CN107653451B - Etching solution composition and method for manufacturing metal pattern using the same - Google Patents
Etching solution composition and method for manufacturing metal pattern using the same Download PDFInfo
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- CN107653451B CN107653451B CN201710619431.XA CN201710619431A CN107653451B CN 107653451 B CN107653451 B CN 107653451B CN 201710619431 A CN201710619431 A CN 201710619431A CN 107653451 B CN107653451 B CN 107653451B
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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
- 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
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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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
- 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
- C23F1/02—Local etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/121—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
- H10K59/1213—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements the pixel elements being TFTs
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Abstract
The present invention relates to an etchant composition and a method for manufacturing a metal pattern using the same. The etching solution composition comprises: hydrogen peroxide; a fluorine-containing compound; an azole compound; a carboxyl group-containing amine compound; a phosphoric acid-based compound; quilt C1‑C5Propylene glycol substituted or unsubstituted with alkyl or by C1‑C5Butanediol substituted or unsubstituted with an alkyl group; and water.
Description
Technical Field
The present invention relates to an etchant composition and a method for manufacturing a metal pattern using the same.
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 Electroluminescence (EL) display device, or the like. The thin film transistor display panel is formed with a scanning signal line or a gate line for transmitting a scanning signal, and a video signal line or a data line for transmitting a video signal, and is configured with a thin film transistor connected to the gate line and the data line, a pixel electrode connected to the thin film transistor, and the like.
In manufacturing such a thin film transistor display panel, metal layers for gate wiring and data wiring are stacked on a substrate, and then a process for etching these metal layers is performed.
Recently, in order to stabilize an image with an increase in area of a display panel, a gate wiring is made of Ti/Cu having excellent conductivity characteristics, which is advantageous for providing a fast response speed. After the gate line is formed, in order to prevent the upper layer from having defects, the end of the gate line needs to have a taper angle in a gentle manner. Furthermore, in order to improve efficiency in the process and save process costs, it is required that the characteristics of the etching solution composition can be maintained for a long time.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide an etchant composition which has excellent heat generation stability and can be repeatedly used for a long period of time, and a method for producing a metal pattern using the same.
According to an aspect, there is provided an etching solution composition comprising: hydrogen peroxide; a fluorine-containing compound; an azole compound; a carboxyl group-containing amine compound; a phosphoric acid-based compound; quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl or by C1-C5Butanediol substituted or unsubstituted with an alkyl group; and water.
According to another aspect, there is provided a method of manufacturing a metal pattern, including the steps of: forming a metal film on a substrate; forming a photoresist pattern on the metal film; and etching the metal film by contacting the etching solution composition to the metal film using the photoresist pattern as a mask.
The etching solution composition exhibits excellent heat generation stability because no heat generation reaction occurs even when the number of the processing steps is accumulated.
Further, the etching solution composition can maintain the characteristics of the new solution even if the number of processing steps is accumulated or the etching solution composition is stored for a predetermined number of days after the production, and thus the etching solution composition can be repeatedly used for a long period of time.
Furthermore, the etching solution composition can be used to manufacture metal patterns, thereby saving the process cost.
Drawings
Fig. 1 to 3 are cross-sectional views for explaining a method of forming a metal pattern according to an embodiment of the present invention.
FIG. 4a is an SEM photograph showing the etching profile of the etchant composition of production example 2 under the condition that the copper concentration is 0 ppm.
FIG. 4b is an SEM photograph showing the etching profile of the etchant composition of production example 2 under the condition that the copper concentration is 7000 ppm.
FIG. 5a is an SEM photograph showing the etching profile after the etching solution composition of production example 2 was stored for 7 days under the condition that the copper concentration was 0 ppm.
FIG. 5b is an SEM photograph showing the etching profile after the etching solution composition of production example 2 was stored for 14 days under the condition that the copper concentration was 0 ppm.
Description of the symbols
110: substrate 122: titanium alloy film
124: copper film 130: photoresist pattern
ML: a metal film MP: metal pattern
Detailed Description
While the invention is susceptible to various modifications and alternative embodiments, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. The effects and features of the present invention and a method for achieving the object can be clearly understood by referring to the embodiments described later in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, and may be implemented in various forms.
In the present specification, terms such as "including" or "having" merely indicate the presence of the features or components described in the specification, and are not intended to exclude the addition of one or more other features or components in advance.
In this specification, when a portion of one film, region, component, or the like is located above or on another portion, the portion includes not only a portion located immediately above the other portion but also a portion having another film, region, component, or the like interposed therebetween.
In the drawings, the sizes of the constituent elements may be enlarged or reduced for convenience of explanation. For example, the size and thickness of each constituent element shown in the drawings are arbitrarily illustrated for convenience of explanation, and the present invention is not limited to the illustrated case.
Hereinafter, an etchant composition according to an embodiment of the present invention and a method for manufacturing a metal pattern using the same will be described in detail.
An etching solution composition according to an embodiment of the present invention includes: hydrogen peroxide; a fluorine-containing compound; an azole compound; a carboxyl group-containing amine compound; a phosphoric acid-based compound; quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5Butanediol substituted or unsubstituted with an alkyl group; and water.
According to an embodiment, the etching solution composition may etch a metal film. The metal film may include: a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or any combination thereof.
The hydrogen peroxide in the etching liquid composition can act as a main oxidant which directly affects etching by coming into contact with the metal film.
The hydrogen peroxide may be used to a degree sufficient to etch the metal film. For example, the hydrogen peroxide content may be as follows: is contained in an amount of 15 to 25 wt% based on 100 wt% of the etching solution composition. Specifically, it may be in the range of 18 to 23 wt%, but is not limited thereto.
If the hydrogen peroxide is contained within the above range, the etching force for the metal film is insufficient, and thus sufficient etching may not be achieved, while if the content exceeds the above range, the heat generation stability is significantly reduced with the increase of copper ions.
In the etching solution composition, the fluorine-containing compound functions as an auxiliary oxidizing agent that affects the etching rate of the metal film.
The fluorine-containing compound is capable of dissociating in water to release F-An ionic compound. For example, the fluorine compound may include: HF. NaF, NH4F、NH4BF4、NH4FHF、KF、KHF2、AlF3、HBF4Or any combination thereof. As another example, the fluorine compound may include NH4FHF。
The fluorine-containing compound may be used to a degree sufficient to adjust the etching rate of the metal film. For example, the fluorine-containing compound may be contained in the following amounts: the fluorine-containing compound is contained in an amount within a range of 0.01 to 5 wt% based on 100 wt% of the etching solution composition. Specifically, it may be in the range of 0.1 to 3 wt%, but is not limited thereto.
If the content of the fluorine-containing compound is less than the above range, the etching rate is caused to be slow, and if the content exceeds the above range, an Undercut (underrout) phenomenon or a damage phenomenon of a lower layer may occur as the etching rate is increased overall.
In the etching solution composition, the azole compound plays a role in improving process benefits by adjusting the etching speed of the metal film and reducing the CD loss of patterns.
The azole compound is not particularly limited as long as it is a compound usable in the art. For example, the azole compound may include: pyrrole (pyrazole) compounds, pyrazole (pyrazole) compounds, imidazole (imidazole) compounds, triazole (triazole) compounds, tetrazole (tetrazole) compounds, pentazole (pentazole) compounds, oxazole (oxazole) compounds, isoxazole (isooxazole) compounds, thiazole (thiazole) compounds, isothiazole (isothiazole) compounds, or any combination thereof. However, it is not limited thereto.
The azole compound represents a substituted or unsubstituted azole compound. The substituted azole compound represents an azole compound substituted by a substituent selected from the group consisting of: deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidino, hydrazine, hydrazono, C1-C60Alkyl radical, C2-C60Alkenyl radical, C2-C60Alkynyl, C1-C60Alkoxy radical, C3-C10Cycloalkyl radical, C1-C10Heterocycloalkyl radical, C3-C10Cycloalkenyl radical, C1-C10Heterocycloalkenyl, C6-C60Aryl radical, C6-C60Aryloxy radical, C6-C60Arylthio group, C1-C60Heteroaryl, a 1-valent non-aromatic condensed polycyclic group.
In one embodiment, the azole compound may include a tetrazole compound. For example, the azole compound may include tetrazoles substituted with alkyl or amino groups. As another example, the azole compound may include 5-methyltetrazole, 5-aminotetrazole, or any combination thereof, but is not limited thereto.
The content of the azole compound may be as follows: in the range of 0.1 to 5 wt% based on 100 wt% of the etching solution composition. Specifically, the content may be in the range of 0.3 to 1.5 wt%. However, it is not limited thereto.
If the content of the azole compound is less than the above range, the etching rate of the metal film is increased, and thus a significant CD loss may occur, whereas if the content exceeds the above range, a man-hour loss may occur as the etching rate of the metal film is decreased.
In the etching solution composition, the carboxyl amine compound has the following functions: the self-decomposition reaction rate of hydrogen peroxide which may occur when the etching solution composition is stored is reduced, thereby contributing to the securing of the storage period and stability, and preventing the etching characteristics from being changed when the etching process is repeated.
The carboxyl group-containing amine compound refers to a water-soluble compound having both a nitrogen (N) atom and a carboxyl group in one molecule. For example, the carboxyl group-containing amine-based compound may include: alanine (alanine), aminobutyric acid (aminobutyric acid), glutamic acid (glutamic acid), glycine (glycine), iminodiacetic acid (iminodiacetic acid), nitrilotriacetic acid (nitrilotriacetic acid), sarcosine (sarcosine), ethylenediaminetetraacetic acid (ethylenediaminetetraacetic acid), or any combination thereof. As another example, the carboxy-containing amine compound can include iminodiacetic acid (iminodiacetic acid). However, it is not limited thereto.
The content of the carboxyl-containing amine compound may be as follows: in the range of 0.5 wt% to 5 wt% based on 100 wt% of the etching solution composition. Specifically, it may be in the range of 1 to 3 wt%.
If the content of the carboxyl amine compound is less than the above range, a passivation film is formed and oxidized after a plurality of etching processes, and thus it is difficult to obtain a sufficient process efficiency, while if the content exceeds the above range, a man-hour loss may occur as the etching rate is slowed.
In the etching solution composition, the phosphoric acid compound increases the etching rate by adjusting the pH, and plays a role in reducing the decomposition reaction of hydrogen peroxide.
The phosphate-based compound may include H3PO2、H3PO3、H3PO4Or any combination thereof. For example, the phosphate-based compound can include H3PO3However, it is not limited thereto.
The content of the phosphate-based compound may be as follows: in the range of 0.3 to 5 wt% based on 100 wt% of the etching solution composition. Specifically, it may be in the range of 0.5 to 3 wt%. However, it is not limited thereto.
If the content of the phosphoric acid-based compound is less than the above range, the pH may not be sufficiently lowered to slow the etching rate, and an exothermic reaction may occur as the concentration of the metal ions in the etching solution increases. In addition, if the content exceeds the above range, a CD loss may occur as the etching rate is increased.
In the etching solution composition, a coating C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5The butane diol substituted or unsubstituted with an alkyl group functions to increase the uniformity of etching by reducing the surface tension. And, quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5The butanediol substituted or unsubstituted with an alkyl group functions as follows: after the metal film is etched, metal ions contained in the etching solution are surrounded, and the mobility of the metal ions is suppressed, thereby suppressing the decomposition reaction of hydrogen peroxide. By reducing the mobility of the metal ions, the process can be stably performed even when the etching solution is repeatedly used for a long period of time. Further, is covered with C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5The butanediol substituted or unsubstituted by the alkyl group can control the exothermic reaction of the etchant composition, thereby contributing to the stability of heat generation.
The quilt C1-C5The propylene glycol substituted or unsubstituted with an alkyl group may include 1, 3-propylene glycol, said propylene glycol being substituted with C1-C5The butylene glycol substituted or unsubstituted with an alkyl group may include 1, 4-butylene glycol, but is not limited thereto.
The quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5The content of the butanediol substituted or unsubstituted with an alkyl group may be as follows: may be in the range of 0.001 wt% to 5 wt% based on 100 wt% of the etching solution composition. Specifically, it may be in the range of 0.1 to 3 wt%. However, it is not limited thereto.
If the quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5If the content of the butylene glycol substituted or unsubstituted with an alkyl group is less than the above range, the uniformity of etching is lowered, and a heat generation reaction may occur as the decomposition reaction of hydrogen peroxide is accelerated. In addition, if the content exceeds the above range, a large amount of bubbles may be generated, and organic foreign substances may be generated after etching.
In addition to containing the components as described above, the etching solution composition may further contain an additive. Examples of the additive include a metal ion sealing agent and a preservative.
The etching solution composition may include, in addition to the components described above, a residual amount of water with respect to 100 wt% of the etching solution composition. The water may be deionized water (deionized water) or ultra pure water (ultrapure water) with minimized impurities.
For example, the water may have a resistivity value of about 18M Ω/cm. As another example, the water may have a resistivity value in a range of 16 M.OMEGA./cm to 20 M.OMEGA./cm.
Any combination of the constituents or constituent contents of the etching liquid composition as described above may be allowed to be applied.
For example, the etchant composition may include: hydrogen peroxide; a fluorine-containing compound; an azole compound; a carboxyl group-containing amine compound; a phosphoric acid-based compound; quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5Butanediol substituted or unsubstituted with an alkyl group; and a residual amount of water. Wherein the etching solution composition accounts for 100 weight percentOn a basis, the hydrogen peroxide may be present in an amount ranging from 15 to 25 wt%; the fluorine-containing compound may be contained in an amount ranging from 0.01 wt% to 5 wt%; the azole compound may be contained in an amount ranging from 0.1 wt% to 5 wt%; the content of the carboxyl group-containing amine compound may be in the range of 0.5 to 5% by weight; the content of the phosphoric acid-based compound may be in the range of 0.3 to 5 wt%; the quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl or by C1-C5The content of the butane diol substituted or unsubstituted with an alkyl group may be in the range of 0.001 wt% to 5 wt%. However, it is not limited thereto.
As another example, the etching solution composition includes: hydrogen peroxide; a fluorine-containing compound; an azole compound; a carboxyl group-containing amine compound; a phosphoric acid-based compound; quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5Butanediol substituted or unsubstituted with an alkyl group; and a residual amount of water. Wherein the hydrogen peroxide may be contained in an amount ranging from 18 wt% to 23 wt%, based on 100 wt% of the etching solution composition; the fluorine-containing compound may be contained in an amount ranging from 0.1 to 3 wt%; the azole compound may be contained in an amount ranging from 0.3 wt% to 1.5 wt%; the content of the carboxyl group-containing amine-based compound may be in the range of 1 to 3% by weight; the content of the phosphoric acid-based compound may be in the range of 0.5 to 3 wt%; the quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5The content of the butane diol substituted or unsubstituted with an alkyl group may be in the range of 0.1 to 3% by weight. However, it is not limited thereto.
The etching solution composition can be produced by a known method. The etchant composition preferably has a purity suitable for use in semiconductor processing.
For example, the following components may be mixed so that the total weight of the components is 100% by weightManufacturing the etching solution composition: hydrogen peroxide; a fluorine-containing compound; an azole compound; a carboxyl group-containing amine compound; a phosphoric acid-based compound; quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5Butanediol substituted or unsubstituted with an alkyl group; and water. The etching solution composition may contain other optional components within a range not affecting the performance thereof. The components may be mixed in any order, and the remaining components may be mixed after premixing any two components, or the components may be mixed at the same time, as long as there is no particular problem such as undesired reaction or generation of precipitates.
According to an embodiment, the etchant composition may etch a single film or a multi-layer film including a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or any combination thereof.
The copper-based metal film may include a copper film, a copper nitride film, a copper oxide film, a copper alloy film, or any combination thereof as a metal film containing copper in the composition of the film. The copper alloy film may be a film composed of an alloy containing copper and manganese, magnesium, zinc, nickel, or any combination thereof.
The molybdenum-based metal film may include a molybdenum film, a molybdenum nitride film, a molybdenum oxide film, a molybdenum alloy film, or any combination thereof as a metal film containing molybdenum in a composition component of the film. The molybdenum alloy film may be a film made of an alloy containing molybdenum and titanium (Ti), niobium (Nb), tungsten (W), or any combination thereof.
The titanium-based metal film may include a titanium film, a titanium nitride film, a titanium oxide film, a titanium alloy film, or any combination thereof, as a metal film containing titanium as a constituent component of the film. The titanium alloy film may be a film composed of an alloy containing nickel, zirconium, molybdenum, or any combination thereof, and titanium.
The multilayer film may include a double film, a triple film, and the like as a film including one or more films.
For example, the etching solution composition may etch a metal film, and the metal film may include a single film including a copper-based metal film, or a double film or a triple film including a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or any combination thereof, but is not limited thereto.
As examples of the multilayer film, a copper film/molybdenum alloy film, a copper alloy film/molybdenum alloy film, a copper film/titanium film, and the like may be included.
The single or multilayer film may have
To
A thickness within the range, however, is not limited thereto. For example, the single or multilayer film may have
To
A thickness within the range, however, is not limited thereto.
Hereinafter, a metal pattern manufacturing method according to another embodiment of the present invention will be described.
Hereinafter, the configuration and operation of the present invention will be described in detail with reference to the embodiments shown in the drawings. The present invention will be described below by way of examples, but the present invention is not limited to the following examples.
Fig. 1 to 3 are cross-sectional views for explaining a metal pattern forming method according to an embodiment of the present invention.
The method for manufacturing the metal pattern MP may include the steps of: forming a metal film ML on the substrate 110; forming a photoresist pattern 130 on the metal film ML; the etching liquid composition is brought into contact with the metal film using the photoresist pattern 130 as a mask, thereby etching the metal film ML.
Referring to fig. 1, a metal film ML is formed on a substrate 110. For a detailed description of the metal film, reference is made to the contents described in the present specification. For fig. 1 to 3, a case where the metal film is a double film including a titanium alloy film 122 and a copper film 124 is exemplarily shown.
The substrate 110 may be a silicon oxide (SiO) containing layerx) The glass substrate of (1). The titanium alloy film 122 and the copper film 124 may be continuously formed on the substrate 110 by chemical vapor deposition, respectively. The titanium alloy film 122 functions as a buffer layer to prevent copper of the copper film 124 from diffusing into a pattern in contact with the copper film 124, particularly from diffusing into a metal oxide semiconductor to damage the pattern. Alternatively, when a pattern or thin film including silicon oxide is formed between the titanium alloy film 122 and the substrate 110, the titanium alloy film 122 may inhibit a chemical reaction between the pattern or thin film and the copper film 124. Although not illustrated in the drawings, a plurality of patterns may be formed on the lower portion of the titanium alloy film 122.
The copper film 124 is formed on the titanium alloy film 122, and when a signal is applied to a metal pattern MP (see fig. 3) formed by patterning the metal film ML, the copper film 124 may become a main wiring layer (main line) to which the signal is substantially applied. The copper film 124 may be a substantially pure copper film containing very little impurity relative to the copper content.
Referring to fig. 2 and 3, a photoresist pattern 130 is formed on the metal film ML, and the etching liquid composition is brought into contact with the metal film ML using the photoresist pattern 130 as a mask, thereby etching the metal film ML.
The contents of the present specification are referred to for the detailed description of the etching solution composition.
With the use of the etching liquid composition, the metal film ML may be etched to form the metal pattern MP with the passage of time.
For example, the metal pattern MP may include a metal wiring, a gate electrode of the TFT, source and drain electrodes of the TFT, or any combination thereof, but is not limited thereto.
The photoresist pattern 130 may be formed using a positive photoresist composition. In contrast, the photoresist pattern 130 may be formed using a negative photoresist composition.
The etching of the metal film ML may be performed according to a method well known in the art, for example, the etching liquid composition may be supplied to the metal film ML by a dipping method, a spraying method, or the like, thereby etching the metal film ML.
Referring again to fig. 3, when the metal film ML is etched using the etching liquid composition, the copper film 124 disposed on the upper portion in the metal film ML is etched first. In the copper film 124, the portion where the photoresist pattern 130 is formed is not exposed to the etching solution composition and thus is not etched by the etching solution composition and remains on the substrate 110.
As the time for which the metal film ML is exposed to the etching solution composition passes, the titanium alloy film 122 exposed by the removal of the copper film 124 is etched, thereby forming the metal pattern MP. At this time, the characteristics of wet etching using the etching liquid composition determine that the copper film 124 may be further partially etched during the time period in which the titanium alloy film 122 is etched.
A taper angle (taper angle) θ of the metal pattern MP is measured with reference to the surface of the substrate 110, and a skew length (skew length) X is defined as a distance between a side of the metal pattern MP and a side of the photoresist pattern 130.
According to another embodiment, there is provided a method of manufacturing an array substrate for a liquid crystal display device, including the steps of: forming a gate electrode on a substrate; forming a gate insulating layer on the substrate including the gate electrode; forming a semiconductor layer on the gate insulating layer; forming a source electrode and a drain electrode on the semiconductor layer; and forming a pixel electrode connected to the drain electrode. Wherein, the manufacturing method can also comprise the following steps: contacting the etching solution composition to the metal film using the photoresist pattern as a mask to etch the metal film to form a gate electrode; the etching solution composition is brought into contact with the metal film using the photoresist pattern as a mask, thereby etching the metal film to form a source electrode and a drain electrode.
The present invention will be described in more detail below with reference to examples. However, the following examples are only for illustrating the present invention more specifically, and the scope of the present invention is not limited by the following examples.
Examples
Production of etching solution compositions of examples 1 to 3 and comparative examples 1 to 5
Etching liquid compositions according to examples 1 to 3 of the present invention and etching liquid compositions according to comparative examples 1 to 5 were manufactured in the same manner as shown in the following table 1. In table 1, the unit indicating the content of each component is "wt%" with the total weight of the etching solution composition taken as 100%.
[ Table 1]
ABF: ammonium bifluoride (Ammoniumbifluoride)
5-MTZ: 5-methyltetrazole (5-methyltetrazole)
IDA: iminodiacetic acid (Iminogenic aicd)
TEG: triethylene glycol (Triethylene glycol)
Evaluation example 1: evaluation of exothermic stability of etching solution composition
7000ppm of copper powder was added to each of the etching solution compositions according to examples 1 to 3 and comparative examples 1 to 5 of the present invention. The respective etching solution compositions were stirred for 1 hour and then placed in a constant temperature bath at 35 ℃ for 72 hours while the temperature change of the etching solutions was observed by a temperature monitor. The results are shown in Table 2.
[ Table 2]
In table 2, the maximum temperature represents the following temperature: the highest temperature measured during monitoring over 72 hours was measured by charging 7000ppm copper powder added to the etchant composition in a thermostatic bath. The exothermic reaction occurrence time represents the following time: and a point of time when the hydrogen peroxide in the etching liquid composition is boiled and overflowed. In examples 1 to 3 of the exothermic reaction time, the mark "-" indicates that no exothermic reaction occurred, and the mark "0" in comparative example 2 indicates that the exothermic reaction occurred immediately during the addition of 7000ppm of copper powder to the etching solution composition.
Referring to said table 2, for examples 1 to 3, unlike comparative examples 1 to 5, it was confirmed that no exothermic reaction occurred, and accordingly, it was confirmed that the etching solution compositions based on examples 1 to 3 were excellent in heat generation stability.
Production of sample 1
An alloy film of titanium and molybdenum was formed on a glass substrate by a chemical vapor deposition method. Next, a copper film was formed on the alloy film of titanium and molybdenum. A photoresist layer is formed on the copper film, and the photoresist layer is exposed and developed, thereby forming a photoresist pattern.
The copper film was etched using the "etching solution composition without copper powder added to the etching solution composition according to example 2" (immediately after production) using the photoresist pattern as a mask, thereby producing sample 1 including a metal pattern.
At this time, the copper film was subjected to interference etching by about 90% based on an etching end point (etching end point) using "the etching solution composition without copper powder added to the etching solution composition according to example 2" to manufacture the metal pattern.
Production of sample 2
The metal pattern was produced in the same manner as in the production of sample 1 except that "an etching solution composition containing 7000ppm of copper powder added to the etching solution composition according to example 2" was used instead of "an etching solution composition containing no copper powder added to the etching solution composition according to example 2" in etching a copper film.
Production of sample 3
The metal pattern was produced in the same manner as in the production of sample 1 except that "an etching solution composition obtained by storing the etching solution composition without copper powder in the etching solution composition according to example 2 for 7 days" was used instead of "an etching solution composition without copper powder in the etching solution composition according to example 2" in etching a copper film.
Production of sample 4
The metal pattern was produced in the same manner as in the production of sample 1 except that "an etching solution composition obtained by storing the etching solution composition without copper powder in the etching solution composition according to example 2 for 14 days" was used instead of "an etching solution composition without copper powder in the etching solution composition according to example 2" in etching a copper film.
Evaluation example 2: cumulative duration evaluation of etchant compositions
The profiles of the metal pattern and the photoresist pattern of the samples 1 and 2 were photographed using a Scanning Electron Microscope (SEM). In order to see whether the characteristics of the etchant composition were maintained when copper ions accumulated, the cone angle, the titanium trace, and the slant length of sample 1 (copper concentration 0ppm) and sample 2 (copper concentration 7000ppm) were evaluated. The results are shown in fig. 4a (sample 1), fig. 4b (sample 2) and table 3.
[ Table 3]
| Cone angle (theta) | Oblique long (X) (um) | Lower track length (um) | |
| Sample 1(0ppm) | 36.47 | 1.06 | 0.109 |
| Sample 2(7000ppm) | 45.99 | 1.06 | 0.109 |
| Amount of change | 9.52 | 0 | 0 |
Referring to table 3, the etchant composition according to example 2 also showed good levels of cone angle, slant length, and lower trace length at a copper ion concentration of 7000 ppm.
Evaluation example 3: shelf life evaluation of etchant composition
The metal patterns and the photoresist patterns of the samples 1, 2 and 3 were photographed for their profiles using a Scanning Electron Microscope (SEM). In order to see whether or not the characteristics of the etching liquid composition were maintained with the passage of the storage period after the production of the etching liquid composition, whether or not the cone angle was maintained, the titanium track, and the slant length were evaluated for sample 1 (copper concentration 0ppm, storage period 0 day), sample 3 (copper concentration 0ppm, storage period 7 days), and sample 4 (copper concentration 0ppm, storage period 14 days). The results are shown in fig. 4a (sample 1), fig. 5a (sample 3), fig. 5b (sample 4) and table 4.
[ Table 4]
Referring to table 4, it can be confirmed that: the etching solution composition manufactured according to example 2 also showed excellent levels of taper angle, slant length, and lower trace length over 14 days.
It was confirmed that the etching liquid composition of evaluation example 1 exhibited excellent heat generation stability by evaluation of heat generation stability of the etching liquid composition. The evaluation of the cumulative duration of the etching solution composition of evaluation example 2 and the evaluation of the storage time of the etching solution composition of evaluation example 3 confirmed that the etching solution composition can be repeatedly used for a long period of time, thereby reducing the process cost.
In the above, the preferred embodiments have been disclosed through the description and the accompanying drawings. Specific terms are used herein, however, these terms are used only for the purpose of illustrating the present invention and are not intended to limit the meaning or the scope of the present invention described in the claims. It is therefore to be understood that various modifications may be made and equivalents may be substituted for elements thereof by those skilled in the art. Therefore, the true technical scope of the present invention should be determined according to the technical idea of the claims.
Claims (12)
1. An etchant composition comprising:
hydrogen peroxide;
a fluorine-containing compound;
an azole compound;
a carboxyl group-containing amine compound;
a phosphoric acid-based compound;
quilt C1-C5Propylene glycol substituted or unsubstituted with alkyl or by C1-C5Butanediol substituted or unsubstituted with an alkyl group; and
the amount of water is controlled by the amount of water,
wherein the phosphate-based compound comprises: h3PO2、H3PO3、H3PO4Or any combination thereof,
based on 100 wt% of the etching solution composition,
the hydrogen peroxide is present in an amount ranging from 15 wt% to 25 wt%;
the fluorine-containing compound is present in an amount ranging from 0.01 wt% to 5 wt%;
the azole compound is contained in an amount ranging from 0.1 to 5% by weight;
the content of the carboxyl amine-containing compound ranges from 0.5 to 5 wt%;
the content of the phosphoric acid-based compound ranges from 0.3 wt% to 5 wt%;
is covered with C1-C5Propylene glycol substituted or unsubstituted with alkyl, or by C1-C5The content of the butane diol substituted or unsubstituted with an alkyl group ranges from 0.001 to 5% by weight.
2. The etching solution composition as claimed in claim 1, wherein the fluorine-containing compound comprises:
HF、NaF、NH4F、NH4BF4、NH4FHF、KF、KHF2、AlF3、HBF4or any combination thereof.
3. The etching solution composition as claimed in claim 1, wherein the azole compound comprises:
an azole compound, a pyrazole compound, an imidazole compound, a triazole compound, a tetrazole compound, a pentazole compound, an oxazole compound, an isoxazole compound, a thiazole compound, an isothiazole compound, or any combination thereof.
4. The etching solution composition according to claim 1, wherein the azole compound comprises tetrazole substituted with an alkyl group or an amino group.
5. The etching solution composition as claimed in claim 1, wherein the carboxyl group-containing amine compound comprises:
alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid, sarcosine, ethylenediaminetetraacetic acid, or any combination thereof.
6. The etching solution composition according to claim 1,
is covered with C1-C5The propylene glycol substituted or unsubstituted with an alkyl group includes 1, 3-propylene glycol,
is covered with C1-C5The butanediol substituted or unsubstituted with an alkyl group includes 1, 4-butanediol.
7. The etching solution composition according to claim 1, wherein the etching solution composition is used for etching a single film or a multilayer film comprising a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or any combination thereof.
8. A method of manufacturing a metal pattern, comprising the steps of:
forming a metal film on a substrate;
forming a photoresist pattern on the metal film; and
contacting the etching solution composition of any one of claims 1 to 7 to the metal film using the photoresist pattern as a mask, thereby etching the metal film.
9. The method of manufacturing a metal pattern according to claim 8, wherein the metal film comprises:
a single film or a multilayer film including a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or any combination thereof.
10. The method of manufacturing a metal pattern according to claim 8, wherein the metal film comprises:
a single film including a copper-based metal film; or
The double film or triple film includes a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or any combination thereof.
11. The method of manufacturing a metal pattern according to claim 8, wherein the metal pattern comprises:
a metal wiring, a gate electrode of a TFT, a source electrode and a drain electrode of a TFT, or any combination thereof.
12. The method of manufacturing a metal pattern according to claim 8, wherein the metal film has
To
A thickness within the range.
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| CN104160486A (en) * | 2012-03-13 | 2014-11-19 | 株式会社Adeka | Etching solution composition and etching method |
| CN104419930A (en) * | 2013-08-27 | 2015-03-18 | 东友精细化工有限公司 | Ethicng liquid composition, and method for preparing array substrate for use in liquid crystal display device |
| CN104562009A (en) * | 2013-10-18 | 2015-04-29 | 东进世美肯株式会社 | Metal wiring etching liquid composition and metal wiring forming method using same |
| CN104838040A (en) * | 2012-12-18 | 2015-08-12 | 东进世美肯株式会社 | Metal-film etching-solution composition and etching method using same |
| CN105441949A (en) * | 2016-01-26 | 2016-03-30 | 苏州诺菲纳米科技有限公司 | Nano-silver etchant, method for preparing patterned nano-silver conducting film and touch sensor |
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| KR101495683B1 (en) * | 2008-09-26 | 2015-02-26 | 솔브레인 주식회사 | Cu or Cu/Mo or Cu/Mo alloy electrode etching liquid in Liquid Crystal Display system |
| CN103052907B (en) * | 2010-07-30 | 2015-08-19 | 东友精细化工有限公司 | For the manufacture of the method for array substrate for liquid crystal display device |
| KR102160286B1 (en) * | 2013-11-04 | 2020-09-28 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
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| CN104160486A (en) * | 2012-03-13 | 2014-11-19 | 株式会社Adeka | Etching solution composition and etching method |
| CN104838040A (en) * | 2012-12-18 | 2015-08-12 | 东进世美肯株式会社 | Metal-film etching-solution composition and etching method using same |
| CN104419930A (en) * | 2013-08-27 | 2015-03-18 | 东友精细化工有限公司 | Ethicng liquid composition, and method for preparing array substrate for use in liquid crystal display device |
| CN104562009A (en) * | 2013-10-18 | 2015-04-29 | 东进世美肯株式会社 | Metal wiring etching liquid composition and metal wiring forming method using same |
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