阅读说明：本技术 一种香豆素吡啶盐类化合物及其应用 (Coumarin pyridinium compound and application thereof ) 是由 王利民 尹鑫鹏 王峰 王桂峰 陈立荣 李俊 邹佩琨 陈昕 王祚璠 沙擎阳 符昌霖 于 2021-09-27 设计创作，主要内容包括：本发明公开了一种香豆素吡啶盐类化合物,结构通式如下所示：R-(1)选自氢、C1～C5烷基、X为卤素；n为0～6的正整数；Y选自键、氧。本发明选用香豆素和吡啶类化合物为原料制备香豆素吡啶盐类化合物,可以作为电镀整平剂,相同摩尔浓度下,双电荷类香豆素吡啶类季铵盐产物对铜离子的抑制作用明显优于市售整平剂JGB。(The invention discloses a coumarin pyridinium compound, which has the following structural general formula: R 1 selected from hydrogen, C1-C5 alkyl, X is halogen; n is a positive integer of 0-6; y is selected from a bond and oxygen. The coumarin pyridinium compound is prepared by taking coumarin and pyridinium compounds as raw materials, can be used as an electroplating leveling agent, and has the inhibiting effect of a double-charge coumarin pyridinium quaternary ammonium salt product on copper ions which is obviously better than that of a commercial leveling agent JGB under the same molar concentration.)

1. The coumarin pyridinium compound is characterized by having the following structural general formula:

R₁selected from hydrogen, C1-C5 alkyl,

X is halogen;

n is a positive integer of 0-6;

y is selected from a bond and oxygen.

2. The coumarin pyridinium compound according to claim 1, wherein R is selected from the group consisting of₁Selected from hydrogen, methyl, ethyl, n-propyl,

X is bromine or iodine;

n is 1, 2, 3, 4;

y is selected from a bond and oxygen.

3. The coumarin pyridinium compound according to claim 2 wherein the coumarin pyridinium compound is selected from one of the following structures:

4. use of a coumarin pyridinium compound according to any one of claims 1 to 3 in the preparation of a plating additive.

5. The use of the coumarin pyridinium compound of claim 4 in the preparation of a plating additive, wherein the plating additive is a plating leveler.

6. The use of a coumarin pyridinium compound according to claim 4 in the preparation of a plating additive wherein the plating is copper plating and the plating solution is copper sulfate.

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a coumarin pyridinium compound and application thereof.

Background

With the rapid development of the information technology in the 21 st century, the chip technology requirement as the core bearing technology is higher and higher. Miniaturization of electronic products requires high-density interconnection of printed circuit boards with signal transmission micro-holes. Copper has good thermal conductivity and other metal properties, and is widely used in the industries of electric power, electronics, building industry, transportation, industrial machine manufacturing, consumer goods, daily necessities and the like. With the rapid development of the modern semiconductor industry, the application of ultra-high purity copper has gained wide attention.

In order to meet the demand for multifunctional, high frequency and high speed performance electronic products, the micropores should be completely filled with electroplated copper without seams or voids, so-called "superfilling" or "bottom-up filling". The electrolytic copper plating technology means that copper is uniformly and flatly attached to the surface to be plated in a three-electrode system. The micro-holes on the metal surface can be perfectly filled, so that the high-density interconnection is realized by using the method of stacking the micro-holes. IC chip substrates and electronic product motherboards in the information industry now require high density interconnects. However, unless certain special additives are used that have a significant impact on the performance and direction of copper deposition, ideal superfilling cannot be achieved due to non-uniformity of local current density. How to maintain the reliability of the interlayer interconnection structure on the printed circuit board with the increasing integration level and how to realize the rapid copper deposition to improve the production efficiency in the increasing production demand are the main research directions for the development of the contemporary electro-coppering technology. The acidic copper sulfate plating solution system is the mainstream of the copper electroplating technology, and the deposition of copper can be regulated and controlled by compounding additives, so that the uniform electroplating of an electrical interconnection structure is realized. However, the additive is of a wide variety and has long been lacking in an effective research method, and thus the mechanism of action of the additive has not yet been clarified. The research on the action mechanism of the additive and the development of a novel additive are the difficulties of the current international research on electroplating technology.

In order to meet the industrial requirements, it is necessary to simultaneously add a plurality of additives (e.g., accelerators, inhibitors andleveler) is added to the electrolytic copper plating solution. In this additive system, the promoter not only binds to chloride ions, which can enhance copper deposition at the bottom, but also can improve the grain structure of the electroplated copper. The inhibitor is rapidly adsorbed on the copper surface in the presence of chloride ions to form a saturated film, which seriously hinders Cu²⁺Diffusion to the copper surface and suppression of the copper deposition rate. In order to improve the filling property of the microporous electrolytic copper plating and improve the uniformity of the copper surface, a leveling agent is also added to the plating solution. This has been demonstrated in a number of studies, where the interaction between additives in the system plays a very important role in the bottom-up filling process.

Coumarin (Coumarin), the scientific name benzo alpha-pyrone, is commonly recognized as the lactone of cis-o-hydroxycinnamic acid, which is the parent nucleus of a large class of coumarins present in the plant kingdom. The coumarin compounds have various types, and different types of substituents and different substitution positions on a ring can generate different types of substituents. The positions of the substituted positions of simple coumarins are mostly the No. 6, No. 7 and No. 8 positions of C, the coumarins are used as a large coplanar group, when the coumarin is combined with pyridine and 4, 4-bipyridine, the synthesized quaternary ammonium salt compound can be well attached to the surface of copper, and can be used as an electroplating leveling agent in a copper plating process.

Disclosure of Invention

The first purpose of the invention is to provide a coumarin pyridinium compound.

The invention also aims to provide application of the coumarin pyridinium compound.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the first aspect of the invention provides a coumarin pyridinium compound, which has the following structural general formula:

R₁selected from hydrogen, C1-C5 alkyl,

X is halogen (fluorine, chlorine, bromine, iodine);

n is a positive integer of 0-6;

y is selected from a bond and oxygen.

When Y is a bond, the benzene ring of coumarin is directly connected with CH₂And (4) connecting.

More preferably, in the coumarin pyridinium compound,

R₁selected from hydrogen, methyl, ethyl, n-propyl,

X is bromine or iodine;

n is 1, 2, 3, 4;

y is selected from a bond and oxygen.

Most preferably, the coumarin pyridinium compound is selected from one of the following structures:

the second aspect of the invention provides an application of the coumarin pyridinium compound in preparation of an electroplating additive.

The electroplating additive is an electroplating leveling agent.

The electroplating is copper electroplating, and the electroplating solution is copper sulfate.

Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:

the invention selects coumarin and pyridine compounds as raw materials to prepare coumarin pyridine salt compounds which can be used as electroplating leveling agents, and also discloses a preparation method of the coumarin pyridine salt compounds and application of the coumarin pyridine salt compounds in electroplating.

The invention designs and synthesizes a series of coumarin pyridinium compounds which are not reported yet, and researches the methodology for synthesizing the coumarin pyridinium compounds; due to the fact that coumarin molecules have good planarity, a conjugated system of the coumarin molecules is easier to adsorb on the surface of a cathode, and deposition of metal copper can be effectively inhibited. Synthesizing a series of coumarin quaternary ammonium salt derivatives, and endowing the derivatives with certain surface activity and water solubility. The potential value of the coumarin quaternary ammonium salt derivative as the electroplating additive is explored through electrochemical tests and copper electroplating, and the organic electroplating additive which is better in leveling effect, higher in yield and more environment-friendly in application performance in electroplating is explored, so that the significance of the method is achieved.

Drawings

FIG. 1 shows Compound A₁Cyclic voltammogram of (a).

FIG. 2 shows Compound B₁Cyclic voltammogram of (a).

FIG. 3 is Compound C₁Cyclic voltammogram of (a).

FIG. 4 is Compound C₂Cyclic voltammogram of (a).

Fig. 5 is a cyclic voltammogram of a commercial leveler JGB.

FIG. 6 is Compound C₁、C₂Polarization profile with a commercial leveler JGB.

FIG. 7 is Compound C₂Schematic diagram of the constant current timing addition curve test of (1).

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

The medicines used in the examples of the present invention are as follows:

TABLE 1

Example 1

Compound a1 was prepared as follows:

(1) preparation of intermediate 2-1

Adding 100ml of carbon tetrachloride into a three-necked flask, then sequentially adding 3.5g of compound 1-1, 3.88g of N-bromosuccinimide and 5mg of azobisisobutyronitrile, carrying out reflux reaction for 1h at 80 ℃ under an argon atmosphere, then supplementing 0.4g of N-bromosuccinimide and 5mg of azobisisobutyronitrile into the reaction mixture, continuing reflux reaction for 1h, evaporating and concentrating the reaction mixture, diluting with water, stirring for 1h, filtering and collecting, and carrying out vacuum drying to obtain the compound 2-1.

(2) Preparation of Compound A1

Dissolving 4.2mmol of compound 2-1 in a mixed solution of 1.5ml of pyridine and 20ml of N, N-dimethylformamide, reacting at 80 ℃ under an argon atmosphere for 24 hours, cooling to room temperature, pouring the reaction mixture into 150ml of ethyl acetate, filtering to collect a precipitate, washing with ethyl acetate, and drying in vacuum to obtain the target compound A1.

Of Compound A1¹H NMR was as follows:¹H NMR(400MHz,D₂O):δ8.94(d,J＝5.6Hz,2H),8.59(t,J＝7.9Hz,1H),8.16–8.03(m,2H),7.95(d,J＝9.6Hz,1H),7.68(d,J＝8.2Hz,1H),7.42–7.33(m,2H),6.45(d,J＝9.6Hz,1H),5.92(s,2H).

of Compound A1¹³C NMR was as follows:¹³C NMR(101MHz,D2O):δ163.39,153.27,146.38,144.85,144.58,136.75,129.53,128.54,125.03,119.64,116.72,116.35,63.61.

example 2

The preparation method of compound B1 is as follows:

(1) preparation of intermediate 2-2

50ml of acetonitrile was charged into a three-necked flask, and then 2.5g of the compound 1-2, 14.5g of the compound 1, 4-dibromobutane, and 10g of cesium carbonate were sequentially added, followed by reflux reaction at 80 ℃ for 5 hours under an argon atmosphere. Cool to room temperature and filter the mixture. The solvent of the reaction mixture is removed by a rotary evaporator, and the residual liquid is dripped into petroleum ether, filtered and dried to obtain the compound 2-2.

(2) Preparation of Compound B1

Dissolving 4, 4-bipyridine (3g, 19.2mmol) in 60ml of N, N-dimethylformamide solution, heating to 80 ℃, dissolving 4.2mmol of compound 2-2 in 5-10 ml of N, N-dimethylformamide solution, dropwise adding the solution into the mixed solution, reacting at 80 ℃ for 24h, cooling to room temperature, pouring the reaction mixture into 300ml of ethyl acetate, filtering, collecting precipitate, washing with ethyl acetate, and drying in vacuum to obtain compound B1.

Of compound B1¹H NMR was as follows:¹H NMR(400MHz,D₂O):δ8.92(d,J＝6.91Hz,2H),8.64(dd,J＝4.6,1.8Hz,2H),8.20(d,J＝6.9Hz,2H),7.68(dd,J＝4.6,1.7Hz,2H),7.60(d,J＝9.5Hz,1H),7.33(d,J＝8.7Hz,1H),6.74(dd,J＝8.7,2.4Hz,1H),6.49(d,J＝2.5Hz,1H),5.97(d,J＝9.4Hz,1H),4.70(t,J＝6.5Hz,2H),3.95(t,J＝5.8Hz,2H),2.33–2.22(m,2H),1.94–1.83(m,2H).

of compound B1¹³C NMR was as follows:¹³C NMR(151MHz,DMSO):δ161.57,160.28,155.37,152.30,151.01,145.39,144.34,140.85,129.54,125.44,121.90,112.72,112.45,67.59,59.99,27.51,25.02.

example 3

Compound C1 was prepared as follows:

(2) preparation of intermediate 4-1

Dissolving 3g of 4, 4-bipyridine in 60ml of N, N-dimethylformamide solution, heating to 80 ℃, dissolving 1.14g of compound 2-1 in 5-10 ml of N, N-dimethylformamide solution, dropwise adding the solution into the mixed solution, reacting at 80 ℃ for 24 hours, cooling to room temperature, pouring the reaction mixture into 300ml of ethyl acetate, filtering, collecting precipitate, washing with ethyl acetate, and drying in vacuum to obtain compound 4-1.

(3) Preparation of Compound C1

0.9g of compound 4-1 and 0.4ml of methyl iodide were dissolved in 30ml of an N, N-dimethylformamide solution, and heated to 80 ℃ under an argon atmosphere, and the reaction was stirred under reflux at 80 ℃ for 5 hours, cooled to room temperature, filtered to collect a precipitate, washed with ethyl acetate, and dried in vacuo to give compound C1.

Of compound C1¹H NMR was as follows:¹H NMR(400MHz,D₂O):9.18(d,J＝6.2Hz,2H),9.01(d,J＝6.2Hz,2H),8.52(dd,J＝25.8,6.2Hz,4H),7.98(d,J＝9.4Hz,1H),7.72(d,J＝8.0Hz,1H),7.38–7.54(m,2H),6.48(d,J＝9.0Hz,1H),6.02(s,2H),4.45(s,3H).

of compound C1¹³C NMR was as follows:¹³C NMR(151MHz,D₂O):δ163.58,153.65,150.95,149.72,146.54,145.98,145.10,136.39,129.94,127.55,126.95,125.56,117.38,116.79,64.08,48.57.

example 4

Preparation of Compound C2

Preparation of C2:

2.5mmol of compound B1 and 6.0mmol of compound 2-1 were dissolved in 60mL of DMSO and the solution was stirred under argon at 80 ℃ and cooled to room temperature after 3 hours. The precipitate was collected by filtration using a small amount of H₂O washed and dried in vacuo to afford the crude product, compound C2 recrystallized in water to afford a light yellow powder in about 70% yield.

Of compound C2¹H NMR was as follows:¹H NMR(400MHz,D₂O):δ8.92(d,J＝6.91Hz,2H),8.64(dd,J＝4.6,1.8Hz,2H),8.20(d,J＝6.9Hz,2H),7.68(dd,J＝4.6,1.7Hz,2H),7.60(d,J＝9.5Hz,1H),7.33(d,J＝8.7Hz,1H),6.74(dd,J＝8.7,2.4Hz,1H),6.49(d,J＝2.5Hz,1H),5.97(d,J＝9.4Hz,1H),4.70(t,J＝6.5Hz,2H),3.95(t,J＝5.8Hz,2H),2.33–2.22(m,2H),1.94–1.83(m,2H).

of compound C2¹³C NMR was as follows:¹³C NMR(151MHz,DMSO):δ161.57,160.28,155.37,152.30,151.01,145.39,144.34,140.85,129.54,125.44,121.90,112.72,112.45,67.59,59.99,27.51,25.02.

example 5

Cyclic voltammetry tests of Compounds A1, B1, C1, C2

Preparing a solution containing 75g/L of CuSO₄·5H₂O and 180g/LH₂SO₄The copper sulfate solution (2) was added dropwise to a copper sulfate solution (100mL) at 2000 rpm in 0.2mL each of 1mmol/L aqueous solutions of the compounds A1, B1, C1 and C2 using a Pt rotary disk electrode as a working electrode, a platinum rod as a counter electrode and Ag/AgCl as a reference electrode, and the cyclic voltammetry curves were measured. The larger the amount of additive added in the cyclic voltammetry test, the smaller the oxidation peak area obtained, corresponding to a stronger inhibition, whereas the test was terminated when the additive concentration reached 10 umol/L.

The specific results are as follows: the results are shown in FIGS. 1 to 4, in which FIG. 1 is a cyclic voltammogram of Compound A1; FIG. 2 is a cyclic voltammogram of Compound B1; FIG. 3 is a cyclic voltammogram of compound C1; FIG. 4 is a cyclic voltammogram of compound C2; as can be seen from fig. 1, 2, 3 and 4, compounds a1-C2 probably showed a trend that the peak area ratio gradually decreased with increasing concentration, indicating that the inhibitory effect of the compounds was stronger with increasing concentration of the compounds; by comparing the cyclic curves of different compounds at the concentration of 2umol/L, it can be seen that the compound C2 has the best effect among the compounds A1, B1, C1 and C2, can achieve the good leveling effect under the condition of small dosage, and has huge application potential.

Comparative example 1

Cyclic voltammetry testing of a commercial leveler JGB

The leveling agent of the existing commercial acid copper electroplating: "Janus Green" (compound of formula D, abbreviated as "JGB") was tested. Preparing a solution containing 75g/L of CuSO₄·5H₂O and 180g/L H₂SO₄The copper sulfate solution (2) is prepared by dropping a compound D aqueous solution with the concentration of 1mmol/L into a copper sulfate solution (100mL) at the rotation speed of 2000 rpm by using a Pt rotary disk electrode as a working electrode, a platinum rod as a counter electrode and Ag/AgCl as a reference electrode, and testing the cyclic voltammetry curve. The larger the amount of additive added in the cyclic voltammetry test, the smaller the resulting oxidation peak area, which corresponds to a stronger inhibition, whereas when the additive concentration reached 30umol/L, the test was terminated and the cyclic voltammetry curve is shown in FIG. 5.

The specific results are as follows: as shown in fig. 5, fig. 5 is a cyclic voltammetry graph of a commercial leveling agent JGB, and from fig. 5, it can be obtained that the leveling effect of the commercial leveling agent JGB is generally at a concentration of 6umol/L, and although the peak area ratio is gradually decreased with the increase of the concentration, the inhibition effect is inferior to that of the compound C2 at a concentration of 2umol/L when the concentration is 30umol/L, and from fig. 5, it can be seen that the leveling effect of the commercial leveling agent JGB is significantly inferior to that of the compounds C1 and C2 at the same molar concentration.

The cyclic voltammetry result is that the area of the oxidation peak under the same concentration is considered, generally, the smaller the area of the oxidation peak, the stronger the corresponding inhibition effect, and the better the leveling effect of the obtained coating in the electroplating process. In the application, the effects of the compounds C1 and C2 are obviously better than those of other compounds and a commercially available leveling agent JGB.

According to the measured cyclic voltammetry curve, the plating inhibition effects of the coumarin quaternary ammonium salt compounds C1 and C2 as the plating leveling agent are obviously better than those of a leveling agent JGB sold in the market, and the coumarin quaternary ammonium salt compounds are expected to be developed into the plating leveling agent with excellent performance.

Example 6

Polarization curve test of Compounds C1, C2

Preparing a solution containing 75g/L of CuSO₄·5H₂O and 180g/LH₂SO₄The copper sulfate solution (2) was prepared by dropping 200. mu.l of an aqueous solution of the compounds A1, B1, C1 and C2 at a concentration of 1mmol/L into a copper sulfate solution (100mL) at 2000 rpm using a Pt rotary disk electrode as a working electrode, a platinum rod as a counter electrode and Ag/AgCl as a reference electrode, and testing the polarization curve. FIG. 6 shows that compound C is shown in FIG. 6₁、C₂The polarization potential of compound C2 is the greatest compared to the polarization curve of the commercial leveler JGB, which indicates that compound C2 has the strongest ability to inhibit copper ion deposition.

Comparative example 2

Polarization curve testing of commercial leveler JGB

The existing commercial acid copper electroplating leveling agent comprises the following components: "Janus Green" (abbreviated as "JGB") was tested. Preparing a solution containing 75g/L of CuSO₄·5H₂O and 180g/L H₂SO₄The copper sulfate solution (2) was prepared by dropping 200. mu.l of 1mmol/L JGB aqueous solution into a copper sulfate solution (100mL) at 2000 rpm using a Pt rotary disk electrode as a working electrode, a platinum rod as a counter electrode and Ag/AgCl as a reference electrode, and testing the polarization curve thereof, as shown in FIG. 6, FIG. 6Is a compound C₁、C₂Polarization profile with a commercial leveler JGB. As can be seen from FIG. 6, when 200. mu.l of the compounds C1, C2 and JGB with a concentration of 1mmol/L are added to the base plating solution, the cathodic polarization potential is shifted negatively, and the copper deposition current density begins to increase when the base electrolyte is about 0V, which indicates that copper begins to deposit on the working electrode at 0V. When 200. mu.l of commercial leveler JGB (Compound D) was added at a concentration of 1mmol/L, the copper deposition current density began to increase as the potential reached-0.07V, indicating that polarization occurred. After addition of 200. mu.l of 1mmol/L of compound C1, the deposition current density of copper began to increase at a potential of-0.11V, indicating that polarization occurred. After addition of 200. mu.l of 1mmol/L of compound C2, the deposition current density of copper began to increase at a potential of-0.17V, indicating that polarization occurred. The larger the value of the deposition potential, the stronger the inhibition ability, and the better the effect, so that the inhibition effect of compound C2 is the best.

Example 7

Galvanostatic addition curve testing of compound C2

Preparing a solution containing 75g/L of CuSO₄·5H₂O and 180g/L H₂SO₄The copper sulfate solution of (1) was prepared by adding 200ppm of polyethylene glycol PEG (average molecular weight: 10000), 2ppm of sodium polydithio dipropyl sulfonate (SPS) and 200. mu.l of a compound C2 solution (solvent: deionized water) at intervals of 1000 seconds at 100rpm and 1000rpm to obtain a constant current timing addition curve, as shown in FIG. 7, FIG. 7 shows a compound C2 solution (average molecular weight: 10000), and Ag/AgCl as a counter electrode and Ag/AgCl as a reference electrode, respectively₂Schematic diagram of the constant current timing addition curve test of (1). As can be seen from FIG. 7, when the addition of compound C2 resulted in the suppression of the depolarization of SPS in the plating solution, the potential started to move in the negative direction, because compound C2 could still suppress the deposition of copper in the presence of SPS and PEG. The deposition at the hole mouth and at the hole inner wall of the through hole was simulated by using 1000rpm and 100rpm rotation speeds, respectively. The potential difference at different rotation speeds is defined as Δ η ═ η (100rpm) η (1000rpm), and may be set to beIt is seen that. DELTA.eta.after addition of Compound C2₄The value of 9mV is positive, from which it can be seen that the adsorption behavior of compound C2 is a convection dependent adsorption, used to characterize the difference in the different inhibitory effects at 1000rpm and 100 rpm. If Δ η is positive, it indicates that strong convection results in less copper deposition and is suitable for plating with vias. Therefore, compound C2 adsorbed more strongly at the hole opening of the PCB (this PCB is a printed circuit board with through holes, used for actual copper plating) than at the middle position of the hole, and thus more adsorbed at the hole opening has the effect of suppressing the deposition of copper at the hole opening. Therefore, the compound C2 can obtain a plating layer with uniform thickness distribution during electroplating under the synergistic effect of PEG and SPS, and the Delta eta can be seen from figure 7₄The inhibition effect of the rotating disk electrode at different rotating speeds is different, and the difference of the deposition potential is about 9 mV.

Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.