Carbazole coupling compound and preparation method and application thereof

Abstract

The present invention discloses a carbazole coupling compound and a preparation method and application thereof. The structure of the compound is shown in the following formula: wherein R is selected from any one of the following; n is an even number of integers from 0 to 20; and X is selected from any one of F, Cl, Br, and I. The carbazole coupling compound synthesized by the present invention contains an N positive center and can be more easily adsorbed on the surface of a copper layer. The large conjugated large plane of the carbazole coupling compound can have a larger coverage area on the electrode surface and can increase cathode polarization, inhibit copper deposition, thereby making the particles of electroplated metal deposition finer and making the copper-plated layer obtain a high preferred crystal plane orientation, more effectively preventing the reduction and deposition of copper ions. The carbazole coupling compound is adsorbed to a place with high current density during electroplating, and can be used as an electroplating leveling additive to play a leveling role.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a carbazole coupling compound and a preparation method thereof, and application of the compound in preparing an electroplating leveler. Background Art

[0002] In the semiconductor industry, the electroplating process is an important and indispensable process among hundreds of processes. In chip manufacturing and high-density interconnection circuit board manufacturing, a large amount of electroplating solution is used in the electroplating process. The electroplating solution is divided into basic components and electroplating additives. The basic components of the electroplating solution are composed of copper sulfate, sulfuric acid and chloride ions, and the electroplating additives usually include three categories: inhibitors, accelerators and levelers. At present, the research on inhibitors and accelerators is relatively mature. The inhibitors used are polyethylene glycol (PEG), polypropylene glycol (PPG) or triblock copolymers of PEG and PPG. The accelerators used are mainly sodium polydisulfide propane sulfonate (SPS) and 3-mercapto-1-propane sulfonate (MPS).

[0003] The leveling agent currently used is Janus Green B (JGB). In order to achieve a better microporous metallization filling effect, researchers have studied and developed compounds such as conjugated large planar organic molecules, quaternary ammonium salts or polymers as leveling agents. The present invention uses carbazole as a starting material to design and synthesize a new type of carbazole coupling compound, which is used as an electroplating additive in an acidic copper sulfate plating solution.

[0004] Carbazole (9H-carbazole), also known as dibenzopyrrole and 9-azafluorene, is a common nitrogen-containing heterocyclic compound. The molecular formula of carbazole is C 12 H9N, with a molecular weight of 167.21 g / mol, is a colorless crystal or light gray powder. It is insoluble in water and inorganic acids, but 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 is traditionally 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 a molecular synthesis substrate, and have conducted a lot of research on the application of these carbazole derivatives in different fields. Summary of the invention

[0005] The present invention is based on the above research. With carbazole as the starting material, a new type of carbazole coupling compound is designed and synthesized, which is used as an electroplating additive in an acidic copper sulfate plating solution. The carbazole coupling compound contains an N positive center, which can be more easily adsorbed on the surface of the copper layer. The large conjugated large plane of the carbazole coupling compound itself can more effectively prevent the reduction and deposition of copper ions. The carbazole coupling compound is adsorbed to a place with high current density during electroplating, and can be used as an electroplating leveling additive to play a leveling role.

[0006] As the research progresses, it is found that the electroplating performance of the existing carbazole coupling compound is better after appropriate structural modification. Based on the structural characteristics of the conjugated large plane of the carbazole coupling compound, the present invention develops a new class of carbazole coupling compounds as electroplating leveling agents for use in electroplating. After a series of electrochemical tests and electroplating experiments, the new carbazole coupling compounds have achieved good results in electroplating through-hole electroplating.

[0007] The first object of the present invention is to provide a carbazole coupling compound, another object is to provide a method for preparing the carbazole coupling compound, and the third object is to provide the use of the carbazole coupling compound in an electroplating additive.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] The first aspect of the present invention provides a carbazole coupling compound, characterized in that the structure is shown in the following formula:

[0010]

[0011] Among them, R is selected from Any of the following:

[0012] n is an even number among 0 to 20;

[0013] X is selected from any one of F, Cl, Br and I.

[0014] Preferably, n is 8, 10 or 12, preferably 12, and the structure of the carbazole coupling compound is as follows:

[0015]

[0016] Among them, R is selected from Any of the following:

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

[0018] More preferably, the carbazole coupling compound of the present invention has a structural formula as shown in any one of the following formulas:

[0019]

[0020] The second aspect of the present invention provides a method for preparing the above-mentioned carbazole coupling compound, comprising the following steps:

[0021] A. Synthesis of intermediate product Cz-X

[0022] An organic solvent is added to a reaction container, and carbazole, an alkane substituted with halogen at the head and tail, and a strong base in a molar ratio of 1:5:3 are added to the reaction container respectively to obtain a light yellow turbid liquid, and the reaction is carried out at 35°C; after the reaction is completed, air condensation is used, and tetramethylammonium bromide is added thereto for reaction, and the molar ratio of tetramethylammonium bromide to carbazole is 0.65:1. After the reaction is completed for 3 hours, heating is stopped, and the reaction is carried out at room temperature for 14 hours; after the reaction is completed, a saturated sodium chloride solution with a volume of 2 times the organic solvent is added to the reaction liquid, and an extractant is added thereto after stirring, and after extraction, washing, and drying, column separation is performed to obtain an intermediate product Cz-X,

[0023]

[0024] B. Synthesis of intermediate product BCz-X

[0025] The intermediate Cz-X, methanesulfonic acid and dichloromethane are sequentially added into a reaction vessel, the molar volume ratio of the intermediate Cz-X to methanesulfonic acid is 1mmol:1ml, and the volume ratio of methanesulfonic acid to dichloromethane is 1:10, and the mixture is stirred at -10°C to 15°C for a few minutes, and then tetrachlorobenzoquinone is added. After reacting for 3 to 5 minutes, a strong alkaline solution is added; after the reaction, an extractant is added thereto, and after extraction, washing and drying, column separation is performed to obtain the intermediate product BCz-X;

[0026] C. Synthesis of carbazole coupling compounds

[0027] Synthesized by the method described in any one of C-1 to C-4

[0028] C-1, Synthesis of Product I

[0029]

[0030] Compound BCz-X, trimethyl quaternary ammonium salt, sodium bicarbonate and a certain amount of acetonitrile in a molar ratio of 1:10:10 are sequentially added into a reaction container, and reacted at 80°C for 12 hours under Ar protection; after cooling to room temperature, the mixture is filtered and washed with methanol, and the filtrate is taken and mixed with 200-300 mesh aluminum hydroxide to prepare a dry sample; the mixture is purified by a chromatographic column, and the eluent is dichloromethane and methanol, to obtain product I;

[0031] C-2, Synthesis of Product II

[0032]

[0033] The intermediate product BCz-X and pyridine and a certain amount of acetonitrile in a molar ratio of 1:10 were added to the reaction container in sequence, and reacted at 80°C for 24 hours under argon protection; after cooling to room temperature, ethyl acetate was used to precipitate and wash the filter cake, and the product II was obtained after vacuum drying;

[0034] C-3, Synthesis of Product III

[0035]

[0036] The intermediate product BCz-X and N,N-dimethylpyridine and a certain amount of acetonitrile in a molar ratio of 1:10 were added to the reaction container in sequence, and reacted at 80°C for 24 hours under argon protection; after cooling to room temperature, ethyl acetate was used to precipitate and wash the filter cake, and the product III was obtained after vacuum drying;

[0037] C-4, product IV synthesis

[0038]

[0039] The intermediate product BCz-X and 4,4-bipyridine and a certain amount of acetonitrile in a molar ratio of 1:10 were added to the reaction container in sequence, and reacted at 80°C for 24 hours under argon protection; after cooling to room temperature, ethyl acetate was used for precipitation and washing of the filter cake, and the product IV was obtained after vacuum drying.

[0040] In the preparation method of the carbazole coupling compound, in step A, the organic solvent is selected from any one of toluene, xylene, ethanol, hexane, and CCl4. In steps A and B, the strong base is selected from sodium hydroxide or potassium hydroxide; when separating the product, the extractant used is any one of dichloromethane, dichloroethane, dichloropropane, trichloroethane, and methyl acetate; when separating by column, petroleum ether and dichloromethane are used to pass through the column.

[0041] The third aspect of the present invention provides the use of the carbazole coupling compound, specifically the use in the preparation of electroplating additives.

[0042] Preferably, the electroplating additive is an electroplating leveler; more preferably, it is a copper electroplating leveler, and the electroplating solution is acidic copper sulfate.

[0043] The fourth aspect of the present invention provides an electroplating leveler, comprising an active component and a solvent, wherein the active component comprises the above-mentioned carbazole coupling compound, preferably the four compounds listed above, and most preferably BCz-BPD.

[0044] Beneficial technical effects of the present invention:

[0045] The present invention designs and synthesizes a series of unreported carbazole coupling compounds, and studies the methodology for synthesizing the carbazole coupling compounds. The carbazole coupling compounds synthesized by the present invention contain an N positive center, which can be more easily adsorbed on the surface of the copper layer. The large conjugated large plane of the carbazole coupling compounds can have a large coverage area on the electrode surface and can increase cathode polarization, inhibit copper deposition, thereby making the particles of electroplated metal deposition finer and making the copper-plated layer obtain a high preferred crystal plane orientation, more effectively preventing the reduction and deposition of copper ions. The carbazole coupling compounds are adsorbed to places with high current density during electroplating, and can be used as electroplating leveling additives to play a leveling role. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 The polarization curves of copper ion deposition on the copper material surface of the compounds BCz-TMA, BCz-PD, BCz-DEMP, and BCz-BPD in Application Example 1 at a concentration of 2 μmol / L, wherein the abscissa is the electrode (vs Ag / AgCl) potential (unit: V), and the ordinate is the current density (unit: A / dm 2 ).

[0047] Figure 2 The polarization curves of copper ion deposition on the copper material surface at the concentrations of 0, 2, 4, 6, 8, and 10 μmol / L of the compound BCz-BPD in Application Example 2, where the abscissa is the electrode (vs Ag / AgCl) potential (unit: V) and the ordinate is the current density (unit: A / dm 2 ).

[0048] Figure 3 Cyclic voltammetry curves of copper ion deposition on the copper material surface of compounds BCz-TMA, BCz-PD, BCz-DEMP, and BCz-BPD in Application Example 3 at a concentration of 2 μmol / L, where the abscissa is the electrode (vs Ag / AgCl) potential (unit: V) and the ordinate is the current density (unit: A / dm 2 ).

[0049] Figure 4 The cyclic voltammetry curves of copper ion deposition on the copper material surface at the concentrations of 0, 2, 4, 6, 8, and 10 μmol / L of the compound BCz-BPD in Application Example 4, where the abscissa is the electrode (vs Ag / AgCl) potential (unit: V) and the ordinate is the current density (unit: A / dm 2 ).

[0050] Figure 5 The graph and TP value of the electroplated through-hole filling effect of the compound BCz-BPD in Application Example 5 at a concentration of 0.5 ppm in an acidic copper sulfate plating solution containing 200 ppm PEG and 2 ppm JGB. DETAILED DESCRIPTION

[0051] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the following specific description is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0052] Example 1 BCz-TMA Synthesis

[0053]

[0054] Add 10mL of toluene (Tol) to a three-necked flask, add 0.167g of carbazole (Cz), 1.130g of 1,6-dibromohexane, and 168mg of potassium hydroxide (KOH) to the flask respectively, and the three are added to form a light yellow turbid liquid, which reacts at 35°C. The air condenses, and 0.1g of tetramethylammonium bromide (TBAB) is added to it, and the reaction is carried out for 3h. After 3h, the heating is stopped and the reaction is allowed to proceed overnight at room temperature. After the reaction is completed, 20mL of saturated sodium chloride solution is added to the reaction solution, stirred for a while, and then 20mL of dichloromethane is added to it. Extract, wash, dry, and pass through a column with petroleum ether and dichloromethane to obtain the intermediate product Cz-Br.

[0055] 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 (101MHz, 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.

[0056]

[0057] The intermediate Cz-Br (1mmol), methanesulfonic acid (1mL) and dichloromethane (10mL) were added to a 100mL three-necked flask in sequence and stirred at -10-15°C for a few minutes. Then tetrachlorobenzoquinone was added and reacted for 3 minutes. After the reaction was completed, sodium hydroxide solution was added, extracted with DCM, washed, dried, and the solvent was removed under reduced pressure. The product BCz-Br was obtained by column chromatography with silica gel and petroleum ether and dichloromethane as eluents.

[0058] 1 H NMR (400MHz, Chloroform-d): δ8.40(d,J=1.7Hz,2H),8.18(d,J=7.7Hz,2H),7.81(dd,J=8.5,1.8Hz,2H),7.46(d,J=8.1Hz,4H),7.40(d,J=8 .2Hz,2H),7.28–7.21(m,2H),4.32(t,J=7.0Hz,4H),3.34(t,J=6.7Hz,4H),1.91(p,J=7.2Hz,4H),1.80(p,J=6.8Hz,4H),1.52–1.38(m,8H).

[0059]

[0060] Compound BCz-Br (1mmol), trimethyl quaternary ammonium salt (NMe3·HCl, 10mmol), sodium bicarbonate (NaHCO3, 10mmol) and acetonitrile (10mL) were added to a 50mL three-necked flask in sequence and reacted at 80°C for 12h under Ar protection. After cooling to room temperature, the mixture was filtered and washed with methanol. The filtrate was taken and dried with 200-300 mesh aluminum hydroxide (Al2O3). Column chromatography was performed with dichloromethane and methanol as eluents to obtain the product BCz-TMA.

[0061] 1 H NMR (400MHz, Methanol-d4): δ8.44(d,J=1.8Hz,2H),8.20(d,J=7.7Hz,2H),7.82 (dd,J=8.5,1.8Hz,2H),7.59–7.51(m,4H),7.47(ddd,J=8.2,6.9,1.2Hz,2H),7. 25–7.20(m,2H),4.43(t,J=6.7Hz,4H),3.18–3.11(m,4H),2.99(s,18H),1.94(p ,J=6.8Hz,4H),1.66–1.57(m,4H),1.41(q,J=8.0,7.3Hz,4H),1.34–1.28(m,4H). 13C NMR (101MHz, DMSO-d6): δ140.50,139.12,132.27,125.83,125.03,122.80,122.34,118.73 ,118.31,109.67,65.28,52.13,42.25,28.44,26.11,25.72,22.06.MS(ESI)m / z:[M-2Br-] 2+ calcdfor C 42 H 56 N4 2+ 308.2247; found 308.2254.

[0062] Example 2 BCz-PD Synthesis

[0063]

[0064] Compound BCz-Br (1 mmol), pyridine (10 mmol) and acetonitrile (10 mL) were added to a 50 mL three-necked flask in sequence 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 was precipitated. The precipitate was filtered and washed with ethyl acetate. The filter cake was vacuum dried to obtain the product BCz-PD;

[0065] 1 H NMR (400MHz, Methanol-d4): δ8.85–8.76(m,4H),8.51–8.41(m,4H),8.19(d,J=7.8Hz,2H),8.01–7.93(m,4H),7.81(dd,J=8.5,1.8Hz,2H),7.56–7.43 (m,6H),7.22(ddd,J=7.9,6.8,1.2Hz,2H),4.47(t,J=7.5Hz,4H),4.40(t, J=6.8Hz, 4H), 1.89 (dt, J=18.2, 7.3Hz, 8H), 1.33 (dd, J=21.2, 10.6Hz, 8H). 13 C NMR (101MHz, DMSO-d6): δ145.45,144.70,140.47,139.08,132.25,128.04,125.81,125.01,122.76,122.31 ,120.57,118.71,118.31,109.62,109.37,60.73,42.23,30.58,28.39,25.97,25.29.MS(ESI)m / z:[M-2Br-] 2+ Calculate for C 46 H48 N4 2+ 328.1934; found 328.1936.

[0066] Example 3 BCz-DEMP Synthesis

[0067]

[0068] Compound BCz-Br (1mmol), N,N-dimethylpyridine (DEMP, 10mmol) and acetonitrile (10mL) were added to a 50mL three-necked flask in sequence and reacted at 80°C for 24h under argon protection. After cooling to room temperature, the reaction solution was poured into 150mL ethyl acetate, and a precipitate was precipitated. It was filtered and washed with ethyl acetate, and the filter cake was vacuum dried to obtain the product BCz-DEMP;

[0069] 1 H NMR (400MHz, Methanol-d4): δ8.44(s,2H),8.18(d,J=7.7Hz,2H),7.84(d,J=7.1Hz ,4H),7.78(d,J=8.5Hz,2H),7.54–7.41(m,6H),7.26–7.17(m,2H),6.73(d,J=7.1Hz ,4H),4.35(t,J=6.7Hz,4H),3.87(t,J=7.3Hz,4H),3.06(d,J=1.1Hz,12H),1.84(p ,J=6.8Hz,4H),1.60(p,J=7.5Hz,4H),1.29(q,J=7.7Hz,4H),1.17(p,J=7.7Hz,4H). 13 C NMR (101MHz, DMSO-d6): δ155.78,141.93,140.48,139.09,132.24,125.82,125.01,122.77,122 .31,120.58,118.72,109.63,107.63,56.63,30.17,28.41,25.98,25.28.MS(ESI)m / z:[M-2Br-] 2+ Calculate for C 50 H 58 N6 2+ 371.2356; found 371.2360.

[0070] Example 4 BCz-BPD Synthesis

[0071]

[0072] Compound BCz-Br (1 mmol), 4,4-bipyridine (10 mmol) and acetonitrile (10 mL) were added to a 50 mL three-necked flask in sequence 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 was precipitated. The precipitate was filtered and washed with ethyl acetate. The filter cake was vacuum dried to obtain the product BCz-BPD;

[0073] 1 H NMR (400MHz, Methanol-d4): δ8.75 (d, J=6.4Hz, 4H), 8.63–8.56 (m, 4H), 8.34 (d, J= 1.8Hz,2H),8.24–8.17(m,4H),8.14(d,J=7.7Hz,2H),7.76–7.66(m,6H),7.44(t,J =5.6Hz,6H),7.19(ddd,J=7.9,4.8,3.3Hz,2H),4.30(dt,J=13.6,7.1Hz,8H),1.82 (p,J=6.8Hz,4H),1.73(p,J=7.6Hz,4H),1.29(t,J=8.1Hz,4H),1.24–1.17(m,4H). 13 C NMR (101MHz, Methanol-d4): δ154.49,151.58,146.04,143.02,142.29,140.77,133.93,127.18,126.72,126.23,124.69,1 24.06,123.23,121.53,120.22,119.25,110.75,110.39,62.34,43.63,31.87,29.58,27.44,26.83.MS(ESI)m / z:[M-2Br-] 2+ Calculate for C 56 H 54 N6 2+ 405.2200; found 405.2212.

[0074] Application Example 1

[0075] A solution containing 60 g / L CuSO4·5H2O copper sulfate, 100 g / L concentrated sulfuric acid and 60 ppm concentrated hydrochloric acid was prepared. A Pt disk electrode was used as a working electrode, a platinum wire electrode was used as a counter electrode and an Ag / AgCl electrode was used as a reference electrode. At a rotation speed of 2000 rpm, 200 μL of 2 μmol / L compounds BCz-TMA, BCz-PD, BCz-DEMP and BCz-BPD (compounds BCz-TMA, BCz-PD, BCz-DEMP and BCz-BPD prepared in Examples 1, 2, 3 and 4, the same below) were added to the solution respectively, and potentiodynamic polarization curve tests were performed.

[0076] Generally speaking, when the same concentration of electroplating additives is added to the plating solution, the deposition current density begins to increase, indicating that the reduction deposition of copper ions has begun; the smaller the deposition potential of the polarization curve, the more obvious the cathode polarization phenomenon is, the stronger the effect of inhibiting the reduction deposition of copper ions is, and the better the leveling effect is in the actual electroplating process.

[0077] Figure 1 The potentiodynamic polarization curve test graphs of compounds BCz-TMA, BCz-PD, BCz-DEMP, and BCz-BPD are shown, and the results show that compounds BCz-PD, BCz-DEMP, and BCz-BPD can increase cathode polarization. In the solution VMS without carbazole coupling compounds, the reduction deposition current of copper ions can be observed when the potential moves from positive to negative and exceeds 0V; and after adding carbazole coupling compounds to the solution, the copper deposition potential shifts negatively. Specifically, Figure 1 The results also show that when 2 μmol / L of BCz-TMA was added to the solution, the potential shifted negatively but was not obvious, and the reduction deposition current of copper ions was observed; when 2 μmol / L of BCz-PD and BCz-DEMP were added to the solution, the potential shifted negatively to -0.05V to -0.08V, and the reduction deposition current of copper ions was observed; when 2 μmol / L of BCz-BPD was added to the solution, the potential shifted negatively to -0.20V, and the reduction deposition current of copper ions was observed. This shows that the inhibition ability of BCz-BPD is stronger than that of BCz-TMA, BCz-PD, and BCz-DEMP, and the leveling effect is better, and BCz-BPD is a more preferred additive.

[0078] Application Example 2

[0079] A solution containing 60 g / L CuSO4·5H2O copper sulfate, 100 g / L concentrated sulfuric acid and 60 ppm concentrated hydrochloric acid was prepared. A Pt disk electrode was used as a working electrode, a platinum wire electrode was used as a counter electrode and an Ag / AgCl electrode was used as a reference electrode. At a rotation speed of 2000 rpm, 0, 2, 4, 6, 8 and 10 μmol / L of compound BCz-BPD (compound BCz-BPD prepared in Example 4, the same below) was added to the solution, respectively, and a potentiodynamic polarization curve test was performed.

[0080] Figure 2 This is a test graph of the potentiodynamic polarization curve of the compound BCz-BPD. The results show that the compound BCz-BPD can increase the cathode polarization. The smaller the deposition potential of the potentiodynamic polarization curve, the more obvious the cathode polarization phenomenon, and the stronger the effect of inhibiting the reduction deposition of copper ions. When the solution does not contain the compound BCz-BPD, the reduction deposition current of copper ions can be observed when the potential moves from positive to negative and exceeds 0V. After the compound BCz-BPD is added to the solution in a gradient, the copper deposition potential shifts negatively in a gradient. When the compound BCz-BPD in the solution reaches 10ppm, the potential reaches -0.23V, and the reduction deposition current of copper ions is observed, indicating that the compound BCz-BPD has a strong inhibitory ability and a good leveling effect.

[0081] Application Example 3

[0082] A solution containing 60 g / L CuSO4·5H2O copper sulfate, 100 g / L concentrated sulfuric acid and 60 ppm concentrated hydrochloric acid was prepared. A Pt disk electrode was used as the working electrode, a platinum wire electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. At a rotation speed of 2000 rpm, 200 μL of 2 μmol / L compounds BCz-TMA, BCz-PD, BCz-DEMP and BCz-BPD were added to the solution respectively, and cyclic voltammetry curve tests were performed.

[0083] Generally speaking, when the same concentration of electroplating additives is added to the plating solution, the smaller the stripping peak (positive peak) area of ​​the cyclic voltammetry curve is, the less copper is deposited on the disk electrode, the stronger the effect of inhibiting the reduction deposition of copper ions is, and the better the leveling effect is in the actual electroplating process.

[0084] Figure 3 The cyclic voltammetry curve test diagrams of compounds BCz-TMA, BCz-PD, BCz-DEMP, and BCz-BPD are shown. The results show that the compounds BCz-TMA, BCz-PD, BCz-DEMP, and BCz-BPD behave differently in the plating solution. When the solution does not contain carbazole coupling compounds, the stripping peak area of ​​the cyclic voltammetry curve is the benchmark; after adding compounds BCz-PD and BCz-DEMP to the solution, the stripping peak area of ​​the cyclic voltammetry curve increases. Figure 3 The results also show that after adding 2 μmol / L of BCz-TMA and BCz-BPD to the solution, the stripping peak area of ​​the cyclic voltammetry curve decreased. Among them, in the plating solution with BCz-TMA added, the stripping peak area of ​​the cyclic voltammetry curve decreased most significantly, indicating that the ability of compound BCz-BPD to inhibit copper ion reduction deposition is stronger than that of compounds BCz-TMA, BCz-PD, and BCz-DEMP, and the leveling effect is better. At the same time, compound BCz-BPD is a more preferred additive.

[0085] Application Example 4

[0086] A solution containing 60 g / L CuSO4·5H2O copper sulfate, 100 g / L concentrated sulfuric acid and 60 ppm concentrated hydrochloric acid was prepared. A Pt disk electrode was used as a working electrode, a platinum wire electrode was used as a counter electrode and an Ag / AgCl electrode was used as a reference electrode. At a rotation speed of 2000 rpm, 0, 2, 4, 6, 8 and 10 μmol / L of the compound BCz-BPD were added to the solution respectively, and cyclic voltammetry curve tests were performed.

[0087] Figure 4 This is the test graph of the cyclic voltammetry curve of the compound BCz-BPD. The results show that the compound BCz-BPD can reduce the stripping peak of the cyclic voltammetry curve. The smaller the stripping peak area obtained by the test, the stronger the effect of inhibiting the reduction and deposition of copper ions. In the solution VMS without the compound BCz-BPD, the oxidation peak area of ​​the cyclic voltammetry curve is the largest; after the compound BCz-BPD is added to the solution in a gradient, the oxidation peak area of ​​the cyclic voltammetry curve decreases in gradient; when the compound BCz-BPD in the solution reaches 10ppm, the oxidation peak area of ​​the cyclic voltammetry curve decreases to approach 0. This shows that the compound BCz-BPD has a strong ability to inhibit the reduction and deposition of copper ions and has a good leveling effect.

[0088] Application Example 5

[0089] Prepare a 1.5L solution containing 60g / L CuSO4·5H2O copper sulfate, 100g / L concentrated sulfuric acid and 60ppm concentrated hydrochloric acid, and add 3000μL 200ppm polyethylene glycol (PEG, average molecular weight is 8000), 150μL 1ppm sodium polydisulfide propane sulfonate (SPS), 0 or 750μL 2ppm compound BCz-BPD to the plating solution in turn to do through-hole electroplating experiments.

[0090] In through-hole electroplating, when the TP value reaches 100%, it means that under the action of electroplating additives, the copper deposition thickness inside and outside the through-hole is the same, achieving the ideal effect. Figure 5 The following are cross-sectional images of through-holes from through-hole electroplating tests without or with 2 ppm of the compound BCz-BPD. Figure 5 As shown in (1), in the through-hole cross section of the through-hole electroplating test without 2ppm compound BCz-BPD, the plating surface in the middle of the through-hole is rough, and the TP value is only 51.67%, which means that the copper deposition thickness inside the through-hole is smaller than that outside the through-hole, which cannot meet the requirements. Figure 5 As shown in (2), in the through-hole cross section of the through-hole electroplating test containing 2ppm of the compound BCz-BPD, the plating surface in the middle of the through-hole becomes smooth, and the TP value is only 99.21%, indicating that the copper deposition thickness inside and outside the through-hole tends to be the same, meeting the requirements. At the same time, Figure 5 It is shown that the compound BCz-BPD improves the effect of through-hole electroplating test and is an effective electroplating leveler.

[0091] The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment, it is not used to limit the present invention. Any technician familiar with this patent can make some changes or modify the technical contents suggested above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the solution of the present invention.

Claims

1. A carbazole coupling compound, characterized in that: The structure of the compound is shown below: Among them, R + Selected from Any one of; X is selected from any one of Cl and Br.

2. The carbazole coupling compound according to claim 1, characterized in that The structural formula is shown in any of the following formulas:

3. The method for preparing the carbazole coupling compound according to any one of claims 1 to 2, characterized in that: The steps include: A. Synthesis of intermediate product Cz-X An organic solvent is added to a reaction container, and carbazole, 1,6-dibromohexane alkane and a strong base are added to the reaction container at a molar ratio of 1:5:3 to obtain a light yellow turbid liquid, and the reaction is carried out at 35°C; after the reaction is completed, air condensation is used, and tetramethylammonium bromide is added thereto for reaction, and the molar ratio of tetramethylammonium bromide to carbazole is 0.65:

1. After the reaction is completed for 3 hours, heating is stopped, and the reaction is carried out at room temperature for 14 hours; after the reaction is completed, a saturated sodium chloride solution with a volume of 2 times the organic solvent is added to the reaction liquid, and an extractant is added thereto after stirring, and after extraction, washing and drying, column separation is performed to obtain an intermediate product Cz-X, B. Synthesis of intermediate product BCz-X The intermediate Cz-X, methanesulfonic acid and dichloromethane are sequentially added into a reaction vessel, the molar volume ratio of the intermediate Cz-X to methanesulfonic acid is 1mmol:1ml, and the volume ratio of methanesulfonic acid to dichloromethane is 1:10, and the mixture is stirred at -10°C to 15°C for a few minutes, and then tetrachlorobenzoquinone is added. After reacting for 3 to 5 minutes, a strong alkaline solution is added; after the reaction, an extractant is added thereto, and after extraction, washing and drying, column separation is performed to obtain the intermediate product BCz-X; C. Synthesis of carbazole coupling compounds Synthesized by the method described in any one of C-1 to C-4 C-1, Synthesis of Product I Compound BCz-X, trimethyl quaternary ammonium salt NMe3·HCl, sodium bicarbonate and a certain amount of acetonitrile in a molar ratio of 1:10:10 are sequentially added into a reaction container, and reacted at 80°C for 12 hours under Ar gas protection; after cooling to room temperature, the mixture is filtered and washed with methanol, and the filtrate is taken and mixed with 200-300 mesh aluminum hydroxide to prepare a dry sample; the mixture is purified by a chromatographic column, and the eluents are dichloromethane and methanol, to obtain product I; C-2, Synthesis of Product II The intermediate product BCz-X and pyridine and a certain amount of acetonitrile in a molar ratio of 1:10 were added to the reaction container in sequence, and reacted at 80°C for 24 hours under argon protection; after cooling to room temperature, ethyl acetate was used to precipitate and wash the filter cake, and the product II was obtained after vacuum drying; C-3, Synthesis of Product III The intermediate product BCz-X and N,N-dimethylpyridine and a certain amount of acetonitrile in a molar ratio of 1:10 were added to the reaction container in sequence, and reacted at 80°C for 24 hours under argon protection; after cooling to room temperature, ethyl acetate was used to precipitate and wash the filter cake, and the product III was obtained after vacuum drying; C-4, product IV synthesis The intermediate product BCz-X, 4,4-bipyridine and a certain amount of acetonitrile in a molar ratio of 1:10 were added to the reaction container in sequence, and reacted at 80°C for 24 hours under argon protection; after cooling to room temperature, ethyl acetate was used for precipitation and washing of the filter cake, and the product IV was obtained after vacuum drying. Wherein, X is selected from any one of Cl and Br, and n is 6.

4. The method for preparing the carbazole coupling compound according to claim 3, characterized in that: in, In step A, the organic solvent is selected from any one of toluene, xylene, ethanol, hexane, and CCl4; In steps A and B, the strong base is selected from sodium hydroxide or potassium hydroxide; When separating the product, the extractant used is any one of dichloromethane, dichloroethane, dichloropropane, trichloroethane, and methyl acetate; When performing column separation, petroleum ether and dichloromethane are used to pass through the column.

5. Use of the carbazole coupling compound according to any one of claims 1 to 2 in the preparation of an electroplating leveler.

6. The use according to claim 5, characterized in that: The electroplating leveler is a copper electroplating leveler.

7. An electroplating leveling agent, characterized in that: The invention comprises an active component and a solvent, wherein the active component comprises the carbazole coupling compound according to any one of claims 1 to 2.

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