Anthraquinone ether quaternary ammonium salt compound as well as preparation method and application thereof

Abstract

The invention discloses an anthraquinone ether quaternary ammonium salt compound, the structural general formula of the anthraquinone ether quaternary ammonium salt compound is as follows: # imgabs0 #, the anthraquinone ether quaternary ammonium salt compound provided by the invention has good electroplating performance, ether chains are introduced to two sides of molecules on the basis of the original quaternary ammonium salt structure, and the anthraquinone ether quaternary ammonium salt compound is further used as an electroplating additive in the copper electroplating process to achieve a leveling effect on the copper surface.

Description

Technical Field

[0001] The present invention belongs to the technical field of electroplating additives, and specifically relates to an anthraquinone ether quaternary ammonium salt compound, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of the semiconductor industry and the new energy industry, the manufacturing requirements for electronic devices and materials involved in these industries are also getting higher and higher. Electroplating copper technology is a key technical point in the manufacturing of integrated circuit chips and copper foils for the cathode current collectors of lithium batteries. The roughness of the copper layer determines the quality and service life of electronic products. How to improve electroplating copper technology has become the goal that people need to explore in the manufacture of high-end electronic devices.

[0003] In the electroplating copper process, a suitable electroplating formulation is the key to determining the electroplating quality. The most core part of a formulation is the electroplating additive used in the formulation. An electroplating additive refers to a chemical substance that can greatly improve the quality of the coating under the condition of using a small amount. Currently, the additives are mainly nitrogen-containing quaternary ammonium salts. Summary of the Invention

[0004] The first object of the present invention is to provide an anthraquinone ether quaternary ammonium salt compound.

[0005] Another object of the present invention is to provide a preparation method of the anthraquinone ether quaternary ammonium salt compound.

[0006] Another object of the present invention is to provide an application of the anthraquinone ether quaternary ammonium salt compound in the preparation of electroplating additives.

[0007] In order to achieve the above objects, the technical scheme adopted by the present invention is as follows:

[0008] In the first aspect of the present invention, an anthraquinone ether quaternary ammonium salt compound is provided, and the general structural formula is as follows:

[0009]

[0010] m is an integer selected from 1 to 18 (preferably 1, 2, 3, 4, 5, 6);

[0011] n is an integer selected from 1 to 18 (preferably 1, 2, 3, 4, 5, 6);

[0012] Y is selected from Cl, F, Br, I, HSO 3 、HSO 4 .

[0013] Most preferably, the structure of the anthraquinone ether quaternary ammonium salt compound is selected from one of the following structures:

[0014] 。

[0015] In a second aspect of the present invention, a method for preparing the anthraquinone ether quaternary ammonium salt compound is provided, comprising the following steps:

[0016]

[0017] Mix imidazole, a base, a bromoether chain compound and a solvent in a molar ratio of 1:1:1 to 8 (preferably 1:1:1), reflux and react for 4 to 12 h (preferably 8 h) under anhydrous and anaerobic conditions, filter by suction, remove the solvent, and obtain Compound 1;

[0018] Mix 1,5-dihydroxyanthraquinone, a dibromoalkane, a base and a solvent in a molar ratio of 1:2 to 8:2 to 8 (preferably 1:5:5), reflux and react for 4 to 12 h (preferably 12 h) under anhydrous and anaerobic conditions, filter by suction, remove the solvent, obtain a crude product, and obtain Compound 2 through column chromatography;

[0019] Mix Compound 1 and Compound 2 and a solvent in a molar ratio of 2 to 12:1 (preferably 8:1), reflux and react for 1 to 24 h (preferably 24 h) under anhydrous and anaerobic conditions, filter by suction, remove the solvent, obtain a crude product, and obtain the anthraquinone ether quaternary ammonium salt compound through column chromatography.

[0020] The bromoether chain compound is selected from triethylene glycol 2-bromoethyl methyl ether, diethylene glycol-2-bromoethyl methyl ether, 1-bromo-2-(2-methoxyethoxy)ethane.

[0021] The base is selected from potassium tert-butoxide and cesium carbonate.

[0022] The solvent is selected from acetonitrile and tetrahydrofuran.

[0023] The dibromoalkane is selected from 1,6-dibromohexane.

[0024] In a third aspect of the present invention, an application of the anthraquinone ether quaternary ammonium salt compound in preparing an electroplating additive is provided.

[0025] The electroplating is copper electroplating.

[0026] Due to the adoption of the above technical solutions, the present invention has the following advantages and beneficial effects:

[0027] The anthraquinone ether quaternary ammonium salt compound of the present invention has good electroplating performance. Ether chains are introduced on both sides of the molecule on the basis of the original quaternary ammonium salt structure, so as to further level the copper surface during the copper electroplating process.

[0028] The anthraquinone ether quaternary ammonium salt compounds of the present invention have good electroplating properties, can achieve planarization of the coating surface and filling of through-silicon vias (TSVs) of wafers. After actual electroplating, the electroplating effect of the electroplated parts was verified by using a metallurgical microscope and an electron scanning electron microscope, and compared with the electroplating effect of Compound B. The anthraquinone ether quaternary ammonium salt compounds are significantly superior to Compound B as electroplating additives in actual electroplating. Brief Description of the Drawings

[0029] Figure 1 It is a schematic diagram of the metallurgical microscope effect of the electroplated part after actual electroplating with Compound A-1 as an electroplating additive.

[0030] Figure 2 It is a schematic diagram of the scanning electron microscope effect of the electroplated part after actual electroplating with Compound A-1 as an electroplating additive.

[0031] Figure 3 It is a schematic diagram of the metallurgical microscope effect of the electroplated part after actual electroplating with Compound A-2 as an electroplating additive.

[0032] Figure 4 It is a schematic diagram of the scanning electron microscope effect of the electroplated part after actual electroplating with Compound A-2 as an electroplating additive.

[0033] Figure 5 It is a schematic diagram of the metallurgical microscope effect of the electroplated part after actual electroplating with Compound A-3 as an electroplating additive.

[0034] Figure 6 It is a schematic diagram of the scanning electron microscope effect of the electroplated part after actual electroplating with Compound A-3 as an electroplating additive.

[0035] Figure 7 It is a schematic diagram of the metallurgical microscope effect of the electroplated part after actual electroplating with anthraquinone quaternary ammonium salt B without an ether chain as an electroplating additive.

[0036] Figure 8 It is a schematic diagram of the scanning electron microscope effect of the electroplated part after actual electroplating with anthraquinone quaternary ammonium salt B without an ether chain as an electroplating additive. Detailed Embodiments

[0037] To more clearly illustrate the present invention, the present invention will be further described below in conjunction with preferred embodiments. Those skilled in the art should understand that the specific content described below is illustrative rather than restrictive, and should not be used to limit the protection scope of the present invention.

[0038] The reagents used in the embodiments of the present invention are shown in Table 1:

[0039] Table 1

[0040] Reagent Name Manufacturer Purity Specification 1,5-Dihydroxyanthraquinone Shanghai Xianding Biotechnology Co., Ltd. 90% 25g 1,6-Dibromohexane Anhui Zesheng Technology Co., Ltd. 98% 25g Acetonitrile Shanghai Titan Technology Co., Ltd. 99% 5L Cesium carbonate Shanghai Aladdin Biochemical Technology Co., Ltd. 99.9% 100g Imidazole Shanghai Xianding Biotechnology Co., Ltd. 98% 25g Potassium tert-butoxide Shanghai Macklin Biochemical Co., Ltd. 98% 500g Tetrahydrofuran Shanghai Macklin Biochemical Co., Ltd. 99.5% 500ml Diethylene glycol 2-bromoethyl methyl ether Shanghai Titan Technology Co., Ltd. 99% 500 mg 1-Bromo-2-(2-methoxyethoxy)ethane Shanghai Aladdin Biochemical Technology Co., Ltd. 99% 500 mg Triethylene glycol 2-bromoethyl methyl ether Shanghai Aladdin Biochemical Technology Co., Ltd. 99% 500 mg Methanol Shanghai Titan Technology Co., Ltd. 99% 5 L Dichloromethane Shanghai Titan Technology Co., Ltd. 99% 5 L Petroleum ether Shanghai Titan Technology Co., Ltd. 99% 5 L Sodium dimethylaminopropanesulfonate Shanghai Titan Technology Co., Ltd. 99% 500 mg Sodium succinate monoestersulfonate Jiangsu Mengde New Materials Co., Ltd. 50% 1 L

[0041] Example 1

[0042] The preparation method of compound A-1 is as follows:

[0043]

[0044] Imidazole (5 mmol, 0.34 g), potassium tert-butoxide (5 mmol, 0.56 g), triethylene glycol 2-bromoethyl methyl ether (5 mmol, 1.35 g) and 10 mL of tetrahydrofuran with a molar ratio of 1:1:1 were mixed, and refluxed for 8 h under anhydrous and anaerobic conditions, then filtered by suction to remove the solvent, obtaining 1 g of compound 1-1;

[0045] 1,5-Dihydroxyanthraquinone (5 mmol, 1.2 g), 1,6-dibromohexane (25 mmol, 6.0 g), cesium carbonate (25 mmol, 8.1 g) and 30 mL of acetonitrile with a molar ratio of 1:5:5 were mixed, and refluxed for 12 h under anhydrous and anaerobic conditions, then filtered by suction to remove the solvent to obtain a crude product, which was purified by column chromatography (dichloromethane:petroleum ether 2:1) to obtain 0.5 g of compound 2-1;

[0046] Compound 1-1 (4 mmol, 1.0 g) and compound 2-1 (0.5 mmol, 0.28 g) and 15 mL of acetonitrile were mixed, and refluxed for 24 h under anhydrous and anaerobic conditions, then filtered by suction to remove the solvent to obtain a crude product, which was purified by column chromatography (methanol:dichloromethane 1:10) to obtain 0.3 g of compound A-1; Yellow liquid, 1 H NMR (400 MHz, DMSO-d6) δ9.33 – 8.98 (m, 2H), 7.89 – 7.81 (m, 2H), 7.80 – 7.77 (m, 2H), 7.70 – 7.60(m, 4H), 7.26 – 7.09 (m, 2H), 4.41 – 4.32 (m, 4H), 4.29 – 4.17 (m, 4H), 4.17– 4.10 (m, 4H), 3.82 – 3.72 (m, 4H), 3.52 – 3.41 (m, 24H), 3.21 (d, J = 10.5Hz, 6H), 1.92 – 1.71 (m, 8H), 1.64 – 1.52 (m, 4H), 1.41 – 1.27 (m, 4H). 13 CNMR (101 MHz, DMSO-d 6) δ 181.90, 159.26, 137.26, 136.83, 135.91, 123.30, 122.69, 120.52, 119.05, 118.92, 71.72, 70.19, 70.06 – 69.86 (m), 68.55, 55.42, 49.26, 46.39, 29.83, 28.81, 25.61, 25.27. HRMS (TOF-ESI): m / z [M / 2]+ calcd for: C 50 H 74 O 12 N 4 2+ : 461.2646; found: 461.26436.

[0047] Example 2

[0048] The preparation method of compound A-2 is as follows

[0049]

[0050] Imidazole (5 mmol, 0.34 g), potassium tert-butoxide (5 mmol, 0.56 g), diethylene glycol-2-bromoethyl methyl ether (5 mmol, 1.13 g) and 10 mL of tetrahydrofuran with a molar ratio of 1:1:1 were mixed, and refluxed for 8 h under anhydrous and anaerobic conditions, then filtered by suction to remove the solvent, and 0.8 g of compound 1-2 was obtained;

[0051] Compound 1-2 (4 mmol, 0.8 g) and compound 2-1 (0.5 mol, 0.28 g) were mixed with 15 mL of acetonitrile, and refluxed for 24 h under anhydrous and anaerobic conditions, then filtered by suction to remove the solvent to obtain a crude product, which was purified by column chromatography (methanol:dichloromethane 1:10) to obtain 0.3 g of compound A-2; Yellow liquid, 1 H NMR (400 MHz, DMSO-d6) δ9.26 (s, 2H), 7.88 – 7.66 (m, 8H), 7.55 – 7.44 (m, 2H), 4.40 – 4.33 (m, 4H), 4.28 – 4.20 (m, 4H), 4.18 – 4.09 (m, 4H), 3.82 – 3.75 (m, 4H), 3.48 (s, 16H), 3.45 (s, 6H), 1.91 – 1.75 (m, 8H), 1.64 – 1.54 (m, 4H), 1.40 – 1.32 (m, 4H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 180.20, 160.36, 138.43, 136.83, 133.41, 122.35, 121.50, 120.23, 117.62, 72.32, 70.56, 68.46, 54.22, 50.72, 46.56, 30.12, 29.42, 27.31, 25.72. HRMS (TOF-ESI): m / z [M / 2]+ calcd for: C 46 H 66 O 10 N 4 2+ : 417.2384; found: 417.2382.

[0052] Example 3

[0053] The preparation method of compound A-3 is as follows

[0054]

[0055] Imidazole (5 mmol, 0.34 g), potassium tert-butoxide (5 mmol, 0.56 g), 1-bromo-2-(2-methoxyethoxy)ethane (5 mmol, 0.91 g) and 10 mL of tetrahydrofuran with a molar ratio of 1:1:1 were mixed, and refluxed under anhydrous and anaerobic conditions for 8 h, filtered by suction, and the solvent was removed to obtain 0.7 g of compound 1-3;

[0056] Compound 1-3 (4 mmol, 0.68 g) and compound 2-1 (0.5 mol, 0.28 g) were mixed with 15 mL of acetonitrile, and refluxed under anhydrous and anaerobic conditions for 24 h, filtered by suction, and the solvent was removed to obtain a crude product, which was purified by column chromatography (methanol:dichloromethane 1:10) to obtain 0.3 g of compound A-3; Yellow liquid. 1 H NMR (400 MHz, DMSO-d 6) δ 9.24(s, 2H), 7.83 – 7.77 (m, 4H), 7.66 – 7.48 (m, 4H), 7.01 (s, 2H), 4.39 – 4.35(m, 4H), 4.14 – 4.07 (m, 4H), 3.77 – 3.75 (m, 4H), 3.52 (d, J = 4.6 Hz, 4H),3.42 – 3.38 (m, 8H), 3.19 (s, 6H), 1.98 – 1.66 (m, 8H), 1.68 – 1.48 (m, 4H),1.44 – 1.25 (m, 4H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 181.91, 159.25, 137.25,136.85, 135.92, 123.23, 123.02, 122.73, 120.52, 119.05, 71.53, 69.80, 68.60,55.44, 49.28, 46.40, 29.81, 28.80, 25.58, 25.26. HRMS (TOF-ESI): m / z [M / 2]+calcd for: C 42 H 58 O 8 N 4 2+ : 273.2122; found: 373.2118.

[0057] Application Example 1

[0058] Compound A-1 is used as an electroplating additive in the electroplating of through-silicon vias (TSVs) on wafers.

[0059] Prepare a copper methylsulfonate solution containing 110 g / L copper methylsulfonate, 15 g / L methylsulfonic acid, 50 mg / L potassium chloride, 1 mol / L compound A-1, 500 ppm PEG10000, 8 ppm TPS (sodium dimethylformamidopropanesulfonate), and 10 ppm AESS (sodium succinate monoestersulfonate). Electroplate the through-silicon vias (TSVs) on wafers for 1 h, 1 h, and 0.5 h respectively at current densities of 0.1 ASD, 0.5 ASD, and 1 ASD. Slice the electroplated wafers and observe the filling condition under a metallurgical microscope. The results are shown in Figure 1 the figure Figure 1Figure 0 shows the metallographic microscope effect of the workpiece after actual electroplating with Compound A-1 as an electroplating additive. As can be seen from the figure, the electroplating solution containing Compound A-1 can achieve perfect filling of the through-silicon vias (TSVs) of the wafer, indicating that Compound A-1 is an excellent electroplating additive. The surface roughness of the wafer plating layer was observed by scanning electron microscopy, and the results are shown in Figure 2 as follows. Figure 2 Figure 1 shows the scanning electron microscope effect of the workpiece after actual electroplating with Compound A-1 as an electroplating additive. As can be seen from the figure, the electroplating solution containing Compound A-1 can achieve grain refinement on the surface of the plating layer, indicating that Compound A-1 is an excellent electroplating additive.

[0060] Application Example 2

[0061] Compound A-2 was applied as an electroplating additive to the electroplating of through-silicon vias (TSVs) of wafers.

[0062] A copper methylsulfonate solution containing 110 g / L copper methylsulfonate, 15 g / L methylsulfonic acid, 50 mg / L potassium chloride, 1 mol / L Compound A-2, 500 ppm PEG10000, 8 ppm TPS (sodium dimethylformamidopropanesulfonate), and 10 ppm AESS (sodium succinate monoestersulfonate) was prepared, and the through-silicon vias (TSVs) of the wafers were electroplated at current densities of 0.1 ASD, 0.5 ASD, and 1 ASD for 1 h, 1 h, and 0.5 h, respectively. The electroplated wafers were sliced and the filling conditions were observed under a metallographic microscope. The results are shown in Figure 3 as follows, Figure 3 Figure 2 shows the metallographic microscope effect of the workpiece after actual electroplating with Compound A-2 as an electroplating additive. As can be seen from the figure, the electroplating solution containing Compound A-2 can achieve the filling of the through-silicon vias (TSVs) of the wafer, indicating that Compound A-2 is an excellent electroplating additive. The surface roughness of the wafer plating layer was observed by scanning electron microscopy, and the results are shown in Figure 4 as follows. Figure 4 Figure 3 shows the scanning electron microscope effect of the workpiece after actual electroplating with Compound A-2 as an electroplating additive. As can be seen from the figure, the electroplating solution containing Compound A-2 can achieve grain refinement on the surface of the plating layer, indicating that Compound A-2 is an excellent electroplating additive.

[0063] Application Example 3

[0064] Compound A-3 was applied as an electroplating additive to the electroplating of through-silicon vias (TSVs) of wafers.

[0065] Prepare a copper methylsulfonate solution containing 110 g / L of copper methylsulfonate, 15 g / L of methylsulfonic acid, 50 mg / L of potassium chloride, 1 mol / L of compound A-3, 500 ppm of PEG10000, 8 ppm of TPS (sodium dimethylformamidopropanesulfonate), and 10 ppm of AESS (sodium succinate monoestersulfonate). Electroplate the through-silicon vias (TSVs) of the wafer for 1 h, 1 h, and 0.5 h at current densities of 0.1 ASD, 0.5 ASD, and 1 ASD respectively. Slice the electroplated wafer and observe the filling condition under a metallurgical microscope. The results are shown in Figure 5 as follows, Figure 5 which is a schematic diagram of the metallurgical microscope effect of the electroplated workpiece after actual electroplating with compound A-3 as an electroplating additive. It can be seen from the figure that the electroplating solution containing compound A-3 can achieve the filling of the through-silicon vias (TSVs) of the wafer, indicating that compound A-3 is an excellent electroplating additive. Observe the surface roughness of the wafer coating with a scanning electron microscope. The results are shown in Figure 6 as follows. Figure 6 which is a schematic diagram of the scanning electron microscope effect of the electroplated workpiece after actual electroplating with compound A-3 as an electroplating additive. It can be seen from the figure that the electroplating solution containing compound A-3 can achieve the refinement of the surface grains of the coating, indicating that compound A-3 is an excellent electroplating additive.

[0066] Comparative Example 1

[0067] Compound B without an ether chain is used as an electroplating additive in the electroplating of through-silicon vias (TSVs) of the wafer.

[0068]

[0069] Prepare a copper methylsulfonate solution containing 110 g / L of copper methylsulfonate, 15 g / L of methylsulfonic acid, 50 mg / L of potassium chloride, 1 mol / L of compound B, 500 ppm of PEG10000, 8 ppm of TPS (sodium dimethylformamidopropanesulfonate), and 10 ppm of AESS (sodium succinate monoestersulfonate). Electroplate the through-silicon vias (TSVs) of the wafer for 1 h, 1 h, and 0.5 h at current densities of 0.1 ASD, 0.5 ASD, and 1 ASD respectively. Slice the electroplated wafer and observe the filling condition under a metallurgical microscope. The results are shown in Figure 7 as follows, Figure 7 which is a schematic diagram of the metallurgical microscope effect of the electroplated workpiece after actual electroplating with anthraquinone quaternary ammonium salt B without an ether chain as an electroplating additive. Observe the surface roughness of the wafer coating with a scanning electron microscope. The results are shown in Figure 8 as follows. Figure 8Schematic diagram of the scanning electron microscope effect of the workpiece after actual electroplating with anthraquinone quaternary ammonium salt B without an ether chain as an electroplating additive. The results show that the plating solution containing compound B additive cannot achieve the filling of the through-silicon vias of the wafer, and there are still flakes on the surface morphology, which is relatively rough and cannot meet the manufacturing requirements.

[0070] The above are only the preferred embodiments of the present invention, and there is no limitation to the present invention in any form. Although the present invention has been disclosed above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art of this patent can make some changes or modifications to equivalent embodiments with equivalent changes by using the technical content prompted above within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention still fall within the scope of the present invention.

Claims

1. An anthraquinone ether quaternary ammonium salt compound, characterized in that: The general structural formula is shown below:

2. m is an integer selected from 1 to 18; n is an integer selected from 1 to 18; Y is selected from Cl, F, Br, I, HSO3, HSO4.

3. The anthraquinone ether quaternary ammonium salt compound according to claim 1, characterized in that: The structure of the anthraquinone ether quaternary ammonium salt compound is selected from one of the following structures: 。 4. A method for preparing anthraquinone ether quaternary ammonium salt compound according to claim 1 or 2, characterized in that: The following steps are involved:

5. Mix imidazole, base, bromoether chain compound and solvent in a molar ratio of 1:1:1-8, reflux for 4-12 h under anhydrous and oxygen-free conditions, filter and remove the solvent to obtain compound 1; Mix 1,5-dihydroxyanthraquinone, dibromoalkane, base and solvent in a molar ratio of 1:2-8:2-8, reflux for 4-12 h in anhydrous and oxygen-free conditions, filter and remove the solvent to obtain a crude product, and obtain compound 2 through column chromatography; Compound 1 and compound 2 are mixed with a solvent in a molar ratio of 2 to 12:1, and refluxed for 1 to 24 hours under anhydrous and oxygen-free conditions, filtered, and the solvent is removed to obtain a crude product, and the anthraquinone ether quaternary ammonium salt compound is obtained by column chromatography; The bromoether chain compound is selected from triethylene glycol 2-bromoethyl methyl ether, diethylene glycol-2-bromoethyl methyl ether, and 1-bromo-2-(2-methoxyethoxy)ethane; The base is selected from potassium tert-butoxide and cesium carbonate; The dibromoalkane is selected from 1,6-dibromohexane.

6. The method for preparing anthraquinone ether quaternary ammonium salt compounds according to claim 3, characterized in that: The solvent is selected from acetonitrile and tetrahydrofuran.

7. Use of the anthraquinone ether quaternary ammonium salt compound according to claim 1 or 2 in the preparation of electroplating additives.

8. The use of the anthraquinone ether quaternary ammonium salt compound according to claim 5 in the preparation of an electroplating additive, characterized in that: The electroplating is copper electroplating.

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