US20070278185A1 - Etching composition and etching process - Google Patents
Etching composition and etching process Download PDFInfo
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- US20070278185A1 US20070278185A1 US11/752,966 US75296607A US2007278185A1 US 20070278185 A1 US20070278185 A1 US 20070278185A1 US 75296607 A US75296607 A US 75296607A US 2007278185 A1 US2007278185 A1 US 2007278185A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
Definitions
- the present invention relates to an etching composition used for etching conductive films which comprises zinc oxide as the main component and are used for display devices such as liquid crystal displays (LCD) and electroluminescence displays and to an etching process using the etching composition.
- LCD liquid crystal displays
- electroluminescence displays and to an etching process using the etching composition.
- ITO indium tin oxide
- IZO indium zinc oxide Due to the decrease in the resources for indium, electrically conductive materials which can be used in place of ITO and IZO have been developed.
- Conductive films containing zinc oxide as the main component are widely used as the Piezoelectric thin films, optical waveguide films and gas sensitive films and are expected as the material which can be used in place of conventional conductive films for display devices.
- the conductive film containing zinc oxide as the main component can be supplied at a lower price with greater stability than indium-based conductive films since zinc is used as the raw material.
- Aluminum and gallium are often added to the zinc oxide films for display devices to decrease electric resistance.
- the above conductive films are formed on a substrate such as a glass substrate in accordance with a process for film formation such as the sputtering process and the ion plating process. Then, etching is conducted using a resist or the like as the mask, and an electrode pattern is formed.
- the etching process includes wet processes and dry processes. An etching composition is used in the wet processes.
- FIG. 1 shows a sectional view of a laminate which is obtained by forming a zinc oxide film 2 on a glass substrate 1 , followed by forming a resist 3 patterned in accordance with the photolithography.
- FIG. 2 shows a sectional view of a laminate obtained after etching the laminate shown in FIG. 1 using the resist 3 as the mask.
- the great accuracy means that the zinc oxide film is etched accurately to give the dimensions shown by the resist pattern. It is preferable that the distance from the end portion of the resist (a) to the end portion of zinc oxide (b) (the amount of the side etching) is decreased as much as possible.
- Residues 4 left remaining after the etching cause formation of the leak current between the electrodes when the residues have the electric conductivity.
- the residues 4 may cause a decrease in adhesion with a film formed above the zinc oxide film 2 . Therefore, the presence of the residues is not preferable.
- An excessively great etching rate is not preferable since the control of the etching becomes difficult.
- An etching rate of about 500 to 2,000 angstrom/min is preferable.
- the concentration of zinc in the etching composition increases with the progress of the etching. Therefore, it is very important for etching of transparent electrodes in the industrial production that the etching composition is a stable fluid having the etching properties such as the etching rate hardly affected by the concentration of zinc in the etching composition.
- the stable etching composition having the etching properties hardly affected by the concentration of zinc is used, the amount of etching of zinc oxide can be further increased.
- an electroluminescence element for displays and a process for producing the element are described. It is described that a transparent conductive film can be formed by etching a zinc oxide film with acetic acid. Although the etching of a zinc oxide film with an aqueous solution of acetic acid can be conducted, this process is not preferable due to the formation of residues.
- an etching composition for transparent electrodes comprising oxalic acid and a polysulfonic acid compound is disclosed.
- This composition relates to ITO films, and no descriptions on the etching of a zinc oxide film can be found at all.
- a zinc oxide film is etched with an aqueous solution of oxalic acid, hardly soluble crystals of zinc oxalate are formed on the substrate and, therefore, this process is not preferable.
- crystals of zinc oxalate cannot be removed by etching.
- the present invention relates to an etching composition which forms almost no residues, enables to conduct the etching at a suitable etching rate and exhibits a suppressed change in the etching properties when a zinc oxide film containing zinc oxide as the main component is etched and an etching process using the composition.
- the present invention provides an etching composition which contains at least one organic carboxylic acid compound selected from acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, maleic acid, glutaric acid, aconitic acid, 1,2,3-propanetricarboxylic acid and ammonium salts of these acids, a polysulfonic acid compound, and water.
- organic carboxylic acid compound selected from acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, maleic acid, glutaric acid, aconitic acid, 1,2,3-propanetricarboxylic acid and ammonium salts of these acids, a polysulfonic acid compound, and water.
- the present invention also provides an etching process which contains etching a conductive film containing zinc oxide as a main component using an etching composition described above.
- FIG. 1 shows a schematic sectional view of a laminate in which a patterned resist is formed.
- FIG. 2 shows a schematic sectional view of a laminate obtained after etching the laminate shown in FIG. 1 .
- FIG. 3 shows an image of the surface by the SEM observation after being etched in Example 2 (the etching composition before adding 0.1% by weight of zinc oxide).
- FIG. 4 shows an image of the surface by the SEM observation after being etched in Comparative Example 5 (the etching composition before adding 0.1% by weight of zinc oxide).
- the etching composition will be described in the following.
- the etching composition of the present invention comprises an organic carboxylic acid compound comprising an organic carboxylic acid and/or an ammonium salt of an organic carboxylic acid, a polysulfonic acid compound, and water.
- the organic carboxylic acid compound is at least one compound selected from acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, maleic acid, glutaric acid, aconitic acid, 1,2,3-propanetricarboxylic acid, and ammonium salts of these acids.
- acetic acid, citric acid, succinic acid, lactic acid, malic acid, tartaric acid and ammonium salts thereof are preferable, and acetic acid and ammonium acetate are more preferable.
- the concentration of the organic carboxylic acid compound comprised in the etching composition of the present invention is 0.1 to 90% by weight, more preferably 0.2 to 80% by weight and most preferably 0.3 to 70% by weight.
- concentration is 0.1 to 90% by weight, the stable etching operation can be conducted while a practically sufficient etching rate is maintained.
- the concentration of the ammonium salt of an organic carboxylic acid compound is 3.0 to 90% by weight, more preferably 4.0 to 80% by weight and most preferably 5.0 to 70% by weight.
- concentration is 3.0 to 90% by weight, the stable etching operation can be conducted while a practically sufficient etching rate is maintained.
- the polysulfonic acid compound comprised in the etching composition of the present invention is a compound selected from condensation products of naphthalenesulfonic acid with formaline (which is preferably a compound obtained by sulfonation using naphthalene and sulfuric acid, followed by condensation by addition of formaline or by condensation by addition of formaline and neutralization with an alkali), ligninsulfonic acid, polystyrenesulfonic acid and alkali salts of these compounds.
- formaline which is preferably a compound obtained by sulfonation using naphthalene and sulfuric acid, followed by condensation by addition of formaline or by condensation by addition of formaline and neutralization with an alkali
- ligninsulfonic acid polystyrenesulfonic acid and alkali salts of these compounds.
- the condensation product of naphthalenesulfonic acid with formaline is available as a commercial product, examples of which include DEMOL N (a trade name; manufactured by KAO Co., Ltd.), LAVELIN FP (a trade name; manufactured by DAIICHI KOGYO SEIYAKU Co., Ltd.) and POLITY N100K (a trade name; manufactured by LION Co., Ltd.)
- the ligninsulfonic acid is available as a commercial product, examples of which include SAN-X (a trade name; manufactured by NIPPON SEISHI CHEMICAL Co., Ltd.).
- SAN-X a trade name; manufactured by NIPPON SEISHI CHEMICAL Co., Ltd.
- the polysulfonic acid compound contains a metal such as sodium, the compound is not suitable for the use in the electronic industry.
- the compound can be used after sodium is removed by the treatment with an ion exchange resin.
- the concentration of the polysulfonic acid compound is in the range of 0.0001 to 10% by weight.
- concentration is in the range of 0.001 to 10% by weight, the effect of removing residues after the etching can be sufficiently exhibited.
- concentration is more preferably 0.001 to 8% by weight and most preferably 0.01 to 1% by weight.
- the etching composition of the present invention may be used after pH is adjusted at a desired value by adding an acid or an alkali. It is preferable that pH is 2 to 9. When pH is in this range, corrosion of aluminum used as the wiring material can be prevented. pH is more preferably 3 to 8 and most preferably 3 to 7.
- the etching composition of the present invention can be prepared by mixing the above materials and water in the prescribed amounts.
- the content of each material can be adjusted within the desired range by suitably adjusting the amount of water.
- the etching process of the present invention comprises etching a conductive film comprising zinc oxide as the main component using the etching composition of the present invention.
- the conductive film used for the etching in accordance with the process of the present invention is not particularly limited as long as the film comprises zinc oxide as the main component.
- the film may comprise one or a plurality of types of metals other than zinc.
- the film comprises at least one of aluminum and gallium since the electric resistance is decreased.
- Zinc oxide is the main component when the content of zinc oxide in the conductive film is the greatest among the components of the conductive film.
- the etching composition of the present invention is used in the condition of a temperature in the range of the room temperature to 80° C., more preferably in the range of the room temperature to 70° C. and most preferably in the range of the room temperature to 60° C.
- the time for etching the zinc oxide film with the etching composition can be suitably set with consideration on the etching rate (about 500 to 2,000 angstrom/min) suitable for the thickness of the treated film and the temperature of the treatment.
- the procedures in the etching process of the present invention are not particularly limited as long as the above etching composition can be uniformly brought at the position for the etching by circulation, and any of the dipping process and the shower process can be used.
- the procedures are not particularly limited as long as the etching composition on the substrate can be replaced, and the process in which the etching composition is made flow down on the inclined substrate, the process in which the substrate itself is shaken (the dipping process with shaking) or the process in which the etching composition is stirred in a tank can be used.
- the shower pressure in the shower process and the method of shaking in the dipping process with shaking can be suitably decided with consideration on the properties of the fluid.
- a zinc oxide film (the thickness: 1,000 angstrom) containing 3% by atom of gallium was formed on a glass substrate in accordance with the sputtering process.
- a resist pattern was formed on the zinc oxide film in accordance with the photolithography.
- Procedure of the treatment The substrate was dipped into the etching composition while the substrate was shaken (the dipping process with shaking).
- Time of dipping The time twice at the time required for the etching (the just-etching time)
- the substrate treated by the etching was cleaned with water and dried by blowing nitrogen gas.
- the etching rate and the condition of residues were examined on the substrate treated by the etching. The results are shown in Table 2.
- the etching rate was obtained by dividing the thickness of the zinc oxide film (1,000 angstrom) with the just-etching time. The presence or the absence of residues was examined by observation using a scanning electron microscope (SEM).
- “Residues after etching” in table 2 shows the result obtained with the composition before adding 0.1% by weight of zinc oxide.
- the result obtained with the composition after adding 0.1% by weight of zinc oxide was the same as the result obtained with the composition before adding 0.1% by weight of zinc oxide.
- TABLE 1 Composition Example 1 1% by wt. acetic acid 0.1% by wt. LAVELIN FP Example 2 5% by wt. acetic acid 0.0001% by wt. LAVELIN FP Example 3 5% by wt. acetic acid 0.1% by wt. LAVELIN FP Example 4 5% by wt. acetic acid 1% by wt. LAVELIN FP Example 5 5% by wt.
- LAVELIN FP A condensation product of naphthalenesulfonic acid with formaline (a compound obtained by sulfonation using naphthalene and sulfuric acid, followed by condensation by addition of formaline and neutralization; the molecular weight: 2,000 ⁇ 5,000; manufactured by DAIICHI KOGYO SEIYAKU Co., Ltd.)
- DEMOL N A condensation product of naphthalenesulfonic acid with formaline (manufactured by KAO Co., Ltd.)
- POLITY N100K A condensation product of naphthalenesulfonic acid with formaline (manufactured by LION Co., Ltd.)
- FIG. 3 and FIG. 4 Images of the surface by the SEM observation after being etched in Example 2 and Comparative Example 5 (both are the etching composition before adding 0.1% by weight of zinc oxide) are shown in FIG. 3 and FIG. 4 , respectively.
- the etching composition used in Example 2 formed no residues of etching.
- the etching composition used in Comparative Example 5 formed many white dots of residues of etching as shown in FIG. 4 .
- the etching composition of the present invention exhibits the excellent properties as the etching composition used in the industrial production.
Abstract
An etching composition which comprises at least one organic carboxylic acid compound selected from acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, maleic acid, glutaric acid, aconitic acid, 1,2,3-propanetricarboxylic acid and ammonium salts of these acids, a polysulfonic acid compound and water, and an etching process which comprises etching a conductive film comprising zinc oxide as the main component using the etching composition described above.
Description
- 1. Field of the Invention
- The present invention relates to an etching composition used for etching conductive films which comprises zinc oxide as the main component and are used for display devices such as liquid crystal displays (LCD) and electroluminescence displays and to an etching process using the etching composition.
- 2. Description of the Related Art
- As the conductive film for display devices such as liquid crystal displays and electroluminescence displays, films of indium tin oxide (ITO) and films of indium zinc oxide (IZO) are widely used. Due to the decrease in the resources for indium, electrically conductive materials which can be used in place of ITO and IZO have been developed.
- Conductive films containing zinc oxide as the main component are widely used as the Piezoelectric thin films, optical waveguide films and gas sensitive films and are expected as the material which can be used in place of conventional conductive films for display devices. The conductive film containing zinc oxide as the main component can be supplied at a lower price with greater stability than indium-based conductive films since zinc is used as the raw material. Aluminum and gallium are often added to the zinc oxide films for display devices to decrease electric resistance.
- The above conductive films are formed on a substrate such as a glass substrate in accordance with a process for film formation such as the sputtering process and the ion plating process. Then, etching is conducted using a resist or the like as the mask, and an electrode pattern is formed. The etching process includes wet processes and dry processes. An etching composition is used in the wet processes.
- It is widely known that zinc oxide is soluble in acids and alkalis. When a transparent electrode of a display device such as a liquid crystal display is formed, the following properties are required for the etching composition:
- (1) A great accuracy of working
- (2) A suppressed amount of residues of etching
- (3) A suitable etching rate
- (4) A suppressed change in the etching property with dissolution of zinc oxide
- (5) No corrosion of materials such as wiring materials
- The related arts will be described more specifically with reference to Figures.
FIG. 1 shows a sectional view of a laminate which is obtained by forming azinc oxide film 2 on a glass substrate 1, followed by forming aresist 3 patterned in accordance with the photolithography.FIG. 2 shows a sectional view of a laminate obtained after etching the laminate shown inFIG. 1 using theresist 3 as the mask. The great accuracy means that the zinc oxide film is etched accurately to give the dimensions shown by the resist pattern. It is preferable that the distance from the end portion of the resist (a) to the end portion of zinc oxide (b) (the amount of the side etching) is decreased as much as possible. - Residues 4 left remaining after the etching cause formation of the leak current between the electrodes when the residues have the electric conductivity. The residues 4 may cause a decrease in adhesion with a film formed above the
zinc oxide film 2. Therefore, the presence of the residues is not preferable. - An excessively great etching rate is not preferable since the control of the etching becomes difficult. An etching rate of about 500 to 2,000 angstrom/min is preferable.
- The concentration of zinc in the etching composition increases with the progress of the etching. Therefore, it is very important for etching of transparent electrodes in the industrial production that the etching composition is a stable fluid having the etching properties such as the etching rate hardly affected by the concentration of zinc in the etching composition. When the stable etching composition having the etching properties hardly affected by the concentration of zinc is used, the amount of etching of zinc oxide can be further increased.
- In Japanese Patent Application Laid-Open No. 8(1996)- 330692, a process for forming an electrode pattern for display devices containing zinc oxide as the main component is described. It is described that etching can be conducted with excellent accuracy without formation of residues by the etching using hydrochloric acid or nitric acid as an acidic solution of 0.005 to 0.2 N. However, when the above etching composition is actually used, the accuracy is insufficient due to a great amount of the side etching, and residues are formed. Moreover, the etching rate changes to a great degree due to the change in the concentration of the acid caused by vaporization of water and dissolution of zinc during the etching, and the stable etching cannot be expected.
- In Japanese Patent No. 3258780, an electroluminescence element for displays and a process for producing the element are described. It is described that a transparent conductive film can be formed by etching a zinc oxide film with acetic acid. Although the etching of a zinc oxide film with an aqueous solution of acetic acid can be conducted, this process is not preferable due to the formation of residues.
- In Japanese Patent No. 3345408, an etching composition for transparent electrodes comprising oxalic acid and a polysulfonic acid compound is disclosed. This composition relates to ITO films, and no descriptions on the etching of a zinc oxide film can be found at all. When a zinc oxide film is etched with an aqueous solution of oxalic acid, hardly soluble crystals of zinc oxalate are formed on the substrate and, therefore, this process is not preferable. Even when a polysulfonic acid compound is added to the aqueous solution of oxalic acid, crystals of zinc oxalate cannot be removed by etching.
- In Solid-State Sensor Actuator Workshop (New York: IEEE, 1992 pp 41-45), it is reported that the etching can be conducted at a suitable etching rate when ammonium chloride is used in the etching. However, etching residues are formed, and this process cannot be used.
- The present invention relates to an etching composition which forms almost no residues, enables to conduct the etching at a suitable etching rate and exhibits a suppressed change in the etching properties when a zinc oxide film containing zinc oxide as the main component is etched and an etching process using the composition.
- As the result of intensive studies by the present inventors, the present invention has been completed as shown in the following.
- The present invention provides an etching composition which contains at least one organic carboxylic acid compound selected from acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, maleic acid, glutaric acid, aconitic acid, 1,2,3-propanetricarboxylic acid and ammonium salts of these acids, a polysulfonic acid compound, and water.
- The present invention also provides an etching process which contains etching a conductive film containing zinc oxide as a main component using an etching composition described above.
-
FIG. 1 shows a schematic sectional view of a laminate in which a patterned resist is formed. -
FIG. 2 shows a schematic sectional view of a laminate obtained after etching the laminate shown inFIG. 1 . -
FIG. 3 shows an image of the surface by the SEM observation after being etched in Example 2 (the etching composition before adding 0.1% by weight of zinc oxide). -
FIG. 4 shows an image of the surface by the SEM observation after being etched in Comparative Example 5 (the etching composition before adding 0.1% by weight of zinc oxide). - The etching composition will be described in the following.
- The etching composition of the present invention comprises an organic carboxylic acid compound comprising an organic carboxylic acid and/or an ammonium salt of an organic carboxylic acid, a polysulfonic acid compound, and water.
- The organic carboxylic acid compound is at least one compound selected from acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, maleic acid, glutaric acid, aconitic acid, 1,2,3-propanetricarboxylic acid, and ammonium salts of these acids. Among the above organic carboxylic acid compounds, acetic acid, citric acid, succinic acid, lactic acid, malic acid, tartaric acid and ammonium salts thereof are preferable, and acetic acid and ammonium acetate are more preferable.
- It is preferable that the concentration of the organic carboxylic acid compound comprised in the etching composition of the present invention is 0.1 to 90% by weight, more preferably 0.2 to 80% by weight and most preferably 0.3 to 70% by weight. When the concentration is 0.1 to 90% by weight, the stable etching operation can be conducted while a practically sufficient etching rate is maintained.
- It is preferable that the concentration of the ammonium salt of an organic carboxylic acid compound is 3.0 to 90% by weight, more preferably 4.0 to 80% by weight and most preferably 5.0 to 70% by weight. When the concentration is 3.0 to 90% by weight, the stable etching operation can be conducted while a practically sufficient etching rate is maintained.
- The polysulfonic acid compound comprised in the etching composition of the present invention is a compound selected from condensation products of naphthalenesulfonic acid with formaline (which is preferably a compound obtained by sulfonation using naphthalene and sulfuric acid, followed by condensation by addition of formaline or by condensation by addition of formaline and neutralization with an alkali), ligninsulfonic acid, polystyrenesulfonic acid and alkali salts of these compounds.
- The condensation product of naphthalenesulfonic acid with formaline is available as a commercial product, examples of which include DEMOL N (a trade name; manufactured by KAO Co., Ltd.), LAVELIN FP (a trade name; manufactured by DAIICHI KOGYO SEIYAKU Co., Ltd.) and POLITY N100K (a trade name; manufactured by LION Co., Ltd.)
- The ligninsulfonic acid is available as a commercial product, examples of which include SAN-X (a trade name; manufactured by NIPPON SEISHI CHEMICAL Co., Ltd.). When the polysulfonic acid compound contains a metal such as sodium, the compound is not suitable for the use in the electronic industry. The compound can be used after sodium is removed by the treatment with an ion exchange resin.
- It is preferable that the concentration of the polysulfonic acid compound is in the range of 0.0001 to 10% by weight. When the concentration is in the range of 0.001 to 10% by weight, the effect of removing residues after the etching can be sufficiently exhibited. The above concentration is more preferably 0.001 to 8% by weight and most preferably 0.01 to 1% by weight.
- The etching composition of the present invention may be used after pH is adjusted at a desired value by adding an acid or an alkali. It is preferable that pH is 2 to 9. When pH is in this range, corrosion of aluminum used as the wiring material can be prevented. pH is more preferably 3 to 8 and most preferably 3 to 7.
- The etching composition of the present invention can be prepared by mixing the above materials and water in the prescribed amounts. The content of each material can be adjusted within the desired range by suitably adjusting the amount of water.
- The etching process will be described in the following.
- The etching process of the present invention comprises etching a conductive film comprising zinc oxide as the main component using the etching composition of the present invention.
- The conductive film used for the etching in accordance with the process of the present invention is not particularly limited as long as the film comprises zinc oxide as the main component. The film may comprise one or a plurality of types of metals other than zinc. In particular, it is preferable that the film comprises at least one of aluminum and gallium since the electric resistance is decreased. Zinc oxide is the main component when the content of zinc oxide in the conductive film is the greatest among the components of the conductive film.
- It is preferable that the etching composition of the present invention is used in the condition of a temperature in the range of the room temperature to 80° C., more preferably in the range of the room temperature to 70° C. and most preferably in the range of the room temperature to 60° C. The time for etching the zinc oxide film with the etching composition can be suitably set with consideration on the etching rate (about 500 to 2,000 angstrom/min) suitable for the thickness of the treated film and the temperature of the treatment.
- The procedures in the etching process of the present invention are not particularly limited as long as the above etching composition can be uniformly brought at the position for the etching by circulation, and any of the dipping process and the shower process can be used. When the dipping process is used, the procedures are not particularly limited as long as the etching composition on the substrate can be replaced, and the process in which the etching composition is made flow down on the inclined substrate, the process in which the substrate itself is shaken (the dipping process with shaking) or the process in which the etching composition is stirred in a tank can be used. The shower pressure in the shower process and the method of shaking in the dipping process with shaking can be suitably decided with consideration on the properties of the fluid.
- The present invention will be described more specifically with reference to Examples and Comparative Examples in the following. However, the present invention is not limited to the examples.
- A zinc oxide film (the thickness: 1,000 angstrom) containing 3% by atom of gallium was formed on a glass substrate in accordance with the sputtering process. A resist pattern was formed on the zinc oxide film in accordance with the photolithography. By using an etching composition shown below in Table 1 or an etching composition obtained by adding 0.1% by weight of zinc oxide to an etching composition shown in Table 1, the etching treatment was conducted under the following condition. The rest of the etching composition was water.
- Temperature of the substrate: 30° C.
- Procedure of the treatment: The substrate was dipped into the etching composition while the substrate was shaken (the dipping process with shaking).
- Time of dipping: The time twice at the time required for the etching (the just-etching time)
- The substrate treated by the etching was cleaned with water and dried by blowing nitrogen gas. The etching rate and the condition of residues were examined on the substrate treated by the etching. The results are shown in Table 2.
- The etching rate was obtained by dividing the thickness of the zinc oxide film (1,000 angstrom) with the just-etching time. The presence or the absence of residues was examined by observation using a scanning electron microscope (SEM).
- “Residues after etching” in table 2 shows the result obtained with the composition before adding 0.1% by weight of zinc oxide. The result obtained with the composition after adding 0.1% by weight of zinc oxide was the same as the result obtained with the composition before adding 0.1% by weight of zinc oxide.
TABLE 1 Composition Example 1 1% by wt. acetic acid 0.1% by wt. LAVELIN FP Example 2 5% by wt. acetic acid 0.0001% by wt. LAVELIN FP Example 3 5% by wt. acetic acid 0.1% by wt. LAVELIN FP Example 4 5% by wt. acetic acid 1% by wt. LAVELIN FP Example 5 5% by wt. acetic acid 0.1% by wt. sodium ligninsulfonate Example 6 5% by wt. acetic acid 0.1% by wt. sodium polystyrenesulfonate Example 7 5% by wt. citric acid 0.1% by wt. LAVELIN FP Example 8 5% by wt. succinic acid 0.1% by wt. LAVELIN FP Example 9 5% by wt. lactic acid 10.0% by wt. LAVELIN FP Example 10 5% by wt. malic acid 0.1% by wt. LAVELIN FP Example 11 5% by wt. tartaric acid 0.1% by wt. LAVELIN FP Example 12 15% by wt. ammonium acetate 0.1% by wt. DEMOL N Example 13 15% by wt. ammonium acetate 0.1% by wt. POLITY N100K Example 14 15% by wt. ammonium succinate 0.1% by wt. LAVELIN FP Example 15 15% ammonium acetate 0.1% by wt. LAVELIN FP 5% by wt. acetic acid Comparative 15% by wt. acetic acid Example 1 Comparative 15% by wt. ammonium acetate Example 2 Comparative 5% by wt. succinic acid Example 3 Comparative 0.1% by wt. hydrochloric acid Example 4 Comparative 5% by wt. acetic acid Example 5 Comparative 1% by wt. LAVELIN FP Example 6 Comparative 1% by wt. LAVELIN FP Example 7 (sodium removed) Comparative 0.5% by wt. LAVELIN FP Example 8 (sodium removed)
LAVELIN FP: A condensation product of naphthalenesulfonic acid with formaline (a compound obtained by sulfonation using naphthalene and sulfuric acid, followed by condensation by addition of formaline and neutralization; the molecular weight: 2,000˜5,000; manufactured by DAIICHI KOGYO SEIYAKU Co., Ltd.)
DEMOL N: A condensation product of naphthalenesulfonic acid with formaline (manufactured by KAO Co., Ltd.)
POLITY N100K A condensation product of naphthalenesulfonic acid with formaline (manufactured by LION Co., Ltd.)
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TABLE 2 Etching rate (Å/min) content of zinc oxide (by wt.) Residues 0 0.1 of etching Example 1 1091 857 excellent Example 2 857 857 excellent Example 3 1333 1200 excellent Example 4 2000 1714 excellent Example 5 1333 1200 excellent Example 6 1333 1200 excellent Example 7 750 706 excellent Example 8 1200 1200 excellent Example 9 1333 1200 excellent Example 10 632 600 excellent Example 11 667 632 excellent Example 12 1091 1000 excellent Example 13 1091 1000 excellent Example 14 750 706 excellent Example 15 2000 2000 excellent Comparative 2000 2000 poor Example 1 Comparative 857 <200 poor Example 2 Comparative 1500 1500 poor Example 3 Comparative 6000 2400 poor Example 4 Comparative 2000 2000 poor Example 5 Comparative <300 etching not examination Example 6 possible not possible Comparative 6000 545 excellent Example 7 Comparative 2000 etching not excellent Example 8 possible
Evaluation of residues
poor: many residues on the entire surface
excellent: no residues at all
- Images of the surface by the SEM observation after being etched in Example 2 and Comparative Example 5 (both are the etching composition before adding 0.1% by weight of zinc oxide) are shown in
FIG. 3 andFIG. 4 , respectively. As shown inFIG. 3 , the etching composition used in Example 2 formed no residues of etching. In contrast, the etching composition used in Comparative Example 5 formed many white dots of residues of etching as shown inFIG. 4 . - It is shown by the results in Tables 1 and 2 that, when the etching composition of the present invention is used, the conductive film comprising zinc oxide as the main component can be etched at a suitable etching rate which is easy for the control, and the formation of residues of etching is suppressed.
- The decrease in the etching rate is small and the change in the etching properties is suppressed even when zinc oxide is dissolved. Therefore, it is shown that the etching composition of the present invention exhibits the excellent properties as the etching composition used in the industrial production.
Claims (8)
1. An etching composition which comprises at least one organic carboxylic acid compound selected from acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, maleic acid, glutaric acid, aconitic acid, 1,2,3-propanetricarboxylic acid and ammonium salts of these acids, a polysulfonic acid compound, and water.
2. An etching composition according to claim 1 , wherein the organic carboxylic acid compound is acetic acid or ammonium acetate.
3. An etching composition according to claim 1 , wherein the organic carboxylic acid compound is acetic acid and ammonium acetate.
4. An etching composition according to claim 1 , wherein the polysulfonic acid compound is a compound selected from condensation products of naphthalenesulfonic acid with formaline, ligninsulfonic acid, polystyrenesulfonic acid and salts of these compounds.
5. An etching composition according to claim 4 , wherein the condensation product of naphthalenesulfonic acid with formaline is a compound obtained by sulfonation using naphthalene and sulfuric acid, followed by condensation by addition of formaline or by condensation by addition of formaline and neutralization with an alkali.
6. An etching composition according to claim 1 , wherein a concentration of the polysulfonic acid compound is 0.0001 to 10% by weight.
7. An etching process which comprises etching a conductive film comprising zinc oxide as a main component using an etching composition described in claim 1 .
8. An etching process according to claim 7 , wherein the conductive film comprises at least one of aluminum and gallium.
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US12/943,639 US8048331B2 (en) | 2006-05-25 | 2010-11-10 | Etching composition and etching process |
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JP2006145440A JP4816250B2 (en) | 2006-05-25 | 2006-05-25 | Etching solution composition and etching method |
JP145440/2006 | 2006-05-25 |
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US12/943,639 Division US8048331B2 (en) | 2006-05-25 | 2010-11-10 | Etching composition and etching process |
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US11/752,966 Abandoned US20070278185A1 (en) | 2006-05-25 | 2007-05-24 | Etching composition and etching process |
US12/943,639 Active US8048331B2 (en) | 2006-05-25 | 2010-11-10 | Etching composition and etching process |
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US (2) | US20070278185A1 (en) |
EP (1) | EP1862525B1 (en) |
JP (1) | JP4816250B2 (en) |
KR (1) | KR20070113981A (en) |
TW (1) | TWI409318B (en) |
Cited By (3)
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US20100288725A1 (en) * | 2009-03-25 | 2010-11-18 | Zhi-Wen Sun | Acid Chemistries and Methodologies for Texturing Transparent Conductive Oxide Materials |
CN111690932A (en) * | 2019-03-13 | 2020-09-22 | 易安爱富科技有限公司 | Etching solution composition for silver-containing metal film |
US20200336836A1 (en) * | 2017-10-11 | 2020-10-22 | Unist(Ulsan National Institute Of Science And Technology) | Nano membrane, method of manufacturing nano membrane, and apparatus for speaker and microphone using nano membrane |
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JP2008047645A (en) * | 2006-08-11 | 2008-02-28 | Tosoh Corp | Etching liquid and etching method of transparent electrode |
JP2008159814A (en) * | 2006-12-22 | 2008-07-10 | Mitsui Mining & Smelting Co Ltd | Etchant for zinc oxide based thin-film, and method for patterning zinc oxide based thin-film |
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KR20110082146A (en) * | 2008-10-29 | 2011-07-18 | 미츠비시 가스 가가쿠 가부시키가이샤 | Texture processing liquid for transparent conductive film mainly composed of zinc oxide and method for producing transparent conductive film having recesses and projections |
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CN105659365B (en) * | 2013-10-30 | 2020-07-31 | 三菱瓦斯化学株式会社 | Etching solution and etching method for oxide substantially composed of zinc, tin and oxygen |
JP6384490B2 (en) * | 2014-01-07 | 2018-09-05 | 三菱瓦斯化学株式会社 | Etching solution and etching method of oxide containing zinc and tin |
KR102128276B1 (en) * | 2014-02-17 | 2020-06-30 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Liquid composition for etching oxides comprising indium, zinc, tin, and oxygen and etching method |
JP6350008B2 (en) * | 2014-06-20 | 2018-07-04 | 三菱瓦斯化学株式会社 | Etching solution and etching method of oxide containing at least indium, gallium, zinc and silicon |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4517106A (en) * | 1984-04-26 | 1985-05-14 | Allied Corporation | Soluble surfactant additives for ammonium fluoride/hydrofluoric acid oxide etchant solutions |
US4620934A (en) * | 1984-04-26 | 1986-11-04 | Allied Corporation | Soluble fluorinated cycloalkane sulfonate surfactant additives for NH4 |
US20020055447A1 (en) * | 2000-09-08 | 2002-05-09 | Norio Ishikawa | Etching liquid composition |
US20030168431A1 (en) * | 2002-02-25 | 2003-09-11 | Ritdisplay Corporation | Etchant composition for silver alloy |
US6828289B2 (en) * | 1999-01-27 | 2004-12-07 | Air Products And Chemicals, Inc. | Low surface tension, low viscosity, aqueous, acidic compositions containing fluoride and organic, polar solvents for removal of photoresist and organic and inorganic etch residues at room temperature |
US20040262569A1 (en) * | 2003-06-24 | 2004-12-30 | Lg.Philips Lcd Co., Ltd. | Etchant for etching double-layered copper structure and method of forming array substrate having double-layered copper structures |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5821336A (en) * | 1981-07-29 | 1983-02-08 | Toshiba Corp | Manufacture of semiconductor element |
JPH03258780A (en) | 1990-03-08 | 1991-11-19 | Konica Corp | Production of 1h-pyrazolo(3,2-c)-1,2,4-triazole-based compound |
JP3258780B2 (en) | 1993-09-09 | 2002-02-18 | 株式会社デンソー | Electroluminescence device and method of manufacturing the same |
JPH08330692A (en) | 1995-05-29 | 1996-12-13 | Asahi Glass Co Ltd | Electrode pattern formation method and base body with electrode |
JP2000232090A (en) * | 1999-02-10 | 2000-08-22 | Toshiba Corp | Method for removing glass passivation film |
JP4055923B2 (en) * | 1999-04-22 | 2008-03-05 | 株式会社Adeka | ITO film removing composition and ITO film removing method using the same |
JP2002033303A (en) * | 2000-07-14 | 2002-01-31 | Mitsubishi Gas Chem Co Inc | Composition for etching |
JP3345408B2 (en) * | 2000-09-08 | 2002-11-18 | 関東化学株式会社 | Etching solution composition |
JP2004137586A (en) * | 2002-10-21 | 2004-05-13 | Mitsubishi Chemicals Corp | Etching liquid, and etching method |
JP4225548B2 (en) * | 2004-01-06 | 2009-02-18 | 三菱瓦斯化学株式会社 | Etching solution composition and etching method |
JP2005277402A (en) * | 2004-02-25 | 2005-10-06 | Mitsubishi Gas Chem Co Inc | Etching composition for laminated film including reflective electrode film and method for forming laminated wiring structure |
KR20060119264A (en) | 2005-05-19 | 2006-11-24 | 삼성전자주식회사 | Back light assembly and liquid crystal display apparatus having the same |
WO2007072950A1 (en) * | 2005-12-22 | 2007-06-28 | Mitsui Mining & Smelting Co., Ltd. | Method for patterning zinc oxide transparent conductive film |
-
2006
- 2006-05-25 JP JP2006145440A patent/JP4816250B2/en active Active
-
2007
- 2007-05-21 KR KR1020070049339A patent/KR20070113981A/en not_active Application Discontinuation
- 2007-05-24 TW TW096118510A patent/TWI409318B/en active
- 2007-05-24 US US11/752,966 patent/US20070278185A1/en not_active Abandoned
- 2007-05-24 EP EP07108809.0A patent/EP1862525B1/en not_active Expired - Fee Related
-
2010
- 2010-11-10 US US12/943,639 patent/US8048331B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4517106A (en) * | 1984-04-26 | 1985-05-14 | Allied Corporation | Soluble surfactant additives for ammonium fluoride/hydrofluoric acid oxide etchant solutions |
US4620934A (en) * | 1984-04-26 | 1986-11-04 | Allied Corporation | Soluble fluorinated cycloalkane sulfonate surfactant additives for NH4 |
US6828289B2 (en) * | 1999-01-27 | 2004-12-07 | Air Products And Chemicals, Inc. | Low surface tension, low viscosity, aqueous, acidic compositions containing fluoride and organic, polar solvents for removal of photoresist and organic and inorganic etch residues at room temperature |
US20020055447A1 (en) * | 2000-09-08 | 2002-05-09 | Norio Ishikawa | Etching liquid composition |
US20030168431A1 (en) * | 2002-02-25 | 2003-09-11 | Ritdisplay Corporation | Etchant composition for silver alloy |
US20040262569A1 (en) * | 2003-06-24 | 2004-12-30 | Lg.Philips Lcd Co., Ltd. | Etchant for etching double-layered copper structure and method of forming array substrate having double-layered copper structures |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100288725A1 (en) * | 2009-03-25 | 2010-11-18 | Zhi-Wen Sun | Acid Chemistries and Methodologies for Texturing Transparent Conductive Oxide Materials |
US8486282B2 (en) * | 2009-03-25 | 2013-07-16 | Intermolecular, Inc. | Acid chemistries and methodologies for texturing transparent conductive oxide materials |
US20200336836A1 (en) * | 2017-10-11 | 2020-10-22 | Unist(Ulsan National Institute Of Science And Technology) | Nano membrane, method of manufacturing nano membrane, and apparatus for speaker and microphone using nano membrane |
US11930339B2 (en) * | 2017-10-11 | 2024-03-12 | Unist(Ulsan National Institute Of Science And Technology) | Nano membrane, method of manufacturing nano membrane, and apparatus for speaker and microphone using nano membrane |
CN111690932A (en) * | 2019-03-13 | 2020-09-22 | 易安爱富科技有限公司 | Etching solution composition for silver-containing metal film |
Also Published As
Publication number | Publication date |
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JP2007317856A (en) | 2007-12-06 |
TW200806778A (en) | 2008-02-01 |
EP1862525B1 (en) | 2014-02-26 |
US8048331B2 (en) | 2011-11-01 |
JP4816250B2 (en) | 2011-11-16 |
EP1862525A3 (en) | 2008-12-31 |
KR20070113981A (en) | 2007-11-29 |
TWI409318B (en) | 2013-09-21 |
US20110049088A1 (en) | 2011-03-03 |
EP1862525A2 (en) | 2007-12-05 |
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