CN113564598A - Copper-titanium corrosive liquid for integrated circuit and production process thereof - Google Patents

Abstract

The invention discloses a copper-titanium corrosive liquid for an integrated circuit, which belongs to the technical field of microelectronic chemical reagents and comprises the following raw materials in percentage by mass: 10-19% of sulfuric acid, 5-8% of nitric acid, 28-33% of acetic acid, 2-5% of potassium persulfate, 2-4% of hydrogen peroxide, 0.05-0.1% of adsorbent and the balance of pure water; the invention also discloses a production process of the corrosive liquid; the corrosion liquid disclosed by the invention has uniform corrosion on the copper-titanium composite metal layer and stable performance, can purify the corrosion liquid, reduce the generation of corrosion waste liquid and prolong the service life of the corrosion liquid due to the addition of the adsorbent, does not corrode a silicon material substrate, silicon nitride and amorphous silicon, simultaneously gives consideration to the yield, safety and environmental friendliness of products, reduces the risk of defects after heavy industry, and can be widely applied to the fields of the preparation of integrated circuit industry, flat panel displays, color filters, touch panels, organic light-emitting diodes and the like.

Description

Copper-titanium corrosive liquid for integrated circuit and production process thereof

Technical Field

The invention belongs to the technical field of microelectronic chemical reagents, and particularly relates to a copper-titanium corrosive liquid for an integrated circuit and a production process thereof.

Background

The existing copper/titanium metal film corrosive liquid is usually hydrogen peroxide and other acid solutions, the copper/titanium metal is oxidized by the hydrogen peroxide, and then the oxide is dissolved by the acid solution, so that the purpose of etching is achieved. Although the hydrogen peroxide stabilizer is added, hydrogen peroxide is still unstable and easy to decompose, and copper ions have a catalytic effect on the decomposition of hydrogen peroxide and can further accelerate the decomposition of hydrogen peroxide, so that the etching process of the copper-titanium laminated film is unstable, and the service life of the etching solution is shortened. Often can add fluoride ion for improving etching rate, but fluoride ion can corrode the silicon material device under the acid condition, it is very unfavorable to technology production, cause certain pollution to operating environment, be unfavorable for operating personnel's health, and the etching solution that became invalid if not carrying out correct processing, still can cause serious pollution to the environment, and along with corrosion process's process, more copper ion and titanium ion get into the etching solution, cause the etching solution metal ion content more, influence the stability of etching solution, influence etching effect.

Disclosure of Invention

The invention aims to provide a copper-titanium corrosive liquid for an integrated circuit and a production process thereof.

The purpose of the invention can be realized by the following technical scheme:

a copper-titanium corrosive liquid for integrated circuits comprises the following raw materials in percentage by mass: 10-19% of sulfuric acid, 5-8% of nitric acid, 28-33% of acetic acid, 2-5% of potassium persulfate, 2-4% of hydrogen peroxide, 0.05-0.1% of adsorbent and the balance of pure water;

the production process of the copper-titanium corrosive liquid for the integrated circuit comprises the following steps:

the first step is as follows: weighing and preparing raw materials such as sulfuric acid, nitric acid, acetic acid, potassium persulfate, hydrogen peroxide, an adsorbent, pure water and the like according to a ratio;

the second step is that: adding required pure water into a material mixing tank, adding potassium persulfate and hydrogen peroxide under stirring, and stirring for 2-4h under the condition of the rotating speed of 100-;

the third step: sequentially adding sulfuric acid, nitric acid and acetic acid into the batching tank, and stirring for 2 hours at the rotating speed of 60-80r/min to obtain a mixture;

the fourth step: and (3) introducing the mixture into a filter, filtering for more than 2 times, adding an adsorbent, and stirring for 20-40min at a constant rotating speed to obtain the copper-titanium etching solution for the integrated circuit.

Further, the concentration of the sulfuric acid is 94-98%, the concentration of the nitric acid is 63-64%, and the concentration of the acetic acid is 98%; the concentration of hydrogen peroxide is 30 percent, and the aperture of the micro-filtration membrane of the filter in the fourth step is 0.03 to 0.10 mu m.

Further, the adsorbent is made by the following steps:

step 1, adding n-amyl alcohol, ethyl orthosilicate and n-hexane into a three-neck flask, stirring for 5min, adding hexadecyl trimethyl ammonium bromide, urea and distilled water, magnetically stirring for 40min, transferring a reaction product into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a 120 ℃ oven for heat preservation for 4h, after the reaction is finished, performing suction filtration, washing a filter cake for 2 times by using acetone and distilled water respectively, then centrifuging for 15min at a rotating speed of 4000r/min, drying the obtained precipitate in the 60 ℃ oven for 12h, and finally roasting in a 550 ℃ muffle furnace for 6h to obtain a mesoporous carrier;

step 2, adding 2-pyridylaldehyde into absolute ethyl alcohol, adding 2-pyridylmethylamine under the stirring condition, stirring for 2 hours at room temperature, adding sodium borohydride, stirring for reaction for 3 hours, filtering after the reaction is finished, cooling the filtrate to 0 ℃, adding a hydrochloric acid solution with the mass fraction of 37 to adjust the pH value to 4, adding the precipitation liquid, standing for 24 hours at room temperature, filtering, washing the filter cake with diethyl ether for 3-5 times, and finally drying at 60 ℃ to constant weight to obtain an intermediate 1;

the reaction process is as follows:

step 3, mixing 6-bromomethyl-2-pyridinemethanol and acetonitrile according to a ratio of 1.12 g: 20mL of the mixture is uniformly mixed to obtain a solution a, an intermediate 1, triethylamine and water-removing acetonitrile are added into a three-neck flask, the solution a is dropwise added into the three-neck flask after stirring for 5min, dropwise adding is finished within 1h, stirring is carried out for reaction for 12h under the protection of argon after dropwise adding is finished, acetonitrile is removed by rotary evaporation after the reaction is finished, a product is dissolved into dichloromethane, the solution is respectively washed for 2 times by a saturated sodium bicarbonate solution and a sodium chloride solution, liquid separation is carried out, an organic layer is dried by anhydrous sodium sulfate, filtering is carried out, and dichloromethane is removed by rotary evaporation to obtain an intermediate 2;

the reaction process is as follows:

step 4, adding the intermediate 2 and acetonitrile into a three-neck flask, stirring for 3min, dropwise adding a hydrochloric acid solution of L-cystine into the three-neck flask, after dropwise adding, adding concentrated sulfuric acid under the condition of a rotation speed of 100-;

the reaction process is as follows:

step 5, adding absolute ethyl alcohol, diphenylamine and sodium hydride into a round-bottom flask, cooling to 0 ℃, stirring for 10min, adding epoxy chloropropane, stirring and reacting for 6h at room temperature, then adding dimethylethanolamine, heating to 80 ℃, stirring and reacting for 8h, filtering after the reaction is finished, performing rotary evaporation on filtrate to remove the absolute ethyl alcohol, and recrystallizing a product in ethyl acetate to obtain an intermediate 4;

the reaction process is as follows:

step 6, adding the intermediate 3, triethylamine and dimethyl sulfoxide into a three-neck flask, adding the intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, stirring for 3min, adding N, N' -dicyclohexylcarbodiimide, heating to 25 ℃, reacting for 3h, concentrating the reaction liquid under reduced pressure to 1/3 volume, adding the concentrated liquid into ethyl acetate 2 times of the volume of the concentrated liquid, extracting, shaking uniformly, placing the mixture into a refrigerator at-1 ℃ for 5h, extracting with ethyl acetate for three times, washing the organic phase with a sodium bicarbonate solution with the mass fraction of 5% and a hydrochloric acid solution with the concentration of 1mmol/L, and drying with anhydrous sodium sulfate to obtain an intermediate 5;

the reaction process is as follows:

and 7, adding the mesoporous carrier, absolute ethyl alcohol and deionized water into a round-bottom flask, performing ultrasonic dispersion for 15min at the frequency of 40-50kHz, adding a coupling agent KH-560, performing ultrasonic dispersion for 10min, adding the intermediate 5, performing stirring reaction for 1-2h, after the reaction is finished, centrifuging for 3-5 times at the rotation speed of 1000-1200r/min, washing the precipitate for 3-5 times by using distilled water, and finally drying at 60 ℃ to constant weight to obtain the adsorbent.

Further, in the step 1, the using amount ratio of n-amyl alcohol, ethyl orthosilicate, n-hexane, hexadecyl trimethyl ammonium bromide, urea and distilled water is 2.5 mL: 5.6-7.9 mL: 30mL of: 3.1-3.9 g: 0.6 g: 30 mL.

Further, in the step 2, the dosage ratio of the 2-pyridinecarboxaldehyde, the absolute ethyl alcohol, the 2-pyridinemethylamine and the sodium borohydride is 0.2 mol: 100mL of: 0.2 mol: 0.37-0.41mol, and the precipitation liquid is formed by mixing absolute ethyl alcohol and ether at the temperature of 0 ℃ according to the volume ratio of 3: 1.

Further, the dosage ratio of the solution a, the intermediate 1, triethylamine and the water-removed acetonitrile in the step 3 is 20 mL: 5.5 mmol: 0.62-0.78 mL: 30 mL.

Further, the dosage ratio of the intermediate 2, acetonitrile, hydrochloric acid solution of L-cystine and concentrated sulfuric acid in the step 4 is 5.8 mmol: 30-38 mL: 20mL of: 1.8-2.5mL, wherein the hydrochloric acid solution of L-cystine is prepared by mixing L-cystine and 15% hydrochloric acid solution in mass fraction according to the following steps of 5.5-5.8 mmol: 20mL of the mixture was mixed.

Further, the dosage ratio of the absolute ethyl alcohol, the diphenylamine, the epichlorohydrin and the dimethylethanolamine in the step 5 is 45.8-52.3 mL: 5 mmol: 5 mmol: 5mmol, and the dosage of the sodium hydride is 1 percent of the mass of the diphenylamine.

Further, the dosage ratio of the intermediate 3, triethylamine, dimethyl sulfoxide and the intermediate 4 in the step 6 is 6 mmol: 3mL of: 68-72 mL: the dosage of 6mmol, 4-dimethylamino pyridine is 3-5% of the mass of the intermediate 3, and the dosage of N, N' -dicyclohexyl carbodiimide is 8-11% of the mass of the intermediate 3.

Further, in the step 7, the dosage ratio of the mesoporous carrier, the absolute ethyl alcohol, the deionized water, the coupling agent KH-560 and the intermediate 5 is 2 g: 25-31 mL: 40mL of: 3-5 mL: 0.8-1.4 g.

The invention has the beneficial effects that:

1. the copper-titanium etching solution for the integrated circuit is prepared by taking sulfuric acid, nitric acid, acetic acid, potassium persulfate, hydrogen peroxide, an adsorbent and pure water as raw materials, has low viscosity, reduces the phenomenon of non-uniformity in the etching process, has stable quality, is used for jointly acting on copper-titanium composite metal by sulfuric acid and nitric acid, titanium is oxidized into oxides with different valence states under the action of hydrogen peroxide, and metal copper is oxidized into CuO or Cu₂O and acetic acid regulate the pH of the corrosive liquid to play a role in buffering, and under the condition of coexistence of sulfuric acid, nitric acid and acetic acid, the etching rate of the corrosive liquid to copper is lower than that of titanium, and in the copper-titanium composite metal layer, copper is on the upper layer, and titanium is on the lower layer, so that the etching angle of the copper-titanium composite metal layer is overlarge, and the later processing of the composite metal layer is unfavorable.

2. The method comprises the steps of taking ethyl orthosilicate as a raw material, taking hexadecyl trimethyl ammonium bromide as a template agent, preparing mesoporous silica as an adsorbent carrier, taking 2-pyridylaldehyde and 2-pyridylmethylamine as raw materials, obtaining an intermediate 1 containing two pyridine structures under the action of a reducing agent sodium borohydride, further carrying out HBr elimination reaction on the intermediate 1 and 6-bromomethyl-2-pyridinemethanol to obtain an intermediate 2 containing three pyridine structures, carrying out esterification reaction on-OH of the intermediate 2 and-COOH of L-cystine under the catalytic action of concentrated sulfuric acid to obtain an intermediate 3 containing a plurality of amino groups and terminal carboxyl groups, taking diphenylamine and epoxy chloropropane as raw materials, carrying out ring-opening reaction on the intermediate 2 to obtain a product, carrying out addition reaction on dimethylethanolamine to obtain a product containing an aromatic amine structure, a mesoporous silica and a mesoporous silica adsorbent, The method comprises the steps of carrying out esterification reaction on an intermediate 4 with a quaternary ammonium salt structure and an alcoholic hydroxyl group to obtain an intermediate 5, carrying out modification treatment on mesoporous silica by using a coupling agent KH-560, grafting epoxy alkyl long chains on the surface of the mesoporous silica, grafting the intermediate 5 containing amino groups onto a mesoporous silica adsorption carrier by using the characteristic that an epoxy group and an amino group are easy to carry out ring-opening reaction, and obtaining an adsorbent, wherein the mesoporous silica is an excellent adsorption material due to the characteristics of stable structure, no physiological toxicity, high specific surface area, high specific volume and the like, and the adsorbent is prepared by modifying the mesoporous silica, aiming at the application of a copper-titanium corrosive liquid, utilizing a soft and hard acid-base theory and utilizing the characteristic that copper ions and titanium ions belong to an intermediate acid and utilizing the intermediate 5 containing aromatic amine and pyridine nitrogen to modify the mesoporous silica, the intermediate 5 is a tetradentate coordination compound containing three pyridines, has good coordination capacity, can form stable coordination compounds with copper ions and titanium ions, contains hydroxyl, amino and ester groups, can form coordination compounds with metal ions, reduces the content of the metal ions in the corrosive liquid, and can achieve the purpose of purifying the corrosive liquid through adsorption treatment.

3. The corrosion liquid disclosed by the invention has uniform corrosion on the copper-titanium composite metal layer and stable performance, can purify the corrosion liquid, reduce the generation of corrosion waste liquid and prolong the service life of the corrosion liquid due to the addition of the adsorbent, can achieve the purpose of recycling metal resources by recovering and extracting adsorbed metal ions, does not contain fluorine, does not corrode a silicon material base material, silicon nitride and amorphous silicon, simultaneously considers the yield, safety and environmental friendliness of products, reduces the risk of defects after heavy industry, and can be widely applied to the fields of the preparation of integrated circuit industry, flat panel displays, color filters, touch panels, organic light emitting diodes and the like.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The adsorbent is prepared by the following steps:

step 1, adding 2.5mL of n-amyl alcohol, 5.6mL of ethyl orthosilicate and 30mL of n-hexane into a three-neck flask, stirring for 5min, adding 3.1g of hexadecyl trimethyl ammonium bromide, 0.6g of urea and 30mL of distilled water, magnetically stirring for 40min, transferring a reaction product into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a 120 ℃ oven for heat preservation for 4h, after the reaction is finished, carrying out suction filtration, washing a filter cake for 2 times by using acetone and distilled water respectively, centrifuging for 15min at a rotating speed of 4000r/min, drying the obtained precipitate in the 60 ℃ oven for 12h, and finally roasting in a 550 ℃ muffle furnace for 6h to obtain a mesoporous carrier;

step 2, adding 0.2mol of 2-pyridylaldehyde into 100mL of absolute ethyl alcohol, adding 0.2mol of 2-pyridylmethylamine under the stirring condition, stirring for 2h at room temperature, adding 0.37mol of sodium borohydride, stirring for reaction for 3h, filtering after the reaction is finished, cooling the filtrate to 0 ℃, adding a hydrochloric acid solution with the mass fraction of 37 to adjust the pH value to 4, adding the eluate, standing for 24h at room temperature, filtering, washing the filter cake with diethyl ether for 3 times, and finally drying at 60 ℃ to constant weight to obtain an intermediate 1;

step 3, mixing 6-bromomethyl-2-pyridinemethanol and acetonitrile according to a ratio of 1.12 g: 20mL of the mixture is uniformly mixed to obtain a solution a, 5.5mmol of an intermediate 1, 0.62mL of triethylamine and 30mL of dehydrated acetonitrile are added into a three-neck flask, the mixture is stirred for 5min, the solution a is dropwise added into the three-neck flask, dropwise addition is finished within 1h, stirring is carried out for 12h under the protection of argon after dropwise addition, acetonitrile is removed by rotary evaporation after the reaction is finished, a product is dissolved into dichloromethane, the dichloromethane is washed for 2 times by a saturated sodium bicarbonate solution and a sodium chloride solution respectively, liquid separation is carried out, an organic layer is dried by anhydrous sodium sulfate, filtration is carried out, and the dichloromethane is removed by rotary evaporation to obtain an intermediate 2;

step 4, adding 5.8mmol of the intermediate 2 and 30mL of acetonitrile into a three-neck flask, stirring for 3min, dropwise adding 20mL of L-cystine hydrochloric acid solution into the three-neck flask, after dropwise adding, adding 1.8mL of concentrated sulfuric acid under the condition of 100r/min of rotation speed, controlling the reaction temperature to be 80 ℃, stirring for reaction for 30min, after the reaction is finished, extracting with ethyl acetate, and removing the ethyl acetate by organic phase rotary evaporation to obtain an intermediate 3; wherein the hydrochloric acid solution of the L-cystine is prepared from L-cystine and 15% hydrochloric acid solution by mass percent according to the following steps of 5.5 mmol: 20mL of the mixture is mixed;

step 5, adding 45.8mL of absolute ethyl alcohol, 5mmol of diphenylamine and sodium hydride into a round-bottom flask, cooling to 0 ℃, stirring for 10min, adding 5mmol of epichlorohydrin, stirring for reaction for 6h at room temperature, then adding 5mmol of dimethylethanolamine, heating to 80 ℃, stirring for reaction for 8h, removing the absolute ethyl alcohol through rotary evaporation after the reaction is finished, and recrystallizing a product in ethyl acetate to obtain an intermediate 4; wherein the using amount of the sodium hydride is 1 percent of the mass of the diphenylamine;

step 6, adding 6mmol of an intermediate 3, 3mL of triethylamine and 68mL of dimethyl sulfoxide into a three-neck flask, adding 6mmol of an intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, stirring for 3min, adding N, N' -dicyclohexylcarbodiimide, heating to 25 ℃, reacting for 3h, concentrating the reaction liquid under reduced pressure to 1/3 volume, adding the concentrated liquid into ethyl acetate 2 times of the volume of the concentrated liquid, extracting, shaking uniformly, placing the mixture into a refrigerator at-1 ℃ for 5h, extracting with ethyl acetate for three times, washing the organic phase with a sodium bicarbonate solution with the mass fraction of 5% and a hydrochloric acid solution with the concentration of 1mmol/L, and drying with anhydrous sodium sulfate to obtain an intermediate 5; the using amount of the 4-dimethylaminopyridine is 3% of the mass of the intermediate 3, and the using amount of the N, N' -dicyclohexylcarbodiimide is 8% of the mass of the intermediate 3;

and 7, adding 2g of mesoporous carrier, 25mL of anhydrous ethanol and 40mL of deionized water into a round-bottom flask, ultrasonically dispersing for 15min at the frequency of 40kHz, adding 3mL of coupling agent KH-560, ultrasonically dispersing for 10min, adding 0.8g of intermediate 5, stirring for reacting for 1h, centrifuging for 3 times at the rotating speed of 1000r/min after the reaction is finished, washing the precipitate for 3 times by using distilled water, and finally drying at the temperature of 60 ℃ to constant weight to obtain the adsorbent.

Example 2

The adsorbent is prepared by the following steps:

step 1, adding 2.5mL of n-amyl alcohol, 7.9mL of ethyl orthosilicate and 30mL of n-hexane into a three-neck flask, stirring for 5min, adding 3.9g of hexadecyl trimethyl ammonium bromide, 0.6g of urea and 30mL of distilled water, magnetically stirring for 40min, transferring a reaction product into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a 120 ℃ oven for heat preservation for 4h, after the reaction is finished, carrying out suction filtration, washing a filter cake for 2 times by using acetone and distilled water respectively, centrifuging for 15min at a rotating speed of 4000r/min, drying the obtained precipitate in the 60 ℃ oven for 12h, and finally roasting in a 550 ℃ muffle furnace for 6h to obtain a mesoporous carrier;

step 2, adding 0.2mol of 2-pyridylaldehyde into 100mL of absolute ethyl alcohol, adding 0.2mol of 2-pyridylmethylamine under the stirring condition, stirring for 2h at room temperature, adding 0.41mol of sodium borohydride, stirring for reaction for 3h, filtering after the reaction is finished, cooling the filtrate to 0 ℃, adding a hydrochloric acid solution with the mass fraction of 37 to adjust the pH value to 4, adding the eluate, standing for 24h at room temperature, filtering, washing the filter cake with diethyl ether for 5 times, and finally drying at 60 ℃ to constant weight to obtain an intermediate 1;

step 3, mixing 6-bromomethyl-2-pyridinemethanol and acetonitrile according to a ratio of 1.12 g: 20mL of the mixture is uniformly mixed to obtain a solution a, 5.5mmol of an intermediate 1, 0.78mL of triethylamine and 30mL of dehydrated acetonitrile are added into a three-neck flask, the mixture is stirred for 5min, the solution a is dropwise added into the three-neck flask, dropwise addition is finished within 1h, stirring is carried out for 12h under the protection of argon after dropwise addition, acetonitrile is removed by rotary evaporation after the reaction is finished, a product is dissolved into dichloromethane, the dichloromethane is washed for 2 times by a saturated sodium bicarbonate solution and a sodium chloride solution respectively, liquid separation is carried out, an organic layer is dried by anhydrous sodium sulfate, filtration is carried out, and the dichloromethane is removed by rotary evaporation to obtain an intermediate 2;

step 4, adding 5.8mmol of the intermediate 2 and 38mL of acetonitrile into a three-neck flask, stirring for 3min, dropwise adding 20mL of L-cystine hydrochloric acid solution into the three-neck flask, after dropwise adding, adding 2.5mL of concentrated sulfuric acid under the condition of the rotation speed of 200r/min, controlling the reaction temperature to be 90 ℃, stirring for reaction for 60min, after the reaction is finished, extracting with ethyl acetate, and removing the ethyl acetate by organic phase rotary evaporation to obtain an intermediate 3; wherein the hydrochloric acid solution of the L-cystine is prepared from the hydrochloric acid solution of the L-cystine with the mass fraction of 15 percent according to the following steps of 5.8 mmol: 20mL of the mixture is mixed;

step 5, adding 52.3mL of absolute ethyl alcohol, 5mmol of diphenylamine and sodium hydride into a round-bottom flask, cooling to 0 ℃, stirring for 10min, adding 5mmol of epichlorohydrin, stirring for reaction for 6h at room temperature, then adding 5mmol of dimethylethanolamine, heating to 80 ℃, stirring for reaction for 8h, removing the absolute ethyl alcohol through rotary evaporation after the reaction is finished, and recrystallizing a product in ethyl acetate to obtain an intermediate 4; wherein the using amount of the sodium hydride is 1 percent of the mass of the diphenylamine;

step 6, adding 6mmol of an intermediate 3, 3mL of triethylamine and 72mL of dimethyl sulfoxide into a three-neck flask, adding 6mmol of an intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, stirring for 3min, adding N, N' -dicyclohexylcarbodiimide, heating to 25 ℃, reacting for 3h, concentrating the reaction liquid under reduced pressure to 1/3 volume, adding the concentrated liquid into ethyl acetate 2 times of the volume of the concentrated liquid, extracting, shaking uniformly, placing the mixture into a refrigerator at-1 ℃ for 5h, extracting with ethyl acetate for three times, washing the organic phase with a sodium bicarbonate solution with a mass fraction of 5% and a hydrochloric acid solution with a concentration of 1mmol/L, and drying with anhydrous sodium sulfate to obtain an intermediate 5; the using amount of the 4-dimethylaminopyridine is 5% of the mass of the intermediate 3, and the using amount of the N, N' -dicyclohexylcarbodiimide is 11% of the mass of the intermediate 3;

and 7, adding 2g of mesoporous carrier, 31mL of anhydrous ethanol and 40mL of deionized water into a round-bottom flask, ultrasonically dispersing for 15min at the frequency of 50kHz, adding 5mL of coupling agent KH-560, ultrasonically dispersing for 10min, adding 1.4g of intermediate 5, stirring for reacting for 2h, centrifuging at the rotation speed of 1200r/min for 5 times after the reaction is finished, washing the precipitate for 5 times by using distilled water, and finally drying at the temperature of 60 ℃ to constant weight to obtain the adsorbent.

Comparative example 1

This comparative example is mesoporous silica sold by Nanjing Keyed Biotechnology Ltd.

The adsorbents of examples 1 to 2 and the mesoporous silica of comparative example 1 were subjected to adsorption performance test: respectively preparing 800mg/mL copper sulfate aqueous solution and titanium tetrachloride aqueous solution, adding 0.1mol/L hydrochloric acid solution to adjust pH to 6, adding 200mg adsorbent into 100mL standard solution, standing for 6h for adsorption, and testing saturated adsorption quantity Q of each group of adsorbent_e，Q_e＝(ρ₀-ρ₁) X V/M, wherein Q_eIs the saturated adsorption capacity of the adsorbent per unit mass to metal ions, mg/g; rho₀The initial mass concentration of the metal ion solution is mg/L; rho₁The mass concentration of the metal ion solution after adsorption balance is mg/L; v is the volume of the metal ion solution, mL; m is the dosage of the adsorbent, mg; the test results are shown in table 1:

TABLE 1

Item	Copper ion Qe(mg/g)	Titanium ion Qe(mg/g)
			Example 1	354.6	328.7
Example 2	351.9	324.5
			Comparative example 1	152.7	132.9

As can be seen from Table 1, the saturated adsorption amounts of copper ions and titanium ions of the adsorbents of examples 1-2 are much larger than that of comparative example 1, which shows that the adsorbents prepared by the present invention have excellent adsorption effects on copper ions and titanium ions.

Example 3

A copper-titanium corrosive liquid for integrated circuits comprises the following raw materials in percentage by mass: 10% of sulfuric acid, 5% of nitric acid, 28% of acetic acid, 2% of potassium persulfate, 2% of hydrogen peroxide, 0.05% of the adsorbent in example 1 and the balance of pure water;

the production process of the copper-titanium corrosive liquid for the integrated circuit comprises the following steps:

adding required pure water into a batching tank, adding potassium persulfate and hydrogen peroxide while stirring, and stirring for 2 hours at the rotating speed of 100 r/min; sequentially adding sulfuric acid, nitric acid and acetic acid into the material preparation tank, and stirring at the rotating speed of 60r/min for 2 hours to obtain a mixture; and (3) introducing the mixture into a filter, filtering for more than 2 times, adding the adsorbent of the embodiment 1, and stirring for 20min at a constant rotating speed to obtain the copper-titanium etching solution for the integrated circuit.

Wherein the concentration of the sulfuric acid is 94%, the concentration of the nitric acid is 63% and the concentration of the acetic acid is 98%; the concentration of hydrogen peroxide is 30 percent, and the aperture of the micro-filtration membrane of the filter in the fourth step is 0.03 mu m.

Example 4

A copper-titanium corrosive liquid for integrated circuits comprises the following raw materials in percentage by mass: 12% of sulfuric acid, 7% of nitric acid, 30% of acetic acid, 4% of potassium persulfate, 3% of hydrogen peroxide, 0.08% of the adsorbent in example 2 and the balance of pure water;

the production process of the copper-titanium corrosive liquid for the integrated circuit comprises the following steps:

adding required pure water into a batching tank, adding potassium persulfate and hydrogen peroxide while stirring, and stirring for 3 hours at the rotating speed of 150 r/min; sequentially adding sulfuric acid, nitric acid and acetic acid into the material preparation tank, and stirring at the rotating speed of 70r/min for 2 hours to obtain a mixture; and (3) introducing the mixture into a filter, filtering for more than 2 times, adding the adsorbent of the embodiment 2, and stirring for 30min at a constant rotating speed to obtain the copper-titanium etching solution for the integrated circuit.

Wherein the concentration of the sulfuric acid is 96%, the concentration of the nitric acid is 63% and the concentration of the acetic acid is 98%; the concentration of hydrogen peroxide is 30 percent, and the aperture of the micro-filtration membrane of the filter in the fourth step is 0.06 mu m.

Example 5

A copper-titanium corrosive liquid for integrated circuits comprises the following raw materials in percentage by mass: 19% of sulfuric acid, 8% of nitric acid, 33% of acetic acid, 5% of potassium persulfate, 4% of hydrogen peroxide, 0.1% of the adsorbent in example 3 and the balance of pure water;

the production process of the copper-titanium corrosive liquid for the integrated circuit comprises the following steps:

adding required pure water into a batching tank, adding potassium persulfate and hydrogen peroxide while stirring, and stirring for 4 hours at the rotating speed of 200 r/min; sequentially adding sulfuric acid, nitric acid and acetic acid into the batching tank, and stirring at the rotating speed of 80r/min for 2 hours to obtain a mixture; and (3) introducing the mixture into a filter, filtering for more than 2 times, adding the adsorbent of the embodiment 3, and stirring for 40min at a constant rotating speed to obtain the copper-titanium etching solution for the integrated circuit.

Wherein the concentration of the sulfuric acid is 98%, the concentration of the nitric acid is 64% and the concentration of the acetic acid is 98%; the concentration of hydrogen peroxide is 30 percent, and the aperture of the micro-filtration membrane of the filter in the fourth step is 0.10 mu m.

Comparative example 2

The adsorbent of example 1 was removed and the remaining raw materials and preparation were unchanged.

Comparative example 3

The comparative example is an acidic recyclable etching solution sold by Shenzhen Baitongda science and technology Limited.

The etching solutions of examples 4 to 6 and comparative examples 2 to 3 were subjected to performance tests:

the copper/titanium laminated film was placed on a glass substrate, etched for a time 1.8 times the etching time calculated from the etching rate, and then observed by an electron microscope, and the flatness and holes after etching were evaluated. The test results are shown in table 2:

TABLE 2

As can be seen from table 2, the etching solutions of examples 4 to 6 have the characteristics of faster etching speed, high flatness after etching, and no occurrence of voids, compared with the etching solutions of comparative examples 2 to 3, and the etching solutions do not contain fluorine, do not corrode silicon substrates, silicon nitride and amorphous silicon, and simultaneously give consideration to product yield, safety and environmental protection, and reduce the risk of defects after rework, and can be widely applied in the fields of the integrated circuit industry, flat panel displays, color filters, touch panels, organic light emitting diodes, and the like.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (10)

1. The copper-titanium corrosive liquid for the integrated circuit is characterized by comprising the following raw materials in percentage by mass: 10-19% of sulfuric acid, 5-8% of nitric acid, 28-33% of acetic acid, 2-5% of potassium persulfate, 2-4% of hydrogen peroxide, 0.05-0.1% of adsorbent and the balance of pure water;

wherein, the adsorbent is prepared by the following steps:

step 1, adding n-amyl alcohol, ethyl orthosilicate and n-hexane into a three-neck flask, stirring for 5min, adding hexadecyl trimethyl ammonium bromide, urea and distilled water, magnetically stirring for 40min, transferring a reaction product into a polytetrafluoroethylene reaction kettle, placing the reaction product into a 120 ℃ oven, preserving heat for 4h, after the reaction is finished, performing suction filtration, washing a filter cake, centrifuging, drying and roasting to obtain a mesoporous carrier;

step 2, adding 2-pyridylaldehyde into absolute ethyl alcohol, stirring, adding 2-pyridylmethylamine, stirring for 2 hours, adding sodium borohydride, stirring for reaction for 3 hours, filtering, cooling the filtrate to 0 ℃, adding a hydrochloric acid solution to adjust the pH value to 4, adding the precipitation solution, standing at room temperature for 24 hours, filtering, washing a filter cake, and drying to obtain an intermediate 1;

step 3, mixing 6-bromomethyl-2-pyridinemethanol and acetonitrile according to a ratio of 1.12 g: 20mL of the mixture is uniformly mixed to obtain a solution a, the intermediate 1, triethylamine and water-removing acetonitrile are added into a three-neck flask, the mixture is stirred for 5min, then the solution a is dropwise added, after the dropwise addition is finished, the mixture is stirred under the protection of argon to react for 12h, and the intermediate 2 is obtained through rotary evaporation, washing and purification;

step 4, adding the intermediate 2 and acetonitrile into a three-neck flask, stirring for 3min, dropwise adding hydrochloric acid solution of L-cystine, adding concentrated sulfuric acid after dropwise adding, controlling the reaction temperature to be 80-90 ℃, stirring for reaction for 30-60min, extracting after the reaction is finished, and performing rotary evaporation to obtain an intermediate 3;

step 5, adding absolute ethyl alcohol, diphenylamine and sodium hydride into a round-bottom flask, cooling to 0 ℃, stirring for 10min, adding epoxy chloropropane, stirring and reacting for 6h at room temperature, then adding dimethylethanolamine, heating to 80 ℃, stirring and reacting for 8h, filtering, performing rotary evaporation on the filtrate, and recrystallizing to obtain an intermediate 4;

step 6, adding the intermediate 3, triethylamine and dimethyl sulfoxide into a three-neck flask, adding the intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, stirring for 3min, adding N, N' -dicyclohexylcarbodiimide, heating to 25 ℃, reacting for 3h, concentrating under reduced pressure, extracting, washing and drying to obtain an intermediate 5;

and 7, adding the mesoporous carrier, absolute ethyl alcohol and deionized water into a round-bottom flask, performing ultrasonic dispersion for 15min, adding a coupling agent KH-560, performing ultrasonic dispersion for 10min, adding the intermediate 5, stirring for reaction for 1-2h, centrifuging for 3-5 times after the reaction is finished, washing, and drying to obtain the adsorbent.

2. The copper-titanium etching solution for integrated circuits as claimed in claim 1, wherein the ratio of n-amyl alcohol, ethyl orthosilicate, n-hexane, cetyl trimethyl ammonium bromide, urea and distilled water in step 1 is 2.5 mL: 5.6-7.9 mL: 30mL of: 3.1-3.9 g: 0.6 g: 30 mL.

3. The copper-titanium etchant solution for integrated circuits of claim 1, wherein the ratio of the 2-pyridylaldehyde, the absolute ethyl alcohol, the 2-pyridylmethyl amine and the sodium borohydride in step 2 is 0.2 mol: 100mL of: 0.2 mol: 0.37-0.41mol, and the precipitation liquid is formed by mixing absolute ethyl alcohol and ether at the temperature of 0 ℃ according to the volume ratio of 3: 1.

4. The copper-titanium etchant solution for integrated circuits according to claim 1, wherein the ratio of the amount of solution a, intermediate 1, triethylamine and acetonitrile removed in step 3 is 20 mL: 5.5 mmol: 0.62-0.78 mL: 30 mL.

5. The copper-titanium etchant solution for integrated circuits according to claim 1, wherein the ratio of the amount of hydrochloric acid solution of intermediate 2, acetonitrile, L-cystine and concentrated sulfuric acid in step 4 is 5.8 mmol: 30-38 mL: 20mL of: 1.8-2.5mL, wherein the hydrochloric acid solution of L-cystine is prepared by mixing L-cystine and 15% hydrochloric acid solution in mass fraction according to the following steps of 5.5-5.8 mmol: 20mL of the mixture was mixed.

6. The copper-titanium etching solution for integrated circuits as claimed in claim 1, wherein the ratio of the amount of absolute ethyl alcohol, diphenylamine, epichlorohydrin and dimethylethanolamine in step 5 is 45.8-52.3 mL: 5 mmol: 5 mmol: 5mmol, and the dosage of the sodium hydride is 1 percent of the mass of the diphenylamine.

7. The copper-titanium etching solution for integrated circuits as claimed in claim 1, wherein the ratio of the amount of intermediate 3, triethylamine, dimethyl sulfoxide and intermediate 4 in step 6 is 6 mmol: 3mL of: 68-72 mL: the dosage of 6mmol, 4-dimethylamino pyridine is 3-5% of the mass of the intermediate 3, and the dosage of N, N' -dicyclohexyl carbodiimide is 8-11% of the mass of the intermediate 3.

8. The copper-titanium etchant solution of claim 1, wherein the amount of the mesoporous carrier, the absolute ethanol, the deionized water, the coupling agent KH-560 and the intermediate 5 in step 7 is 2 g: 25-31 mL: 40mL of: 3-5 mL: 0.8-1.4 g.

9. The copper-titanium etching solution for integrated circuits as claimed in claim 1, wherein the sulfuric acid concentration is 94-98%, the nitric acid concentration is 63-64%, and the acetic acid concentration is 98%; the concentration of hydrogen peroxide is 30 percent.

10. The process of claim 1, comprising the steps of:

the first step is as follows: weighing and preparing raw materials such as sulfuric acid, nitric acid, acetic acid, potassium persulfate, hydrogen peroxide, an adsorbent, pure water and the like according to a ratio;

the second step is that: adding required pure water into a material mixing tank, adding potassium persulfate and hydrogen peroxide under stirring, and stirring for 2-4h under the condition of the rotating speed of 100-;

the third step: sequentially adding sulfuric acid, nitric acid and acetic acid into the batching tank, and stirring for 2 hours at the rotating speed of 60-80r/min to obtain a mixture;

the fourth step: and (3) introducing the mixture into a filter, filtering for more than 2 times, adding an adsorbent, and stirring for 20-40min at a constant rotating speed to obtain the copper-titanium etching solution for the integrated circuit.