nonionic surfactant, an anti-rust agent and water. Hereinafter, a cleaning agent including water is referred to as a cleaning solution, and the properties and characteristics of components contained in the cleaning solution will be described in more detail.
The alkaline compound has a role of improving the etching property and the rinsing property. On the other hand, the content of the alkaline compound constituting the cleaning liquid according to the present invention is preferably 0.01 to 5% by weight, based on the weight. For the formation of the alkali compound, ammonium hydroxide, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and mixtures of two or more of these may be used. Of these, tetramethylammonium hydroxide or ammonium hydroxide show particularly excellent effects.
The glycol or glycol ether compound serves as a solvent for dissolving organic contaminants and exhibits excellent performance in improving the cleaning power by lowering the surface tension of the cleaning liquid including the cleaning liquid. On the other hand, the glycol and the glycol ether compound constituting the cleaning liquid according to the present invention preferably contain 0.3 to 20% by weight, based on the total weight of the cleaning liquid composition. For the composition of the glycol and glycol ether compound, diethylene glycol butyl ether (DEGBE), diethylene glycol ethyl ether (DEGEE), diethylene glycol methyl ether (DEGME), diethylene glycol propyl ether (DEGPE), ethylene glycol A glycol ether compound such as ethyl ether, ethylene glycol methyl ether, and ethylene glycol butyl ether, and an ethylene compound such as ethylene glycol, and at least one compound selected therefrom is used.
The chelating agent forms coordination bonds with metal ions through donor atoms such as oxygen or nitrogen, thereby facilitating the control of the etchability and further enhancing the dispersion stability of the particles. On the other hand, the chelating agent contained in the cleaning liquid according to the present invention preferably contains 0.01 to 0.5% by weight, based on the total weight of the cleaning liquid composition. The aminopolycarboxylic acid family may include ethylenediamine tetraacetic acid (salt) (EDTA), diethylenetriamine pentaacetic acid (salt) (DTPA), and the hydroxycarboxylic acid series (Salt), hydroxyacetic acid (salt), and at least one compound selected therefrom is used.
Surfactants play a role in improving the ability to remove particles by lowering surface tension and improving wettability. At this time, the wettability can be confirmed by the contact angle test, which means the property of spreading on the surface when water drops are dropped on the surface. On the other hand, the surfactant contained in the cleaning liquid according to the present invention preferably contains 0.01 to 0.5% by weight, based on the total weight of the cleaning liquid composition. Also, a nonionic surfactant is mainly used for the constitution of the surfactant, and polyoxyethylene alkylphenyl ether, which is a nonionic surfactant, as a polyethylene glycol type nonionic surfactant which is an ethylene oxide adduct of a higher alcohol and an alkylphenol, Ethoxylated alcohol (carbon number 12 to 14), and polyoxyethylene butylphenyl ether, and one kind of compound selected therefrom is used. However, ethoxylated tetramethyl dodecylidene (Surfynol-465), dimethylhexenol (Sulfynol-61) and the like may also be utilized.
The rust inhibitor suppresses the corrosion of the materials constituting the wiring such as copper or aluminum and prevents the generation of an oxide film which may interfere with the display manufacturing process after cleaning. On the other hand, the rust inhibitor contained in the cleaning liquid according to the present invention preferably contains 0.001 to 3% by weight, more preferably 0.008 to 0.05% by weight, based on the total weight of the cleaning liquid composition. For the construction of the rust inhibitor, a triazole-based compound, an imidazole-based compound or a thiazole-based compound may be used. As the triazole-based compound, benzotriazole or tolyltriazole is used. As the imidazole- , 2-mercaptobenzimidazole, and the thiazole-based ones include benzothiazole, 2-mercaptobenzothiazole, and derivatives thereof. At this time, the respective compounds may be used alone or in a mixture of two or more.
Table 1 shows the evaluations of particle removal performance, organic removal performance, and corrosion performance based on the composition ratios of the cleaning liquid prepared by the components contained in the cleaning liquid described above. TMAH is tetramethylammonium hydroxide, DEGBE is diethylene glycol butyl ether, MEG is ethylene glycol, EA is ethoxylated alcohol, EDTA is ethylene diamine tetraacetic acid, 2-MBT is 2- Benzothiazole, and BT means benzotriazole. In addition, the ++ indicated by the corrosiveness shows that the cleaning power is excellent, the corrosion prevention power is excellent, the cleaning power is excellent, the corrosion prevention power is excellent, and - shows excellent washing power but significant corrosion.
Referring to Table 1, Examples 1 to 7 and Comparative Examples 1 to 5 are confirmed in order to evaluate the cleaning power (particle removal force). That is, the cleaning liquid prepared in accordance with Table 1 was placed in a spraying apparatus, and the non-cleaned NEG glass (370 mm X 470 mm) was immersed in a cleaning tank, subjected to a primary spray cleaning, a secondary bubble jet cleaning, a final spray cleaning, And the contact angle of the glass before and after cleaning was measured for each solution. In addition, the number of glass particles before cleaning was measured, and after a cleaning test, the number of particles of glass after cleaning was measured to evaluate the particle removability in a comprehensive manner.
Examples 1 to 7 and Comparative Examples 1 to 5 are confirmed in order to evaluate corrosion by referring to Table 1. That is, the rinsing solution prepared according to Table 1 was added in an amount different from that of the rust inhibitor, which was heated to 50, and a metal glass in which copper was deposited on the glass was immersed in the solution for 60 minutes. The change in height of the metal layer was observed by scanning electron microscopy (SEM).
Alkaline
(weight%)
compound
(weight%)
(weight%)
(weight%)
(weight%)
(0.3)
(0.3)
(0.2)
(0.5)
(0.08)
(0.3)
(0.3)
(0.2)
(0.5)
(0.08)
(One)
(0.3)
(0.2)
(0.5)
(0.08)
(One)
(1.2)
(0.2)
(0.5)
(0.08)
(One)
(3)
(0.2)
(0.5)
(0.08)
(2.5)
(1.2)
(0.2)
(0.5)
(0.08)
(2.5)
(3)
(0.2)
(0.5)
(0.08)
(0.3)
(0.3)
(0.2)
(0.5)
(One)
(0.3)
(0.2)
(0.5)
(One)
(0.3)
(0.2)
(0.5)
(0.08)
(1.8)
(0.3)
(0.2)
(0.5)
(0.08)
(1.8)
(0.3)
(0.2)
(0.5)
(0.08)
As shown in Table 1, according to Examples 1 to 7, the cleaning liquid according to the present invention has excellent cleaning power and does not show any corrosiveness. On the other hand, it was confirmed that Comparative Example 1 and Comparative Example 2 had a detergency lower than those of Examples 1 to 7 but had a superior cleaning property and a considerable amount of corrosion, and Comparative Example 3, Comparative Example 4, Comparative Example 5 was found to be less detergent than Example 1 to Example 7, but was superior in cleaning property and superior in corrosion resistance.
On the other hand, when Examples 1 to 7 were measured by a scanning transfer microscope (SEM), it was confirmed that the change in the height of the metal layer before and after the immersion of the cleaning liquid was within 20%. 1 and 2, FIG. 1 is a view showing the height (1) (1013 nm) of the Cu pattern before immersion, and FIG. 2 is a graph showing the height 2 (994 nm, 956 nm, 919 nm), the change in the height of the metal layer can be confirmed by the present invention. At this time, the height of the Cu pattern after immersion in FIG. 2 was 0.1%, 0.08%, and 0.06% from the top.
As described above, the cleaning liquid according to the present invention can be used as a cleaning liquid in a wide variety of applications such as oil, contamination from the human body (fingerprints, etc.), resin, plasticizer (dioctyl phthalate etc.) Powder and the like) to be cleaned can be preferably used. The cleaning liquid according to the present invention can be used for a flat panel display substrate (a glass substrate for a liquid crystal panel, a color filter substrate, an array substrate, a plasma display substrate and an organic EL substrate), a semiconductor container plate (a semiconductor element and a silicon wafer, , A solar cell substrate, and the like, and can be used as a material for cleaning.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be understood that various modifications and changes may be made without departing from the scope of the appended claims.
1: height of Cu pattern before immersion
2: height of Cu pattern after immersion
Claims (11)
Wherein the cleaning liquid is composed of an alkaline compound, a surfactant, an ether compound, a rust inhibitor and a chelating agent.
Wherein the alkali compound is 0.01 to 5% by weight.
Wherein the surfactant is 0.01 to 0.5% by weight.
Wherein the glycol or glycol ether compound is 0.3 to 20% by weight.
Wherein the rust inhibitor is 0.001 to 3% by weight.
Wherein the chelating agent is 0.01 to 0.5 wt%.
The above-
Characterized in that any one of ammonium hydroxide, ammonium hydroxide, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, and a mixture of one or more of these is selected and used.
The glycol or glycol ether compound may be,
(DEG EB), diethylene glycol ethyl ether (DEGEE), diethylene glycol methyl ether (DEGME), diethylene glycol propyl ether (DEGPE), ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether And an ethylene compound such as ethylene glycol are selected and mixed to be used for the detergent for electronic parts of various substrates.
Wherein the chelating agent comprises an aminopolycarboxylic acid-based and a hydroxycarboxylic acid-based,
The aminopolycarboxylic acid system includes ethylenediaminetetraacetic acid (salt) (EDTA) and diethylenetriaminepentaacetic acid (salt) (DTPA)
The hydroxycarboxylic acid system has citric acid (salt), hydroxyacetic acid (salt)
Wherein one of them is selected and used.
The nonionic surface-
As polyethylene glycol type nonionic surfactants which are ethylene oxide adducts of higher alcohols and alkylphenols,
Wherein the nonionic surfactant is selected from polyoxyethylene alkylphenyl ether, ethoxylated alcohol (carbon number 12 to 14), and polyoxyethylene butylphenyl ether. detergent.
The rustproofing agent includes a triazole-based compound, an imidazole-based compound, and a thiazole-based compound,
Examples of the triazole compound include benzotriazole and tolyl triazole,
The imidazole system includes benzimidazole and 2-mercaptobenzimidazole,
Examples of thiazole-based compounds include benzothiazole and 2-mercaptobenzothiazole,
Wherein one of these derivatives is selected and used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140010800A KR20150089792A (en) | 2014-01-28 | 2014-01-28 | Cleaning agent for electonic materials composed of various substrates |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140010800A KR20150089792A (en) | 2014-01-28 | 2014-01-28 | Cleaning agent for electonic materials composed of various substrates |
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| KR20150089792A true KR20150089792A (en) | 2015-08-05 |
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| KR1020140010800A KR20150089792A (en) | 2014-01-28 | 2014-01-28 | Cleaning agent for electonic materials composed of various substrates |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763573A (en) * | 2019-04-02 | 2020-10-13 | 昆山欣谷微电子材料有限公司 | Alkaline glass substrate cleaning fluid composition |
| CN116376642A (en) * | 2023-04-10 | 2023-07-04 | 北京中铁科新材料技术有限公司 | Environment-friendly nano insulator cleaning agent and preparation method thereof |
-
2014
- 2014-01-28 KR KR1020140010800A patent/KR20150089792A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763573A (en) * | 2019-04-02 | 2020-10-13 | 昆山欣谷微电子材料有限公司 | Alkaline glass substrate cleaning fluid composition |
| CN116376642A (en) * | 2023-04-10 | 2023-07-04 | 北京中铁科新材料技术有限公司 | Environment-friendly nano insulator cleaning agent and preparation method thereof |
| CN116376642B (en) * | 2023-04-10 | 2024-03-22 | 北京中铁科新材料技术有限公司 | Environment-friendly nano insulator cleaning agent and preparation method thereof |
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