A wet electronic chemical based on phenyl azo naphthol quaternary ammonium salt compound and application thereof

Abstract

The application discloses a phenyl azo naphthol quaternary ammonium salt compound, and a general structure is shown as follows: The compound has stable structure and good solubility, can be dissolved in a copper electroplating solution system as a copper electroplating additive, and has a large conjugated π bond and electron-deficient N positive ion, so that the compound is more easily adsorbed on the surface of a copper layer; the large planarity and N positive center can more effectively inhibit the deposition of copper ions, so that the compound can be applied to industrial copper electroplating as a copper electroplating leveling additive.

Description

Technical Field

[0001] This invention belongs to the field of quaternary ammonium salt technology, specifically, it relates to a phenylazonaphthol-containing quaternary ammonium salt compound and its application in the electronics field. Background Technology

[0002] With rapid technological advancements, the market demand for electronic chemicals is increasing. Conductive components in various electronic products, including semiconductor components, printed circuit boards (PCBs), high interconnect density PCBs (HDI-PCBs), and integrated circuits (ICs), all rely on copper plating processes. Before the advent of PCBs, electronic components were interconnected by direct wire connections. To reduce wiring and lower costs, researchers began exploring methods to replace wiring with printing for interconnection. In the 1950s, the demand for PCBs surged due to the emergence of semiconductor transistors. With the rapid development of ICs and the increasing sophistication of electronic devices, the difficulty of wire connections increased, leading to the evolution of PCBs from single-sided boards to double-sided boards, multilayer boards, and ultimately, high-density arbitrary interconnects. The future development trend of PCBs remains towards high density, high precision, high-speed transmission, and system miniaturization. In PCB production, efficiently achieving interlayer interconnection is paramount, with mainstream methods including through-hole filling and blind via filling. With technological advancements and the demands of electronic products, copper plating through-hole and blind via filling technologies are indispensable in semiconductor manufacturing, a crucial aspect of IC chip production. In the past, PTH in PCBs was mainly used to conduct lines between different layers, so there was no need to fill the holes with copper. Nowadays, due to the demand for high-density interconnects, the conduction between layers has evolved into using blind vias filled with copper and then stacked on top of each other. This not only saves space, but also greatly improves conductivity and enhances conductivity.

[0003] To achieve defect-free superfilling, the composition of electroplating additives is essential. Currently, the additives required for industrial production include inhibitors, accelerators, and leveling agents. Among them, electroplating leveling agents play a decisive role in the accelerator-inhibitor-leveling agent system. Excellent electroplating leveling agents can level the coating during the blind / through electroplating process, enabling it to achieve perfect filling.

[0004] Currently, commonly used leveling agents are nitrogen-containing or nitrogen / sulfur compounds, such as thiourea and its derivatives (H2N-CS-NH2), benzimidazole (C6H4-N-NH-SH) compounds, benzothiazole (C6H4-NS-SH) compounds, dimethylphenylammonium ((CH3)2=N-C6H5) compounds, and polyethyleneimine compounds (H[-NH-CH2-CH2-]). n -NH2), dye compounds (Jenner Green, Methylene Blue, Nile Blue, Crystal Violet, Phthalocyanine, etc.).

[0005] Sudan I, commonly known as "Sudan Red No. 1," "Oil-soluble Yellow," "Lightfast Orange," and "Sudan Yellow," is a common pigment frequently used for coloring shoe polish, floor wax, and greases. It is also used as a biological dye and a colorant for acrylic glass. Its stable structure allows it to withstand most electroplating systems without causing haze or other issues. However, despite its widespread use, Sudan Red has seen limited research and application, particularly in electroplating. As an azo dye, Sudan Red possesses extremely strong coloring properties. The azo groups exhibit strong hydrophilicity and lipophilicity, and its synthesized quaternary ammonium salt compounds also exhibit excellent water solubility, making it highly suitable for copper sulfate solutions used in electroplating. The large conjugated π bonds, high planarity, and electron-deficient nature of the Sudan Red molecule facilitate adsorption onto copper surfaces. Furthermore, the positive nitrogen centers of the quaternary ammonium salts effectively inhibit copper ion deposition, resulting in excellent leveling properties in copper electroplating. Compared to commercially available leveling agents like JGB, Sudan Red offers advantages such as lower cost, higher efficiency, and superior inhibition performance. Applying Sudan Red dye to copper electroplating can achieve excellent production efficiency while reducing Sudan Red's environmental pollution and realizing sustainable development.

[0006] Regarding additives, most of the additives used in high-end products in China are currently sourced from the United States, Japan, Germany, and other countries. Domestic additive manufacturers in China offer a limited variety of high-quality chemicals to meet diverse needs, and these are not yet serialized. Furthermore, in the manufacturing process of printed circuit boards, various additives in the copper plating solution can significantly influence the electrochemical behavior of copper electrodeposition. The microscopic physical or chemical behavior of these additives on the electrode surface is difficult to observe, and the mechanism by which leveling agents achieve their leveling effect is not fully understood. This hinders high-level research in this area. However, this issue is gradually being recognized, and with technological advancements, research on electroplating leveling agents will become increasingly in-depth. Summary of the Invention

[0007] The first objective of this invention is to provide a phenylazonaphthol quaternary ammonium salt compound.

[0008] Another object of the present invention is to provide the application of the phenylazonaphthol-containing quaternary ammonium salt compound in the preparation of electroplating leveling agents.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] A first aspect of the present invention provides a phenylazonaphthol quaternary ammonium salt compound with the following general structural formula:

[0011]

[0012] Where n is selected from positive integers from 1 to 18 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.);

[0013] R is selected from

[0014]

[0015] X is selected from Br, F, Cl, I, HSO3, HSO4, HCO3, CF3CO3, H2PO4, OTf, OTs, and BF4.

[0016] Preferably, the structure of the phenylazonaphthol quaternary ammonium salt compound is selected from one of the following structures:

[0017]

[0018] A second aspect of the present invention provides the application of the phenylazonaphthol-containing quaternary ammonium salt compound in the preparation of an electroplating leveling agent.

[0019] The electroplating is copper electroplating, and the electroplating solution is copper sulfate.

[0020] A third aspect of the present invention provides the application of the phenylazonaphthol-containing quaternary ammonium salt compound in combination with polyethylene glycol and sodium polydisulfide dipropane sulfonate (SPS) in the preparation of an electroplating leveling agent.

[0021] The average molecular weight of the polyethylene glycol is 10,000.

[0022] By adopting the above technical solution, the present invention has the following advantages and beneficial effects:

[0023] This invention provides phenylazo-2-naphthol derivatives and studies the methodology for synthesizing them. Phenyzo-2-naphthol, commonly known as "Sudan Red I," is a common pigment. Due to the presence of intermolecular hydrogen bonds, this pigment exhibits excellent solubility and thermal stability. Most Sudan Red pigments have melting points greater than 131°C. Even after being prepared as quaternary ammonium salt derivatives, the structure remains stable, allowing for use at higher temperatures without causing phenomena such as fogging in the plating. While Sudan Red is a common pigment, its research and application in other areas, particularly electroplating, are limited. This invention opens up new avenues for the research and commercial application of Sudan Red. Furthermore, applying Sudan Red dyes to copper electroplating can achieve excellent production efficiency while reducing the environmental pollution caused by Sudan Red, thus realizing sustainable development.

[0024] The method for synthesizing phenylazonaphthol-containing quaternary ammonium salt compounds according to this invention has the advantages of high efficiency, low cost, and high feasibility. Currently, the synthesis research of Sudan Red, the raw material for this invention, is relatively mature. Therefore, the raw material for this invention is easier to synthesize and has lower cost compared to other commercial electroplating leveling agents. The entire synthesis of the phenylazonaphthol-containing quaternary ammonium salt compounds involves only two steps, requires no stringent external environmental control, has simple reaction steps, high yield, and readily available products, which lays the foundation for its application as an electroplating additive.

[0025] Sudan Red pigment itself possesses large conjugated π bonds, but not all quaternary ammonium salt groups introduced into Sudan Red for modification achieve good electrochemical effects. Compound B of this invention exhibits significantly better electrochemical performance than compound C. Furthermore, electrochemical testing and practical applications show that compound B is more readily adsorbed onto the copper layer surface, and its positive N-center can more effectively inhibit copper ion deposition. It can serve as an electroplating leveling additive, demonstrating superior inhibition performance compared to the currently commercially available leveling agent JGB. In addition, the good water solubility of quaternary ammonium salt compounds makes them more suitable for acidic copper plating bath systems, making them a feasible and efficient copper plating additive.

[0026] The compound of this invention has a stable structure and good solubility, and can be used as an additive for copper plating in copper plating solution systems. Its large conjugated π bond and electron-deficient N positive ion make it easier to adsorb onto the surface of the copper layer. Its large planarity and positive N center can more effectively inhibit the deposition of copper ions, and it can be used as an electroplating leveling additive in industrial copper plating. Attached Figure Description

[0027] Figure 1 This is the cyclic voltammetry curve for compound B.

[0028] Figure 2 This is the cyclic voltammetry curve for compound C.

[0029] Figure 3 The cyclic voltammetry curve of commercially available leveling agent H (JGB) is shown.

[0030] Figure 4 This is the polarization curve of compound B.

[0031] Figure 5 For different rotational speeds, with a current density of 2A / dm 2 Add a curve graph to the timer.

[0032] Figure 6 This is a cross-sectional view of the through-hole filling test of compound B.

[0033] Figure 7 This is a cross-sectional view of the through-hole filling test of JGB. Detailed Implementation

[0034] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0035] The Sudan I quaternary ammonium salt compound synthesized in this invention has a quaternary ammonium salt structure. Through the nitrogen positive ion in the structure, i.e., the quaternization center, it can have a large coverage area on the electrode surface and increase the cathode polarization, inhibiting copper deposition, thereby making the electroplating particles finer and the copper plating layer obtain a highly preferred crystal orientation. Therefore, it can be used as a quaternary ammonium salt leveling agent for acidic copper electroplating.

[0036] The reagents used in the embodiments of this invention are shown in Table 1:

[0037] Table 1

[0038] Reagent name Manufacturer Purity Specification Sudan I Shanghai Aladdin Bio-Chem Technology Co., Ltd. 99.9％ 500g 1,6-dibromohexane Shanghai Titan Technology Co., Ltd. 97.0％ 1 kg Acetone Shanghai Maikelin Biochemical Technology Co., Ltd. 99.9％ 500ml Acetonitrile Shanghai Titan Technology Co., Ltd. 99.9％ 2.5L Methylene chloride Shanghai Titan Technology Co., Ltd. 99.9％ 2.5L Methanol Shanghai Titan Technology Co., Ltd. 99.9％ 2.5L Petroleum ether Shanghai Titan Technology Co., Ltd. 60-90℃ 2.5L Potassium hydroxide Shanghai Titan Technology Co., Ltd. 98％ 500g 4,4'-dipyridyl Shanghai Titan Technology Co., Ltd. 99％ 100g Pyridine Shanghai Titan Technology Co., Ltd. 99％ 500ml 2-benzylpyridine Shanghai Titan Technology Co., Ltd. 99％ 25ml Nicotinamide Shanghai Titan Technology Co., Ltd. 99％ 500g Quinoline Shanghai Titan Technology Co., Ltd. 99％ 500ml Copper sulfate pentahydrate Shanghai Titan Technology Co., Ltd. ≥99.0％ 1 kg Sulfuric acid National Pharmaceutical Group Chemical Reagent Co., Ltd. 95.0～98.0％ 500ml Hydrochloric acid National Pharmaceutical Group Chemical Reagent Co., Ltd. 36.0～38.0％ 500ml

[0039] Example 1

[0040]

[0041] Phenylazo-2-naphthol (4.966 g, 10 mmol), 1,6-dibromohexane (9.759 g, 20 mmol), and potassium hydroxide (2.244 g, 20 mmol) were dissolved in 30 mL of acetone. The mixture was heated and stirred under reflux for 12 h. The mixture was extracted three times with water using a separatory funnel. The resulting organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The mixture was then purified by silica gel column chromatography to give 2.716 g of liquid product, with a yield of 54.69%. 1 H NMR(400MHz, CDCl3)δ8.34(dd,J=8.5,1.2Hz,1H),8.08–7.92(m,2H),7.88–7.80(m,2H),7.62–7.49(m,4H),7.45 –7.35(m,2H),4.16(t,J=6.2Hz,2H),3.31(t,J=6.8Hz,2H),1.82–1.73(m,4H),1.44(dq,J=10.4,5.5,5.0Hz,4H).

[0042]

[0043] Compound A (2 mmol, 0.823 g) and quinoline (10 mmol, 1.292 g) were dissolved in 20 mL of acetonitrile and placed in a pressure-resistant reaction flask. The mixture was mixed under normal pressure, heated and stirred at 80 °C for 12 h. The reaction was monitored by thin-layer chromatography until complete. Acetonitrile was removed by rotary evaporation, and the product was purified by neutral alumina column chromatography to obtain 0.426 g of the corresponding product, with a yield of 46.22%. 1 HNMR(400MHz,DMSO-d6)δ9.53(dd,J=5.9,1.5Hz,1H),9.21(d,J=8.3Hz,1H),8.50(d ,J=9.0Hz,1H),8.41(dd,J=8.3,1.5Hz,1H),8.20–8.05(m,3H),7.99–7.92(m,2H),7. 87(d,J=8.1Hz,1H),7.82–7.75(m,2H),7.52–7.37(m,6H),4.95(t,J=7.5Hz,2H),4. 09(t,J=6.1Hz,2H),1.81(p,J=7.7Hz,2H),1.61(p,J=6.3Hz,2H),1.42–1.29(m,4H); 13 C NMR(101MHz,DMSO-d6)δ153.37,150.09,148.08,147.86,137.80,136.10, 136.04,131.69,131.63,131.25,130.32,130.18,129.87,129.03,128.55, 128.33,128.21,124.94,122.86,122.59,122.54,119.43,119.34,116.96, 70.01,57.64,29.97,29.07,25.80,25.40.MS(ESI)m / z:1 / 2[M-2Br]+calcd for C 31 H 30 N3O + Found: 460.24;

[0044] Example 2

[0045]

[0046] Compound A (2 mmol, 0.823 g) and 4,4'-bipyridine (10 mmol, 1.562 g) were dissolved in 20 mL of acetonitrile and placed in a pressure-resistant reaction flask. The mixture was mixed under normal pressure, heated and stirred at 80 °C for 12 h. The reaction was monitored by thin-layer chromatography until complete. Acetonitrile was removed by rotary evaporation, and the product was purified by neutral alumina column chromatography to obtain 0.3419 g of the corresponding product, with a yield of 35.06%. 1 H NMR (400MHz, DMSO-d6) δ9.30(d,J=6.4Hz,2H),8.83(d,J=5.6Hz,2H),8.63(d,J=6.3H z,2H),8.22(d,J=8.5Hz,1H),8.06–7.97(m,3H),7.91(dd,J=7.8,5.6Hz,3H),7.65–7. 50(m,5H),7.43(t,J=7.5Hz,1H),4.65(t,J=7.3Hz,2H),4.16(t,J=6.2Hz,2H),1.88( p,J=7.4Hz,2H),1.68(p,J=6.5Hz,2H),1.45(p,J=7.2Hz,2H),1.32(q,J=8.1Hz,2H).; 13 C NMR(101MHz,DMSO-d6)δ152.97,152.21,151.01,147.63,145.33,140.87,135.61,131.33,131.29,129.57,128.61,128.42,128.13,127.92, 127.80,125.41,124.54,122.43,122.19,121.97,118.68,116.54,69.61,60.26,30.75,28.59,25.05,24.90.MS(ESI)m / z:1 / 2[M-2Br]+calcd for C 32 H 31 N4O + : 487.25; Found: 487.25.

[0047] Example 3

[0048]

[0049] Compound A (2 mmol, 0.823 g) and pyridine (10 mmol, 0.791 g) were dissolved in 20 mL of acetonitrile and placed in a pressure-resistant reaction flask. The mixture was mixed under normal pressure, heated and stirred at 80 °C for 12 h. The reaction was monitored by thin-layer chromatography until complete. Acetonitrile was removed by rotary evaporation, and the product was purified by neutral alumina column chromatography to obtain 0.4366 g of the corresponding product, with a yield of 53.17%.1 HNMR(400MHz,DMSO-d6)δ9.09–9.04(m,2H),8.52(tt,J=7.9,1.5Hz,1H),8.19–8.13(m,1 H),8.08(dd,J=7.9,6.3Hz,2H),7.95(d,J=9.1Hz,1H),7.89–7.82(m,3H),7.57–7.45(m,5 H),7.38(ddd,J=8.0,6.8,1.2Hz,1H),4.51(t,J=7.5Hz,2H),4.09(t,J=6.2Hz,2H),1.76( p,J=7.6Hz,2H),1.60(p,J=6.5Hz,2H),1.36(dd,J=10.8,4.9Hz,2H),1.23–1.17(m,2H).; 13 CNMR(101MHz,DMSO-d6)δ152.53,147.19,145.07,144.32,135.20,130.89,130.83,129.11,128.18,127.69,127.48,127.37 ,124.10,122.00,121.74,118.24,116.12,69.14,60.20,30.34,28.16,27.80,24.62,24.42.MS(ESI)m / z:1 / 2[M-2Br]+calcd for C 27 H 28 N3O + :410.22; Found:410.22.

[0050] Example 4

[0051]

[0052] Compound A (2 mmol, 0.823 g) and 2-benzylpyridine (10 mmol, 1.692 g) were dissolved in 20 mL of acetonitrile and placed in a pressure-resistant reaction flask. The mixture was mixed under normal pressure, heated and stirred at 80 °C for 12 h. The reaction was monitored by thin-layer chromatography until complete. Acetonitrile was removed by rotary evaporation, and the product was purified by neutral alumina column chromatography to obtain 0.0843 g of the corresponding product, with a yield of 8.42%. 1HNMR(400MHz,DMSO-d6)δ9.07–9.01(m,1H),8.43(td,J=7.9,1.5Hz,1H),8.1 7–8.13(m,1H),7.94(dd,J=8.1,5.9Hz,2H),7.87–7.77(m,4H),7.52–7.43(m, 5H),7.36(ddd,J=8.0,6.7,1.2Hz,1H),7.26–7.14(m,5H),4.49(d,J=5.3Hz, 2H),4.07(q,J=5.8Hz,2H),1.51(dt,J=20.4,7.5Hz,4H),1.29–1.16(m,4H).; 13 C NMR(101MHz,DMSO-d6)δ156.69,153.42,148.11,146.63,146.00,136.10,135.64,135 .56,131.72,131.69,130.26,129.95,129.67,129.63,129.60,129.57,129.06,128.5 6,128.35,128.21,128.02,126.60,124.96,122.87,122.59,117.00,70.03,57.43,43 .09,37.84,30.56,30.18,28.98,28.70,25.66,25.32.MS(ESI)m / z:1 / 2[M-2Br]+calcd for C 34 H 34 N3O + : 500.27; Found: 500.27.

[0053] Application Example 1

[0054] Cyclic voltammetry test of compound B prepared in Example 1

[0055] A copper sulfate solution containing 140 g / L CuSO4·5H2O, 200 mL / L H2SO4, and 140 μL / L HCl was prepared. Using a Pt rotating disk electrode as the working electrode, a platinum rod as the counter electrode, and Ag / AgCl as the reference electrode, at a rotation speed of 2000 rpm, different concentrations (0, 2, 4, 6, 8, and 10 μmol / L, compound B dissolved in deionized water) of compound B were added to the aforementioned copper sulfate solution containing chloride ions. Cyclic voltammetry was then performed. The results are as follows: Figure 1 As shown, Figure 1This is a cyclic voltammogram of compound B. The cyclic voltammograms show the inhibitory effect of compound B prepared in Example 1 on copper ion deposition on the surface of copper materials at different concentrations, and the comparison with the blank control. The horizontal axis represents the electrode (Ag / AgCl) potential (in volts), and the vertical axis represents the current density (in amperes / dm²). 2 The test was terminated when the concentration reached 10 μmol / L.

[0056] The specific results are as follows: (Results are as follows) Figure 1 As shown in the figure, the peak area ratio gradually decreases with increasing concentration, indicating that compound B can be adsorbed on the cathode surface and form a barrier layer on the cathode surface to hinder copper deposition, thereby increasing the resistance to the copper deposition reaction. Moreover, the inhibitory effect is stronger with increasing concentration of compound B. Comparing the cycle curves of different compounds, it can be seen that compound B can achieve a good leveling effect and has significant application value.

[0057] Comparative Example 1

[0058] The synthesized compound C: phenylazo-2-naphthol-nicotinamide quaternary ammonium salt (compound shown in the figure below, abbreviated as "compound C") was used for testing. A copper sulfate solution containing 140 g / L CuSO4·5H2O, 200 mL / L H2SO4, and 140 μL / L HCl was prepared. Using a Pt rotating disk electrode as the working electrode, a platinum rod as the counter electrode, and Ag / AgCl as the reference electrode, at a rotation speed of 2000 rpm, different concentrations (0, 2, 4, 6, 8, and 10 μmol / L, compound C dissolved in deionized water) of compound C solution were added to the above copper sulfate solution containing chloride ions, and cyclic voltammetry was performed. The larger the amount of additive added during cyclic voltammetry, the smaller the oxidation peak area, corresponding to a stronger inhibition effect. The test was terminated when the additive concentration reached 10 μmol / L. The cyclic voltammetry curves are shown in [Figure showing the cyclic voltammetry curves]. Figure 2 As shown, Figure 2 This is the cyclic voltammetry curve for compound C.

[0059]

[0060] The cyclic voltammetry results show that, at the same mass concentration, compound C has a larger oxidation peak area and a weaker corresponding inhibition effect, while compound B has a smaller oxidation peak area and a stronger corresponding inhibition effect. Therefore, the leveling effect of compound B is significantly better than that of compound C. This indicates that not all phenylazo-2-naphthol quaternary ammonium salt compounds have electrochemical properties.

[0061] Comparative Example 2

[0062] The commercially available acidic copper plating leveling agent, "Jenner Green B" (compound shown in the figure below, abbreviated as "JGB"), was used for testing. A copper sulfate solution containing 140 g / L CuSO4·5H2O, 200 mL / L H2SO4, and 140 μL / L HCl was prepared. Using a Pt rotating disk electrode as the working electrode, a platinum rod as the counter electrode, and Ag / AgCl as the reference electrode, at a rotation speed of 2000 rpm, different concentrations of JGB solution (0, 2, 4, 6, 8, and 10 μmol / L, JGB dissolved in deionized water) were added to the aforementioned chloride-containing copper sulfate solution, and cyclic voltammetry was performed. The higher the amount of additive added during cyclic voltammetry, the smaller the oxidation peak area, corresponding to a stronger inhibition effect. The test was terminated when the additive concentration reached 10 μmol / L. The cyclic voltammetry curves are shown in [Figure showing the cyclic voltammetry curves]. Figure 3 As shown, Figure 3 The cyclic voltammetry curve of commercially available leveling agent H (JGB) is shown.

[0063]

[0064] The cyclic voltammetry results show that, at the same mass concentration, the oxidation peak area of ​​JGB is larger, and the corresponding inhibition effect is weaker, while the oxidation peak area of ​​compound B is smaller, and the corresponding inhibition effect is stronger. Therefore, the leveling effect of compound B is significantly better than that of JGB.

[0065] Application Example 2

[0066] Polarization curve test of compound B

[0067] A copper sulfate solution containing 140 g / L CuSO4·5H2O, 200 mL / L H2SO4, and 140 μL / L HCl was prepared. Using a Pt rotating disk electrode as the working electrode, a platinum rod as the counter electrode, and Ag / AgCl as the reference electrode, at a rotation speed of 2000 rpm, different concentrations (2, 4, 6, 8, and 10 μmol / L, compound B dissolved in deionized water) of compound B solution were added to the aforementioned copper sulfate solution containing chloride ions, and polarization curves were measured. The results are as follows: Figure 4 As shown, Figure 4 The polarization curve of compound B is shown, with a scan rate of 2 mV / s. -1 Based on the inhibition effect of compound B on copper ion deposition on the surface of copper materials at different concentrations and the polarization curves of the blank control, the horizontal axis represents the electrode (Ag / AgCl) potential (unit: volt), and the vertical axis represents the current density (unit: ampere / decimeter). 2 ).

[0068] The specific results are as follows: As shown in the figure, the peak area ratio gradually decreases with increasing concentration. After adding compound B to the solution, the copper deposition potential shifts negatively. When the concentration of compound B in the solution reaches 6 μmol / L, the potential reaches -0.19 V before a copper deposition current is observed. This indicates that the inhibitory effect of the compound increases with increasing concentration. Comparing the polarization curves of different compounds, it can be seen that compound B achieves a good leveling effect, demonstrating significant application value.

[0069] Application Example 3

[0070] The synergistic inhibition performance of compound B as a leveling agent with PEG and SPS was tested.

[0071] A copper sulfate solution containing 140 g / L CuSO4·5H2O, 200 mL / L H2SO4, and 140 μL / L HCl was prepared. Using a Pt rotating disk electrode as the working electrode, a platinum rod as the counter electrode, and Ag / AgCl as the reference electrode, 200 ppm of polyethylene glycol (PEG, average molecular weight 10000), 2 ppm of sodium polydithiopropane sulfonate (SPS), and 500 μL of compound B solution (dissolved in deionized water) were added to the solution every 1000 seconds at rotation speeds of 200 rpm and 1500 rpm, respectively. The galvanostatic addition curve was obtained. The results are as follows: Figure 5 As shown, Figure 5 For different rotational speeds, with a current density of 2A / dm 2 A time-added curve was plotted. Based on time-added tests of compound B at different rotational speeds, the horizontal axis represents time (in seconds), and the vertical axis represents potential (in volts). From... Figure 5 As can be seen, the addition of compound B suppresses the depolarization caused by SPS, resulting in a negative potential shift. This indicates that compound B can still inhibit copper deposition in the presence of SPS and PEG. Rotation speeds of 1500 rpm and 200 rpm were used to simulate deposition at the orifice and inner wall of the via, respectively. The potential difference at different rotation speeds is defined as Δη = η(200 rpm) - η(1500 rpm), and Δη4 = 14.2 mV is positive, indicating that the adsorption behavior of compound B is convective-dependent, used to characterize the difference in inhibition at 1500 rpm and 200 rpm. A positive Δη indicates strong convection leading to less copper deposition, suitable for via electroplating. Therefore, the adsorption of compound B at the orifice of the PCB board (this PCB board is a printed circuit board with through-holes, used for actual copper plating) is stronger than at the center of the hole, inhibiting copper deposition at the orifice. The synergistic effect of PEG and SPS allows for a uniformly distributed plating layer during electroplating. Figure 5It can be seen that Δη=14.2mV means that the suppression effect of the rotating disk electrode is different at different rotation speeds, and the deposition potential difference is about 14.2mV.

[0072] Figure 5 In the middle, the current density at different rotational speeds is 2A / dm. 2 As can be seen from the time-added curve, when the inhibitor polyethylene glycol (PEG) was added at the initial 1000s, the potential decreased significantly and tended to stabilize. When the accelerator sodium polydisulfide dipropane sulfonate (SPS) was added at 2000s, the potential increased significantly and tended to stabilize, indicating that PEG and SPS have an antagonistic effect. When the compound of the present invention was added at 3000s, the potential decreased significantly and tended to stabilize, indicating that the compound of the present invention has an antagonistic effect with SPS.

[0073] Application Example 4

[0074] Preparation of plating solution: Prepare a copper sulfate solution containing 220 g / L CuSO4·5H2O, 35 ml / L H2SO4, and 100 mg / L Cl ions. Add 3 mg / L sodium polydisulfide dipropane sulfonate (SPS), 0.5 g / L polyethylene glycol (average molecular weight 10000), and compound B obtained in Example 1 at 1 mmol / L to the solution to prepare an acidic copper sulfate electroplating solution.

[0075] A Harlem cell experiment was conducted using a corrugated phosphor bronze plate as the anode and a PCB board as the cathode at room temperature and a current density of 2 A / dm³. 2 Under constant-rate aeration and bubbling conditions, electroplating for 75 minutes resulted in complete copper coverage on the PCB board, with good plating solution flow. The results were as follows: Figure 6 As shown, Figure 6 This is a cross-sectional view of the through-hole filling test of compound B. Metallographic microscopy revealed that the specimen and through-holes were completely covered by a copper layer, which was bright and smooth. The results indicate that using compound B as a leveling agent, compounded with other compounds, in the electroplating of through-holes in printed circuit boards can improve the uniformity of the plating thickness, resulting in a brighter and smoother copper plating. When the concentration of compound B in the copper plating solution was 3.5 ppm, the TP value reached an excellent 111%.

[0076] The above experiment was conducted using JGB as a control example, and the results are as follows: Figure 7 As shown, Figure 7 This is a cross-sectional view of the through-hole filling test of JGB. Figure 7 The figure shows the through-hole filling cross section of JGB. As can be seen from the figure, the filling effect of commercial leveling agent JGB is worse than that of the present invention. On the one hand, in terms of morphology, the filling shape retention effect is not good, and there are obvious protrusions at the orifice, which is not conducive to high-density interconnection. On the other hand, in terms of filling capacity, the middle of the through hole is too thin and the orifice is thick, and the TP value does not reach 100%. Figure 6The image shows a cross-sectional view of the via filling test of compound B. Comparing the two images, it can be found that the present invention can achieve a super conformal effect in the electrochemical filling of copper, with both the orifice and the inside of the orifice being flat, resulting in a good morphology, which in turn can obtain better conductivity. In addition, the via filling capability of the present invention is strong, which can make the thickness inside the orifice and the surface similar, or even slightly thicker inside the orifice than the surface, with a TP value exceeding 100%, which is beneficial for high-density interconnection.

[0077] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A compound containing a phenylazonaphthol quaternary ammonium salt, characterized in that, The structure of the phenylazonaphthol quaternary ammonium salt compound is selected from one of the following structures: 。 2. The application of the phenylazonaphthol quaternary ammonium salt compound of claim 1 in the preparation of an electroplating leveling agent.

3. The application of the phenylazonaphthol-containing quaternary ammonium salt compound according to claim 2 in the preparation of electroplating leveling agents, characterized in that, The electroplating is copper electroplating, and the electroplating solution is copper sulfate.

4. The application of the phenylazonaphthol quaternary ammonium salt compound of claim 1 in combination with polyethylene glycol and sodium dithiodipropane sulfonate in the preparation of an electroplating leveling agent.

5. The application of the phenylazonaphthol quaternary ammonium salt compound according to claim 4, used in combination with polyethylene glycol and sodium dithiodipropane sulfonate, in the preparation of an electroplating leveling agent, characterized in that, The average molecular weight of the polyethylene glycol is 10,000.

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