Carbazole-containing quaternary ammonium salt compounds, their preparation methods and applications

Abstract

The present invention discloses carbazole quaternary ammonium salt compounds, their preparation methods and applications. The structure of the compounds is shown by the following formula: wherein, R is selected from any one of ; n is an even number among integers from 0 to 20; X is selected from any one of F, Cl, Br, and I. The synthesized carbazole quaternary ammonium salt compounds of the present invention can have a large coverage area on the electrode surface through the nitrogen positive ion, i.e., the quaternization center, in the structure and can increase the cathode polarization, inhibit copper deposition, so that the electroplated particles are finer and the copper plating layer obtains a high preferred crystal plane orientation, enabling it to be used as a quaternary ammonium salt leveling agent for acidic copper electroplating.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical synthesis, and particularly relates to a carbazole-containing quaternary ammonium salt compound, a preparation method thereof and an application thereof. Background Art

[0002] Electroplating technology is used in aspects such as energy conservation, surface treatment of materials, and new materials, and is widely used in many industries such as clothing accessories, food packaging, building materials, the automotive industry, aerospace materials, portable electronic products, and the integrated circuit industry. It is a discipline and technology that develops as rapidly as the economy. The emergence and development of electroplating technology have greatly improved people's clothing, food, housing, and transportation, contributed to the R & D breakthroughs in the materials industry, and promoted the economic development of the country.

[0003] The application directions of electroplating technology are divided into decorative electroplating and functional electroplating. Decorative electroplating is mainly to electroplate the surface of the workpiece, covering a thin layer of metal on the surface of the workpiece, which plays roles such as ornamental, anti-corrosion, and wear resistance. For example, when installing faucets and car logos during decoration, which are generally made of plastic, in order to improve the use texture, increase ornamental value, save energy and reduce costs, a layer of metal is usually electroplated on the surface. This type of electroplating technology has a low threshold and is easy to master.

[0004] Functional electroplating generally refers to the precision processing of precision instruments and components, which can exhibit excellent and stable performance in specific scenarios such as vacuum, high pressure, and high current density, and is commonly used in key fields such as precision instruments, aerospace, and integrated circuits. This type of electroplating technology has high industry barriers, complex technology, strict requirements, and high trial-and-error costs. With the popularization and large-scale use of 5G globally, people's handheld and wearable devices, smart homes, and smart cities have been realized, and the integrated circuit behind these scenarios has contributed a lot.

[0005] The integrated circuit industry chain is huge, with an output value exceeding one trillion yuan. It is a leading industry in modern industry, promoting the continuous development of global technology upgrading and energy conservation and environmental protection. The upstream industry of integrated circuits is knowledge-intensive industries such as computer-aided design software, precision instruments, and new materials, and its downstream is consumer market fields such as smart homes, personal portable devices, communication devices, new energy vehicles, and smart cities. It can be said that the integrated circuit industry is the hub of the modern social system. Integrated circuits mainly involve industries such as new materials, precision instruments, computer software-aided design, and advanced manufacturing. They cover a wide range of fields, are knowledge-intensive industries, and have high industrial added value. With the emergence and proposal of the Internet, Moore's Law, the Internet of Things, and the Internet of Everything, it has greatly promoted and driven the development of the integrated circuit industry, making it account for an increasing proportion of the national economy. The integrated circuit industry is divided into: design, manufacturing, testing and packaging, and the materials, equipment, and software used in this process. Electroplating is an indispensable process in manufacturing and testing and packaging, and electroplating additives are one of the key materials in the integrated circuit electroplating process.

[0006] Integrated circuits, also known as chips, are fabricated through eight major processes: wafer manufacturing, oxidation, lithography, etching, thin film deposition, interconnect, testing, and packaging. The interconnect process includes two types: aluminum (Al) interconnect process and copper (Cu) interconnect process. Al is prone to corrosion and has a relatively low melting point. In addition, metal deposits need to be added in the Al interconnect process to separate Al from the wafer to prevent it from reacting with the wafer. However, with the process upgrade, the electrical performance of Al circuits cannot meet the requirements. Since Cu has lower resistance and better electrical performance, the Cu interconnect process is adopted. In the Cu interconnect process, a Cu seed layer is first deposited on the barrier layer, and then electroplating is used to fill blind vias or through-hole patterns with high aspect ratios. Finally, mechanical polishing is used to remove the excess copper.

[0007] The basic plating solution for electroplating copper contains copper sulfate, sulfuric acid, and chloride ions. To achieve better filling effects, three types of electroplating additives are also added: inhibitors (commonly polyethylene glycol (PEG)), accelerators (commonly sodium 3,3'-dithiodipropanesulfonate (SPS)), and leveling agents.

[0008] Carbazole (9H-carbazole), also known as dibenzopyrrole and 9-azaphenalene, is a common nitrogen-containing heterocyclic compound. Its molecular formula is C 12 H 9 N, with a molecular weight of 167.21 g / mol. It is a colorless crystal or light gray powder, insoluble in water and inorganic acids, slightly soluble in ethanol, acetone, and benzene, but soluble in solvents such as acetic acid, chloroform, and carbon disulfide. It is obtained by distillation from coal tar and has traditionally been used as a raw material for dyes and pigments. In recent years, many researchers have synthesized a large number of carbazole derivatives using carbazole as the molecular synthesis substrate and carried out extensive research on the applications of these carbazole derivatives in different fields.

[0009] The present invention designs and synthesizes a series of previously unreported carbazole quaternary ammonium salt derivatives. Carbazole itself has a large conjugated π bond, which is more likely to adsorb on the surface of the copper layer, and its N+ center can more effectively inhibit the deposition of copper ions. It can be used as an electroplating leveling additive, especially as an electroplating additive in acidic copper sulfate plating solutions, playing a leveling role. After testing, good results have been obtained. Summary of the Invention

[0010] Based on the above research, the present invention uses carbazole as the starting material to design and synthesize a new class of compounds for use as electroplating additives in acidic copper sulfate plating solutions. With the in-depth research, it is found that by appropriately modifying the structure of the existing carbazole quaternary ammonium salt compounds, their electrical properties are more excellent. Based on the various excellent properties and structural characteristics of carbazole, the present invention has developed a series of carbazole quaternary ammonium salt compounds for use as electroplating additives in electroplating. After a series of tests, good results have been obtained.

[0011] The first object of the present invention is to provide a carbazole quaternary ammonium salt compound, another object is to provide a preparation method of the carbazole quaternary ammonium salt compound, and the third object is to provide its application in electroplating additives.

[0012] To achieve the above objects, the technical solutions adopted by the present invention are as follows:

[0013] In the first aspect of the present invention, a carbazole quaternary ammonium salt compound is provided, which is characterized in that the structure is shown as the following formula:

[0014]

[0015] Wherein, R is selected from any one of ;

[0016] n is an even number among integers from 0 to 20;

[0017] X is selected from any one of F, Cl, Br, and I.

[0018] Further preferably, n is 8, 10 or 12, and more preferably 12. The structure of the compound is shown as follows:

[0019]

[0020] Wherein, R is selected from any one of ;

[0021] X is selected from any one of F, Cl, Br, and I.

[0022] Even more preferably, X is Cl or Br, and more preferably Br. The structural formula of the carbazole quaternary ammonium salt compound is shown as any one of the following formulas:

[0023]

[0024]

[0025] In the second aspect of the present invention, a preparation method of the above-mentioned carbazole quaternary ammonium salt compound is provided. First, carbazole is made into an intermediate product M, and then the intermediate product M reacts with pyridine or 4,4-bipyridine to make product II or III. Then, product III reacts with methyl iodide or benzyl bromide to make product IV or V. The specific synthesis steps are as follows:

[0026] A. Synthesis of intermediate product M

[0027] Add an organic solvent to the reaction vessel, and add carbazole, an alkane with halogen substitution at both ends, and a strong base with a molar ratio of 1:5:3 into the reaction vessel respectively to obtain a light yellow turbid liquid, and react at 35 °C; after the reaction is completed, air condensation is adopted, and tetrabutylammonium bromide is added thereto for reaction. The molar ratio of tetrabutylammonium bromide to carbazole is 0.65:1. After reacting for 3 h, heating is stopped, and the reaction is carried out at room temperature for 14 h; after the reaction is completed, add a saturated sodium chloride solution with a volume twice that of the organic solvent to the reaction solution, stir, and then add an extractant thereto. After extraction, washing, and drying, column separation is carried out to obtain the intermediate product M,

[0028]

[0029] B. Synthesis of carbazole quaternary ammonium salt compounds

[0030] Synthesize by the method described in any one of B-1 to B-4

[0031] B-1. Synthesis of product I

[0032]

[0033] Add compound M, trimethyl quaternary ammonium salt, sodium bicarbonate and a certain amount of acetonitrile with a molar ratio of 1:5:5 into the reaction vessel in sequence, and react at 80 °C for 12 h under Ar protection; after cooling to room temperature, carry out suction filtration, wash with methanol, and take the filtrate to make a dry sample with 200-300 mesh aluminum hydroxide; purify by chromatography column, and the eluent is dichloromethane and methanol to obtain product I;

[0034] B-2. Synthesis of product II

[0035]

[0036] Add intermediate M-1, pyridine and a certain amount of acetonitrile with a molar ratio of 1:5 into the reaction vessel in sequence, and react at 80 °C for 24 h under argon protection; after cooling to room temperature, precipitate with ethyl acetate and wash the filter cake, and obtain product II after vacuum drying;

[0037] B-3. Synthesis of product III

[0038]

[0039] Add intermediate M-1, bipyridine and a certain amount of acetonitrile with a molar ratio of 1:5 into the reaction vessel in sequence, and react at 80 °C for 24 h under argon protection; after cooling to room temperature, precipitate with ethyl acetate and wash the filter cake, and obtain product III after vacuum drying;

[0040] B-4. Synthesis of product IV or V

[0041]

[0042] The product III with a molar ratio of 1:5, methyl iodide or benzyl bromide, and a certain amount of acetonitrile are successively added to a reaction vessel and reacted at 80 °C for 5 h; after cooling to room temperature, the product is precipitated with ethyl acetate and the filter cake is washed, and after vacuum drying, product IV or V is obtained.

[0043] Preferably, in step A, the organic solvent is selected from any one of toluene, xylene, ethanol, hexane, CCl 4 among others;

[0044] The strong base is selected from sodium hydroxide or potassium hydroxide;

[0045] When performing product separation, the extraction agent used is any one of dichloromethane, dichloroethane, dichloropropane, trichloroethane, methyl acetate;

[0046] When performing column separation, petroleum ether and dichloromethane are used for column chromatography.

[0047] In the third aspect of the present invention, the application of the carbazole quaternary ammonium salt compound is provided, specifically the application in the preparation of electroplating additives.

[0048] Preferably, the electroplating additive is an electroplating leveling agent; more preferably a copper electroplating leveling agent, and the electroplating solution is acidic copper sulfate.

[0049] In the fourth aspect of the present invention, an electroplating leveling agent is provided, which includes an active component and a solvent. The active component includes the above-mentioned carbazole quaternary ammonium salt compound, preferably the five compounds listed above, and most preferably the latter three compounds.

[0050] Advantageous technical effects of the present invention:

[0051] The present invention designs and synthesizes a series of unreported carbazole quaternary ammonium salt compounds, and studies the methodology for synthesizing the carbazole quaternary ammonium salt compounds. The synthesized carbazole quaternary ammonium salt compound, with this quaternary ammonium salt structure, through the nitrogen cation in the structure, i.e., the quaternization center, can have a large coverage area on the electrode surface and can increase the cathodic polarization, inhibit copper deposition, thereby making the electroplating particles finer and enabling the copper plating layer to obtain a high preferred crystal plane orientation, so that it can be used as a quaternary ammonium salt leveling agent for acidic copper electroplating. Description of the Drawings

[0052] Figure 1 Cyclic voltammograms of the inhibition effect of compound I-3 in Application Example 1 on copper ion deposition on the copper material surface at concentrations of 0, 2, 4, 6, 8, 10 μmol / L and the blank control, where the abscissa is the potential of the electrode (Ag / AgCl) (unit: volt), and the ordinate is the current density (unit: ampere / dm 2 )

[0053] Figure 2 Cyclic voltammograms of the inhibition effects of Compounds I-1, I-2, I-3, I-4, and I-5 according to Application Example 2 on copper ion deposition on the surface of a copper material at a concentration of 2 μmol / L and of the blank control, where the abscissa is the potential of the electrode (Ag / AgCl) (unit: volt) and the ordinate is the current density (unit: ampere per decimeter 2 ).

[0054] Figure 3 Polarization curves of the inhibition effects of Compound I-3 according to Application Example 3 on copper ion deposition on the surface of a copper material at concentrations of 0, 2, 4, 6, 8, and 10 μmol / L and of the blank control, where the abscissa is the potential of the electrode (Ag / AgCl) (unit: volt) and the ordinate is the current density (unit: ampere per decimeter 2 ).

[0055] Figure 4 Polarization curves of the inhibition effects of Compounds I-1, I-2, I-3, I-4, and I-5 according to Application Example 4 on copper ion deposition on the surface of a copper material at a concentration of 2 μmol / L and of the blank control, where the abscissa is the potential of the electrode (Ag / AgCl) (unit: volt) and the ordinate is the current density (unit: ampere per decimeter 2 ).

[0056] Figure 5 Chronoamperometric addition curves at a constant current of the inhibition effects of Compounds I-1, I-2, I-3, I-4, and I-5 according to Application Example 5 on copper ion deposition on the surface of a copper material at a concentration of 2 ppm, where the abscissa is the time (s) and the ordinate is the potential of the electrode (Ag / AgCl) (unit: volt). Detailed implementation manners

[0057] To illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the protection scope of the present invention.

[0058] Example 1

[0059]

[0060] Add 10 mL of toluene (Tol) to a three-necked flask, and add 0.167 g of carbazole (S-1), 1.130 g of 1,6-dibromohexane, and 168 mg of potassium hydroxide (KOH) to the flask. After adding the three substances, it becomes a pale yellow turbid liquid and reacts at 35 °C. Condense with air, add 0.1 g of tetrabutylammonium bromide (TBAB) to it, and react for 3 h. After 3 h, stop heating and react at room temperature for 14 h. After the reaction is completed, add 20 mL of saturated sodium chloride solution to the reaction solution, stir for a while, and then add 20 mL of dichloromethane. Extract, wash, dry, and column-chromatograph with petroleum ether and dichloromethane to obtain the intermediate product M-1.

[0061] 1 HNMR(400MHz,Chloroform-d):δ8.10(d,J=7.7Hz,2H),7.46(t,J=7.6Hz,2H),7.38(d,J=8.2Hz,2H),7.22(t,J=7.4Hz,2H),4.29(t,J=7.2Hz,2H),3.34(dt,J=7.7,3.8Hz,2H),1.88(p,J=7.4Hz,2H),1.79(p,J=7.0Hz,2H),1.42(dp,J=24.2,7.6Hz,4H); 13 C NMR(400MHz,Chloroform-d):δ140.48,125.74,122.93,120.49,118.90,108.72,42.89,33.90,32.68,28.95,28.04,26.59.

[0062]

[0063] Add compound M-1 (1 mmol), trimethylammonium salt (NMe 3 ·HCl, 5 mmol), sodium bicarbonate (NaHCO 3 , 5 mmol) and acetonitrile (10 mL) to a 50 mL three-necked flask in sequence, and react at 80 °C for 12 h under Ar protection. After cooling to room temperature, filter by suction, wash with methanol, and take the filtrate to make a dry sample with 200 - 300 mesh aluminum hydroxide (Al 2 O 3 ). Purify by column chromatography, and the eluent is dichloromethane and methanol to obtain the product I-1.

[0064] 11H NMR (400 MHz, Chloroform-d): δ 8.06 (d, J = 7.8 Hz, 2H), 7.47–7.37 (m, 4H), 7.23–7.17 (m, 2H), 4.30 (t, J = 6.8 Hz, 2H), 3.35–3.30 (m, 2H), 3.23 (s, 9H), 1.86 (p, J = 6.8 Hz, 2H), 1.52 (dq, J = 12.9, 7.5 Hz, 2H), 1.38–1.25 (m, 4H); 13 13C NMR (400 MHz, Methanol-d4): δ 141.80, 126.72, 124.05, 121.14, 119.88, 110.02, 67.59, 53.43, 53.40, 53.35, 43.42, 29.66, 27.63, 27.06, 23.65. MS (ESI) m / z: [M - Br - + calcd for C 21 H 29 N 2 + 309.2325; found 309.2332.

[0065] Example 2

[0066]

[0067] Compound M-1 (1 mmol), pyridine (5 mmol) and acetonitrile (10 mL) were successively added into a 50 mL three-necked flask, and the reaction was carried out at 80 °C for 24 h under argon protection. After cooling to room temperature, the reaction solution was poured into 150 mL of ethyl acetate, and a precipitate was formed. The precipitate was filtered, washed with ethyl acetate, and the filter cake was dried in vacuo to obtain product I-2;

[0068] 1 1H NMR (400 MHz, Methanol-d4): δ 8.84–8.77 (m, 2H), 8.48 (tt, J = 7.8, 1.4 Hz, 1H), 8.03 (d, J = 7.8 Hz, 2H), 7.96 (t, J = 7.0 Hz, 2H), 7.47–7.35 (m, 4H), 7.15 (ddd, J = 8.0, 6.9, 1.2 Hz, 2H), 4.44 (t, J = 7.5 Hz, 2H), 4.33 (t, J = 6.8 Hz, 2H), 1.84 (tq, J = 12.3, 7.0, 5.6 Hz, 4H), 1.30 (pd, J = 9.0, 8.1, 3.4 Hz, 4H); 13 ​¹³C NMR (400 MHz, DMSO-d6): δ 145.43, 144.68, 139.95, 128.03, 125.66, 122.00, 120.28, 118.65, 109.22, 60.72, 42.06, 30.54, 28.28, 25.93, 25.24. MS (ESI) m / z: [M - Br⁻] + calcd for C 23 H 25 N 2 + 329.2012; found 329.2019.

[0069] Example 3

[0070]

[0071] Compound M-1 (1 mmol), bipyridine (5 mmol) and acetonitrile (10 mL) were successively added to a 50 mL three-necked flask and reacted at 80 °C for 24 h under argon protection. After cooling to room temperature, the reaction solution was poured into 150 mL of ethyl acetate, and a precipitate formed. It was filtered, washed with ethyl acetate, and the filter cake was dried in vacuo to obtain product I-3;

[0072] 1 ¹H NMR (400 MHz, DMSO-d6): δ 9.04–8.96 (m, 2H), 8.69–8.64 (m, 2H), 8.44–8.37 (m, 2H), 7.94 (d, J = 7.7 Hz, 2H), 7.85–7.81 (m, 2H), 7.39 (d, J = 8.2 Hz, 2H), 7.24 (ddd, J = 8.2, 7.1, 1.2 Hz, 2H), 7.02–6.95 (m, 2H), 4.39 (t, J = 7.3 Hz, 2H), 4.19 (t, J = 7.0 Hz, 2H), 1.68 (t, J = 7.3 Hz, 2H), 1.57 (t, J = 7.2 Hz, 2H), 1.20–1.05 (m, 4H); 13 ¹³C NMR (400 MHz, Methanol-d4): δ 152.27, 151.05, 145.30, 140.94, 140.01, 125.74, 125.41, 122.06, 121.99, 120.35, 118.73, 109.30, 60.42, 42.15, 30.62, 28.37, 26.05, 25.31. MS (ESI) m / z: [M - Br - + calcd for C 28 H 28 N​3 + 406.2278; found 406.2282.

[0073] Example 4

[0074]

[0075] Compound I-3 (1 mmol), methyl iodide (CH 3 ·I, 5 mmol) and acetonitrile (20 mL) were successively added to a 50 mL three-necked flask and reacted at 80 °C for 5 h. After cooling to room temperature, the reaction solution was poured into 150 mL of ethyl acetate, and a precipitate formed. It was filtered, washed with ethyl acetate, and the filter cake was dried under vacuum to obtain product I-4;

[0076] 1 1H NMR (400 MHz, DMSO-d6): δ 9.32 (d, J = 6.5 Hz, 2H), 9.28 (d, J = 6.3 Hz, 2H), 8.74 (dd, J = 6.8, 3.4 Hz, 4H), 8.14 (d, J = 7.7 Hz, 2H), 7.59 (d, J = 8.2 Hz, 2H), 7.48–7.40 (m, 2H), 7.18 (t, J = 7.4 Hz, 2H), 4.63 (t, J = 7.3 Hz, 2H), 4.43 (s, 3H), 4.40 (t, J = 6.9 Hz, 2H), 1.95–1.86 (m, 2H), 1.78 (t, J = 6.5 Hz, 2H), 1.40–1.28 (m, 4H); 13 13C NMR (400 MHz, Methanol-d4): δ 148.50, 148.16, 146.65, 145.73, 139.98, 126.52, 126.10, 125.71, 122.03, 120.34, 118.70, 109.29, 60.88, 48.12, 42.13, 30.63, 28.37, 26.04, 25.29. MS (ESI) m / z: [M - 2Br - 2+ calcd for C 29 H 31 N 3 2+ 421.2507; found 421.2517.

[0077] Example 5

[0078]

[0079] ​Compound I-3 (1 mmol), benzyl bromide (5 mmol) and acetonitrile (20 mL) were successively added to a 50 mL three-necked flask and reacted at 80 °C for 5 h. After cooling to room temperature, the reaction solution was poured into 150 mL of ethyl acetate, and a precipitate was formed. The precipitate was filtered, washed with ethyl acetate, and the filter cake was dried under vacuum to obtain product I-5;

[0080] 1 1H NMR (400 MHz, DMSO-d6): δ 9.56 (d, J = 6.3 Hz, 2H), 9.35 (d, J = 6.3 Hz, 2H), 8.76 (dd, J = 19.1, 6.3 Hz, 4H), 8.13 (d, J = 7.8 Hz, 2H), 7.61 (dd, J = 20.6, 8.0 Hz, 4H), 7.50–7.40 (m, 5H), 7.18 (t, J = 7.4 Hz, 2H), 5.98 (s, 2H), 4.64 (t, J = 7.4 Hz, 2H), 4.40 (t, J = 6.9 Hz, 2H), 1.94–1.85 (m, 2H), 1.77 (t, J = 7.2 Hz, 2H), 1.40–1.27 (m, 4H); 13 13C NMR (404 MHz, Methanol-d4): δ 141.40, 137.47, 137.47, 132.25, 124.84, 121.79, 121.34, 120.95, 118.95, 118.68, 117.26, 114.49, 111.65, 110.40, 100.54, 56.40, 53.63, 34.02, 22.78, 20.26, 18.19, 17.49. MS (ESI) m / z: [M-H-2Br - 2+ calcd for C 35 H 35 N 3 2+ 496.2820; found 496.2748.

[0081] Application Example 1

[0082] Prepare a solution containing 60 g / L of CuSO 4 ·5H 2 O copper sulfate, 100 g / L concentrated sulfuric acid and 60 ppm concentrated hydrochloric acid. Using a Pt rotating electrode as the working electrode, a platinum wire as the counter electrode and Ag / AgCl as the reference electrode, at a rotation speed of 2000 revolutions per minute, 0, 2, 4, 6, 8, 10 μmol / L of compound I-3 (the compound I-3 prepared in Example 3, the same below) were added to the solution respectively, and cyclic voltammetry curve tests were performed. ​

[0083] Generally speaking, when adding electroplating additives with the same concentration to the plating solution, the smaller the oxidation peak area of the cyclic voltammetry curve, the stronger the inhibitory effect, and the better the leveling effect in the actual electroplating process. Figure 3 It is the test chart of the cyclic voltammetry curve of Compound I-3. The results show that Compound I-3 can reduce the oxidation peak of the cyclic voltammetry curve. The smaller the oxidation peak area obtained by the test, the stronger the inhibitory effect. When Compound I-3 is not contained in the solution, the oxidation peak area of the cyclic voltammetry curve is the largest. After adding Compound I-3 to the solution in a gradient manner, the oxidation peak area of the cyclic voltammetry curve decreases in a gradient manner. When the concentration of Compound I-3 in the solution reaches 10 ppm, the oxidation peak area of the cyclic voltammetry curve decreases to almost 0, indicating that Compound I-3 has a strong inhibitory ability and a good leveling effect.

[0084] Application Example 2

[0085] Prepare a solution containing 60 g / L CuSO 4 ·5H 2 O copper sulfate, 100 g / L concentrated sulfuric acid and 60 ppm concentrated hydrochloric acid. Using a Pt rotating electrode as the working electrode, a platinum wire as the counter electrode and Ag / AgCl as the reference electrode, under the condition that the rotation speed is 2000 revolutions per minute, add 2 μmol / L 200 μL of Compounds I-1, I-2, I-3, I-4, I-5 to the solution respectively, and conduct cyclic voltammetry curve tests.

[0086] Figure 2 It is the test chart of the cyclic voltammetry curves of Compounds I-1, I-2, I-3, I-4, I-5. The results show that Compounds I-1, I-2, I-3, I-4, I-5 can all increase the cathodic polarization. When the carbazole quaternary ammonium salt compound is not contained in the solution, the oxidation peak area of the cyclic voltammetry curve is the largest; after adding the carbazole quaternary ammonium salt compound to the solution, the oxidation peak areas of the cyclic voltammetry curves all decrease; Figure 2 The results in it also show that when adding 2 μmol / L of Compounds I-1 and I-2 to the solution respectively, the decrease in the oxidation peak area of the cyclic voltammetry curve is less, while when adding 2 μmol / L of Compounds I-3, I-4, I-5 to the solution respectively, the decrease in the oxidation peak area of the cyclic voltammetry curve is obvious, indicating that the inhibitory abilities of Compounds I-3, I-4, I-5 are stronger than those of Compounds I-1, I-2, and the leveling effects are better. Compounds I-3, I-4, I-5 are more preferred additives.

[0087] Application Example 3

[0088] Prepare a solution containing 60 g / L CuSO 4 ·5H 2A solution of 60 g / L CuSO₄·5H₂O copper sulfate, 100 g / L concentrated sulfuric acid, and 60 ppm concentrated hydrochloric acid. Using a Pt rotating electrode as the working electrode, a platinum wire as the counter electrode, and Ag / AgCl as the reference electrode, at a rotation speed of 2000 revolutions per minute, 0, 2, 4, 6, 8, and 10 μmol / L of Compound I-3 were added to the solution respectively, and a cathodic polarization curve test was performed.

[0089] Generally speaking, when the same concentration of electroplating additive is added to the plating solution, the deposition current density begins to increase, indicating the occurrence of cathodic polarization; the smaller the deposition potential of the polarization curve, the stronger the inhibitory effect, and the better the leveling effect during the actual electroplating process. Figure 3 It is a test chart of the cathodic polarization curve of Compound I-3. The results show that Compound I-3 can increase cathodic polarization. When there is no Compound I-3 in the solution, the copper deposition current can be observed when the potential moves from positive to negative by more than 0 volts. After adding Compound I-3 to the solution in a gradient manner, the copper deposition potential undergoes a gradient negative shift. When the concentration of Compound I-3 in the solution reaches 10 ppm and the potential reaches -0.22 V, the copper deposition current is observed, indicating that Compound I-3 has a strong inhibitory ability and a good leveling effect.

[0090] Application Example 4

[0091] Prepare a solution containing 60 g / L CuSO 4 ·5H 2 A solution of 60 g / L CuSO₄·5H₂O copper sulfate, 100 g / L concentrated sulfuric acid, and 60 ppm concentrated hydrochloric acid. Using a Pt rotating electrode as the working electrode, a platinum wire as the counter electrode, and Ag / AgCl as the reference electrode, at a rotation speed of 2000 revolutions per minute, 2 μmol / L and 200 μL of Compound I-1, I-2, I-3, I-4, and I-5 were added to the solution respectively, and a cathodic polarization curve test was performed.

[0092] Figure 4 It is a test chart of the cathodic polarization curves of Compound I-1, I-2, I-3, I-4, and I-5. The results show that Compound I-1, I-2, I-3, I-4, and I-5 can all increase cathodic polarization. When there is no carbazole quaternary ammonium salt compound in the solution, the copper deposition current can be observed when the potential moves from positive to negative by more than 0 volts; after adding the carbazole quaternary ammonium salt compound to the solution, the copper deposition potential undergoes a negative shift; Figure 2The results also show that when 2 μmol / L of Compound I-1 and I-2 are added to the solution respectively, when the potential shifts negatively to -0.02 V to -0.08 V, the deposition current of copper is observed. When 2 μmol / L of Compound I-3, I-4, and I-5 are added to the solution respectively, when the potential shifts negatively to -0.16 to -0.18, the deposition current of copper is observed. This indicates that the inhibitory ability of Compound I-3, I-4, and I-5 is stronger than that of Compound I-1 and I-2, and the leveling effect is better. Compound I-3, I-4, and I-5 are more preferred additives, which is consistent with Figure 2 the results.

[0093] Application Example 5

[0094] Prepare a solution containing 60 g / L of CuSO 4 ·5H 2 O copper sulfate, 100 g / L of concentrated sulfuric acid, and 60 ppm of concentrated hydrochloric acid. Use a Pt rotating electrode as the working electrode, a platinum wire as the counter electrode, and Ag / AgCl as the reference electrode. The rotation speed is 2000 revolutions per minute. Every 1000 seconds, 200 ppm of polyethylene glycol (PEG, average molecular weight of 8000) and 1 ppm of sodium polydithiopropane sulfonate (SPS) are added to the plating solution in sequence. At 3000 seconds, 2 ppm of Compound I-1, I-2, I-3, I-4, and I-5 are added respectively to conduct a constant current chronoamperometry curve test.

[0095] Figure 5 is the constant current chronoamperometry curve of Compound I-1, I-2, I-3, I-4, and I-5. As Figure 5 shown, when 200 ppm of the inhibitor PEG (average molecular weight of 8000) is added to the electroplating solution at 1000 s, the potential decreases and polarization occurs; when 1 ppm of sodium polydithiopropane sulfonate (SPS) is added at 2000 s, the potential increases and the polarization is inhibited; when 2 ppm of Compound I-1, I-2, I-3, I-4, and I-5 are added respectively at 3000 s, the polarization phenomenon is enhanced. At the same time, Figure 5The results in the middle reflect the interaction mechanism among the three additives. There is an antagonistic effect between compounds I-1, I-2, I-3, I-4, I-5 and the accelerator sodium polydithiopropane sulfonate (SPS), while there is a synergistic effect with the inhibitor polyethylene glycol (PEG). When 2 μmol / L of compounds I-1 and I-2 are respectively added to the solution, the potential slightly decreases, and then the potential of the system is observed to stabilize. However, when 2 μmol / L of compounds I-3, I-4, and I-5 are respectively added to the solution, a larger decrease in potential is observed before the potential of the system stabilizes. This indicates that the inhibitory ability of compounds I-3, I-4, and I-5 is stronger than that of compounds I-1 and I-2. Compounds I-3, I-4, and I-5 are more preferred additives with better leveling effects, which is consistent with Figure 2 and Figure 4 the results of.

[0096] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art of this patent, without departing from the scope of the technical solution of the present invention, can make some changes or modifications using the technical content prompted above into equivalent embodiments of equivalent changes. However, as long as the content does not depart from the technical solution of the present invention, any simple modification, equivalent change, and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the present invention.

Claims

1. Application of carbazole quaternary ammonium salt compounds in the preparation of electroplating additives, characterized in that, the structural formula of the carbazole quaternary ammonium salt compounds is shown as any one of the following:

2. The application according to claim 1, characterized in that: the electroplating additive is an electroplating leveling agent.

3. The application according to claim 2, characterized in that: the electroplating leveling agent is a copper electroplating leveling agent.

4. An electroplating leveling agent, characterized in that, it includes an active component and a solvent, and the active component includes a carbazole quaternary ammonium salt compound shown as any one of the following structures:

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