CN115852371A - Etching composition for copper-based metal film, copper-based metal wiring, and thin film transistor array substrate - Google Patents
Etching composition for copper-based metal film, copper-based metal wiring, and thin film transistor array substrate Download PDFInfo
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Abstract
The present invention provides an etching composition for a copper-based metal film, a copper-based metal wiring, and a thin film transistor array substrate, wherein the etching composition for a copper-based metal film comprises hydrogen peroxide, a fluorine-containing compound, an azole compound, a water-soluble compound having a nitrogen atom and a carboxyl group, a phosphate compound, and a sulfate compound, the phosphate compound and the sulfate compound are ammonium salts of phosphoric acid and sulfuric acid, respectively, and a Y value defined by specific formula 1 is less than 16. The etching composition of the present invention does not generate precipitates and can perform the collective etching of a copper-based film, a molybdenum alloy film and a silicon film with excellent etching characteristics.
Description
Technical Field
The present invention relates to an etching composition for a copper-based metal film, and more particularly, to an etching composition for a copper-based metal film, which does not generate precipitates and can simultaneously etch a copper-based film, a molybdenum alloy film and a silicon film with excellent etching characteristics.
Background
A liquid crystal layer and a wiring for transmitting a signal to an OLED element are formed on a Thin Film Transistor (TFT) substrate of a Liquid Crystal Display (LCD) and an Organic Light Emitting Diode (OLED) display. The wiring of the thin film transistor substrate includes a gate wiring and a data wiring. The gate lines include gate lines to which gate signals are applied and gate electrodes of the thin film transistors, and the data lines include data lines to which data signals are applied and source and drain electrodes constituting data electrodes of the thin film transistors, the data lines being connected to the gate lines.
Copper metal, which has low resistance and is free from environmental problems, is generally used as such a wiring. However, since copper has a problem of low adhesion to a glass substrate and diffusion to a lower film, molybdenum is used as a lower barrier metal.
Such metal wiring is patterned into wiring by an etching process. Conventionally, an etching composition used for etching a multi-layer metal film made of a copper/molybdenum (alloy) film contains a fluorine-containing compound to etch the molybdenum (alloy) film and citric acid as a treatment number enhancer [ see korean patent laid-open No. 10-2015-0004972 ].
However, the above etching composition cannot etch a silicon film, and thus has a limitation in a process that requires a separate dry etching (dry etching) step.
Further, when the precipitates are generated in the etching step, there are problems such as an increase in the defect rate and the need for maintenance work (PM) of a facility for removing the precipitates.
Therefore, there is a need to develop an etching composition for a copper-based metal film, which does not generate precipitates and can etch a copper-based film, a molybdenum alloy film, and a silicon film at a time with excellent etching characteristics.
Disclosure of Invention
Problems to be solved
An object of the present invention is to provide an etching composition for a copper-based metal film, which does not generate precipitates and can perform a collective etching of a copper-based film, a molybdenum alloy film and a silicon film with excellent etching characteristics.
Another object of the present invention is to provide a copper-based metal wiring formed using the etching composition.
It is still another object of the present invention to provide a thin film transistor array substrate including the copper-based metal wiring.
Means for solving the problems
In one aspect, the present invention provides an etching composition for a copper-based metal film, comprising hydrogen peroxide, a fluorine-containing compound, an azole compound, a water-soluble compound having a nitrogen atom and a carboxyl group, a phosphate compound, and a sulfate compound,
the above-mentioned phosphate compounds and sulfate compounds are ammonium salts of phosphoric acid and sulfuric acid, respectively,
the Y value defined by the following mathematical formula 1 is less than 16.
[ mathematical formula 1]
Y＝(A+B)/(C+D)
In the above-mentioned formula, the compound has the following formula,
a is the content of the sulfate compound,
b is the content of a water-soluble compound having a nitrogen atom and a carboxyl group,
c is the content of the phosphate compound,
d is the content of fluorine-containing compounds.
In one embodiment of the present invention, the copper-based metal film may be a single-layer film of copper or a copper alloy; or a multilayer film comprising one or more films selected from the group consisting of copper films and copper alloy films and one or more films selected from the group consisting of molybdenum films and molybdenum alloy films.
The etching composition for a copper-based metal film according to one embodiment of the present invention can etch a silicon film and a copper-based metal film together.
In one embodiment of the present invention, the silicon film may be one or more films selected from the group consisting of an amorphous silicon film (a-Si), a hydrogenated amorphous silicon film (a-Si: H), an N-type doped amorphous silicon film (N + a-Si), and an N-type doped hydrogenated amorphous silicon film (N + a-Si: H).
The etching composition for a copper-based metal film according to an embodiment of the present invention may further include one or more of a polyol-type surfactant and an acetate compound.
The etching composition for a copper-based metal film according to one embodiment of the present invention may contain 5 to 25 wt% of hydrogen peroxide, 0.001 to 0.4 wt% of a fluorine-containing compound, 0.1 to 5 wt% of an azole compound, 0.1 to 3.5 wt% of a water-soluble compound having a nitrogen atom and a carboxyl group, 0.01 to 0.2 wt% of a phosphate compound, and 0.1 to 2 wt% of a sulfate compound, based on the total weight of the composition, and may contain the balance of water, such that the total weight of the composition becomes 100 wt%.
In another aspect, the present invention provides a copper-based metal wiring formed using the etching composition for a copper-based metal film.
In another aspect, the present invention provides a thin film transistor array substrate including the copper-based metal wiring.
The thin film transistor array substrate according to an embodiment of the present invention may include a silicon semiconductor layer.
Effects of the invention
The etching composition for copper-based metal films of the present invention can perform collective etching of copper-based films, molybdenum alloy films, and silicon films with excellent etching characteristics without generating precipitates.
Detailed Description
The present invention will be described in more detail below.
One embodiment of the present invention relates to an etching composition for a copper-based metal film, which includes hydrogen peroxide (a), a fluorine-containing compound (B), an azole compound (C), a water-soluble compound (D) having a nitrogen atom and a carboxyl group, a phosphate compound (E), and a sulfate compound (F), wherein the phosphate compound and the sulfate compound are ammonium salts of phosphoric acid and sulfuric acid, respectively, and a Y value defined by the following numerical formula 1 is less than 16.
[ mathematical formula 1]
Y＝(A+B)/(C+D)
In the above-mentioned formula, the compound has the following formula,
a is the content of the sulfate compound,
b is the content of a water-soluble compound having a nitrogen atom and a carboxyl group,
c is the content of the phosphate compound,
d is the content of the fluorine-containing compound.
The etching composition for copper-based metal films according to one embodiment of the present invention has a Y value defined by the above formula 1 of less than 16, for example, 3 or more and less than 16, preferably 4 or more and less than 14, and more preferably 5 or more and less than 12.
If the Y value defined by the above equation 1 satisfies the above range, the shift (Skew) uniformity is excellent even if the number of processed sheets increases, the rate of change in taper angle (T/a) is small, the generation of residue can be suppressed, and the etching characteristics with respect to the lower silicon film can be secured, so that the batch wet etching can be performed instead of the dry etching process.
In the case where the Y value defined by the above equation 1 is 16 or more, as the number of processed sheets increases, the offset uniformity may decrease, the taper angle change rate may increase, a residue may be generated, or it may be difficult to ensure etching characteristics for the lower silicon film.
In one embodiment of the present invention, the copper-based metal film may be a single-layer film containing copper or a copper alloy in a film constituent component; or a multilayer film comprising one or more films selected from the group consisting of copper films and copper alloy films and one or more films selected from the group consisting of molybdenum films and molybdenum alloy films.
The copper alloy is an alloy of copper and one or more metals selected from aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta), and tungsten (W), and is a concept including a nitride of copper or an oxide of copper.
The molybdenum alloy is an alloy of molybdenum and one or more metals selected from aluminum (Al), niobium (Nb), tungsten (W), titanium (Ti), and nickel (Ni), and is a concept including a nitride of molybdenum or an oxide of molybdenum.
Examples of the multilayer film include two-layer films such as a copper/molybdenum film, a copper/molybdenum alloy film, and a copper alloy/molybdenum alloy film; three films such as a molybdenum/copper/molybdenum film, a molybdenum alloy/copper/molybdenum alloy film, and a molybdenum alloy/copper alloy/molybdenum alloy film. The copper/molybdenum film is a film including a molybdenum layer and a copper layer formed on the molybdenum layer, the copper/molybdenum alloy film is a film including a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, the copper alloy/molybdenum alloy film is a film including a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, the molybdenum/copper/molybdenum film is a film including a molybdenum layer, a copper layer formed on the molybdenum layer, and a molybdenum layer formed on the copper layer, the molybdenum alloy/copper/molybdenum alloy film is a film including a molybdenum alloy layer, a copper layer formed on the molybdenum alloy layer, and a molybdenum alloy layer formed on the copper layer, and the molybdenum alloy/copper alloy/molybdenum alloy film is a film including a molybdenum alloy layer, a copper alloy layer formed on the molybdenum alloy layer, and a molybdenum alloy layer formed on the copper alloy layer.
In particular, the etching composition of the present invention can be applied to a multilayer film including one or more films selected from a copper film and a copper alloy film and one or more films selected from a molybdenum film and a molybdenum alloy film.
The thickness of the copper film and the copper alloy film may be set to
Preferably, it may be
In the range of (1), the thickness of the molybdenum film and the molybdenum alloy film may be ^ or ^ a>
Can preferably be +>
The range of (1).
In one embodiment of the present invention, the copper-based metal film may be formed on a glass substrate or a silicon film.
The etching composition for a copper-based metal film according to one embodiment of the present invention can etch a silicon film and a copper-based metal film together.
Therefore, the etching composition for a copper-based metal film according to one embodiment of the present invention can collectively etch a gate electrode, a gate wiring, source/drain electrodes, a data wiring, and a silicon film located below a display device including the copper-based metal film and the silicon film.
The silicon film may be one or more films selected from the group consisting of an amorphous silicon film (a-Si), a hydrogenated amorphous silicon film (a-Si: H), an N-type doped amorphous silicon film (N + a-Si), and an N-type doped hydrogenated amorphous silicon film (N + a-Si: H).
The components of the etching composition according to one embodiment of the present invention will be described in more detail below.
Hydrogen peroxide (A)
In one embodiment of the present invention, the hydrogen peroxide (H) is 2 O 2 ) The component (A) is a main oxidant which affects the etching of the copper-based metal film.
The content of the hydrogen peroxide may be 5 to 25% by weight, preferably 13 to 23% by weight, based on the total weight of the composition. When the content of the hydrogen peroxide is less than 5 wt%, the copper-based metal film may not be etched or the etching rate may be very slow, and when the content is more than 25 wt%, the etching rate may be entirely increased, so that the process control may be difficult, and the heat generation stability may be greatly lowered due to the increase of copper ions.
Fluorine-containing Compound (B)
In one embodiment of the present invention, the fluorine-containing compound (B) is an auxiliary oxidant which affects the etching rate of the molybdenum (alloy) film, and functions to regulate the etching rate of the molybdenum (alloy) film and suppress the generation of residue.
The fluorine-containing compound is a compound that can be dissociated in water or the like to provide fluorine ions or polyatomic fluorine ions. As the above-mentioned fluorine-containing compound, a fluorine-containing compound generally used in the art can be used, and examples thereof include Hydrogen Fluoride (HF), sodium fluoride (NaF), and ammonium fluoride (NH) 4 F) Ammonium hydrogen fluoride (NH) 4 F 2 ) Ammonium fluoroborate (NH) 4 BF 4 ) Ammonium hydrogen fluoride (NH) 4 FHF), potassium fluoride (KF), potassium hydrogen fluoride (KHF) 2 ) Aluminum fluoride (AlF) 3 ) Tetrafluoroboric acid (HBF) 4 ) And the like, they may be used alone or in a mixture of two or more.
The content of the fluorine-containing compound may be 0.001 to 0.4% by weight, preferably 0.1 to 0.35% by weight, based on the total weight of the composition. When the content of the fluorine-containing compound is less than 0.001 wt%, the etching rate of the molybdenum (alloy) film may be slow and a residue may be generated, and when the content is more than 0.4 wt%, the etching rates of the molybdenum (alloy) film and the silicon film may be too high, and the glass substrate may be etched to a large extent and thus may be difficult to be applied to a rework process.
In addition, when the content of the fluorine-containing compound is more than 0.4% by weight, si precipitates may be generated. For example, the Si precipitates may be Na 2 [SiF 6 ]Or K 2 [SiF 6 ]Such morphology generation has a disadvantage that precipitates are generated in an etching apparatus (etcher), and the defect rate increases during the etching process, which requires PM in the apparatus.
SiO 2 +6F-→SiF 6 2- +O 2
SiF 6 2- +2Na→Na 2 [SiF 6 ]
SiF 6 2- +2K→K 2 [SiF 6 ]
Azole compounds (C)
In one embodiment of the present invention, the azole compound (C) adjusts an etching rate of the copper-based metal film, and serves to reduce a critical dimension loss (CD loss), i.e., a side etch (side etch), of the pattern and to improve a margin in a process.
The azole compound is not particularly limited as long as it is an azole compound used in the present technical field, and for example, an azole compound having 1 to 30 carbon atoms is preferable. Examples of the azole compound include triazole compounds, aminotetrazole compounds, imidazole compounds, indole compounds, purine compounds, pyrazole compounds, pyridine compounds, pyrimidine compounds, pyrrole compounds, pyrrolidine compounds, and pyrroline compounds, and specific examples thereof include 5-aminotetrazole, benzotriazole (benzotriazole), tolyltriazole (tolyltriazole), pyrazole (pyrazole), imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, methyltriazole, methyltetrazole, and 4-propylimidazole. They may be used alone or as a mixture of two or more.
The content of the azole compound may be 0.1 to 5% by weight, preferably 0.1 to 1.5% by weight, based on the total weight of the composition. In the case where the content of the azole compound is less than 0.1 wt%, the etching rate may be increased to significantly cause a critical dimension loss, and in the case where it is more than 5 wt%, the etching rate may be too slow to cause a loss of process time and an etching residue may be generated.
Water-soluble Compound (D) having Nitrogen atom and carboxyl group
In one embodiment of the present invention, the water-soluble compound (D) having a nitrogen atom and a carboxyl group prevents a self-decomposition reaction of hydrogen peroxide which may occur during storage of the etching composition and prevents a change in etching characteristics when etching a large number of substrates. In general, in the case of an etching composition using hydrogen peroxide, hydrogen peroxide undergoes self-decomposition during storage, and the storage time is not long, and explosion may occur. On the other hand, in the case where the water-soluble compound having a nitrogen atom and a carboxyl group is contained, the decomposition rate of hydrogen peroxide is reduced by approximately 10 times, which is advantageous for ensuring the storage time and stability. In particular, in the case of a copper layer, when a large amount of copper ions remain in the etching composition, a passivation film may be formed and further etching may not be performed after oxidation black, but such a phenomenon can be prevented when the compound (D) is added.
Examples of the water-soluble compound having a nitrogen atom and a carboxyl group include alanine (alanine), aminobutyric acid (aminobutyric acid), glutamic acid (glutamic acid), glycine (glycine), iminodiacetic acid (iminodiacetic acid), nitrilotriacetic acid (nitrilotriacetic acid), and sarcosine (sarcosine), and these may be used alone or as a mixture of two or more.
The content of the water-soluble compound having a nitrogen atom and a carboxyl group may be in the range of 0.1 to 3.5% by weight, preferably 0.5 to 3.0% by weight, based on the total weight of the composition. When the content of the compound is less than 0.1 wt%, a passivation film may be formed after etching a large number of substrates (about 500 sheets) and a sufficient process margin may not be easily obtained, and when the content is more than 3.5 wt%, the etching rate of the molybdenum-containing film may be reduced to generate a residue and cause a loss of process time.
Phosphate compound (E)
In one embodiment of the present invention, the phosphate compound (E) is a component for improving the profile of the tapered surface of the pattern, and an ammonium salt of phosphoric acid is used. In particular, in the present invention, by using an ammonium salt as the phosphate compound, the solubility in water is high and the generation of precipitates can be suppressed. For example, in the case of using a metal salt instead of an ammonium salt as the phosphate compound, al precipitation is generated from MoAlTi in a molybdenum (alloy) film. The precipitate can be Na 3 AlF 6 Or K 3 AlF 6 Such morphology generation has a disadvantage that precipitates are generated in an etching apparatus, a defect rate increases in an etching process, and PM in the apparatus is required.
Al 3+ +6F-→AlF 6 3-
AlF 6 3- +3Na + →Na 3 AlF 6 (precipitation generation)
AlF 6 3- +3K + →K 3 AlF 6 (precipitate formation)
AlF 6 3- +NH 4 + →(NH 4 ) 3 AlF 6 (No precipitate)
The above ammonium salt of phosphoric acid is a salt in which one or both hydrogen ions of phosphoric acid are replaced with ammonium ions. Examples thereof include ammonium dihydrogen phosphate and diammonium hydrogen phosphate, which may be used alone or as a mixture of two or more thereof.
The content of the phosphate compound may be in the range of 0.01 to 0.2 wt%, preferably 0.02 to 0.15 wt%, based on the total weight of the composition. In the case where the content of the above-mentioned phosphate compound is less than 0.01 wt%, the etching profile may be deteriorated, and in the case where it is more than 0.2 wt%, the taper angle of the copper-based metal film may be increased, the etching rate of the copper-based metal film may be increased or the etching rate of the molybdenum (alloy) film may be slowed. Further, if the content of the phosphate compound is out of the above range, the etching rate of the lower silicon film may be slow.
Sulfate Compound (F)
In one embodiment of the present invention, the sulfate compound (F) is an ammonium salt of sulfuric acid as a component that serves to improve the profile of the tapered surface of the pattern and to adjust the etching rate of the copper-based metal film. In particular, it is possible to provide,
in the present invention, by using an ammonium salt as the sulfate compound, the solubility in water is high and the generation of precipitates can be suppressed. For example, in the case of using a metal salt instead of an ammonium salt as the sulfate compound, al precipitation is generated from MoAlTi in the molybdenum (alloy) film. The precipitate can be Na 3 AlF 6 Or K 3 AlF 6 Such morphology generation has a disadvantage that precipitates are generated in an etching apparatus, a defect rate increases in an etching process, and PM in the apparatus is required.
Al 3+ +6F - →AlF 6 3-
AlF 6 3- +3Na + →Na 3 AlF 6 (precipitate formation)
AlF 6 3- +3K + →K 3 AlF 6 (precipitation generation)
AlF 6 3- +NH 4 + →(NH 4 ) 3 AlF 6 (No precipitate)
The ammonium salt of sulfuric acid mentioned above is a salt in which one or both hydrogen ions of sulfuric acid are replaced with ammonium ions. Examples thereof include ammonium sulfate (ammonium sulfate) and ammonium bisulfate (ammonium bisulfate), and these may be used alone or as a mixture of two or more thereof.
The content of the sulfate compound may be in the range of 0.1 to 2 wt%, preferably 0.1 to 1.6 wt%, based on the total weight of the composition. When the content of the sulfate compound is less than 0.1 wt%, the etching force may be insufficient and sufficient etching may not be achieved, and when the content is more than 2 wt%, the etching rate may be increased as a whole, and therefore, process control may not be easily performed.
Polyol type surfactant (G)
The etching composition for a copper-based metal film according to an embodiment of the present invention may further include a polyol-type surfactant (G) to reduce surface tension and improve etching uniformity. The polyol-type surfactant (G) can also serve to suppress the activity of copper ions and to suppress the decomposition reaction of hydrogen peroxide by surrounding the copper ions eluted from the etching composition after the etching of the copper film. If the activity of copper ions is reduced in this way, a stable process can be performed without generating heat during the use of the etching composition.
Examples of the polyhydric alcohol-type surfactant include glycerin (glycerol), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol), and polyethylene glycol (polyethylene glycol), and these may be used alone or as a mixture of two or more.
The content of the polyol-type surfactant may be in the range of 0.001 to 5% by weight, preferably 1.0 to 3.0% by weight, based on the total weight of the composition. In the case where the content of the above polyol-type surfactant is less than 0.001% by weight, decomposition of hydrogen peroxide may be accelerated, and in the case where it is more than 5% by weight, a large amount of foam may be generated.
Acetate compound (H)
The etching composition for a copper-based metal film according to an embodiment of the present invention may further include an acetate compound (H) to adjust an etching rate. The acetate compound (H) serves to increase the pH and prevent the etching rate of the copper-based metal film from becoming too high.
The acetate compound may be a salt in which hydrogen ions of acetic acid are substituted with alkali metal ions, alkaline earth metal ions, or ammonium ions, but is not limited thereto. Specific examples thereof include sodium acetate (sodium acetate), potassium acetate (potassium acetate), and ammonium acetate (ammonium acetate), and these may be used alone or as a mixture of two or more.
The content of the acetate compound may be 0.1 to 2% by weight, preferably 0.2 to 1.0% by weight, based on the total weight of the composition. When the content of the acetate compound is less than 0.1 wt%, the etching rate is increased as a whole, and thus, the process control may be difficult, and when the content is more than 2 wt%, the etching rate is decreased and the production efficiency may be lowered.
The etching composition according to an embodiment of the present invention may contain water in an amount to make the total weight of the composition 100 wt%. In the present invention, the water is not particularly limited, and is preferably deionized water, and more preferably deionized water having a resistivity of 18M Ω · cm or more, which indicates the degree of removal of ions in the water.
The "balance" in the present invention means a balance for making the total weight of the composition containing the essential components of the present invention and additional components 100 wt%, and the composition of the present invention is not limited to the inclusion of the additional components by the meaning of the "balance".
The etching composition for a copper-based metal film according to one embodiment of the present invention may contain 5 to 25 wt% of hydrogen peroxide, 0.001 to 0.4 wt% of a fluorine-containing compound, 0.1 to 5 wt% of an azole compound, 0.1 to 3.5 wt% of a water-soluble compound having a nitrogen atom and a carboxyl group, 0.01 to 0.2 wt% of a phosphate compound, and 0.1 to 2 wt% of a sulfate compound, based on the total weight of the composition, and may contain the balance of water, such that the total weight of the composition becomes 100 wt%.
The etching composition for a copper-based metal film according to one embodiment of the present invention may contain 5 to 25 wt% of hydrogen peroxide, 0.001 to 0.4 wt% of a fluorine-containing compound, 0.1 to 5 wt% of an azole compound, 0.1 to 3.5 wt% of a water-soluble compound having a nitrogen atom and a carboxyl group, 0.01 to 0.2 wt% of a phosphate compound, 0.1 to 2 wt% of a sulfate compound, and 0.001 to 5 wt% of a polyol-type surfactant, based on the total weight of the composition, and may contain the balance of water, which makes the total weight of the composition 100 wt%.
The etching composition for a copper-based metal film according to one embodiment of the present invention may contain 5 to 25 wt% of hydrogen peroxide, 0.001 to 0.4 wt% of a fluorine-containing compound, 0.1 to 5 wt% of an azole compound, 0.1 to 3.5 wt% of a water-soluble compound having a nitrogen atom and a carboxyl group, 0.01 to 0.2 wt% of a phosphate compound, 0.1 to 2 wt% of a sulfate compound, and 0.1 to 2 wt% of an acetate compound, based on the weight of the entire composition, and may contain the balance of water, such that the weight of the entire composition becomes 100 wt%.
The etching composition for a copper-based metal film according to one embodiment of the present invention may contain 5 to 25 wt% of hydrogen peroxide, 0.001 to 0.4 wt% of a fluorine-containing compound, 0.1 to 5 wt% of an azole compound, 0.1 to 3.5 wt% of a water-soluble compound having a nitrogen atom and a carboxyl group, 0.01 to 0.2 wt% of a phosphate compound, 0.1 to 2 wt% of a sulfate compound, 0.001 to 5 wt% of a polyol-type surfactant, and 0.1 to 2 wt% of an acetate compound, based on the total weight of the composition, and may contain the balance of water so that the total weight of the composition becomes 100 wt%.
The etching composition according to an embodiment of the present invention may further contain an additive generally used in the art, for example, a sequestering agent, an anticorrosive, and the like, in addition to the above components.
The above-mentioned components used in the etching composition according to one embodiment of the present invention can be produced by a generally known method, and preferably have a purity for use in a semiconductor process.
The etching composition according to one embodiment of the present invention can realize a tapered profile having excellent etching uniformity and straightness when etching a copper-based metal film. In addition, the etching composition according to an embodiment of the present invention does not generate residue, and thus does not have problems such as electrical short, wiring failure, and luminance degradation. In addition, the etching composition according to an embodiment of the present invention can etch the gate electrode, the gate wiring, the source/drain electrodes, the data wiring, and the silicon film located below all at once. Therefore, the etching composition according to an embodiment of the present invention can simplify the process and maximize the process yield because the wet etching process can be performed using only one etching composition without using several kinds of etching compositions, and can reduce the process time and cost because the dry etching process can be replaced.
Therefore, the etching composition for copper-based metal films according to one embodiment of the present invention can be used very effectively in the production of thin film transistor array substrates, particularly thin film transistor array substrates for liquid crystal display devices, which exhibit large-screen and/or high-brightness circuits.
One embodiment of the present invention relates to a copper-based metal wiring formed using the etching composition for a copper-based metal film.
The copper-based metal wiring according to an embodiment of the present invention can be manufactured by performing an etching process generally known in the art using the etching composition.
For example, the copper-based metal wiring according to an embodiment of the present invention can be manufactured by performing an etching process including the steps of: forming a copper-based metal film on a substrate; forming a photoresist film on the copper-based metal film and patterning the photoresist film; and etching the copper-based metal film with the etching composition. Alternatively, a step of forming a silicon film before forming a copper-based metal film on the substrate may be further included.
One embodiment of the present invention relates to a thin film transistor (thin film transistor) array substrate including the copper-based metal wiring. For example, the thin film transistor array substrate of the present invention may be a thin film transistor array substrate for a display device, and particularly, may be a thin film transistor array substrate for a display device including a silicon semiconductor layer.
The thin film transistor array substrate according to an embodiment of the present invention may be manufactured by, for example, a) forming a gate electrode on a substrate; b) Forming a gate insulating layer on the substrate including the gate electrode; c) Forming a semiconductor layer (silicon film) on the gate insulating layer; d) Forming a source/drain electrode on the semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein each electrode is formed by etching with the etching composition in the steps a), c) and/or d).
In an embodiment of the present invention, the display device may be a liquid crystal display device, an OLED, or the like, but is not limited thereto.
The present invention will be described in more detail below with reference to examples, comparative examples and experimental examples. It is apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention and the scope of the present invention is not limited thereto.
Examples and comparative examples:
the respective components were mixed as shown in table 1 below, and water was added to make the balance 100 wt% as a whole, thereby producing an etching composition (unit: wt%).
[ Table 1]
B-1: ammonium bifluoride (Ammonium bifluoride)
C-1: 5-aminotetrazole (5-aminotetrazole)
D-1: iminodiacetic acid
E-1: ammonium dihydrogen phosphate (ammonium dihydrogen phosphate)
E-2: sodium dihydrogen phosphate (sodium dihydrogen phosphate)
E-3: potassium dihydrogen phosphate (potassium dihydrogen phosphate)
F-1: ammonium sulfate (ammonium sulfate)
F-2: sodium sulfate (sodium sulfate)
F-3: potassium sulfate (potassium sulfate)
G-1: triethylene glycol (triethylene glycol)
H-1: ammonium acetate (ammonium acetate)
Experimental example 1:
for the fabricated etching compositions, Y values defined by the following mathematical formula 1 were calculated and shown in the following table 2.
[ mathematical formula 1]
Y＝(A+B)/(C+D)
In the above-mentioned formula, the compound of formula,
a is the content of the sulfate compound,
b is the content of a water-soluble compound having a nitrogen atom and a carboxyl group,
c is the content of the phosphate compound,
d is the content of fluorine-containing compounds.
In order to evaluate the etching performance of the etching composition produced, copper-based metal wiring was produced as follows, and then the etching properties at this time were measured.
< production of copper-based Metal Wiring >
On a glass substrate (100 mm x 100 mm)
Evaporating N-type doped amorphous silicon film (N + a-Si) with thickness, sequentially evaporating Cu/MoAlTi->
The double-layer film is patterned by a photolithography process, and then an etching process is performed.
In this case, a jet etching system test facility (model name: ETCHER (TFT), SEMES) was used in the etching step, and the temperature of the etching composition in the etching step was about 33 ℃. The etching time may vary depending on the etching temperature, but is usually about 90 seconds.
(1) Etching rate of copper metal film
The etching rate was calculated by dividing the thickness of the copper (Cu) metal film by the etching time required for the copper metal film to disappear by etching, and evaluated according to the following evaluation criteria.
< evaluation criteria for etching Rate >
O: the method has the advantages of good performance,
second/second
X: in the case of a bad situation,
/sec,. Based on>
Second/second
(2) Offset variation and taper angle variation
After etching, the etching cross section was observed by SEM (S-4700, hitachi Co.) and the shift change and the taper angle change were evaluated according to the following evaluation criteria. At this time, the shift change and the taper angle change during the time when the concentration of copper in the etching composition was increased from 0ppm to 5000ppm were measured with increasing the number of processed sheets.
< evaluation criteria for offset Change >
O: good, less than delta 0.15 mu m
X: failure,. DELTA.0.15 μm or more
< evaluation criteria for taper Angle Change >
O: good at a value of 10 DEG or less
X: failure at more than Δ 10 °
(3) Residue of molybdenum alloy film
After the etching, the residue of the MoAlTi film was observed.
(4) Damage of glass substrate
The glass substrate was etched for 100 seconds, and the thickness after etching was measured, thereby measuring the etching rate.
< criteria for evaluating glass substrate Damage >
O: the method has the advantages that the quality is good,
less than second
X: failure greater than
Second/second
(5) Silicon film etching rate
After the copper-based metal film was etched from the substrate surface, the substrate was etched at intervals of 10 seconds from the time when the silicon film was exposed, and then the etched thickness was divided by the etching time by using SEM (Hitachi product, model name S-4700) to calculate the etching rate, and evaluated according to the following evaluation criteria.
< evaluation criteria for silicon film etching Rate >
O: the method has the advantages of good performance,
more than/second, is selected>
Less than second
X: poor, less than
/sec > greater than >>
Second/second
(6) Generation of precipitates
Whether or not precipitates were generated was observed before and after the etching step.
The results of the measured etching physical properties are shown in table 2 below.
[ Table 2]
As shown in table 2, it was confirmed that the etching compositions for copper-based metal films of examples 1 to 7, in which the Y value defined by formula 1 was less than 16 and the phosphate compound and the sulfate compound were ammonium salts of phosphoric acid and sulfuric acid, respectively, did not generate precipitates, exhibited excellent etching rate characteristics for the copper-based metal film, and had small variations in off-set and taper angle even though the number of processed sheets was increased, and also exhibited excellent etching rate characteristics for the silicon film.
Further, it was confirmed that the etching compositions for copper-based metal films of comparative examples 1 to 4 and 7 to 10, in which the Y value defined by the numerical formula 1 is 16 or more or the phosphate compound or the sulfate compound is a metal salt of phosphoric acid or sulfuric acid, could not simultaneously ensure the deposit generation property, the etching rate property with respect to the copper-based metal film, the shift with the increase of the number of processed sheets, the change of taper angle, and the etching rate property of the silicon film.
On the other hand, the etching composition for copper-based metal film of comparative example 5 in which the water-soluble compound having a nitrogen atom and a carboxyl group is excessive even if the Y value is less than 16 generates a molybdenum alloy film residue, and the etching composition for copper-based metal film of comparative example 6 in which the fluorine-containing compound is excessive even if the Y value is less than 16 cannot be used in the process because the glass substrate is damaged greatly.
While certain features of the invention have been described in detail above, it will be apparent to those skilled in the art that such detail is solely for that purpose and that the invention is not limited thereto. Those skilled in the art to which the invention pertains will be able to effect numerous applications and modifications within the scope of the present invention based on the foregoing.
Therefore, the actual scope of the invention is to be defined by the scope of the appended claims and their equivalents.
Claims (9)
1. An etching composition for copper-based metal films, comprising hydrogen peroxide, a fluorine-containing compound, an azole compound, a water-soluble compound having a nitrogen atom and a carboxyl group, a phosphate compound and a sulfate compound,
the phosphate compound and the sulfate compound are ammonium salts of phosphoric acid and sulfuric acid, respectively,
the Y value defined by the following mathematical formula 1 is less than 16,
mathematical formula 1
Y＝(A+B)/(C+D)
In the formula, the raw materials are mixed,
a is the content of the sulfate compound,
b is the content of a water-soluble compound having a nitrogen atom and a carboxyl group,
c is the content of the phosphate compound,
d is the content of fluorine-containing compounds.
2. The etching composition for copper-based metal film according to claim 1, wherein the copper-based metal film is a single-layer film of copper or a copper alloy; or a multilayer film including one or more films selected from a copper film and a copper alloy film and one or more films selected from a molybdenum film and a molybdenum alloy film.
3. The etching composition for copper-based metal film according to claim 1, wherein the silicon film and the copper-based metal film are etched together.
4. The etching composition for copper-based metal films according to claim 3, wherein the silicon film is one or more films selected from the group consisting of an amorphous silicon film, a hydrogenated amorphous silicon film, an N-type doped amorphous silicon film and an N-type doped hydrogenated amorphous silicon film.
5. The etching composition for copper-based metal films according to claim 1, further comprising one or more of a polyol-type surfactant and an acetate compound.
6. The etching composition for a copper-based metal film according to claim 1, comprising 5 to 25% by weight of hydrogen peroxide, 0.001 to 0.4% by weight of a fluorine-containing compound, 0.1 to 5% by weight of an azole compound, 0.1 to 3.5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group, 0.01 to 0.2% by weight of a phosphate compound, and 0.1 to 2% by weight of a sulfate compound, based on the total weight of the composition, and the balance of water for making the total weight of the composition 100% by weight.
7. A copper-based metal wiring formed using the etching composition for a copper-based metal film according to any one of claims 1 to 6.
8. A thin film transistor array substrate comprising the copper-based metal wiring of claim 7.
9. The thin film transistor array substrate of claim 8, comprising a silicon semiconductor layer.
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| KR1020210126660A KR20230043588A (en) | 2021-09-24 | 2021-09-24 | Composition for Etching Copper-Containing Metal Layer |
| KR10-2021-0126660 | 2021-09-24 |
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