CN115305472A - Etching solution composition and etching method using same - Google Patents
Etching solution composition and etching method using same Download PDFInfo
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- CN115305472A CN115305472A CN202210844846.8A CN202210844846A CN115305472A CN 115305472 A CN115305472 A CN 115305472A CN 202210844846 A CN202210844846 A CN 202210844846A CN 115305472 A CN115305472 A CN 115305472A
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- 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
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- C23F1/18—Acidic compositions for etching copper or alloys thereof
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Abstract
The invention provides an etching solution composition for etching a copper-containing metal layer. The etching solution composition contains hydrogen peroxide, an azole compound, a fluoride ion source, an inorganic acid, and an organic amine compound. Wherein the organic amine compound is a compound which does not contain an amino acid and a quaternary ammonium hydroxide, and the pH value of the etching solution composition is greater than or equal to 1.5 and less than or equal to 2.5. Therefore, the etching solution composition provided by the invention has excellent copper bearing capacity, can reduce the consumption of the etching solution, and reduces the solution changing frequency and the waste liquid output.
Description
The present invention is a divisional application based on the patent application having the application number of 2016112374052, 2016, 12 and 28, entitled "etchant composition and etching method using the same".
Technical Field
The present invention relates to an etching solution composition, and more particularly, to an etching solution composition for etching a copper-containing metal layer and an etching method using the same.
Background
The wiring material of the middle-small size lcd mainly comprises aluminum or aluminum alloy, and with the development of large-size panels, the display needs lower resistance-capacitance signal delay (RC delay), shorter charging time and lower aperture ratio, so the wiring material is turned into the search for copper and its alloy with high conductivity and better electromigration resistance.
The copper-containing wiring is fabricated by depositing a copper-containing metal layer on a substrate, determining a desired circuit pattern using a photoresist as a mask, and etching by wet etching. However, since the adhesion between the silicon-containing layer of the panel substrate and copper is poor, the copper-containing metal layer may be a single layer containing copper, or a multi-layer metal containing copper and other metals, such as copper/titanium, copper/nickel, copper/molybdenum, and copper/molybdenum nitride. The performance of the etching method described above is required to satisfy the following requirements: (1) A favorable cross-sectional shape, in which the taper angle (taper) of the copper-containing wiring cross-section is required to be a positive taper angle; (2) less etching metal residue; and (3) the distance between the end of the copper-containing wiring and the photoresist boundary (CD bias) is not less than 0.25 μm and not more than 0.75 μm.
However, in addition to the above requirements, the etching performance during the etching process needs to satisfy the above requirements, since the copper metal of the layer to be etched is dissolved into the etching solution, and the etching solution is generally used in batch, when the copper carrying capacity reaches the upper use limit, the production line needs to be halted or reduced to drain the whole batch of etching solution and replenish new etching solution to continue the production, which not only causes the production line to be stopped and the cost to be consumed, but also adds the environmental burden due to a large amount of waste liquid to be drained.
In view of the above, it is an object of the present invention to further improve the composition of the etching solution and prolong the service life of the etching solution while maintaining the stability of the etching solution.
Disclosure of Invention
The invention aims to provide an etching solution composition which has excellent copper bearing capacity, can reduce the consumption of the etching solution and reduce the solution changing frequency and the output of waste solution.
One embodiment of the present invention provides an etchant composition for etching a copper-containing metal layer, the etchant composition comprising hydrogen peroxide, an azole compound, a fluoride ion source, an inorganic acid, and an organic amine compound, wherein the organic amine compound is a compound containing no amino acid or quaternary ammonium hydroxide, and the ph of the etchant composition is 1.5 or more and 2.5 or less.
The etching solution composition according to the foregoing aspect, which may further comprise a hydrogen peroxide stabilizer.
According to the etching liquid composition of the foregoing aspect, the organic amine compound may be ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, cyclopropylamine, dipropylamine, diethylamine, n-butylamine, di-n-butylamine, isobutylamine, diisobutylamine, 1, 6-hexamethylenediamine, n-hexylamine, or sec-butylamine.
According to the etching solution composition of the foregoing aspect, the organic amine compound may be N-methylethanolamine, N-methyl-diethanolamine, N-dimethylethanolamine, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, diethylethanolamine, isopropanolamine, diisopropanolamine, diglycolamine, isobutanolamine, 2-ethylamino ethanol, or 2-methylamino ethanol.
According to the etching liquid composition of the foregoing aspect, the inorganic acid may be sulfuric acid, phosphoric acid, or nitric acid.
According to the etching solution composition of the foregoing aspect, the fluoride ion source may be hydrofluoric acid, ammonium fluoride, ammonium bifluoride, potassium fluoride, potassium bifluoride, sodium fluoride, sodium hydrogen fluoride, lithium fluoride, hexafluorosilicic acid, tetrafluoroboric acid, or potassium fluoroborate.
The etching solution composition according to the foregoing aspect includes, based on 100 weight percent of the etching solution composition, 4 to 10 weight percent of hydrogen peroxide, 0.2 to 1 weight percent of an azole compound, 0.1 to 0.5 weight percent of a fluoride ion source, 3 to 7 weight percent of an inorganic acid, and 1 to 7 weight percent of an organic amine compound. Furthermore, the etching solution composition may further comprise 0.01 to 0.1 weight percent of a hydrogen peroxide stabilizer.
According to the etching liquid composition of the foregoing aspect, the copper carrying capacity (loading capacity) of the etching liquid composition is 9000ppm or more and 15000ppm or less.
According to another aspect of the present invention, there is provided an etching method comprising contacting a copper-containing metal layer with the etching solution composition.
The above summary is intended to provide a simplified summary of the disclosure in order to provide a basic understanding to the reader of the disclosure. This summary is not an extensive overview of the disclosure and is intended to neither identify key/critical elements of the embodiments nor delineate the scope of the embodiments.
The invention includes:
1. an etching solution composition for etching a copper-containing metal layer, the etching solution composition comprising:
4 to 10 weight percent hydrogen peroxide;
0.2 to 1 weight percent of an azole compound;
0.1 to 0.5 weight percent of a fluoride ion source;
3 to 7 weight percent of an inorganic acid; and
1 to 7 weight percent of an organic amine compound,
wherein the organic amine compound is a compound not containing amino acids or quaternary ammonium hydroxides, and the pH value of the etching solution composition is greater than or equal to 1.5 and less than or equal to 2.5.
2. The etching solution composition according to item 1, further comprising a hydrogen peroxide stabilizer.
3. The etching liquid composition according to item 1, wherein the organic amine compound is ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, cyclopropylamine, dipropylamine, diethylamine, n-butylamine, di-n-butylamine, isobutylamine, diisobutylamine, 1, 6-hexamethylenediamine, n-hexylamine or sec-butylamine.
4. The etching solution composition as described in item 1, wherein the organic amine compound is N-methylethanolamine, N-methyl-diethanolamine, N-dimethylethanolamine, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, diethylethanolamine, isopropanolamine, diisopropanolamine, diglycolamine, isobutanolamine, 2-ethylamino ethanol, or 2-methylamino ethanol.
5. The etching solution composition according to item 1, wherein the inorganic acid is sulfuric acid, phosphoric acid or nitric acid.
6. The etchant composition of item 1, wherein the fluoride ion source is hydrofluoric acid, ammonium fluoride, ammonium bifluoride, potassium fluoride, potassium bifluoride, sodium fluoride, sodium bifluoride, lithium fluoride, hexafluorosilicic acid, tetrafluoroboric acid, or potassium fluoroborate.
7. The etching solution composition according to item 1, wherein the etching solution composition further comprises, based on 100 wt% of the etching solution composition:
0.01 to 0.1 weight percent of the hydrogen peroxide stabilizer.
8. The etching liquid composition as described in item 1, wherein the etching liquid composition has a copper carrying capacity of 9000ppm or more and 15000ppm or less.
9. An etching method, comprising:
contacting a copper-containing metal layer with the etching solution composition of any one of items 1 to 8.
Drawings
In order to make the aforementioned and other objects, features, advantages and embodiments of the present invention comprehensible, the following description is made with reference to the accompanying drawings:
FIG. 1A is a SEM image of a copper-containing metal layer etched by an etchant composition of example 1 at a low copper concentration;
FIG. 1B is a SEM image of a copper-containing metal layer etched by the etchant composition of example 1 at a high copper concentration;
FIG. 2A is a SEM image of a copper-containing metal layer etched with the etchant composition of example 2 at a low copper concentration;
FIG. 2B is a SEM image of a copper-containing metal layer etched by the etchant composition of example 2 at a high copper concentration;
FIG. 3A is a SEM image of a copper-containing metal layer etched by the etchant composition of example 3 at a low copper concentration;
FIG. 3B is a SEM image of a copper-containing metal layer etched by the etchant composition of embodiment 3 at a high copper concentration;
FIG. 4A is a SEM image of a copper-containing metal layer etched with the etching solution composition of example 4 at a low copper concentration; and
FIG. 4B is a SEM image of a copper-containing metal layer etched by the etchant composition of example 4 at a high copper concentration.
Detailed Description
Embodiments of the invention are discussed in more detail below. However, this embodiment may be an application of various inventive concepts, which may be embodied within various specific ranges. The particular embodiments are illustrative only and not limiting to the scope of the disclosure.
[ etching solution composition ]
The invention aims to provide an etching solution composition for etching a copper-containing metal layer, and particularly, the etching solution composition can be used for etching a single-layer metal containing copper, a multilayer metal layer such as copper/titanium, copper/nickel, copper/molybdenum nitride, molybdenum/copper/molybdenum nitride, molybdenum nitride/copper/molybdenum nitride and the like.
The etching solution composition comprises hydrogen peroxide, an azole compound, a fluoride ion source, an inorganic acid, and an organic amine compound. The azole compound and the organic amine compound are used for improving the stability of the etching solution composition, so that the etching solution composition can still maintain the etching performance under high copper concentration, wherein the azole compound is used for adjusting the lateral etching capability of the copper-containing metal layer to avoid the phenomenon of uneven etching.
In addition, during the etching process, the metal in the layer to be etched will dissolve into the etching solution to reduce the service life of the etching solution, and at present, a chelating agent is usually added into the etching solution to improve the stability of the etching solution, but the compounds such as amino acids are often not decomposed by organisms, and the Chemical Oxygen Demand (COD) or Biochemical Oxygen Demand (BOD) in the wastewater is too high. Therefore, the etching solution composition of the invention can improve the service life of the etching solution without containing compounds such as amino acids and quaternary ammonium hydroxide, so as to effectively improve the problems.
According to the etching solution composition, the pH (pH) thereof is greater than or equal to 1.5 and less than or equal to 2.5, or the pH of the etching solution composition may be 1.5 to 2.4, or the pH of the etching solution composition may be 1.99 to 2.15.
Specifically, the content of the hydrogen peroxide may be 4 to 10 wt%, or the content of the hydrogen peroxide may be 5 to 8 wt%, or the content of the hydrogen peroxide may be 5.1 to 6.9 wt%, based on 100 wt% of the etching solution composition. When the content of hydrogen peroxide is less than 4 weight%, the required etching ability may not be provided. When the content of hydrogen peroxide is more than 10% by weight, the storage property of the chemical solution may be deteriorated.
In addition, since hydrogen peroxide is decomposed and emits heat at a high copper concentration, which makes the etching rate difficult to control, and the temperature rise catalyzes the self-decomposition reaction to cause a risk, the etching solution composition may optionally include at least one additive such as a hydrogen peroxide stabilizer to improve the stability of the etching solution composition. Specifically, based on 100 wt% of the etching solution composition, the hydrogen peroxide stabilizer may be contained in an amount of 0.01 wt% to 0.1 wt%, and preferably contained in an amount of 0.02 wt% to 0.04 wt%, i.e., the etching solution composition of the present invention can obtain an etching solution composition with a low decomposition rate of hydrogen peroxide by using only a low amount of hydrogen peroxide stabilizer based on all components and the content ratio thereof. In addition, the hydrogen peroxide stabilizer used for etching the copper-containing metal layer may be phenylurea or phenolsulfonic acid and derivatives thereof, but the present invention is not intended to be limited thereto.
The fluoride ion source may be hydrofluoric acid, ammonium fluoride, ammonium bifluoride, potassium fluoride, potassium bifluoride, sodium fluoride, sodium hydrogen fluoride, lithium fluoride, hexafluorosilicic acid, tetrafluoroboric acid, or potassium fluoroborate. In addition, when the content of the fluoride ion source is too small, the desired etching capability may not be provided, but when the content of the fluoride ion source is too large, there is a possibility that the silicon-containing substrate may be damaged, so that the content of the fluoride ion source in the etching liquid composition may be 0.1 to 0.5 wt% based on 100 wt% of the etching liquid composition.
The inorganic acid may be sulfuric acid, phosphoric acid or nitric acid, and the content of the inorganic acid may be 3 to 7 wt%, or 3 to 6 wt%, or 3.5 to 5.01 wt% based on 100 wt% of the etching solution composition. Further, the aforementioned acids may be used alone, or two or more of them may be used simultaneously. In other words, the inorganic acid may be used alone or in combination of two or more.
Furthermore, the azole compound may be contained in an amount of 0.2 to 1 wt% based on 100 wt% of the etching solution composition, and the azole compound may be triazole, tetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, thiazole, pyrrolidine, or pyrroline and derivatives thereof. Furthermore, in an acidic environment, the azole compound can control the etching rate of the copper-containing metal layer to avoid the uneven etching, and the content of the azole compound in the etching solution composition of the present invention can be preferably increased to 0.4 wt% to 1 wt% to increase the etching uniformity.
Then, as mentioned above, the organic amine compound is used to improve the stability of the etchant composition, so that the proper amount of the organic amine compound can maintain the etching performance of the etchant composition even at high copper concentration. On the contrary, when the content of the organic amine compound is too small, the stability of the etching solution composition is affected, so that the etching rate cannot be maintained in the later etching period, and the production efficiency is further reduced. Therefore, the content of the organic amine compound may be 1 to 7 wt%, or the content of the organic amine compound may be 1 to 5 wt%, or the content of the organic amine compound may be 1.7 to 4 wt%, based on 100 wt% of the etching solution composition. Based on the use of the azole compound, the organic amine compound may be any one or a combination of a plurality of aliphatic amine compounds, alcohol amine compounds or other organic amines, that is, only one organic amine compound may be used, or two or more organic amine compounds may be used at the same time. It should be noted that, in the present invention, the organic amine compound does not include amino acids and quaternary ammonium hydroxide compounds in order to avoid the environmental burden while increasing the lifetime of the etching solution composition.
Specifically, when the organic amine compound is a fatty amine compound, it may be ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, cyclopropylamine, dipropylamine, diethylamine, n-butylamine, di-n-butylamine, isobutylamine, diisobutylamine, 1, 6-hexamethylenediamine, n-hexylamine or sec-butylamine. And when the organic amine compound is an alcohol amine compound, it may be N-methylethanolamine, N-methyl-diethanolamine, N-dimethylethanolamine, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, diethylethanolamine, isopropanolamine, diisopropanolamine, diglycolamine, isobutanolamine, 2-ethylamino ethanol, or 2-methylamino ethanol.
In addition, the etching solution composition uses water as a solvent, and the water can be, but is not limited to, distilled water, deionized water, and preferably deionized water. In addition, the amount of water varies depending on the sum of the amounts of other components in the etchant composition, and in the presence of the other components, water is added to make the amount of the etchant composition 100% by weight, in other words, the sum of the amounts of hydrogen peroxide, azole compound, fluoride ion source, inorganic acid, organic amine compound, water, and additives which may be contained is 100% by weight.
Therefore, the etching solution composition can make the CD difference of the copper-containing wiring fall within the acceptable range of more than or equal to 0.25 micrometer and less than or equal to 0.75 micrometer within the range of the Over-etching rate (Over etching rate) required by the actual production line, and can maintain the etching performance from low copper concentration to high copper concentration. Particularly, based on the combination of the components and the proportion thereof, the copper bearing capacity of the etching solution composition can be increased to 9000ppm to 15000ppm.
It should be noted that the aforementioned "high copper concentration" refers to a copper ion concentration of more than 6000ppm, and the aforementioned "post-etching period" refers to a period of time in which the copper ion concentration of the etching solution composition is more than 6000ppm after the etching solution composition is used for etching (usually after multiple etching). In contrast, "low copper concentration" means a copper ion concentration of 0 or more and 6000ppm or less.
[ etching method ]
An etching method comprises contacting a copper-containing metal layer with the etching solution composition, wherein the copper-containing metal layer may be a copper-containing single-layer metal or a copper-containing multi-layer metal (such as copper/titanium), and the details thereof are as described above and will not be described herein again.
Based on the above embodiments, specific examples are provided below to illustrate the etchant composition of the present invention and its achievable effects.
[ examples ]
First, the etching solution compositions of examples 1 to 4 were prepared. The ph values of the etching solution compositions of examples 1 to 4 are shown in table 1, and the components of the etching solution compositions of examples 1 to 4 are shown in table 2.
TABLE 1 pH of etching solution compositions of examples 1 to 4
| Examples | 1 | 2 | 3 | 4 |
| pH value of the product | 1.99 | 2.15 | 2.14 | 2.05 |
TABLE 2 Components of etching solution compositions of examples 1 to 4 (unit: weight percent)
Then, 500 angstroms are deposited on the glass substrate sequentially
The titanium layer and the 3000 angstrom copper layer form a copper/titanium double-layer metal layer, and then a photoresist is coated on the glass substrate deposited with the double-layer metal layer, and exposure and development are carried out to form a photomask. Subsequently, the etching solution compositions of examples 1 to 4 are used to etch the double-layer metal layer at an etching temperature of 30 ℃ to 35 ℃. At this time, etching performances of examples 1 to 4 are shown in table 3 below.
In table 3, the total etching time refers to the time taken from the start of etching to the end of etching. The etching angle (i.e., the Taper angle, taper), CD difference and chamfer angle are cross-sectional views of the glass substrate deposited with the double metal layer after being etched by the etching solution compositions of examples 1 to 4 respectively, observed by scanning electron microscope image. And measuring the angle of the section of the double-layer metal layer of the obtained section after cutting the glass substrate deposited with the double-layer metal layer, namely the etching angle. The chamfering is an angle at which the bottom of the cross section of the double metal layer is connected to the glass substrate, and if the angle is larger than 90 degrees, it is judged as chamfering and evaluated as "x", and if no chamfering is found, it is evaluated as "o". For CD difference, the horizontal distance from the photoresist end point to the bottom end point of the bilayer metal layer is measured.
In addition, as mentioned above, the low copper concentration refers to the copper ion concentration in the etching solution composition at the first etching, and the copper ion content of the etching solution composition before etching is about 0ppm. The term "high copper concentration" refers to the concentration of copper ions contained in the etching solution composition after etching the metal layer for a plurality of times, and refers to the maximum copper carrying capacity of each example, for example, the difference between the etching angle and the CD measured in example 1 at a high copper concentration refers to the etching performance when etching the double-layer metal layer with the etching solution composition containing copper ions at a concentration of about 9000ppm.
Table 3 etching performance of examples 1 to 4
Referring to table 3 together with fig. 1A to 4B, fig. 1A and 1B are scanning electron microscope images obtained by etching a copper-containing metal layer at low copper concentration and high copper concentration by using the etchant composition of embodiment 1 of the present invention, fig. 2A and 2B are scanning electron microscope images obtained by etching a copper-containing metal layer at low copper concentration and high copper concentration by using the etchant composition of embodiment 2 of the present invention, fig. 3A and 3B are scanning electron microscope images obtained by etching a copper-containing metal layer at low copper concentration and high copper concentration by using the etchant composition of embodiment 3 of the present invention, and fig. 4A and 4B are scanning electron microscope images obtained by etching a copper-containing metal layer at low copper concentration and high copper concentration by using the etchant composition of embodiment 4 of the present invention, respectively.
First, as shown in table 3 and fig. 1A to 1B, a copper/titanium double-layer metal layer is etched using the etchant composition according to embodiment 1 of the present invention, wherein the organic amine compound in the etchant composition of embodiment 1 is an alcohol amine compound, and the organic amine compound is specifically isopropanolamine. Further, the azole compound in example 1 is 5-amino-1H-1, 2,3, 4-tetrazole. In this case, as can be seen from Table 3, the CD difference between the low copper concentration and the high copper concentration is 0.41 μm and 0.67 μm, respectively, both falling within the standard range of 0.25 μm to 0.75. Mu.m. In addition, the etching angle at the time of low copper concentration was 53 degrees and the etching angle at the time of high copper concentration was 42 degrees, which also fell within the standard range of 30 to 60 degrees, and it was found from fig. 1A and 1B that the copper/titanium double-layer metal layer was etched with the etching solution composition of example 1 of the present invention at both the low copper concentration and the high copper concentration without chamfering, i.e., both were evaluated as "o".
Next, as shown in table 3 and fig. 2A to 4B, the copper/titanium double-layer metal layer is etched by using the etching solution compositions according to embodiments 2 to 4 of the present invention, wherein the organic amine compound in the etching solution compositions of embodiments 2 to 4 is a fatty amine compound, and specifically, ethylenediamine. In addition, the azole compound in example 2 is also 5-amino-1H-1, 2,3, 4-tetrazole. At this time, as can be seen from table 3, the CD difference between the low copper concentration and the high copper concentration of examples 2 to 4 falls within the standard range of 0.25 μm to 0.75 μm. In addition, the etching angles of examples 2 to 4 were 48 degrees, 35 degrees, and 36 degrees at low copper concentrations, and 45 degrees, 43 degrees, and 45 degrees at high copper concentrations, respectively, all falling within the standard range of 30 degrees to 60 degrees. And it can be seen from fig. 2A to 4B that the etching solution compositions of examples 2 to 4 did not have a chamfer when etching the copper/titanium double-layer metal layer at both low and high copper concentrations, i.e., all were evaluated as "o".
It can be seen that even though the concentration of copper ions contained in the etching solution composition of example 4 is up to 15000ppm, the etching performance (CD difference of 0.72 μm, etching angle of 45 °) can be maintained within the standard range, i.e. the maximum copper carrying capacity of the etching solution composition of example 4 of the present invention can be up to 15000ppm. Similarly, the maximum copper carrying capacity of the etching solution compositions of examples 2 and 3 can also reach 9000ppm.
[ comparative example ]
Next, etching solution compositions of comparative examples 1 to 4 were prepared; the ph and the components of the etching solution compositions of comparative examples 1 to 4 are shown in table 4, wherein the ph and the component ratio of the etching solution compositions of comparative examples 1 and 3 are out of the range, the component ratio of the etching solution compositions of comparative examples 2 is out of the range, the organic amine compound is not added, and the ph and the component ratio of the etching solution compositions of comparative examples 4 are out of the range. The etching performance of the etching solution compositions of comparative examples 1 to 4 was recorded by the same etching method and evaluation standard as those of the examples, and is shown in table 5.
TABLE 4 pH and composition of comparative examples 1 to 4 (unit: weight percent)
TABLE 5 etching Performance of comparative examples 1 to 4
As shown in comparative examples 1 and 2, when the ph of the etchant composition is less than 1.5, the etching rate of copper is too high regardless of the addition of the organic amine compound, which causes uneven etching and failure in patterning. On the contrary, as shown in comparative example 3, when the ph of the etchant composition is greater than 2.5, the etching rate of copper is too slow, which may cause uneven etching and failure of patterning. The concentration of the inorganic acid and the organic amine compound in the etchant composition provided in comparative example 4 exceeds 7 wt%, and even though etching at a low copper concentration (3000 ppm) still has a certain etching performance, the etching rate is also slowed down at a high copper concentration (6000 ppm), which results in uneven etching and non-patterning.
Accordingly, the etching solution composition provided by the invention simultaneously comprises hydrogen peroxide, azole compounds, fluoride ion source, inorganic acid and organic amine compounds, so that the etching solution composition can maintain good etching performance under a high copper concentration of 9000ppm to 15000ppm, namely the etching solution composition has excellent copper bearing capacity and longer service life, can reduce the consumption of the etching solution, reduce the solution changing frequency and the output of waste liquid, and simultaneously meets the current requirement on environmental protection.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. An etching solution composition for etching a copper-containing metal layer, the etching solution composition comprising:
4 to 10 weight percent hydrogen peroxide;
0.4 to 1 weight percent of an azole compound;
0.1 to 0.5 weight percent of a fluoride ion source;
3 to 7 weight percent of an inorganic acid; and
1 to 7 weight percent of an organic amine compound,
wherein the organic amine compound is a compound which does not contain amino acids or quaternary ammonium hydroxide, and the pH value of the etching solution composition is greater than or equal to 1.5 and less than or equal to 2.5,
wherein the organic amine compound is ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, dipropylamine, diethylamine, di-n-butylamine, isobutylamine, diisobutylamine, 1, 6-hexamethylenediamine, n-hexylamine or sec-butylamine, or
Wherein the organic amine compound is N-methylethanolamine, N-methyl-diethanolamine, N-dimethylethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, diethylethanolamine, isopropanolamine, diisopropanolamine, diglycolamine, isobutanolamine, 2-ethylamino ethanol or 2-methylamino ethanol,
wherein the inorganic acid is nitric acid.
2. An etching solution composition for etching a copper-containing metal layer, the etching solution composition comprising:
4 to 10 weight percent hydrogen peroxide;
0.2 to 1 weight percent of an azole compound;
0.1 to 0.5 weight percent of a fluoride ion source;
3 to 7 weight percent of an inorganic acid; and
1 to 2.13 weight percent of an organic amine compound,
wherein the organic amine compound is a compound containing no amino acid or quaternary ammonium hydroxide, and the pH of the etching solution composition is greater than or equal to 1.5 and less than or equal to 2.5,
wherein the organic amine compound is diethylenetriamine, triethylenetetramine, diethylamine, 1, 6-hexamethylenediamine or n-hexylamine, or
Wherein the organic amine compound is N-methylethanolamine, N-methyl-diethanolamine, triethanolamine, diisopropanolamine or diglycolamine,
wherein the inorganic acid is nitric acid.
3. The etching solution composition as claimed in claim 1 or 2, further comprising a hydrogen peroxide stabilizer.
4. The etchant composition of claim 1 or 2, wherein the fluoride ion source is hydrofluoric acid, ammonium fluoride, ammonium bifluoride, potassium fluoride, potassium bifluoride, sodium fluoride, sodium hydrogen fluoride, lithium fluoride, hexafluorosilicic acid, tetrafluoroboric acid, or potassium fluoroborate.
5. The etching solution composition according to claim 1 or 2, wherein the etching solution composition further comprises, based on 100 weight percent of the etching solution composition:
0.01 to 0.1 weight percent of the hydrogen peroxide stabilizer.
6. The etching solution composition as claimed in claim 1 or 2, wherein the copper carrying capacity of the etching solution composition is greater than or equal to 9000ppm and less than or equal to 15000ppm.
7. An etching method, comprising:
contacting a copper-containing metal layer with the etching solution composition of any one of claims 1 to 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104144243A TWI618817B (en) | 2015-12-29 | 2015-12-29 | Etchant composition and etching method using thereof |
| TW104144243 | 2015-12-29 | ||
| CN201611237405.2A CN106929853A (en) | 2015-12-29 | 2016-12-28 | Etching solution composition and etching method using same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611237405.2A Division CN106929853A (en) | 2015-12-29 | 2016-12-28 | Etching solution composition and etching method using same |
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| WO2019033307A1 (en) * | 2017-08-16 | 2019-02-21 | 深圳市柔宇科技有限公司 | Waste liquid storage device and wet etching system |
| JP6443649B1 (en) * | 2018-03-23 | 2018-12-26 | パナソニックＩｐマネジメント株式会社 | Etching solution for copper thick film |
| TWI646222B (en) * | 2018-04-25 | 2019-01-01 | 達興材料股份有限公司 | Etching liquid composition for etching a multilayer film containing a copper or copper alloy layer and a molybdenum or molybdenum alloy layer, an etching method using the etching liquid composition, and a method for manufacturing a display device or an IGZO-containing semiconductor using the etching method |
| CN111286738A (en) * | 2020-01-17 | 2020-06-16 | 江阴江化微电子材料股份有限公司 | Production process of acidic copper etching solution |
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| TWI495763B (en) * | 2013-11-01 | 2015-08-11 | Daxin Materials Corp | Etchant composition and etching method |
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| TW201723228A (en) | 2017-07-01 |
| TWI618817B (en) | 2018-03-21 |
| CN106929853A (en) | 2017-07-07 |
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