Copper-molybdenum etching solution composition and preparation method and application thereof

Abstract

The invention discloses a copper-molybdenum etching solution composition as well as a preparation method and application thereof, and relates to the technical field of etching solutions. The corrosion and corrosion inhibitor is prepared from the following raw materials in percentage by mass: 10.00 to 20.00 weight percent of hydrogen peroxide, 2.00 to 5.00 weight percent of an acidic composition, 0.10 to 1.10 weight percent of a corrosion inhibition composition, 0.10 to 1.00 weight percent of a complexing agent, 1.00 to 4.00 weight percent of a hydrogen peroxide stabilizer and the balance of water. The copper-molybdenum etching liquid composition formed according to the formula can simultaneously etch copper, molybdenum and alloy metal layers thereof, the etching steps are simplified, and the production efficiency is improved. The corrosion inhibition composition comprises polyaspartic acid and hexadecyl trimethyl ammonium bromide, the polyaspartic acid and the hexadecyl trimethyl ammonium bromide synergistically play a role in corrosion inhibition, and along with the increase of the concentration of copper ions and molybdenum ions, the stability of the etching speed and good etching morphology can be ensured.

Description

Technical Field

[0001] The present invention relates to the technical field of etching solutions, and in particular to a copper-molybdenum etching solution composition, a preparation method thereof, and applications thereof. Background Art

[0002] As flat panel displays advance toward higher generations, requirements for yield, stability, resolution, and response time are becoming increasingly stringent. This in turn drives increasing performance requirements for electrodes, the core components of display panels. As key structures driving display signals, electrodes' line width accuracy, edge flatness, conductivity, and environmental stability directly impact the panel's display quality and reliability.

[0003] Currently, electrodes are primarily fabricated using an etching process, which involves selectively etching the metal layer through a patterned photoresist mask using an etching solution to form a fine electrode pattern. However, most current copper etching solutions suffer from a degradation of etching performance over time, leading to defects such as severe chamfers, etching indentations, and large variations in etching on one side.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The present invention aims to provide a copper-molybdenum etching solution composition, a preparation method thereof and an application thereof.

[0006] The present invention is achieved in that: In a first aspect, the present invention provides a copper-molybdenum etching solution composition, wherein the raw materials, by mass percentage, include: 10.00wt%~20.00wt% of hydrogen peroxide, 2.00wt%~5.00wt% of an acidic composition, 0.10wt%~1.10wt% of a corrosion inhibition composition, 0.10wt%~1.00wt% of a complexing agent, and 1.00wt%~4.00wt% of a hydrogen peroxide stabilizer, with the balance being water.

[0007] The corrosion inhibition composition includes polyaspartic acid and cetyltrimethylammonium bromide.

[0008] By controlling the formulation of the copper-molybdenum etching solution composition, it can simultaneously etch copper, molybdenum, and their alloy layers, simplifying the etching process and improving production efficiency. The use of polyaspartic acid and hexadecyltrimethylammonium bromide as corrosion inhibitors synergistically ensures that the etching rate is controlled within an appropriate range and improves the stability of the taper angle after etching.

[0009] In an optional embodiment, the corrosion inhibition composition satisfies at least one of the following conditions: The mass ratio of polyaspartic acid to cetyltrimethylammonium bromide is 1 to 10: 1. By controlling the mass ratio of polyaspartic acid to cetyltrimethylammonium bromide within the above range, the synergistic corrosion inhibition effect of the two can be ensured.

[0010] After adding the corrosion-inhibiting composition to the electrolyte in a three-electrode system, the corrosion potential of copper is less than -0.20V. The three-electrode system comprises a copper working electrode, a platinum counter electrode, a saturated calomel reference electrode, and a 3.50wt% to 5.00wt% sodium chloride solution as the electrolyte. This ensures that the corrosion-inhibiting composition can effectively inhibit the copper and molybdenum etching solution.

[0011] In an optional embodiment, the pH of the copper-molybdenum etching solution composition is 1.8~2.5 to ensure the stability of the etching rate.

[0012] In an optional embodiment, the acidic composition includes an inorganic salt and an organic acid, wherein the inorganic salt includes at least one of ammonium bisulfate, ammonium sulfate, and ammonium dihydrogen phosphate; and the organic acid includes at least one of malonic acid, citric acid, and tartaric acid. Improving the selection of the above inorganic salt and organic acid can effectively control the pH of the copper-molybdenum etching solution composition, improve the taper angle of the etched product, and ensure a stable etching rate.

[0013] In an optional embodiment, the mass ratio of the inorganic salt to the organic acid is 1:1~4 to ensure that the pH of the copper-molybdenum etching solution composition is within the above range.

[0014] In an optional embodiment, the complexing agent includes at least one of ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid, and iminodiacetic acid. By adding the complexing agent to complex with the copper ions in the etching solution, the decomposition effect of the copper ions on hydrogen peroxide is reduced, thereby preventing the hydrogen peroxide from decomposing too quickly and causing an exothermic explosion.

[0015] In an optional embodiment, the hydrogen peroxide stabilizer includes at least one of iminodisuccinic acid, toluenesulfonic acid, and hydroxyethylidene diphosphonic acid. By adding the above-mentioned hydrogen peroxide stabilizer, the safety of the copper-molybdenum etching solution composition can be ensured, and the exothermic explosion caused by excessive decomposition of hydrogen peroxide can be avoided.

[0016] In a second aspect, the present invention provides a method for preparing a composition according to any of the aforementioned embodiments, comprising mixing hydrogen peroxide, an acidic composition, a corrosion inhibitor composition, a complexing agent, a hydrogen peroxide stabilizer, and water in a proportion. The preparation method is simple and easy to operate, and the obtained copper-molybdenum etching solution composition has good etching stability and better product performance after etching.

[0017] In a third aspect, the present invention provides an application of a composition according to any one of the aforementioned embodiments in etching a copper-molybdenum composite material, comprising etching the copper-molybdenum composite material using the composition to increase the service life of the copper-molybdenum etching solution composition.

[0018] In an optional embodiment, the copper-molybdenum composite material includes a copper layer and a molybdenum layer.

[0019] The thickness of the copper layer is 3000~6000Å, and the thickness of the molybdenum layer is 150~350Å.

[0020] The material of the molybdenum layer includes pure molybdenum or molybdenum alloy.

[0021] The present invention has the following beneficial effects: The present invention provides a copper-molybdenum etching liquid composition, a preparation method thereof, and an application thereof. By controlling the formula of the copper-molybdenum etching liquid composition, the composition can simultaneously etch copper, molybdenum, and alloy metal layers thereof, simplifying the etching steps and improving production efficiency. By selecting polyaspartic acid and hexadecyltrimethylammonium bromide as the raw materials of the corrosion inhibition composition, polyaspartic acid can form a chelate with metal ions and adsorb on the metal surface to form a protective layer. At the same time, the O and N in the carbonyl group of polyaspartic acid contain lone pairs of electrons, which can be chemically adsorbed with the d orbitals in the Cu atoms. At this time, due to the chemical adsorption, the metal surface is negatively charged, which makes it easier to adsorb the cationic surfactant hexadecyltrimethylammonium bromide. Hexadecyltrimethylammonium bromide is easy to form spherical micelles, is not easy to diffuse, and can play a role in corrosion inhibition. As the concentrations of copper ions and molybdenum ions increase, the stability of the etching rate and the good etching morphology can be guaranteed. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0023] Figure 1 A scanning electron microscope image of a product after etching the copper-molybdenum etching solution composition provided in Example 3 of the present invention at a copper ion concentration of 0 ppm; Figure 2 A scanning electron microscope image of a product after etching the copper-molybdenum etching solution composition provided in Example 3 of the present invention at a copper ion concentration of 2000 ppm; Figure 3 A scanning electron microscope image of a product after etching the copper-molybdenum etching solution composition provided in Example 3 of the present invention at a copper ion concentration of 4000 ppm; Figure 4A scanning electron microscope image of a product after etching the copper-molybdenum etching solution composition provided in Example 3 of the present invention at a copper ion concentration of 6000 ppm; Figure 5 A scanning electron microscope image of the product after etching the copper-molybdenum etching solution composition provided in Example 3 of the present invention at a copper ion concentration of 8000 ppm. DETAILED DESCRIPTION

[0024] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0025] The features and performance of the present invention are further described in detail below with reference to the embodiments.

[0026] In a first aspect, the present invention provides a copper-molybdenum etching solution composition, wherein the raw materials, by mass percentage, include: 10.00wt%~20.00wt% of hydrogen peroxide, 2.00wt%~5.00wt% of an acidic composition, 0.10wt%~1.10wt% of a corrosion inhibition composition, 0.10wt%~1.00wt% of a complexing agent, and 1.00wt%~4.00wt% of a hydrogen peroxide stabilizer, with the balance being water.

[0027] By controlling the formula of the copper-molybdenum etching solution composition, the composition can simultaneously etch copper, molybdenum and their alloy metal layers, simplifying the etching steps and improving production efficiency.

[0028] Preferably, the raw materials of the copper-platinum etching liquid composition include, by mass percentage, 12.00wt%~18.00wt% of hydrogen peroxide, 3.00wt%~5.00wt% of acidic composition, 0.20wt%~0.60wt% of corrosion inhibition composition, 0.20wt%~0.60wt% of complexing agent and 2.00wt%~4.00wt% of hydrogen peroxide stabilizer, with the remainder being water. By controlling the formula of the copper-platinum etching liquid composition within the above range, the service life of the etching solution can be improved while meeting its etching performance.

[0029] Hydrogen peroxide is the primary oxidant for copper. When its content is within the above range, the etching rates of the copper and molybdenum layers are more stable, and the morphology of the etched product is superior. When the hydrogen peroxide content is too high, the overall etching rate is too fast. After the corrosion inhibitor composition is added, the alkalinity of the corrosion inhibitor composition accelerates the decomposition rate of hydrogen peroxide, which is prone to sudden boiling and leads to unstable safety. When the hydrogen peroxide content is too low, the overall etching rate is too slow, the etching efficiency is low, and etching residue is likely to occur.

[0030] The corrosion inhibition composition includes polyaspartic acid and cetyltrimethylammonium bromide. By selecting polyaspartic acid and cetyltrimethylammonium bromide as the raw materials of the corrosion inhibition composition, polyaspartic acid can form a chelate with metal ions and adsorb on the metal surface to form a protective layer. At the same time, the O and N in the carbonyl group of polyaspartic acid contain lone pairs of electrons, which can undergo chemical adsorption with the d orbitals of Cu atoms. At this time, due to chemical adsorption, the metal surface has a negative charge, which is more susceptible to adsorption of the cationic surfactant cetyltrimethylammonium bromide. Cetyltrimethylammonium bromide easily forms spherical micelles and is not easy to diffuse, which can play a corrosion inhibition role. As the concentration of copper ions and molybdenum ions increases, the etching rate stability and good etching morphology can be guaranteed.

[0031] In an optional embodiment, the corrosion inhibition composition satisfies at least one of the following conditions: The mass ratio of polyaspartic acid to cetyltrimethylammonium bromide is 1-10:1.

[0032] After the corrosion inhibition composition is added to the electrolyte in a three-electrode system, the corrosion potential of copper is less than -0.20V; the three-electrode system is: the working electrode is a copper sheet, the counter electrode is a platinum sheet, the reference electrode is a saturated calomel, and the electrolyte is a 3.50wt% to 5.00wt% sodium chloride solution.

[0033] By controlling the mass ratio of polyaspartic acid and cetyltrimethylammonium bromide within the above range, the synergistic corrosion inhibition effect of the two can be ensured. When the mass ratio of the two is higher or lower than the above range, the etching performance of the obtained copper-molybdenum etching solution composition is not significantly different from that of the single addition of any of the above corrosion inhibition compositions, indicating that when the mass ratio of polyaspartic acid and cetyltrimethylammonium bromide is 1 to 10:1, polyaspartic acid and cetyltrimethylammonium bromide can play an excellent synergistic corrosion inhibition role in the etching solution system provided by the present invention, thereby improving the service life of the copper-molybdenum etching solution composition.

[0034] In addition, the mass ratio of polyaspartic acid and hexadecyltrimethylammonium bromide can be adjusted according to the actual thickness of the copper layer and the molybdenum layer in the material to be etched, but the adjustment also needs to be within the mass range required above. For example, the mass ratio of polyaspartic acid and hexadecyltrimethylammonium bromide can be any ratio of 1:1, 2:1, 4:1, 6:1, 8:1 or 10:1, or a range value consisting of any two ratios.

[0035] Furthermore, based on the mass of the copper-molybdenum etching solution composition, the combination of the mass percentage of polyaspartic acid and the mass percentage of cetyltrimethylammonium bromide in the corrosion inhibition composition can be, for example, any ratio of 1.00wt%+0.10wt%, 0.10wt%+0.01wt% or 0.05wt%+0.05wt%.

[0036] By adjusting the mass ratio of polyaspartic acid and hexadecyltrimethylammonium bromide, the corrosion inhibition effect of the corrosion inhibition composition can be adjusted to etch metal film layers of different thicknesses, thereby achieving the effect of simultaneously etching copper and molybdenum layers. As etching proceeds, the concentrations of copper ions and molybdenum ions in the copper-molybdenum etching solution composition increase, which can also ensure the stability of the product etching rate and good etching morphology.

[0037] The corrosion inhibition composition can form a protective film on the surface of metallic copper, which plays a role in corrosion inhibition. Therefore, when the corrosion inhibition effect of the corrosion inhibition composition on copper is detected by the above-mentioned three-electrode system, the corrosion potential of copper is detected to be less than -0.20V, which proves that the corrosion inhibition composition can play a good corrosion inhibition role in the copper-molybdenum etching solution composition.

[0038] From the above analysis, it can be seen that the corrosion-inhibiting composition has a significant impact on the performance of the copper-molybdenum etching solution composition. Therefore, it is particularly important to control its content within the range required by the present invention. When the content of the corrosion-inhibiting composition is too high, the corrosion inhibition effect is too strong, the total etching rate is too slow, and copper and molybdenum cannot be effectively etched; when the content of the corrosion-inhibiting composition is too low, the total etching rate is too fast, affecting the service life of the copper-molybdenum etching solution composition.

[0039] In an optional embodiment, the pH value of the copper-molybdenum etching solution composition is 1.8-2.5, for example, it can be any value of 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4 or 2.5 or a range value consisting of any two values.

[0040] By controlling the pH of the copper-platinum etching solution composition within the above range, the stability of the etching rate can be ensured. When the pH of the copper-platinum etching solution composition is less than 1.8, the synergistic effect of the corrosion inhibition composition is suppressed. At this time, as etching proceeds, the concentration of metal ions in the copper-platinum etching solution composition increases, and the etching rate is significantly accelerated, resulting in a deterioration of the etching morphology; when the pH of the copper-platinum etching solution composition is greater than 2.5, the etching rate is reduced, and as etching proceeds, the concentration of metal ions in the copper-platinum etching solution composition increases, and metal residues or precipitation phenomena will occur in the copper-platinum etching solution composition.

[0041] In order to better control the pH of the copper-molybdenum etching solution composition within the above range, the present invention also provides a method for selecting the acidic composition.

[0042] In an optional embodiment, the acidic composition includes an inorganic salt and an organic acid, the inorganic salt includes at least one of ammonium bisulfate, ammonium sulfate, and ammonium dihydrogen phosphate; the organic acid includes at least one of malonic acid, citric acid, and tartaric acid.

[0043] By selecting an inorganic salt and an organic acid as the acidic composition, wherein the inorganic salt is also a weakly acidic inorganic salt, its main function is to control the pH value of the etching solution within an appropriate range; the organic acid selected above can provide a certain chelating ability, thereby improving the cone angle of the etched product and ensuring the stability of the etching rate.

[0044] In an optional embodiment, the mass ratio of the inorganic salt to the organic acid is 1:1~4, and the mass percentage of the inorganic salt is ≥1.00wt% based on the mass of the copper-molybdenum etching solution composition.

[0045] For example, based on the mass of the copper-platinum etching solution composition, the combination of the mass percentage of the inorganic salt and the mass percentage of the organic acid in the acidic composition can be, for example, any ratio of 1.00wt%+1.00wt%, 1.00wt%+2.00wt%, 1.00wt%+3.00wt%, or 1.00wt%+4.00wt%.

[0046] Furthermore, the mass ratio of the inorganic salt to the organic acid can be any ratio of 1:1, 1:2, 1:3 or 1:4, or a range consisting of any two ratios.

[0047] By controlling the mass ratio of the inorganic salt and the organic acid within the above range, especially controlling the mass percentage of the inorganic salt, the pH of the copper-molybdenum etching solution composition can be more easily adjusted to a range of 1.8 to 2.5, thereby ensuring the etching effect of the copper-molybdenum etching solution composition.

[0048] As can be seen from the above analysis, the acidic composition has a significant impact on the performance of the copper-platinum etching solution composition. Therefore, it is particularly important to control its content within the scope required by the present invention. When the content of the acidic composition is too high, the acidity of the copper-platinum etching solution composition is enhanced, and the etching rate is too fast, affecting the service life of the etching solution; when the content of the acidic composition is too low, the acidity of the copper-platinum etching solution composition is weak, and the etching rate is too slow, affecting the etching efficiency and the quality of the product after etching. In an optional embodiment, the complexing agent includes at least one of ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid and iminodiacetic acid. As etching proceeds, the metal ion concentration in the copper-platinum etching solution composition increases, and the etching performance of the etching solution deteriorates, thereby affecting the service life of the etching solution. By adding the above-mentioned complexing agent, the complexing agent can be complexed with the copper ion in the etching solution, reducing the decomposition effect of the copper ion on hydrogen peroxide, avoiding the exothermic explosion phenomenon caused by the excessive decomposition of hydrogen peroxide.

[0049] When the content of the complexing agent is lower than the lower limit of the range required by the present invention, as the etching reaction proceeds, the complexing agent is insufficient to complex the metal ions in the copper-molybdenum etching solution composition, thereby affecting the service life of the etching solution; when the content of the complexing agent is higher than the upper limit of the range required by the present invention, the etching speed will be accelerated and the etching morphology will be deteriorated.

[0050] In an optional embodiment, the hydrogen peroxide stabilizer includes at least one of iminodisuccinic acid, toluenesulfonic acid, and hydroxyethylidene diphosphonic acid. By adding the above-mentioned hydrogen peroxide stabilizer, the safety of the copper-molybdenum etching solution composition can be ensured, and the exothermic explosion caused by excessive decomposition of hydrogen peroxide can be avoided.

[0051] When the content of the hydrogen peroxide stabilizer is lower than the lower limit of the range required by the present invention, more hydrogen peroxide is likely to cause explosive boiling during the etching process, and the service life of the copper-molybdenum etching solution composition is significantly reduced; when the content of the hydrogen peroxide stabilizer is higher than the upper limit of the range required by the present invention, the etching effect of hydrogen peroxide is affected, resulting in poor morphology of the etched product.

[0052] In a second aspect, the present invention provides a method for preparing the composition according to any one of the aforementioned embodiments, comprising mixing hydrogen peroxide, an acidic composition, a corrosion inhibition composition, a complexing agent, a hydrogen peroxide stabilizer, and water in proportion.

[0053] Preferably, in order to ensure the safety and stability of the mixing process of the raw materials, the solid raw materials are weighed according to the ratio, deionized water is added and stirred, and then hydrogen peroxide is added, and the mixture is filtered after stirring to obtain a copper-molybdenum etching solution composition.

[0054] In a third aspect, the present invention provides an application of a composition according to any one of the aforementioned embodiments in etching a copper-molybdenum composite material, comprising etching the copper-molybdenum composite material using the composition to increase the service life of the copper-molybdenum etching solution composition.

[0055] In an optional embodiment, the copper-molybdenum composite material includes a copper layer and a molybdenum layer.

[0056] The thickness of the copper layer is 3000~6000Å, and the thickness of the molybdenum layer is 150~350Å.

[0057] The material of the molybdenum layer includes pure molybdenum or a molybdenum alloy, wherein the molybdenum alloy includes any one of a molybdenum-niobium alloy, a molybdenum-titanium alloy and a molybdenum-titanium-nickel alloy.

[0058] Example 1 The present embodiment provides a copper-molybdenum etching solution composition having a pH of 2.1. The raw materials, by mass percentage, include: 10.00 wt% of hydrogen peroxide, 1.00 wt% of ammonium bisulfate, 3.00 wt% of malonic acid, 0.40 wt% of polyaspartic acid, 0.05 wt% of hexadecyltrimethylammonium bromide, 0.40 wt% of a complexing agent, and 3.00 wt% of a hydrogen peroxide stabilizer, with the balance being water.

[0059] The acidic composition consists of ammonium bisulfate and malonic acid; the corrosion inhibition composition consists of polyaspartic acid and hexadecyltrimethylammonium bromide; the complexing agent is ethylenediaminetetraacetic acid; and the hydrogen peroxide stabilizer is iminodisuccinic acid.

[0060] After the corrosion inhibition composition was added to the electrolyte in a three-electrode system, the corrosion potential of copper was -0.25 V; the three-electrode system was: the working electrode was a copper sheet, the counter electrode was a platinum sheet, the reference electrode was a saturated calomel, and the electrolyte was a 5.00 wt% sodium chloride solution.

[0061] This embodiment also provides a method for preparing the copper-molybdenum etching solution composition, comprising weighing the solid raw materials according to a ratio, first adding deionized water and stirring, then adding hydrogen peroxide, stirring, and filtering to obtain the copper-molybdenum etching solution composition.

[0062] Examples 2 to 14 and Comparative Examples 1 to 15 also provide a copper-molybdenum etching solution composition and a preparation method thereof, wherein the preparation method is the same as that of Example 1, except that the raw material ratio of the copper-molybdenum etching solution composition is different from that of Example 1, as shown in Table 1.

[0063] Table 1 Formula of copper-molybdenum etching solution composition

[0064] Test Example 1 The copper-molybdenum etching liquid compositions provided in the above examples and comparative examples were etched, and the properties of the etched products were tested. The etching method comprises transferring 10 kg of the copper-molybdenum etching liquid compositions of Examples 1-14 and Comparative Examples 1-15 into an etching apparatus, and etching the copper-molybdenum composite material after the temperature of the copper-molybdenum etching liquid composition reaches 30±0.1°C.

[0065] The copper-molybdenum composite material is a composite thin film substrate composed of a copper layer and a molybdenum layer, the thickness of the copper layer is 3500Å, the thickness of the molybdenum layer is 300Å, and the material of the molybdenum layer is molybdenum / molybdenum niobium / molybdenum titanium nickel.

[0066] The time required to complete etching of all copper and molybdenum is defined as the EPD. The total etching time is 1.3 times the EPD, which means a 30% overetch to ensure the formation of product morphology such as the taper angle. After etching, rinse with water within 2 seconds, dry the surface, and evaluate post-etching performance parameters using a scanning electron microscope (SEM).

[0067] As the etching proceeds, the metal ion concentration in each copper-molybdenum etching solution composition increases. 2+ The copper-molybdenum composite material was etched by the above-mentioned etching method in the copper-molybdenum etching solution composition with a concentration of 0ppm, 2000ppm, 4000ppm, 6000ppm and 8000ppm, and the cone angle and unilateral etching amount of the etched product were detected to obtain the following results as shown in Table 2, Table 3 and Table 4: Figures 1 to 5 Results shown.

[0068] Table 2 Cone angle of copper-molybdenum composite material after etching

[0069] The meanings of the shapes in Table 2 are as follows: : Good [cone angle 40°~60°] ▲: Generally [cone angle is 60°~65° or <40°] ×: The copper-molybdenum etching solution composition cannot be used and tested safely because the cone angle is too large or too small at this copper concentration, or the temperature rises sharply, precipitates are present, or the copper powder cannot be dissolved.

[0070] Table 3 Single-side etching amount of copper-molybdenum composite material after etching (unit: μm)

[0071] In Table 3, “×” indicates that the copper-molybdenum etching solution composition has too much or too little unilateral etching amount at this copper concentration, or the temperature rises sharply / precipitates / copper powder cannot be dissolved, and cannot be used and tested normally and safely.

[0072] It can be seen from Tables 2 and 3 that the copper-molybdenum etching solution composition provided in the embodiment of the present invention performs better than the copper-molybdenum etching solution composition provided in the comparative example in terms of cone angle and unilateral etching amount, and still has good etching performance when the copper ion concentration in the copper-molybdenum etching solution composition is high, which has significant advantages.

[0073] Among them, the schemes with a copper concentration of 4000ppm in Example 4, 0ppm in Examples 5 and 8, and 2000ppm in Examples 6 and 7 in Table 2 are abnormal conditions. These abnormalities are due to variations in the cone angle caused by experimental fluctuations. However, in Examples 4-8, after each abnormal condition, at least two groups of experimental schemes with different concentrations achieved the same cone angle. The experimental data in Table 3 also demonstrates that the etching effects of these examples are relatively excellent.

[0074] In addition, it can be seen from Examples 1 to 3 and Comparative Examples 1 to 2 that an appropriate concentration of hydrogen peroxide can ensure that the product cone angle morphology after etching is good and the unilateral etching amount is appropriate. The hydrogen peroxide concentration in Comparative Example 1 is too low, so that the copper-platinum etching solution composition provided therein can only meet the etching under a copper ion concentration of 2000ppm, and the copper-platinum etching solution composition has a short etching life; the hydrogen peroxide concentration in Comparative Example 2 is too high, so that the copper-platinum etching solution composition provided therein can only meet the etching under a copper ion concentration of 4000ppm, and the copper-platinum etching solution composition has a short etching life.

[0075] As shown in Examples 3 to 6 and Comparative Examples 3 to 7, Comparative Examples 3 and 4 are respectively the schemes for adding ammonium bisulfate or malonic acid separately, and Comparative Examples 5 to 7 are for adjusting the mass ratio of ammonium bisulfate and malonic acid. The copper platinum etching solution composition provided by Comparative Example 3 can only meet the etching under 2000ppm copper ion concentration, and the copper platinum etching solution composition provided by Comparative Examples 4, 5 and 7 can only meet the etching under 4000ppm copper ion concentration, and Comparative Example 6 can only meet the etching under 6000ppm copper ion concentration, and the copper platinum etching solution composition etching life is all shorter. It is illustrated that the embodiment of the present invention selects the acidic composition of inorganic salt and organic acid composition and controls its proportioning, which is conducive to improving the service life of copper platinum etching solution composition.

[0076] As can be seen from Examples 3, 7 to 10 and Comparative Examples 8 to 11, Comparative Examples 8 and 9 are solutions for adding polyaspartic acid or hexadecyltrimethylammonium bromide alone, respectively, and Comparative Examples 10 and 11 are solutions for adjusting the mass ratio of polyaspartic acid and hexadecyltrimethylammonium bromide. The etching effect of Comparative Example 11 is similar to that of Comparative Examples 8 and 9. Both can only perform well at a copper ion concentration of 0 ppm. As the copper ion concentration increases, the etching performance deteriorates until it cannot be etched. Although Comparative Example 10 can still be etched at a copper ion concentration of 8000 ppm, the cone angle morphology is general, and the unilateral etching amount is large, and the product performance is not as good as the examples.

[0077] As can be seen from Examples 3, 11, 12 and Comparative Examples 12 and 13, too high or too low a complexing agent content can also affect the service life of the copper-platinum etching solution composition. The service life of the copper-platinum etching solution compositions of Comparative Examples 12 and 13 can only reach a copper ion concentration of 4000ppm at the longest. If the copper ion concentration is too high, the etching operation cannot be continued.

[0078] As can be seen from Examples 3, 13, 14 and Comparative Examples 14 and 15, excessive or low levels of hydrogen peroxide stabilizer also affect the service life of the copper-platinum etching solution composition. The service life of the copper-platinum etching solution composition of Comparative Example 14 is the longest at a copper ion concentration of only 2000ppm. Since the copper ion concentration is too high, etching cannot be continued. Although Comparative Example 15 can still etch at a copper ion concentration of 8000ppm, the cone angle morphology is average, and the unilateral etching amount is large, and the product performance is not as good as the embodiment.

[0079] Depend on Figures 1 to 5 It can be seen that the copper platinum etching solution composition provided by the embodiment of the present invention is 0ppm, 2000ppm, 4000ppm, 6000ppm and 8000ppm in solution, which can ensure good cone angle morphology. When copper ion concentration is 0ppm, the cone angle of the product after etching is 45~46°, and it is straight and not bent, and the etching effect is very good; when copper ion concentration is 2000ppm, the cone angle of the product after etching is 44~45°, and it is straight and not bent, and the etching effect is very good; when copper ion concentration is 4000ppm, the cone angle of the product after etching is 45~46°, and it is straight and not bent, and the etching effect is very good; when copper ion concentration is 6000ppm, the cone angle of the product after etching is 48~49°, and it is straight and not bent, and the etching effect is very good; when copper ion concentration is 8000ppm, the cone angle of the product after etching is 51~52°, and no residual situation occurs.

[0080] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A copper-molybdenum etching solution composition, characterized in that, The raw materials, calculated by weight percentage, include: 10.00 wt% to 20.00 wt% of hydrogen peroxide, 2.00 wt% to 5.00 wt% of an acidic composition, 0.10 wt% to 1.10 wt% of a corrosion inhibition composition, 0.10 wt% to 1.00 wt% of a complexing agent, and 1.00 wt% to 4.00 wt% of a hydrogen peroxide stabilizer, with the balance being water; The corrosion inhibition composition comprises polyaspartic acid and cetyltrimethylammonium bromide.

2. The composition according to claim 1, characterized in that The corrosion inhibition composition satisfies at least one of the following conditions: 1) The mass ratio of the polyaspartic acid to the cetyltrimethylammonium bromide is 1 to 10:1; 2) After the corrosion inhibition composition is added to the electrolyte in a three-electrode system, the corrosion potential of copper is less than -0.20 V; the three-electrode system is: the working electrode is a copper sheet, the counter electrode is a platinum sheet, the reference electrode is a saturated calomel, and the electrolyte is a 3.50wt% to 5.00wt% sodium chloride solution.

3. The composition according to claim 1, characterized in that The pH value of the copper-molybdenum etching solution composition is 1.8-2.

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4. The composition according to claim 3, characterized in that The acidic composition includes an inorganic salt and an organic acid. The inorganic salt includes at least one of ammonium bisulfate, ammonium sulfate, and ammonium dihydrogen phosphate; and the organic acid includes at least one of malonic acid, citric acid, and tartaric acid.

5. The composition according to claim 4, characterized in that The mass ratio of the inorganic salt to the organic acid is 1:1-4.

6. The composition according to claim 1, characterized in that The complexing agent includes at least one of ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid and iminodiacetic acid.

7. The composition according to claim 1, characterized in that The hydrogen peroxide stabilizer includes at least one of iminodisuccinic acid, toluenesulfonic acid and hydroxyethylidene diphosphonic acid.

8. A method for preparing the composition according to any one of claims 1 to 7, characterized in that: The method comprises mixing the hydrogen peroxide, the acidic composition, the corrosion inhibition composition, the complexing agent, the hydrogen peroxide stabilizer and water in proportion.

9. Use of the composition according to any one of claims 1 to 7 in etching a copper-molybdenum composite material, characterized in that: The method comprises etching the copper-molybdenum composite material by using the composition.

10. The use according to claim 9, characterized in that The copper-molybdenum composite material comprises a copper layer and a molybdenum layer; The thickness of the copper layer is 3000-6000 Å, and the thickness of the molybdenum layer is 150-350 Å; The material of the molybdenum layer includes pure molybdenum or molybdenum alloy.

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