Etching liquid composition

Abstract

The present invention relates to an etching liquid composition comprising: hydrogen peroxide; a carboxyl compound; a fluorine-containing compound; and a nitrogen-containing cyclic compound, in which the content of the hydrogen peroxide is 0.001 wt% to 4 wt%. Moreover, the present invention relates to an etching liquid composition comprising: hydrogen peroxide; a carboxyl compound; a fluorine-containing compound; and a nitrogen-containing cyclic compound; wherein the weight ratio of the fluorine-containing compound to the nitrogen-containing cyclic compound is 1: 0.01 to 1: 3.

Description

Technical Field

[0001] This invention relates to an etching solution composition, and more specifically, to an etching solution composition for etching metal wiring films. Background Technology

[0002] With the development of the display field that presents various electrical signal information in a visual way, various flat panel display devices with excellent characteristics such as thinness, light weight, and low power consumption are constantly being researched and developed.

[0003] On the other hand, as the display area of ​​display devices increases, the various wirings and electrodes contained in the display devices need to be formed of materials with the lowest possible resistivity. Therefore, the various wirings and electrodes contained in the display devices can contain metals.

[0004] Furthermore, various wirings and electrodes contained in a display device can be formed by patterning processes such as photolithography, including etching. However, when wirings or electrodes are composed of multilayer films with different properties, there are limitations to forming wirings or electrodes with the desired characteristics by etching. Summary of the Invention

[0005] Technical issues

[0006] The purpose of this invention is to provide an etching solution composition that gives a metal wiring film an excellent etching profile after etching.

[0007] Furthermore, the present invention aims to provide an etching solution composition that can reduce damage to the upper layer film and minimize undercut of the lower layer film when the metal wiring film is a multilayer film.

[0008] In addition, the present invention aims to provide a method for etching a metal wiring film using the above-described etching solution composition.

[0009] The technical problem of this invention is not limited to the technical problem described above. Through the following description, those skilled in the art can clearly understand other technical problems that are not mentioned.

[0010] Technical solution

[0011] To achieve the above objectives, the present invention provides an etching solution composition comprising: hydrogen peroxide; a carboxyl compound; a fluorine-containing compound; and a nitrogen-containing cyclic compound; wherein the content of the hydrogen peroxide is from 0.001% to 4% by weight.

[0012] Furthermore, the present invention provides an etching solution composition comprising: hydrogen peroxide; a carboxyl compound; a fluorinated compound; and a nitrogen-containing cyclic compound; wherein the weight ratio of the fluorinated compound to the nitrogen-containing cyclic compound is from 1:0.01 to 1:3.

[0013] The above etching solution composition may include: 0.1% to 5% by weight of a carboxyl compound; 0.01% to 2% by weight of a fluorine-containing compound; 0.001% to 1% by weight of a nitrogen-containing cyclic compound; and the balance being water.

[0014] The above-mentioned etching solution composition may further include at least one of the following: 1% to 5% by weight of a diol compound, 0.01% to 5% by weight of a phosphate compound, 0.001% to 2% by weight of an acetate, and 0.001% to 1% by weight of an amino acid derivative.

[0015] The aforementioned amino acid derivatives may be selected from the group consisting of L-pyroglutamic acid, sodium pyrrolidinecarboxylate, zinc pyrrolidinecarboxylate, and combinations thereof.

[0016] The weight ratio of hydrogen peroxide to fluorine-containing compounds can be from 1:0.01 to 1:9.

[0017] The weight ratio of hydrogen peroxide to nitrogen-containing cyclic compounds can be from 1:0.1 to 1:1.5.

[0018] The weight ratio of the above-mentioned fluorine-containing compound to the above-mentioned nitrogen-containing cyclic compound can be from 1:0.1 to 1:3.

[0019] The aforementioned carboxyl compound can be at least one selected from the group consisting of iminodiacetic acid, oxalic acid, acetic acid, formic acid, acrylic acid, lactic acid, amino acids, propionic acid, oleic acid, benzoic acid, salicylic acid, malic acid, and combinations thereof.

[0020] The aforementioned diol compounds may be at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and combinations thereof.

[0021] The aforementioned phosphate compound may be at least one selected from the group consisting of monoammonium phosphate, monosodium phosphate, disodium phosphate, diammonium phosphate, trisodium phosphate, and combinations thereof.

[0022] The aforementioned acetate can be at least one selected from the group consisting of ammonium acetate, sodium acetate, potassium acetate, and combinations thereof.

[0023] The aforementioned fluorine-containing compound may be at least one selected from the group consisting of ammonium hydrogen fluoride (NH4F·HF), ammonium fluoride (NH4F), sodium hydrogen fluoride (NaHF2), sodium fluoride (NaF), potassium hydrogen fluoride (KHF2), potassium fluoride (KF), hydrofluoric acid (HF), and combinations thereof.

[0024] The nitrogen-containing cyclic compounds mentioned above may not contain alkyl or aryl groups.

[0025] The aforementioned nitrogen-containing cyclic compounds may be at least one selected from the group consisting of benzotriazole, aminotetrazole, methyltetrazole, aminomercaptotriazole, and combinations thereof.

[0026] The metal concentration in the above etching solution can be below 500 ppm.

[0027] The above-mentioned etching solution composition can be used to etch metal films including at least one selected from the group consisting of copper, molybdenum, titanium and molybdenum-titanium alloys.

[0028] The above-mentioned etching solution composition can be an etching solution composition used for semiconductor packaging.

[0029] Beneficial effects

[0030] The present invention can provide an etching solution composition that gives the metal wiring film an excellent etching profile after etching.

[0031] In addition, an etching solution composition can be provided that reduces damage to the upper layer and minimizes undercut of the lower layer when the metal wiring film is a multilayer film.

[0032] The effects of this invention are not limited to those described above, and should be understood to include all effects inferred from the structure of the invention as described in the detailed description or claims. Detailed Implementation

[0033] Embodiments of the invention will be described in more detail below. However, this is provided by way of example only, and the invention is not limited thereto; it is defined only by the scope of the appended claims.

[0034] In one embodiment of the present invention, an etching solution composition comprising hydrogen peroxide, a carboxyl compound, a fluorine-containing compound, and a nitrogen-containing cyclic compound is provided.

[0035] In one embodiment, the above-described etching solution composition can be used to etch a metal film comprising at least one selected from the group consisting of copper, molybdenum, titanium, and molybdenum-titanium alloys.

[0036] In one embodiment, the metal film may be a single-layer metal film containing copper, or a multilayer film with two or more layers (multiple films).

[0037] The aforementioned multilayer films may include, for example, copper / titanium bilayer films with titanium metal films as the lower layer and copper metal films as the upper layer, titanium / copper bilayer films with copper metal films as the lower layer and titanium metal films as the upper layer, bilayer films of copper metal films / molybdenum-titanium alloy films, and multilayer films of three or more layers in which copper metal films / copper metal films / titanium metal films or copper metal films / titanium metal films / copper metal films, etc., are stacked alternately.

[0038] In one embodiment, the multilayer film can be a copper / titanium film bilayer film with a titanium metal film as the lower layer and a copper metal film as the upper layer.

[0039] In one embodiment, hydrogen peroxide, as an oxidant for copper and titanium metal films, can be used as a major component in etching metal films.

[0040] Based on the total weight of the etching solution composition, the hydrogen peroxide content can be from 0.001 wt% to 4 wt%, 0.001 wt% to 3 wt%, 0.001 wt% to 2 wt%, 0.001 wt% to 1.5 wt%, 0.001 wt% to 1.2 wt%, or 0.001 wt% to 1 wt%. When the etching solution composition contains hydrogen peroxide within the above-mentioned numerical range, damage to the copper metal film as the upper layer can be reduced, and undercut of the titanium metal film as the lower layer can be decreased.

[0041] In one embodiment, the carboxyl compound can be used as a chelating agent for titanium ions to control the reaction between hydrogen peroxide and titanium ions, and can be used as a component for selectively oxidizing and etching titanium metal films without etching copper metal films.

[0042] For example, the aforementioned carboxyl compounds may include at least one selected from the group consisting of iminodiacetic acid, oxalic acid, acetic acid, formic acid, acrylic acid, lactic acid, amino acids, propionic acid, oleic acid, benzoic acid, salicylic acid, malic acid, and combinations thereof.

[0043] In one embodiment, the carboxyl compound may include iminodiacetic acid.

[0044] Based on the total weight of the etching solution composition, the content of the aforementioned carboxyl compound can be from 0.1 wt% to 5 wt%, 0.1 wt% to 4 wt%, 0.2 wt% to 3 wt%, 0.3 wt% to 2 wt%, or 0.5 wt% to 2 wt%. When the etching solution composition contains carboxyl compounds within the above numerical ranges, the etching performance can be improved by selectively oxidizing the Ti film by controlling the reaction between hydrogen peroxide and titanium ions.

[0045] In one embodiment, the fluorine-containing compound can be used as an oxidizing etchant for titanium metal films.

[0046] For example, the aforementioned fluorine-containing compounds may include at least one selected from the group consisting of ammonium hydrogen fluoride (NH4F·HF), ammonium fluoride (NH4F), sodium hydrogen fluoride (NaHF2), sodium fluoride (NaF), potassium hydrogen fluoride (KHF2), potassium fluoride (KF), hydrofluoric acid (HF), and combinations thereof.

[0047] In one embodiment, the fluorinated compound may include ammonium hydrogen fluoride.

[0048] Based on the total weight of the etching solution composition, the content of the aforementioned fluorinated compound can be from 0.01 wt% to 2 wt%, 0.04 wt% to 2 wt%, 0.08 wt% to 2 wt%, 0.1 wt% to 2 wt%, or 0.5 wt% to 1 wt%. When the etching solution composition contains fluorinated compounds within the above numerical ranges, the etching rate can be easily adjusted.

[0049] In one embodiment, the aforementioned nitrogen-containing cyclic compound can be used as a corrosion inhibitor to slow down the etching rate of copper and titanium metal films.

[0050] In one embodiment, the nitrogen-containing cyclic compound may not contain alkyl and aryl groups.

[0051] For example, the nitrogen-containing cyclic compounds mentioned above may include at least one selected from the group consisting of benzotriazole, aminotetrazole, methyltetrazole, aminomercaptotriazole, and combinations thereof.

[0052] In one embodiment, the nitrogen-containing cyclic compound may include aminotetrazole.

[0053] Based on the total weight of the etching solution composition, the content of the aforementioned nitrogen-containing cyclic compound can be from 0.001 wt% to 1 wt%, 0.008 wt% to 0.9 wt%, 0.01 wt% to 0.8 wt%, 0.1 wt% to 0.7 wt%, or 0.15 wt% to 0.5 wt%. When the etching solution composition contains nitrogen-containing cyclic compounds within the above numerical ranges, the etching rate can be easily adjusted.

[0054] In one embodiment, the weight ratio of hydrogen peroxide to the fluorine-containing compound can be 1:0.01 to 1:9, 1:0.90 to 1:7, 1:1 to 1:6, 1:1.2 to 1:5, 1:1.5 to 1:4, or 1:1.8 to 1:3.6. When the weight ratio of hydrogen peroxide to the fluorine-containing compound meets the above-mentioned numerical range, damage to the copper metal film as the upper layer can be reduced, and the undercut of the titanium metal film as the lower layer can be decreased.

[0055] In one embodiment, the weight ratio of hydrogen peroxide to the nitrogen-containing cyclic compound can be 1:0.1 to 1:1.5, 1:0.2 to 1:1.4, 1:0.3 to 1:1.3, 1:0.4 to 1:1.2, 1:0.5 to 1:1.1, or 1:0.68 to 1:1. When the weight ratio of hydrogen peroxide to the nitrogen-containing cyclic compound meets the above-mentioned numerical range, damage to the copper metal film as the upper layer can be reduced, and the undercut of the titanium metal film as the lower layer can be decreased.

[0056] In one embodiment, the weight ratio of the fluorinated compound to the nitrogen-containing cyclic compound can be 1:0.01 to 1:3, 1:0.05 to 1:2.7, 1:0.08 to 1:2.3, 1:0.1 to 1:2.3, 1:0.12 to 1:2.0, or 1:0.15 to 1:0.19. When the weight ratio of the fluorinated compound to the nitrogen-containing cyclic compound meets the above-mentioned numerical range, damage to the copper metal film as the upper layer can be reduced, and the undercut of the titanium metal film as the lower layer can be decreased.

[0057] In one embodiment, the etching solution composition may further include at least one of diol compounds, phosphate compounds, acetate compounds, and amino acid derivatives.

[0058] In one embodiment, the aforementioned diol compound can be used as a stabilizer for hydrogen peroxide, serving as a component to suppress the decrease in stability caused by the exothermic reaction resulting from the decomposition of hydrogen peroxide and the reduction in the amount of titanium metal film processed.

[0059] The aforementioned diol compounds may include at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and combinations thereof.

[0060] In one embodiment, the aforementioned diol compound may include triethylene glycol.

[0061] Based on the total weight of the etching solution composition, the content of the aforementioned diol compounds can be from 1% to 5% by weight, 1% to 4% by weight, 1% to 3% by weight, or 1% to 2% by weight. When the etching solution composition contains diol compounds within the above numerical range, the hydrogen peroxide decomposition reaction that may occur during repeated use of the etching solution can be suppressed, thereby ensuring the stability of the etching solution.

[0062] In one embodiment, the phosphate compound can be used as an auxiliary oxidizing etchant for titanium metal films, serving as a component to prevent a decrease in etching rate and to adjust the cone angle during pattern formation.

[0063] The aforementioned phosphate compounds may include at least one selected from the group consisting of monoammonium phosphate, monosodium phosphate, disodium phosphate, diammonium phosphate, trisodium phosphate, and combinations thereof.

[0064] In one embodiment, the phosphate compound may include monoammonium phosphate.

[0065] Based on the total weight of the etching solution composition, the content of the phosphate compound can be from 0.01 wt% to 5 wt%, 0.03 wt% to 4 wt%, 0.05 wt% to 3 wt%, 0.08 wt% to 2 wt%, or 0.1 wt% to 1 wt%. When the etching solution composition contains phosphate compounds within the above numerical ranges, it can prevent a decrease in etching rate and help pattern formation by adjusting the cone angle.

[0066] In one embodiment, the acetate can be used as a pH adjuster, serving as a component to slow down the etching rate of the copper metal film and increase the etching rate of the titanium metal film by increasing the pH value of the etching solution.

[0067] The aforementioned acetate may include at least one selected from the group consisting of ammonium acetate, sodium acetate, potassium acetate, and combinations thereof.

[0068] In one embodiment, the acetate may include ammonium acetate.

[0069] Based on the total weight of the etching solution composition, the content of the acetate can be from 0.001 wt% to 2 wt%, 0.005 wt% to 1.5 wt%, 0.008 wt% to 1 wt%, 0.01 wt% to 0.7 wt%, or 0.05 wt% to 0.5 wt%. When the etching solution composition contains acetate within the above-mentioned numerical range, the pH of the etching solution can be adjusted to allow hydrogen peroxide to etch the titanium metal film more effectively.

[0070] In one embodiment, the above-mentioned amino acid derivative can be used as a service life improver, serving as a component to prevent changes in etching rate due to the increase in the cumulative number of titanium metal films.

[0071] In one embodiment, the amino acid derivative may include a pyrrolidone derivative.

[0072] For example, the aforementioned pyrrolidone derivatives may include one selected from the group consisting of L-pyroglutamic acid, sodium pyrrolidone carboxylate, zinc pyrrolidone carboxylate, and combinations thereof.

[0073] In one embodiment, the amino acid derivative may include L-pyroglutamic acid.

[0074] Based on the total weight of the etching solution composition, the content of the above-mentioned amino acid derivatives can be 0.001 wt% to 1 wt%, 0.005 wt% to 1 wt%, 0.008 wt% to 1 wt%, 0.01 wt% to 1 wt%, 0.05 wt% to 1 wt%, or 0.1 wt% to 1 wt%. When the above-mentioned etching solution composition contains amino acid derivatives within the above-mentioned numerical ranges, the stability of the etching solution composition can be improved, thereby extending its service life.

[0075] In one embodiment, the weight ratio of hydrogen peroxide to amino acid derivative can be 1:0.001 to 1:20, 1:0.005 to 1:15, 1:0.01 to 1:10, 1:0.05 to 1:5, or 1:0.1 to 1:2. When the weight ratio of hydrogen peroxide to amino acid derivative meets the above-mentioned numerical range, a high cumulative number of processed tablets can be maintained.

[0076] In one embodiment, the weight ratio of the carboxyl compound to the amino acid derivative can be 1:0.002 to 1:20, 1:0.004 to 1:17, 1:0.008 to 1:14, 1:0.01 to 1:9, 1:0.08 to 1:5, or 1:0.2 to 1:2. When the weight ratio of the carboxyl compound to the amino acid derivative meets the above-mentioned numerical range, a high cumulative number of processed tablets can be maintained.

[0077] In one embodiment, in addition to the above-described components, the etching solution composition may also include a balance of water.

[0078] In one embodiment, the above-described etching solution composition can be used for semiconductor packaging.

[0079] In one embodiment, the metal concentration in the etching solution can be below 500 ppm. When the metal concentration in the etching solution falls within the above-mentioned value range, the performance and safety of the etching solution can be maintained. That is, when the metal concentration in the etching solution is between 0 ppm and 500 ppm, etching performance and stability can be maintained, thereby increasing the cumulative number of wafers processed.

[0080] In one embodiment of the present invention, an etching method for a metal film is provided, the method comprising the step of etching a metal film (or metal wiring film) formed on a substrate using an etching solution prepared from the above-described etching solution composition.

[0081] In one embodiment, the substrate can be a glass substrate with silicon dioxide (SiO2) as the main component or a substrate made of transparent plastic. Specifically, the substrate made of plastic can be polyethersulfone (PES), polyacrylate, polyetherimide, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide (PPS), polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate (CAP), etc. However, the technical concept of the present invention is not limited to this, and can also be applied to various substrates in the fields of displays and semiconductors.

[0082] In one embodiment, the metal film may be a single-layer metal film containing copper, or a multilayer film with two or more layers (multiple films).

[0083] In one embodiment, the method for forming the metal film described above can employ a common deposition method commonly used in the art.

[0084] In one embodiment, when etching the copper / titanium metal film bilayer film using an etching solution prepared from the above-described etching solution composition, the undercut of the titanium metal film can be 150 nm or less.

[0085] When the undercut is below 150nm, the contact area between the UBM and the bump increases, the reliability of the bump is improved, which helps to form high-performance integrated circuits.

[0086] In one embodiment, when the target film (metal film) is etched using an etchant prepared from the above-described etchant composition, the linewidth of the etched pattern can be less than 2 μm.

[0087] When the linewidth of the above pattern is less than 2μm, a microcircuit structure with higher integration than existing technologies can be realized. Furthermore, since ICs can be embedded on one or both sides of the substrate, thin-film integration can be achieved through substrate stacking. In particular, it can be applied to UBM processes.

[0088] In this specification, the term "UBM (Under-Bump Metallization)" refers to a multilayer metal layer formed between the electrodes and bumps to facilitate adhesion and prevent diffusion into the chip, since it is difficult to form solder balls or bumps directly on the electrodes of a semiconductor chip.

[0089] The above description illustrates the technical concept of the present invention through one embodiment. Those skilled in the art can make various modifications and variations without departing from the essential characteristics of the invention. Therefore, the embodiments described in this invention are not intended to limit the technical concept of the invention, but are merely illustrative, and the scope of the technical concept of the invention should not be limited solely by these embodiments. The scope of protection of this invention should be interpreted by the claims, and all technical concepts falling within the equivalent scope should be considered to fall within the scope of the claims of this invention.

[0090] Example

[0091] [Preparation Examples and Comparative Preparation Examples] Preparation of Etching Solution Compositions

[0092] The etching solution composition was prepared according to the composition shown in Tables 1 and 2 below, and the balance water was added so that the total weight of the etching solution composition was 100% by weight.

[0093] Except for Preparation Examples 5 to 16 in Table 1 below, all others used L-pyroglutamic acid as an amino acid derivative.

[0094] Table 1

[0095]

[0096]

[0097]

[0098] Table 2

[0099]

[0100] [Experimental Example]

[0101] Metal concentration in the etching solution used to confirm the cumulative number of wafers processed.

[0102] Etching solutions with concentrations shown in Tables 3 and 4 were prepared by adding titanium powder to the etching solution compositions obtained in Tables 1 and 2. (Examples 1 to 83 and Comparative Examples 1 to 10)

[0103] Using etching solutions with concentrations shown in Tables 3 and 4, the substrate (2x2cm) with deposited Ti was etched. 2 The Ti film was etched, and the time required for etching was measured. The etching time of the Ti film was based on the etch endpoint detection (EPD) of the Ti film as detected by the naked eye.

[0104] The criteria for determining the cumulative number of processed wafers are as follows: if the difference between the etching time measured using a contaminated etching solution and the time measured using a clean etching solution without added titanium powder is greater than 1 second, the etching performance is considered unsustainable, and the maximum metal concentration value at which the etching performance can be maintained is recorded. The higher the contamination level (i.e., metal concentration) of the etching solution at which the etching performance can be maintained, the greater the cumulative number of processed wafers is determined.

[0105] Etching rate measurement (E / R)

[0106] Using etching solutions with concentrations shown in Tables 3 and 4 (Examples 1 to 83 and Comparative Examples 1 to 10), etching was performed on a Ti-deposited substrate (2x2cm). 2 Etching was performed, and the time required for the Ti film to be etched was measured. The etching time of the Ti film was based on the etch endpoint detection (EPD) of the Ti film as observed visually. The etching rate (E / R) was calculated by dividing the thickness of the etched Ti film by the etch time (EPD), and the results are shown in Tables 3 and 4.

[0107] Undercut Measurement

[0108] The Cu / Ti film was etched using etching solutions with the concentrations shown in Tables 3 and 4. After etching, the substrate was cleaned and dried, and then the etched cross-section was observed using FIB-SEM (Focused Ion Beam Scanning Electron Microscopy) (the cut surface was observed after cutting the substrate cross-section). The results are shown in Tables 3 and 4 below.

[0109] As a standard for undercut measurement, the indentation length from the copper film to the titanium film in the bilayer film (Cu / Ti film) under the copper electroplating layer is measured. If the average value of the undercut on both sides is less than 150nm, it is marked as "X"; if it is greater than 150nm, it is marked as "○".

[0110] Cu damage

[0111] The Cu / Ti film was etched using etchant solutions with concentrations shown in Tables 3 and 4 below, and the results are shown in Tables 3 and 4 below.

[0112] Cu damage is calculated based on the substrate thickness (thickness before etching - thickness after etching / etching time). The evaluation criteria based on the above measurement method are as follows: when Cu damage is greater than or equal to 1 nm / min but less than 5 nm / min, it is marked with ◎; when Cu damage is greater than or equal to 5 nm / min but less than 10 nm / min, it is marked with ○; when Cu damage is greater than or equal to 10 nm / min but less than 15 nm / min, it is marked with △; and when Cu damage is greater than or equal to 15 nm / min, it is marked with X.

[0113] Table 3

[0114]

[0115]

[0116] Table 4

[0117] Metal concentration (ppm) E / R (nm / min) Undercut Cu damage (nm / min) Comparative Example 1 500 40 ○ ◎ Comparative Example 2 500 90 X ◎ Comparative Example 3 500 84 ○ X Comparative Example 4 500 85 ○ X Comparative Example 5 500 82 ○ X Comparative Example 6 500 79 ○ X Comparative Example 7 500 77 ○ △ Comparative Example 8 500 75 ○ △ Comparative Example 9 500 35 ○ △ Comparative Example 10 500 45 ○ ○

[0118] As can be seen from Examples 1 to 16, when L-pyroglutamic acid, which is a pyrrolidone derivative, is used in amino acid derivatives, the etching rate can still be maintained at ±70 nm / min even if the etch solution contamination increases, and the undercut of the lower film and Cu damage to the upper film can be reduced, thus confirming its excellent etching profile.

[0119] As can be seen from Examples 17 to 34, when the content of amino acid derivative is 0.001% to 1% by weight, the etching rate can be maintained at 70 nm / min, and the undercut of the lower film and Cu damage to the upper film can be reduced, thus confirming its excellent etching profile.

[0120] Referring to Examples 35 to 45 and Comparative Examples 1 to 8, it can be seen that when the hydrogen peroxide content is 0.001% to 4% by weight, especially below 1% by weight, the undercut of the lower film and the Cu damage of the upper film can be significantly reduced.

[0121] As can be seen from Examples 46 to 60, when the weight ratio of hydrogen peroxide and fluorine-containing compounds is controlled within a specific range, the etching rate can be maintained at ±70 nm / min, and the undercut of the lower film and the Cu damage of the upper film are low.

[0122] As can be seen from Examples 61 to 70, when the weight ratio of hydrogen peroxide to nitrogen-containing cyclic compound is 1:0.1 to 1:1.5, the etching rate can be maintained at 60 to 70 nm / min, and the undercut of the lower film can be reduced.

[0123] Referring to Examples 71 to 83 and Comparative Examples 9 to 10, it can be seen that when the weight ratio of the fluorinated compound to the nitrogen-containing cyclic compound is 1:0.01 to 1:3, the undercut of the lower membrane can be reduced.

[0124] Although the present invention has been described with reference to embodiments, the present invention is not limited to the embodiments disclosed in this specification. Various modifications and variations can be made by those skilled in the art within the scope of the inventive concept, and all such modifications and variations should be considered within the scope of protection of the present invention. Furthermore, even if the technical effects of the configuration according to the present invention are not explicitly stated in the description of the embodiments, the technical effects reasonably foreseeable from such configuration should also be recognized as effects included in the present invention.

Claims

1. An etching solution composition, characterized in that, include: Hydrogen peroxide; Carboxyl compounds; Fluorine-containing compounds; And nitrogen-containing cyclic compounds; wherein the content of the hydrogen peroxide is from 0.001% to 4% by weight.

2. An etching solution composition, characterized in that, include: Hydrogen peroxide; Carboxyl compounds; Fluorine-containing compounds; And nitrogen-containing cyclic compounds; wherein the weight ratio of the fluorine-containing compound to the nitrogen-containing cyclic compound is 1:0.01 to 1:

3.

3. The etching solution composition according to claim 1 or 2, characterized in that, include: 0.1% to 5% by weight of carboxyl compounds; 0.01% to 2% by weight of fluorinated compounds; 0.001% to 1% by weight of nitrogen-containing cyclic compounds; and the balance being water.

4. The etching solution composition according to claim 1 or 2, characterized in that, It also includes at least one of the following: 1% to 5% by weight of a diol compound, 0.01% to 5% by weight of a phosphate compound, 0.001% to 2% by weight of an acetate, and 0.001% to 1% by weight of an amino acid derivative.

5. The etching solution composition according to claim 4, characterized in that, The amino acid derivative is selected from the group consisting of L-pyroglutamic acid, sodium pyrrolidinecarboxylate, zinc pyrrolidinecarboxylate, and combinations thereof.

6. The etching solution composition according to claim 1 or 2, characterized in that, The weight ratio of hydrogen peroxide to the fluorine-containing compound is from 1:0.01 to 1:

9.

7. The etching solution composition according to claim 1 or 2, characterized in that, The weight ratio of hydrogen peroxide to the nitrogen-containing cyclic compound is from 1:0.1 to 1:1.

5.

8. The etching solution composition according to claim 1 or 2, characterized in that, The carboxyl compound is at least one selected from the group consisting of iminodiacetic acid, oxalic acid, acetic acid, formic acid, acrylic acid, lactic acid, amino acids, propionic acid, oleic acid, benzoic acid, salicylic acid, malic acid, and combinations thereof.

9. The etching solution composition according to claim 4, characterized in that, The diol compound is at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and combinations thereof.

10. The etching solution composition according to claim 4, characterized in that, The phosphate compound is at least one selected from the group consisting of monoammonium phosphate, monosodium phosphate, disodium phosphate, diammonium phosphate, trisodium phosphate, and combinations thereof.

11. The etching solution composition according to claim 4, characterized in that, The acetate is at least one selected from the group consisting of ammonium acetate, sodium acetate, potassium acetate, and combinations thereof.

12. The etching solution composition according to claim 1 or 2, characterized in that, The fluorine-containing compound is at least one selected from the group consisting of ammonium hydrogen fluoride (NH4F·HF), ammonium fluoride (NH4F), sodium hydrogen fluoride (NaHF2), sodium fluoride (NaF), potassium hydrogen fluoride (KHF2), potassium fluoride (KF), hydrofluoric acid (HF), and combinations thereof.

13. The etching solution composition according to claim 1 or 2, characterized in that, The nitrogen-containing cyclic compound does not contain alkyl or aryl groups.

14. The etching solution composition according to claim 13, characterized in that, The nitrogen-containing cyclic compound is at least one selected from the group consisting of benzotriazole, aminotetrazole, methyltetrazole, aminomercaptotriazole, and combinations thereof.

15. The etching solution composition according to claim 1 or 2, characterized in that, The metal concentration in the etching solution is below 500 ppm.

16. The etching solution composition according to claim 1 or 2, characterized in that, Used for etching metal films comprising at least one selected from the group consisting of copper, molybdenum, titanium, and molybdenum-titanium alloys.

17. The etching solution composition according to claim 1 or 2, characterized in that, The etching solution composition is an etching solution composition used for semiconductor packaging.

Images