CN111621785A - Metal film etching composition and etching method using same - Google Patents
Metal film etching composition and etching method using same Download PDFInfo
- Publication number
- CN111621785A CN111621785A CN201910212233.0A CN201910212233A CN111621785A CN 111621785 A CN111621785 A CN 111621785A CN 201910212233 A CN201910212233 A CN 201910212233A CN 111621785 A CN111621785 A CN 111621785A
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- Prior art keywords
- metal film
- etching
- acid
- film
- etching composition
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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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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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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- 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
- C23F1/26—Acidic compositions for etching refractory metals
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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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
Abstract
The present invention relates to a metal film etching composition and an etching method using the same. The metal film etching composition according to the present invention comprises hydrogen peroxide, an organic acid, a glycol polymer and water, has a pH range of 3.0 to 4.4, has a high selectivity or an infinite selectivity for a metal film such as copper or molybdenum with respect to a lower film such as a silicon film or a transparent conductive film, has excellent hydrogen peroxide stability in a relatively high pH range, and can continuously maintain initial excellent characteristics even when etching is repeated and reused many times. In addition, not only a stripe profile having excellent linearity can be realized at the time of etching, but also the effect of excellent characteristics of reducing a CD loss (CD loss) and suppressing generation of a residue is obtained. Further, since the composition has high stability, it has improved storage stability capable of continuously maintaining excellent characteristics in the initial stage even before or after use, and has an effect of suppressing heat generation without generating precipitates during etching.
Description
Technical Field
The present invention relates to a metal film etching composition.
Background
In general, a Thin Film Transistor display panel (TFT) is used as a circuit substrate for independently driving each pixel in a liquid crystal display device, an organic EL (Electro Luminescence) display device, or the like. The TFTs include scanning signal lines or gate lines for transmitting scanning signals and video signal lines or data lines for transmitting video signals, and include thin film transistors connected to the gate lines and the data lines, pixel electrodes connected to the thin film transistors, and the like. The process of forming the wiring of such a TFT generally includes: a sputtering step for forming a metal film; a photoresist forming process of forming a desired pattern based on photoresist coating, exposure, and development; an etching step for forming wiring; and a stripping step of removing unnecessary photoresist after forming the wiring.
Conventionally, in order to manufacture substrates of semiconductor devices and TFT-LCDs, aluminum or aluminum alloy layers have been frequently used as wiring materials for gate electrodes and data line electrodes of TFTs, but in order to realize large-sized displays, it is necessary to reduce the resistance of the electrode wiring, and for this reason, copper and/or molybdenum, which are metals having low resistance, are used for wiring formation. Thus, studies on etching compositions used for etching wirings containing copper and/or molybdenum are being actively conducted.
For etching copper-and/or molybdenum-containing wiring, a composition of an etching solution having a strong oxidizing ability is required. For example, KR10-2018-0077610A discloses a metal film etching composition comprising hydrogen peroxide, a fluorine-containing compound, a tetrazole-based compound, a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, a sulfate compound and a polyol-type surfactant.
However, such conventional metal film etching compositions do not have a high selectivity ratio for metal films such as copper and/or molybdenum. Therefore, there is a limitation in inducing corrosion of a lower film such as a silicon film or a transparent conductive film located below the metal film. Therefore, it is difficult to form a precise pattern, the quality is degraded, the economy is degraded, and the like, and the patterning of the metal film is greatly restricted.
Therefore, it is necessary to study a metal film etching composition which can fundamentally substantially block the corrosion of a lower film such as a silicon film or a transparent conductive film and has a high selectivity ratio for a film of a transition metal such as copper or molybdenum.
Documents of the prior art
Patent document
(patent document 1) KR10-2018-0077610A (2018.07.09)
Disclosure of Invention
The purpose of the present invention is to provide a metal film etching composition having a high selectivity or an infinite selectivity (ratio of) for a metal film such as copper or molybdenum with respect to a lower film such as a silicon film or a transparent conductive film
)。
The purpose of the present invention is to provide a metal film etching composition which is excellent in hydrogen peroxide stability even in a relatively high pH range.
Another object of the present invention is to provide a metal film etching composition which can maintain excellent initial characteristics even when etching is repeated and reused a plurality of times, and can maintain a low taper angle even when the number of processed sheets is increased
Another object of the present invention is to provide a metal film etching composition which can realize a linear stripe profile during etching and has excellent characteristics of reducing a CD loss (CD loss) and suppressing generation of a residue.
Another object of the present invention is to provide a metal film etching composition having improved storage stability, which can maintain excellent characteristics in an initial stage before or after use, due to high stability of the composition.
Another object of the present invention is to provide a metal film etching composition which does not generate precipitates during etching and can suppress heat generation.
The metal film etching composition according to the present invention is characterized by comprising hydrogen peroxide, an organic acid, a glycol-based polymer and water, and having a pH in the range of 3.0 to 4.4.
In one example of the present invention, the organic acid may include iminodisuccinic acid.
In one example of the present invention, the organic acid may further include one or more selected from malonic acid, glycolic acid, acetic acid, formic acid, citric acid, oxalic acid, butyric acid, valeric acid, propionic acid, tartaric acid, gluconic acid, and the like.
In one embodiment of the present invention, the glycol polymer may include polyethylene glycol.
A metal film etching composition according to an example of the present invention may include 10 to 40 wt% of hydrogen peroxide, 0.1 to 10 wt% of an organic acid, 0.1 to 5 wt% of a glycol-based polymer, and the balance of water.
The metal film etching composition according to an example of the present invention may further include one or two or more ammonium compounds selected from ammonium phosphate, ammonium hydrogen phosphate, ammonium superphosphoric acid, ammonium fluoride, ammonium hydrogen fluoride, and the like.
The metal film etching composition according to an example of the present invention may further include an azole compound.
The metal film etching composition according to an example of the present invention may further include any one or two or more hydrogen peroxide stabilizers selected from cyclohexylamine, n-hexylamine, isohexylamine, neohexylamine, and the like.
The metal film etching composition according to an example of the present invention may further include any one or more pH adjusters selected from sodium hydroxide, potassium hydroxide, and the like.
The metal film etching composition according to an embodiment of the present invention may include hydrogen peroxide, 5-aminotetrazole, cyclohexylamine, iminodisuccinic acid, iminodiacetic acid, ammonium phosphate, ammonium fluoride, and polyethylene glycol.
According to the metal film etching composition of one example of the present invention, the metal film can be selectively etched at a high selectivity ratio or an infinite selectivity ratio with respect to the silicon film selected from one or more of the silicon oxide film, the silicon nitride film, and the indium oxide film selected from one or more of the indium zinc oxide film, the indium tin oxide film, the indium gallium zinc oxide film, and the metal film selected from one or more of the copper metal film, the molybdenum metal film, and the like.
In one example of the present invention, the silicon film may include at least one selected from a silicon oxide film, a silicon nitride film, and the like, and the metal film may include at least one selected from a copper metal film, a molybdenum metal film, and the like.
The metal film etching method according to the present invention may include a step of etching the metal film using the above metal film etching composition.
The metal film etching composition according to the present invention has the following effects: the lower film such as a silicon film or a transparent conductive film has a high selectivity or an infinite selectivity for a metal film such as copper or molybdenum.
The metal film etching composition according to the present invention has an effect of being excellent in hydrogen peroxide stability also in a relatively high pH range.
The metal film etching composition according to the present invention has the following effects: even if etching is repeated and reused many times, the initial excellent characteristics can be maintained, and even if the number of processed sheets is increased, the taper angle can be maintained low.
The metal film etching composition according to the present invention not only can realize a band profile having excellent linearity during etching, but also has excellent effects of reducing CD loss (CD loss) and suppressing the generation of residue.
The metal film etching composition according to the present invention has the following effects: the composition has high stability, and thus has improved storage stability, which can continuously maintain excellent characteristics in the initial stage even before or after use.
The metal film etching composition according to the present invention has an effect of suppressing heat generation without generating precipitates during etching.
Even if an effect is not explicitly mentioned in the present invention, the effect described in the specification expected from the technical features of the present invention and its inherent effect are considered to be equivalent to those described in the specification of the present invention.
Drawings
Fig. 1 is a scanning electron microscope picture of a test piece after etching with an etching composition according to example 1 of the present invention.
Detailed Description
The metal film etching composition and the etching method using the same according to the present invention will be described in detail below with reference to the accompanying drawings.
The drawings described in the present specification are provided as examples to fully convey the concept of the present invention to those skilled in the art. Therefore, the present invention is not limited to the illustrated drawings, but may be embodied in other forms, and the drawings may be exaggerated to clarify the idea of the present invention.
Unless otherwise defined, technical and scientific terms used herein have the meaning commonly understood by those having ordinary knowledge in the art to which the present invention pertains, and a description of well-known functions and constructions that may unnecessarily affect the gist of the present invention is omitted in the following description and the accompanying drawings.
The singular forms of the terms used in this specification may be construed to include the plural forms unless otherwise specified.
Unless otherwise defined, the% unit used in the present specification without being specifically stated refers to weight%.
The present invention provides a metal film etching composition which has a very high selectivity or a substantially infinite selectivity by increasing the etching rate of a film of a transition metal such as copper or molybdenum, and particularly by remarkably reducing the etching rate of a film such as a silicon film or a transparent conductive film used as a substrate or a lower film.
The present inventors repeated diligent efforts to minimize etching of films such as silicon films and transparent conductive films, and found that when the composition is of a specific composition in a specific pH range, the etching rate of the film is significantly reduced and the maximum etching rate is at most
Etching can be substantially prevented at all.
That is, even when the metal film etching composition according to the present invention satisfies the specific pH range described below, but does not satisfy the specific composition described below, the etching rate of a film such as a silicon film or a transparent conductive film greatly exceeds the etching rate of a film such as a transparent conductive film
And corrosion of the above-described film cannot be prevented at a significant level. Further, even if the above composition satisfies the above specific composition, corrosion of the above film cannot be prevented at a significant level similarly in the case where the above specific pH range is not satisfied.
Specifically, the metal film etching composition according to the present invention comprises hydrogen peroxide, an organic acid, a glycol-based polymer, and water, and has a pH range of 3.0 to 4.4, thereby having a high selectivity ratio for a metal film such as copper or molybdenum with respect to a film such as a silicon film or a transparent conductive film.
The organic acid preferably contains Iminodisuccinic acid (IDS). When this condition is satisfied, that is, when the pH and the composition containing iminodisuccinic acid in the above range are satisfied, the film has a high selectivity ratio to a metal film such as copper or molybdenum with respect to a film such as a transparent conductive film containing indium, gallium, zinc, or the like. Specifically, when an organic acid containing iminodisuccinic acid and a glycol-based polymer are used together, the adsorption of the composition on the lower film surface of the metal film becomes smooth, the surface protection effect is maximized, and the film can have the effect on a metal film such as copper or molybdenum, as compared with a film such as a silicon film or a transparent conductive filmInfinite selection ratio. That is, the film such as a transparent conductive film containing indium, gallium, zinc, or the like can be prevented from being corroded in reality. On the other hand, when iminodisuccinic acid is not contained, it is impossible to have an infinite selectivity ratio for a metal film such as copper or molybdenum with respect to a film such as the transparent conductive film even when the iminodisuccinic acid is used together with a glycol polymer. For example, in the organic acid containing iminodisuccinic acid and the glycol-based polymer, when they are used alone, that is, when they are not used simultaneously, the infinite selectivity effect is not exhibited, and only when they are used simultaneously, the infinite selectivity effect can be achieved. Here, "infinite selection ratio
"means that the etching rate of a film such as a silicon film or a transparent conductive film is set to
The etching rate of a metal film such as copper or molybdenum is a significant value that can be substantially etched while substantially preventing etching.
As described above, the infinite selection ratio effect exhibited to satisfy a specific pH range and a specific composition may be caused by the following reasons: with the surface of the lower film being negatively charged in the above pH range, iminodisuccinic acid having a cation and a glycol-based polymer easily move to the surface, and the etching inhibitor (inhibitor) action is smoothly performed.
The glycol polymer is preferably polyethylene glycol (PEG), and more preferably, the glycol polymer has a hydroxyl group (-OH) at the end to further exhibit the above-described effects, and thus, may be more preferably used. The weight average molecular weight of the polyethylene glycol may be a liquid phase or a solid phase at normal temperature (25 ℃), and may be 150 to 10000g/mol, preferably 180 to 2000g/mol, as an example, and when this condition is satisfied, the problem of the lower film protective effect being reduced due to an excessively low weight average molecular weight and the problem of uneven etching such as layer separation and a reduction in solubility of the etching composition due to an excessively high weight average molecular weight can be prevented. When a low-molecular-weight glycol compound such as ethylene glycol, propylene glycol, or diethylene glycol is used instead of the glycol polymer, the etching rate of a film of a transition metal such as copper or molybdenum is significantly reduced, and there may be problems such as generation of precipitates, heat generation, and reduction in storage stability.
The metal film etching composition according to the present invention may further contain other kinds of organic acids than iminodisuccinic acid. For example, the organic acid other than iminodisuccinic acid may contain one or two or more selected from iminodiacetic acid, malonic acid, glycolic acid, acetic acid, formic acid, citric acid, oxalic acid, butyric acid, valeric acid, propionic acid, tartaric acid, gluconic acid, and the like. As a specific example, as an organic acid other than iminodisuccinic acid, Iminodiacetic acid (Iminodiacetic acid) is preferably further used in terms of effective etching by chelation and improvement of stability. In addition, in terms of effective etching of metals such as copper and molybdenum, etching by chelation, and improvement in stability, it is preferable to further use any one or more organic acids selected from Malonic acid (Malonic acid) and Glycolic acid (glyconic acid). However, this is merely a preferable example, and other organic acids may be used, and therefore the present invention is not necessarily limited to this and will be explained.
The composition ratio of the metal film etching composition according to an example of the present invention is not particularly limited, since it can be appropriately adjusted to the extent that the above-described effects can be achieved. However, as an example, it preferably contains 10 to 40% by weight of hydrogen peroxide, 0.1 to 10% by weight of an organic acid, 0.1 to 5% by weight of a glycol-based polymer, and the balance of water, and more preferably contains 15 to 35% by weight of hydrogen peroxide, 2 to 8% by weight of an organic acid, 0.2 to 2% by weight of a glycol-based polymer, and the balance of water. However, this is merely a preferable example, and the present invention is not necessarily limited to this example.
In terms of well achieving the above effects, in the composition according to the present invention, the organic acid containing iminodisuccinic acid among the organic acids is preferably used in an amount of 0.1 to 3% by weight, more preferably 0.2 to 2% by weight.
In addition, in the composition according to the present invention, when an organic acid other than iminodisuccinic acid is further used, the above organic acid is preferably used in an amount of 0.5 to 8% by weight, more preferably 1 to 5% by weight, relative to the total weight of the composition. However, this is merely a preferable example, and the present invention is not necessarily limited to this example.
In a more preferred embodiment, the weight ratio of the organic acid containing iminodisuccinic acid to the glycol polymer in the composition of the present invention may be 1:0.1 to 2, preferably 1:0.2 to 1.5.
The metal film etching composition according to an example of the present invention may further include one or two or more ammonium compounds selected from ammonium phosphate, ammonium hydrogen phosphate, ammonium superphosphoric acid, ammonium fluoride, ammonium hydrogen fluoride, and the like. When the above conditions are satisfied, the etching rate of a metal such as copper, molybdenum, or a molybdenum alloy can be increased, which is preferable. When an ammonium compound is further used, it is more preferable to use 2 or more different ammonium compounds simultaneously. When the ammonium-based compound is used, it is preferably used in an amount of 0.3 to 6% by weight, more preferably 0.5 to 4% by weight, based on the total weight of the composition. In this case, when a phosphoric acid-based compound such as ammonium phosphate, ammonium hydrogen phosphate, or ammonium superphosphate is used together with a fluorine-based compound such as ammonium fluoride or ammonium bifluoride, it is preferable to use 0.5 to 5% by weight of the phosphoric acid-based compound and 0.01 to 0.5% by weight of the fluorine-based compound. However, this is merely a preferable example, and the present invention is not necessarily limited to this example.
The metal film etching composition according to an example of the present invention may further include an azole compound. The azole compound is not particularly limited as long as it can inhibit the etching rate of the metal film to form a good etching profile and improve the etching inhibition property for the film such as silicon film and transparent conductive film, and may include, for example, imidazole, pyrazole, 1,2, 3-triazole, 1,2, 4-triazole, tetrazole, pentazole, triazole, and the like,
Oxazole, iso
Azole, 1,2,3-
Oxadiazole, oxadiazole,
Diazole and furazan
1,3,4-
One or more of oxadiazole, thiazole, isothiazole, thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole and derivatives thereof. Specifically, examples of the azole compound include 5-aminotetrazole, 5-methyltetrazole, tetrazole, pyrrole, imidazole, pyrazole, triazole, and pyrrolidine, and more preferably a tetrazole compound selected from 5-aminotetrazole, 5-methyltetrazole, and tetrazole. When the azole compound is further contained, it is preferable in terms of improving the etching profile of the metal film and preventing etching of a silicon film, a transparent conductive film, and the like, and in terms of maintaining the initial etching prevention performance more stably even if the composition is repeatedly used. The azole compound is used in an amount of preferably 0.1 to 2% by weight, more preferably 0.2 to 1% by weight, based on the total weight of the composition. However, this is merely a preferable example, and the present invention is not necessarily limited to this example.
The metal film etching composition according to an example of the present invention may further include any one or two or more hydrogen peroxide stabilizers selected from cyclohexylamine, n-hexylamine, isohexylamine, neohexylamine, and the like. When the above conditions are satisfied, it is preferable that the hydrogen peroxide as a main component is stabilized to maintain the initial etching prevention performance more stably, and that the hydrogen peroxide is also stable over a long period of time. When the hydrogen peroxide stabilizer is used, it is preferably used in an amount of 0.1 to 2% by weight, more preferably 0.2 to 1% by weight, based on the total weight of the composition. However, this is merely a preferable example, and the present invention is not necessarily limited to this example.
The metal film etching composition according to an example of the present invention may further include any one or more pH adjusters selected from sodium carbonate, ammonia, sodium hydroxide, potassium hydroxide, and the like. These are used to satisfy the above pH range, and the content of the pH adjuster to be used may be appropriately adjusted to the above pH range. As a specific example, the pH adjuster may be used in an amount of usually 0.01 to 5 wt%, specifically 0.1 to 2 wt%, based on the total weight of the composition, but the present invention is not limited thereto.
As described above, the metal film etching composition according to the present invention prevents etching of a film such as a silicon film, a transparent conductive film, or the like, and etching of a metal film is excellent.
As a specific example, the etching rate of the metal film by the metal film etching composition according to the present invention may be 10 to 10
As a more specific example, the etch rate for copper may be 70 to
Specifically, it may be 80 to
The etch rate for molybdenum may be 10 to
Specifically, it may be 12 to 12
The silicon film may be selected from at least one of a silicon oxide film and a silicon nitride film. However, in addition to this, the etching prevention effect on various silicon films can be exhibited.
The transparent conductive film is a transparent conductive film used in the present technical field, and specifically, may be exemplified by one or two or more Indium Oxide films selected from Indium Zinc Oxide (IZO) films, Indium Tin Oxide (ITO) films, Indium Gallium Zinc Oxide (IGZO) films, and the like. However, in addition to this, the etching prevention effect on various transparent conductive films can be exhibited.
The metal film may be one or two or more selected from copper, molybdenum, titanium, indium, zinc, tin, tungsten, silver, gold, chromium, manganese, iron, cobalt, nickel, niobium, and an alloy thereof. More specifically, a copper film, a copper/molybdenum film, a copper/titanium film, a copper/molybdenum alloy film, or a copper/indium alloy film may be used, and a copper/molybdenum film, a copper/molybdenum alloy film, or the like may be used as examples. However, in addition to this, the etching characteristics of various transition metals can be improved.
As a specific example, the copper/molybdenum film or the copper/molybdenum alloy film may be a multilayer film in which one or more copper (Cu) films and one or more molybdenum (Mo) films and/or molybdenum alloy films (Mo-alloy) are stacked on each other, and the multilayer film may include a Cu/Mo (Mo-alloy) double film, a Cu/Mo (Mo-alloy)/Cu, or a Mo (Mo-alloy)/Cu/Mo (alloy) triple film. The order of the films may be appropriately adjusted according to the substance and the bondability of the substrate. However, this is merely an example of the present invention, and the present invention is not necessarily limited to this.
As a specific example, the molybdenum alloy film may be formed of molybdenum-tungsten (Mo-W), molybdenum-titanium (Mo-Ti), molybdenum-niobium (Mo-Nb), molybdenum-chromium (Mo-Cr), or molybdenum-tantalum (Mo-Ta), and the molybdenum film or the molybdenum alloy film is 100 to 100 from the viewpoint of performing residue-free and effective etching
The copper film may have a thickness of 1000 to
The thickness of (3) is evaporated. However, this is merely a preferable example, and the present invention is not necessarily limited to this example.
The metal film according to the present invention may be used in an etching step, and the etching step may be a normal etching step, and may include, for example, a step of etching the metal film using the metal film etching composition.
Specifically, the etching step may include the steps of: a step of evaporating a metal film on a substrate; forming a photoresist film on the metal film and then patterning the photoresist film; and a step of etching the metal film formed with the patterned photoresist film using the metal film etching composition according to the present invention. The metal film formed on the substrate at this time may be a single film, a double metal film or a multiple metal film (multilayer metal film), wherein in the case of the double metal film or the multiple metal film, the stacking order thereof is not particularly limited.
As a more specific example, the etching process may include a step of forming a semiconductor structure between the substrate and the metal film, that is, in the case of a copper/molybdenum film, or between the substrate and the copper film or between the substrate and the molybdenum film, as an example. The semiconductor structure may be a semiconductor structure for a display device such as a liquid crystal display device or a plasma display panel. Specifically, the above semiconductor structure may contain one or more layers selected from a dielectric film, a conductive film, and an amorphous or polycrystalline silicon film, and these semiconductor structures may be manufactured by a conventional method.
The present invention will be described in detail below with reference to examples, but these are merely for describing the present invention in more detail, and the scope of the present invention is not limited to the following examples.
[ example 1]
The etching compositions of example 1 were prepared by mixing the respective components at the component contents shown in table 1 below.
[ example 2 to example 12]
The etching compositions of examples 2 to 12 were prepared by mixing the respective components at the component contents shown in table 1 below.
Comparative examples 1 to 11
Etching compositions of comparative examples 1 to 11 were prepared by mixing the respective components at the component contents shown in table 1 below.
[ TABLE 1]
[ Experimental example 1]
< evaluation of whether precipitates were formed, whether heat was generated, etching performance, and change with time during storage >
The etching compositions produced in examples 1 to 12 and comparative examples 1 to 10 were evaluated for the occurrence of precipitates, the generation of heat, the etching performance (CD skew, taper (taper)), and the change with time in storage characteristics.
Specifically, a molybdenum alloy film is formed on the lower films of a silicon oxide film, an indium zinc oxide film, an indium tin oxide film and an indium gallium zinc oxide film, respectively
Depositing a copper film on the molybdenum alloy film by vapor deposition
After the deposition, a pattern was formed by a photolithography process to manufacture a test piece. Further, the etching composition was evaluated for the characteristics of generation of precipitates, heat generation, etching performance, and change with time during storage when the copper content was 3000, 4000, and 5000 ppm.
Whether or not precipitates were formed was ○, whether or not precipitates were formed was ×, whether or not heat was generated was ○ when the etching time was increased by 5 ℃ or more, and whether or not there was no temperature change was ×, and the etching performance (critical dimension bias (CD skew, taper) was evaluated using a mini-etcher (mini-etcher) apparatus with each test piece being evaluated at 50% OE based on EPD, specifically, the critical dimension bias (CD skew) was 0.60 μm to 1.00 μm as a good levelThe evaluation was performed, and the taper (taper) was evaluated as a good level when it was 30 degrees or more and less than 45 degrees. With respect to the change with time upon storage, in order to confirm the storage stability of the etching composition, the change was evaluated by a mini-etcher (in days)
The evaluation was carried out with good, poor and very poor results (change over time: 0 to 5 days).
The results are shown in table 2 and table 3 below.
[ TABLE 2]
[ TABLE 3 ]
As is clear from table 2 and table 3, in examples 1 to 10, no precipitates were generated, no heat was generated, etching performance was good, and long-term storage stability was excellent. On the contrary, it was confirmed that the comparative examples had two or more of the above-mentioned problems, or had heat generation, poor etching performance, or lowered long-term storage stability. In particular, it was confirmed from comparative examples 9 to 11 that even when iminodisuccinic acid and a glycol compound were used, no effect was exhibited when the glycol compound was a low molecular weight compound such as ethylene glycol, propylene glycol, or diethylene glycol other than polyethylene glycol.
[ Experimental example 2]
< evaluation of etching selection ratio of metal film to lower film >
Etching selectivity of the etching compositions produced in examples 1 to 12 and comparative examples 1 to 8 to the metal film of the lower film was evaluated. And whether there was a molybdenum alloy residue was evaluated.
Specifically, the thickness of the test piece before etching was measured by an Ellipsometer (Ellipsometer, J.A WOOLLAM, M-2000U) as a film thickness measuring device. The etching process was performed on the test piece using each of the etching compositions maintained at an etching temperature of 32 ℃ in a quartz bath (bath). The etching time is controlled to be the same. After the test piece after the etching was finished was washed with ultrapure water, the remaining etching composition was completely dried by a drying apparatus, and the thickness was measured to evaluate the etching rate. Further, the molybdenum alloy residue was analyzed by surface observation at the time of SEM analysis.
[ TABLE 4 ]
As is clear from table 4 above, in examples 1 to 8, the etching rates of the lower films of the silicon oxide film, the silicon nitride film, the indium zinc oxide film, the indium tin oxide film, and the indium gallium zinc oxide film were set to be equal to
Substantially no etching is performed. On the contrary, it can be confirmed that the comparative examples have at least
The above etching rate cannot completely block the etching itself of the lower film.
In particular, it was confirmed from examples 1, 11, 12, 2 and 3 that it was difficult to fundamentally prevent the etching of the lower film when iminodisuccinic acid and polyethylene glycol were used alone, and only when these were used together, the etching of the lower film could be fundamentally prevented.
In addition, it was confirmed from comparative examples 4 to 6 and 8 that even when iminodisuccinic acid and polyethylene glycol were used together, etching of the lower film could not be prevented fundamentally when the pH range was not satisfied from 3.0 to 4.4. The reason for this is considered to be that, in the above pH range, iminodisuccinic acid and polyethylene glycol having a cation move to the surface as the membrane surface is positively charged, thereby well performing the etching inhibitor (inhibitor) action.
Claims (11)
1. A metal film etching composition characterized in that,
comprising hydrogen peroxide, an organic acid, a glycol polymer and water,
the pH range is 3.0 to 4.4.
2. The metal film etching composition according to claim 1, wherein the organic acid comprises iminodisuccinic acid.
3. The metal film etching composition according to claim 2, wherein the organic acid further comprises one or more selected from malonic acid, glycolic acid, acetic acid, formic acid, citric acid, oxalic acid, butyric acid, valeric acid, propionic acid, tartaric acid, and gluconic acid.
4. The metal film etching composition according to claim 1, wherein the glycol-based polymer comprises polyethylene glycol.
5. The metal film etching composition according to claim 1, wherein the metal film etching composition comprises 10 to 40% by weight of hydrogen peroxide, 0.1 to 10% by weight of an organic acid, 0.1 to 5% by weight of a glycol-based polymer, and the balance of water.
6. The metal film etching composition according to claim 1, wherein the metal film etching composition further comprises any one or two or more ammonium-based compounds selected from ammonium phosphate, ammonium hydrogen phosphate, ammonium superphosphoric acid, ammonium fluoride, and ammonium hydrogen fluoride.
7. The metal film etching composition according to claim 1, wherein the metal film etching composition further comprises an azole compound.
8. The metal film etching composition according to claim 1, further comprising a hydrogen peroxide stabilizer selected from any one or two or more of cyclohexylamine, n-hexylamine, isohexylamine, and neohexylamine.
9. The metal film etching composition according to claim 1, further comprising a pH adjuster of any one or more selected from sodium hydroxide and potassium hydroxide.
10. The metal film etching composition according to claim 2, wherein the metal film etching composition selectively etches a metal film at an infinite selection ratio with respect to a silicon film which is any one or more selected from the group consisting of a silicon oxide film and a silicon nitride film, or an indium-based oxide film which is any one or two or more selected from the group consisting of an indium zinc oxide film, an indium tin oxide film and an indium gallium zinc oxide film, and the metal film is any one or more selected from the group consisting of a copper metal film and a molybdenum metal film.
11. A metal film etching method comprising a step of etching a metal film using the metal film etching composition as claimed in any one of claims 1 to 10.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621786A (en) * | 2019-02-28 | 2020-09-04 | 易案爱富科技有限公司 | Metal film etching composition |
| CN112981405A (en) * | 2021-02-23 | 2021-06-18 | 江苏艾森半导体材料股份有限公司 | Titanium-tungsten etching solution and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012064001A1 (en) * | 2010-11-12 | 2012-05-18 | 오씨아이 주식회사 | Composition for etching metal films |
| CN107236957A (en) * | 2016-03-28 | 2017-10-10 | 东友精细化工有限公司 | Copper system metal film etch combination |
| CN107630219A (en) * | 2016-07-19 | 2018-01-26 | 东友精细化工有限公司 | The manufacture method of metal film etchant and array substrate for display device |
| CN108018556A (en) * | 2016-10-31 | 2018-05-11 | 易案爱富科技有限公司 | Etch combination |
| CN108950557A (en) * | 2018-07-19 | 2018-12-07 | 深圳市华星光电半导体显示技术有限公司 | A kind of copper/molybdenum etching liquid composition and its application |
| CN111621786A (en) * | 2019-02-28 | 2020-09-04 | 易案爱富科技有限公司 | Metal film etching composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102293675B1 (en) * | 2015-03-24 | 2021-08-25 | 동우 화인켐 주식회사 | Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same |
| KR102455790B1 (en) * | 2015-12-22 | 2022-10-19 | 주식회사 이엔에프테크놀로지 | Copper Etchant Composition |
| KR20180077610A (en) | 2016-12-29 | 2018-07-09 | 동우 화인켐 주식회사 | Metal film etchant composition manufacturing method of an array substrate for display device |
-
2019
- 2019-02-28 KR KR1020190024259A patent/KR102494016B1/en active IP Right Grant
- 2019-03-20 CN CN201910212233.0A patent/CN111621785A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012064001A1 (en) * | 2010-11-12 | 2012-05-18 | 오씨아이 주식회사 | Composition for etching metal films |
| CN107236957A (en) * | 2016-03-28 | 2017-10-10 | 东友精细化工有限公司 | Copper system metal film etch combination |
| CN107630219A (en) * | 2016-07-19 | 2018-01-26 | 东友精细化工有限公司 | The manufacture method of metal film etchant and array substrate for display device |
| CN108018556A (en) * | 2016-10-31 | 2018-05-11 | 易案爱富科技有限公司 | Etch combination |
| CN108950557A (en) * | 2018-07-19 | 2018-12-07 | 深圳市华星光电半导体显示技术有限公司 | A kind of copper/molybdenum etching liquid composition and its application |
| CN111621786A (en) * | 2019-02-28 | 2020-09-04 | 易案爱富科技有限公司 | Metal film etching composition |
Non-Patent Citations (1)
| Title |
|---|
| 熊炯辉: "金属表面酸蚀抛光液中H_2O_2的稳定剂", 化学世界, no. 10, pages 386 - 388 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621786A (en) * | 2019-02-28 | 2020-09-04 | 易案爱富科技有限公司 | Metal film etching composition |
| CN112981405A (en) * | 2021-02-23 | 2021-06-18 | 江苏艾森半导体材料股份有限公司 | Titanium-tungsten etching solution and preparation method and application thereof |
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