Copper interconnection electroplating leveling agent and application thereof

Abstract

The invention provides a copper interconnection electroplating leveling agent and application thereof. The copper interconnection electroplating leveling agent is obtained by reacting an amide compound with an organic nitrogen-containing compound. The polymer leveling agent provided by the invention is added into electroplating liquid for copper interconnection electroplating, so that the diffusion migration capability can be improved, the adsorption and desorption activity can be balanced, the generation of in-hole filling morphology defects and subsequent reliability risks can be avoided, the surface coverage and the adsorption stability can be improved, the effective working concentration window of an additive can be expanded, and the service life of the additive can be prolonged. Therefore, the electroplating quality and reliability of the electroplating liquid composition in trepanning filling and pattern co-plating are comprehensively improved; the requirements of electroplating filling and pattern co-plating of the opening structure in a certain depth-to-width ratio span range on the wafer and the substrate can be met, and the method has the industrial application advantages of being wide in adaptive scene, easy and convenient to maintain and control, low in production cost and the like; the method can be applied to the fields of integrated circuit manufacturing, integrated circuit packaging, circuit board manufacturing and photovoltaic manufacturing which relate to hole structure copper interconnection electroplating.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electronic plating, and particularly relates to a copper interconnection plating leveler and application thereof. BACKGROUND

[0002] Electronic copper plating is a basic and general technology for realizing electrical interconnection in horizontal and vertical directions in chip manufacturing, advanced packaging and circuit board manufacturing, so as to realize the filling of different opening structures such as damascene trenches, rewiring layers, micro-bumps, through silicon vias, through glass vias and micro-blind holes in a flat and uniform manner. In addition to copper sulfate, sulfuric acid and chloride ions in the plating solution, organic additives such as inhibitors, accelerators and levelers need to be added to solve the control of plating appearance, growth morphology and material properties, and the leveler is the core component that determines the filling mode and performance of the plating solution.

[0003] With the development of miniaturization and integration of integrated circuits, copper interconnection plating filling on semiconductors and circuit boards also faces new development challenges: on the one hand, the aspect ratio range of opening interconnection structures is further expanded, including not only large aspect ratio through silicon vias of more than 10:1, but also small aspect ratio rewiring layer pattern holes of less than 0.5:1, and high-performance plating levelers and plating solution formulations need to be developed to match the design and processing of new interconnection structures; on the other hand, it is expected in actual production that the same plating solution can meet the defect-free filling of different sizes and types of interconnection structures through simple adjustment of component concentration and current density, so as to reduce the cost problems and quality fluctuations caused by plating solution switching. The appearance requirements of the opening structure plating filling generally include: (1) bright and flat appearance, uniform thickness; (2) as small as possible recess or protrusion value of the hole opening, different patterns coplanar; (3) no defects such as cavities and gaps in the hole; (4) on the premise of filling quality, as high as possible current density and as large as possible process control window.

[0004] In order to meet the filling of complex opening interconnection structures, the industry has developed various plating solutions with different leveler molecular systems and multiple levelers. However, in the process of technical update and iteration, how to design and synthesize new additives to accurately control the morphology and optimize the performance of the plating solution and the plated material has always been the focus and difficulty of the industry. Therefore, how to provide a plating solution that can adapt to different opening types and sizes, accurately control the growth morphology and guarantee the material performance has become a problem to be solved. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a copper interconnection electroplating leveler and its application. The polymer leveler provided by the present application is added to the electroplating solution for copper interconnection electroplating. It can not only improve the diffusion migration ability and balance adsorption and desorption activity, avoid the generation of hole filling morphology defects and subsequent reliability risks, but also improve the surface coverage and adsorption stability, expand the effective working concentration window of the additive, and thus comprehensively improve the electroplating quality and reliability of the electroplating solution composition in hole filling and pattern co-electroplating. It can meet the electroplating filling and pattern co-electroplating of hole structures with a certain aspect ratio span range on wafers and substrates, has the industrial application advantages of wide adaptation scene, simple maintenance and control, and low production cost, and can be applied to the fields of integrated circuit manufacturing, integrated circuit packaging, circuit board manufacturing and photovoltaic manufacturing involving copper interconnection electroplating of hole structures.

[0006] To achieve the purpose of the present application, the following technical solutions are adopted:

[0007] In a first aspect, the present application provides a copper interconnection electroplating leveler, which is obtained by reacting an amide compound and an organic nitrogen-containing compound.

[0008] The structure of the amide compound is shown in Formula I:

[0009]

[0010] Formula I;

[0011] In the formula, x is selected from oxygen or sulfur, each R1 is independently selected from any one of imino, methylene, amido, carbonyl, ureido, hydrazido or benzenesulfonamido, R2 is selected from substituted or unsubstituted C1-C12 alkylene or substituted or unsubstituted C1-C12 alkylenoxy, and R3 is selected from an aliphatic halogenated hydrocarbon group shown in Formula II or an aromatic halogenated hydrocarbon group shown in Formula III.

[0012]

[0013] In the formula, x1 and x2 are independently selected from any one of fluorine, chlorine, bromine or iodine, y is selected from carbonyl or methylene, n is an integer from 1 to 5 (1, 2, 3, 4, 5), and R4 is selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy.

[0014] The organic nitrogen-containing compound includes an aliphatic tertiary amine compound or an aromatic nitrogen heterocyclic compound.

[0015] The specific leveler is prepared by sequentially reacting specific raw materials, and has a first ion coordination group (such as urea, thiourea, urea condensate, acylurea, etc.), which regulates the in-hole migration and covering capacity of the leveler; a second coordination adsorption group (such as ether, alcohol, ketone, ester), which regulates the non-selective adsorption stability of the leveler at the interface; and a third electrostatic adsorption group (such as quaternary ammonium, conjugated heterocycle), which regulates the selective adsorption strength of the leveler at the discharge site. The synergistic effect of the three types of groups can improve the filling performance of the leveler for various open-hole interconnection structures of the plated wafer and substrate, avoid the generation of in-hole filling morphology defects and subsequent reliability risks, and at the same time, the polymer molecular system can improve the surface coverage and adsorption stability, expand the effective working concentration window of the additive, and thus meet the requirements of industrial applications.

[0016] Preferably, the structure of the aliphatic tertiary amine compound is shown as formula IV:

[0017]

[0018] Formula IV;

[0019] In the formula, R5 is selected from any one of substituted or unsubstituted C1-C20 alkylene, substituted or unsubstituted C1-C20 alkylenoxy, R6, R7, R8, R9 are independently selected from any one of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy;

[0020] Preferably, the substituted substituent includes a methyl group or an ethyl group.

[0021] Preferably, the R6, R7, R8, R9 are independently selected from a methyl group or an ethyl group.

[0022] Preferably, the structure of the aromatic nitrogen heterocyclic compound is shown as formula V or formula VI:

[0023]

[0024] wherein represents any one of a heteroaromatic ring, a heteroaromatic ring annulus or a heteroaromatic ring annulus containing at least one unbound hydrogen atom of a nitrogen atom, R 10 is selected from substituted or unsubstituted C1-C6 alkylene, represents any one of a heteroaromatic ring, a heteroaromatic ring annulus or a heteroaromatic ring annulus containing at least two unbound hydrogen atoms of a nitrogen atom.

[0025] Preferably, the organic nitrogen-containing compound comprises any one of N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,3-diaminobutane, N,N,N',N'-tetramethyl-p-phenylenediamine, bisdimethylaminoethylether, 4,4'-bipyridine, 4,4-trimethylenedipyridine, 1,2-bis(4-pyridyl)ethane, 1,3-bis(2-pyridyl)propane, pyrazine, N-methylimidazole ring, 1-ethylimidazole, 1-isopropylimidazole, 1-propylimidazole, 1,5-naphthyridine, quinoxaline, or phenoxazine, preferably N,N,N',N'-tetramethyl-1,6-hexanediamine or 4,4'-bipyridine.

[0026] Preferably, the amide compound is obtained from the reaction of an isocyanate halide or an isothiocyanate halide with a bis-primary amine compound.

[0027] Preferably, the isocyanate halide comprises an aliphatic isocyanate halide or an aromatic isocyanate halide.

[0028] The isothiocyanate halide comprises an aliphatic isothiocyanate halide or an aromatic isothiocyanate halide.

[0029] Preferably, the aliphatic isocyanate halide or aliphatic isothiocyanate halide has a structure as shown in Formula VII:

[0030]

[0031] Formula VII;

[0032] wherein x3 is selected from fluorine, chlorine, bromine, or iodine, y1 is selected from carbonyl or methylene, z is selected from oxygen or sulfur, and n is an integer from 1 to 5.

[0033] Preferably, the aromatic isocyanate halide or aromatic isothiocyanate halide has a structure as shown in Formula VIII:

[0034]

[0035] Formula VIII;

[0036] wherein x4 is selected from fluorine, chlorine, bromine, or iodine, z1 is selected from oxygen or sulfur, and R 11 is selected from hydrogen, C1-C6 alkyl, or C1-C6 alkoxy.

[0037] Preferably, the isocyanate halide comprises any one of p-chlorophenyl isocyanate, m-chlorophenyl isocyanate, o-chlorophenyl isocyanate, 2-chloroethyl isocyanate, 3-chloropropyl isocyanate, chloroacetyl isocyanate, 6-chlorohexyl isocyanate, p-bromophenyl isocyanate, m-bromophenyl isocyanate, or o-bromophenyl isocyanate, preferably 3-chloropropyl isocyanate or chloroacetyl isocyanate.

[0038] Preferably, the isothiocyanate halide comprises any one of 2-chloroethyl isothiocyanate, 2-bromoethyl isothiocyanate, 3-bromopropyl isothiocyanate, 3-chloropropyl isothiocyanate, p-chlorophenyl isothiocyanate, m-chlorophenyl isothiocyanate, or o-chlorophenyl isothiocyanate, preferably 3-chloropropyl isothiocyanate.

[0039] Preferably, the bis-primary amine compound has a structure as shown in Formula IX:

[0040]

[0041] Formula IX;

[0042] wherein R 12 is selected from C1-C20 substituted or unsubstituted alkylene or C1-C20 substituted or unsubstituted alkyleneoxy, each R 13 is independently selected from any one of imino, methylene, amido, carbonyl, ureido, hydrazido, or phenylsulfonamido, preferably methylene.

[0043] Preferably, the bis-primary amine compound comprises any one of propylenediamine, butylenediamine, pentanediamine, hexanediamine, 2,2'-(ethylenedioxy)bis(ethylamine), 1,11-diamino-3,6,9-trioxaundecane, 4,7,10-trioxa-1,13-tridecanediamine, polyetheramine, p-xylylenediamine, adipic dihydrazide, 6-aminohexanamide, suberhydrazide, heptanedihydrazide, adipic dihydrazide, 1,3-phenylenediamine, or 1,4-phenylenediamine, preferably 4,7,10-trioxa-1,13-tridecanediamine or polyetheramine.

[0044] Preferably, the copper interconnect electroplating leveler has a weight average molecular weight of 200-10000 g / mol, such as 200 g / mol, 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, or 10000 g / mol, etc., but not limited to the above listed values, other unlisted values within the above range are also applicable, preferably 500-5000 g / mol.

[0045] In a second aspect, the present application provides a copper interconnect electroplating solution composition, which comprises water, a copper salt, hydrochloric acid, sulfuric acid, an inhibitor (e.g., polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, etc.), an accelerator (e.g., 3-mercapto-1-propanesulfonic acid sodium, polydithiopropanesulfonic acid sodium, N,N-dimethyl dithiocarbamic acid propane sulfonic acid sodium, 3-(benzo[d]thiazol-2-ylmercapto)-propane sulfonic acid sodium, (O-ethyl dithiocarbonate)-S-(3-sulfopropyl) potassium salt, 3-isothiouronium propane sulfonic acid inner salt, etc.), and a copper interconnect electroplating leveler as described above.

[0046] Preferably, the concentration of the copper interconnect electroplating leveler is 0.5-100 mg / L, such as 0.5 mg / L, 10 mg / L, 20 mg / L, 30 mg / L, 40 mg / L, 50 mg / L, 60 mg / L, 70 mg / L, 80 mg / L, 90 mg / L, or 100 mg / L, etc., but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are also applicable.

[0047] In a third aspect, the present application further provides a copper interconnect electroplating method for filling an open hole structure, which comprises the following steps:

[0048] The cathode substrate with an open hole interconnect structure and completed metallization and the anode are immersed in the electroplating solution composition as described above, and then electroplating is performed between the cathode substrate and the anode.

[0049] Preferably, the cathode substrate comprises any one of a silicon-based wafer, an organic substrate, or a glass substrate.

[0050] Preferably, in the open hole interconnect structure of the cathode substrate, the aspect ratio is (0.1-4):1, such as 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1, etc., but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are also applicable.

[0051] Compared with the prior art, the present application has the following beneficial effects:

[0052] (1) The present application provides a copper interconnect electroplating solution composition, which contains a reaction product of at least one amide compound and an organic nitrogen-containing compound as a leveler. Through the synergy and regulation of multiple functional groups, the diffusion and migration ability and the balance of adsorption and desorption activity can be improved, the defects in hole filling morphology and the subsequent reliability risk can be avoided, the polymer molecular system can improve the surface coverage and adsorption stability, and the effective working concentration window of the additive can be expanded, thereby comprehensively improving the filling quality and reliability of the electroplating solution composition in the open hole interconnect structure.

[0053] (2) The application provides a method for applying the copper interconnection electroplating solution composition, and the method can meet electroplating filling of small aspect ratio opening structures in wafers and substrates, has industrial application advantages of wide application scenarios, simple maintenance and control and low production cost, and can be applied to the fields of integrated circuit manufacturing, integrated circuit packaging, circuit board manufacturing and photovoltaic manufacturing related to electroplating filling of copper interconnection of opening structures. BRIEF DESCRIPTION OF DRAWINGS

[0054] Figure 1 is a cross-section metallographic section of a micro blind hole of a high-density interconnection board electroplated in Test 1;

[0055] Figure 2 is a cross-section focused ion beam imaging of a wafer pattern hole of a re-routed layer electroplated in Test 13.

[0056] Figure 3 is a cross-section metallographic section of a micro blind hole of a high-density interconnection board electroplated in Comparative Example 1;

[0057] Figure 4 is a cross-section focused ion beam imaging of a wafer pattern hole of a re-routed layer electroplated in Comparative Example 2. DETAILED DESCRIPTION

[0058] The technical solutions of the application are further illustrated below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only used to help understand the application and should not be regarded as specific limitations on the application.

[0059] Example 1

[0060] The embodiment provides a copper interconnection electroplating leveler, and a specific preparation method is as follows:

[0061] 4.4g 4,7,10-trioxa-1,13-tridecanediamine and 40ml dichloromethane are added into a three-necked flask. Then, 30ml dichloromethane solution containing 4.78g 3-chloropropyl isocyanate is added dropwise into the three-necked flask at room temperature. The stirring is performed for 12 hours under water bath temperature control at 25℃. The reaction is stopped, and the dichloromethane in the mixed solution is removed by means of reduced pressure distillation to obtain white solid intermediate 1 (8.72g, 95%). 1.15g intermediate 1 and 0.4g 4,4'-dipyridyl are added into a three-necked flask, 10ml ethylene glycol is added, and then the temperature is increased to 135℃, and the stirring is performed for 24 hours. The reaction is stopped, and the ethylene glycol in the mixed solution is removed by means of reduced pressure distillation to obtain 1.56g brownish yellow viscous product 1.

[0062] Example 2

[0063] The embodiment provides a copper interconnection electroplating leveler, and a specific preparation method is as follows:

[0064] Into a three-necked flask, 1.15 g of intermediate 1 and 0.43 g of N,N,N',N'-tetramethyl-1,6-hexanediamine were added, and 10 mL of ethylene glycol was added and heated to 135 °C, and stirred for 24 hours. The reaction was stopped, and the ethylene glycol was removed by distillation under reduced pressure to obtain 1.58 g of brown-yellow viscous product 2.

[0065] Example 3

[0066] This example provides a copper interconnect electroplating leveler, and the specific preparation method is as follows:

[0067] Into a three-necked flask, 4.6 g of polyetheramine (commercial product D230) and 40 mL of dichloromethane were added. Then, 30 mL of dichloromethane solution of 4.79 g of chloroacetyl isocyanate was added dropwise into the three-necked flask at room temperature. The reaction was stirred for 12 hours under water bath temperature control at 35 °C. The reaction was stopped, and the dichloromethane was removed by distillation under reduced pressure to obtain white solid intermediate 2 (7.13 g, yield 76%). Into a three-necked flask, 1.17 g of intermediate 2 and 0.45 g of 4,4'-bipyridine were added, and 10 mL of ethylene glycol was added and heated to 135 °C, and stirred for 24 hours. The reaction was stopped, and the ethylene glycol was removed by distillation under reduced pressure to obtain 1.70 g of brown-yellow viscous product 3.

[0068] Example 4

[0069] This example provides a copper interconnect electroplating leveler, and the specific preparation method is as follows:

[0070] Into a three-necked flask, 1.17 g of intermediate 2 and 0.5 g of N,N,N',N'-tetramethyl-1,6-hexanediamine were added, and 10 mL of ethylene glycol was added and heated to 135 °C, and stirred for 24 hours. The reaction was stopped, and the ethylene glycol was removed by distillation under reduced pressure to obtain 1.72 g of brown-yellow viscous product 4.

[0071] Example 5

[0072] This example provides a copper interconnect electroplating leveler, and the specific preparation method is as follows:

[0073] Into a flask, 4.4 g of 4,7,10-trioxa-l,13-tridecanediamine, 1 g of triethylamine and 40 mL of dichloromethane were added. Subsequently, a solution of 5.4 g of 3-chloropropyl isothiocyanate in 30 mL of dichloromethane was added dropwise into the flask at room temperature. The reaction was stirred for 12 hours at 25°C in a water bath. The reaction was stopped and the solvent was removed by distillation under reduced pressure to obtain white solid intermediate 3 (6.17 g, 63%). Into a flask, 1.23 g of intermediate 3 and 0.4 g of 4,4'-dipyridyl were added, and 10 mL of ethylene glycol was added and heated to 135°C, and the reaction was stirred for 24 hours. The reaction was stopped and the ethylene glycol in the mixture was removed by distillation under reduced pressure to obtain 1.72 g of brown-yellow viscous product 5.

[0074] Example 6

[0075] This example provides a copper interconnection electroplating leveler, and the specific preparation method is as follows:

[0076] Into a flask, 1.23 g of intermediate 3 and 0.43 g of N,N,N',N'-tetramethyl-l,6-hexanediamine were added, and 10 mL of ethylene glycol was added and heated to 135°C, and the reaction was stirred for 24 hours. The reaction was stopped and the ethylene glycol in the mixture was removed by distillation under reduced pressure to obtain 1.75 g of brown-yellow viscous product 6.

[0077] Example 7

[0078] This example provides a copper interconnection electroplating leveler, and the specific preparation method is as follows: except that 3-chloropropyl isocyanate is replaced by an equal molar amount of 3-chloropropyl isothiocyanate, the rest is consistent with example 1.

[0079] Finally, 1.61 g of brown-yellow viscous product 7 was obtained.

[0080] Example 8

[0081] This example provides a copper interconnection electroplating leveler, and the specific preparation method is as follows: except that 3-chloropropyl isocyanate is replaced by an equal molar amount of 2-chloroethyl isocyanate, the rest is consistent with example 1.

[0082] Finally, 1.55 g of light yellow viscous product 8 was obtained.

[0083] Example 9

[0084] This example provides a copper interconnection electroplating leveler, and the specific preparation method is as follows: except that 4,7,10-trioxa-l,13-tridecanediamine is replaced by an equal molar amount of pentanediamine, the rest is consistent with example 1.

[0085] Finally, 1.32 g of brown-yellow viscous product 9 was obtained.

[0086] Example 10

[0087] This embodiment provides a copper interconnection electroplating leveler. The preparation method is consistent with that of Example 1, except that 4,4'-dipyridyl is replaced by 4,4-trimethylene dipyridyl in an equal molar amount.

[0088] Finally, 1.44 g of yellow viscous product 10 was obtained.

[0089] Effect evaluation:

[0090] An electroplating solution composition 1 was prepared according to the following formula and mixed uniformly: pure water 1500 mL, copper sulfate pentahydrate 220 g / L, 98 wt% concentrated sulfuric acid 28 ml / L, 37 wt% hydrochloric acid 0.15 ml / L, accelerator polydithiodipropyl sulfonic acid sodium 2 mg / L, inhibitor polyethylene glycol (weight average molecular weight 20000) 400 mg / L, and leveler reaction product 15 mg / L of Example 1-10.

[0091] The electroplating solution composition 1 was used to carry out a Halling tank electroplating test according to the following method: the cathode was a high-density interconnection plate sample with a cutting size of 100×50 mm (length×width), which was formed into three kinds of aperture structures with a depth-to-width ratio of 125×100, 100×75 and 100×50 μm (pore diameter×pore depth) by chemical copper plating and flash copper plating, respectively; the anode was a phosphorus copper plate (phosphorus content 0.05 wt.%) with a cutting size of 120×60 mm (length×width); the volume of the electroplating solution composition was 1500 ml, the temperature was 25°C, air stirring was applied at 7.2 L / min, the current density was 1.8 A / dm 2 , and the electroplating time was 43 min. After the sample was electroplated, it was washed with pure water and dried by cold air, and then a cross-section metallographic slice of the micro-blind hole was prepared, and the filling defect, surface copper thickness value (about 10 μm of the bottom copper was not counted) and center depression value (the results of Test 1 are shown in Table 1) were observed. Figure 1

[0092]

[0093] As can be seen from the above table and Figure 1 , the leveler products 1-4 prepared by Examples 1-4 of the present application can achieve defect-free filling for the micro-blind hole with a depth-to-width ratio of 0.5-0.8 for the electroplating of high-density interconnection plates, the surface copper thickness value is about 15 μm, and the center depression value is -2.0~-6.0 μm, which meets the technical requirements of electroplating for circuit board manufacturing.

[0094] ​The electroplating solution composition 2 was prepared according to the following formula and mixed uniformly: pure water 1500 mL, copper sulfate pentahydrate 200 g / L, 98 wt% concentrated sulfuric acid 56 ml / L, 37 wt% hydrochloric acid 0.15 ml / L, accelerator polydithiodipropyl sulfone sodium 2 mg / L, inhibitor polyethylene glycol (weight average molecular weight 20000) 400 mg / L, and leveler reaction product of examples 5-10 20 mg / L.

[0095] The electroplating solution composition 2 was used to carry out the following plating test in a Halling tank: the cathode was a re-distribution layer wafer die with a cutting size of 25x25 (lengthxwidth, unit: mm), which was formed with two second-order opening structures of lower layer 30x5 μm (aperturexhole depth) and upper layer 60x10 μm (aperturexhole depth), and lower layer 50x5 μm (aperturexhole depth) and upper layer 60x10 μm (aperturexhole depth) by multiple photoetching and sputtering; the anode was a phosphor copper plate (phosphor content 0.05 wt.%) with a cutting size of 120x60 (lengthxwidth, unit: mm); the volume of the electroplating solution composition was 1500 ml, the temperature was 25°C, air agitation was applied at 7.2 L / min, the current density was 3 A / dm 2 , and the plating time was 18 min. After the wafer die was plated, it was rinsed with pure water and dimethyl sulfoxide was used to remove the upper layer photoresist, then cross-section cutting was carried out using a focused ion beam and the filling defects, hole center and edge difference value (difference value = height of plated layer at hole center - height of plated layer at hole edge) were observed, and the results are shown in Table 13. Figure 2

[0096]

[0097] As can be seen from the above table and Figure 2 , the leveler products 4-6 prepared in examples 4-6 can achieve defect-free filling for the re-distribution layer wafer die with a second-order opening structure of aspect ratio 0.1-0.17, and the hole center and edge difference value is between -0.5-0.5 μm, which meets the requirements of wafer-level packaging plating technology.

[0098] In addition, when the electroplating solution composition 1 (comparative example 1) prepared using gentian violet B as the leveler was used to plate a high-density interconnection board (results shown in Table 14 Figure 3 ), the face copper thickness value was about 15 μm and the center depression value was 20.5 μm, which did not meet the filling efficiency requirements of the circuit board manufacturing and had a significant gap with examples 1-4; when the electroplating solution composition 2 (comparative example 2) prepared using gentian violet B as the leveler was used to plate a re-distribution layer wafer die (results shown in Table 15 Figure 4 ), the re-distribution layer wafer die was not filled and the hole center and edge difference value was about -4 μm, which did not meet the filling efficiency requirements of wafer-level packaging and had a significant gap with examples 4-6, indicating that it is not suitable for small aspect ratio openings.​

[0099] And from the above data can be found, the application by using specific raw materials, can further reduce the hole difference value, and effectively control the recess value range, improve the product effect.

[0100] Applicant declares that the copper interconnection electroplating leveler and its application of the present application are illustrated by the above examples, but the present application is not limited to the above examples, that is, it does not mean that the present application must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

[0101] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above embodiments, and within the technical concept scope of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0102] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present application will not further illustrate various possible combination manners.

Claims

1. A copper interconnect electroplating leveling agent, characterized in that, The copper interconnect electroplating leveling agent is obtained by reacting an amide compound with an organic nitrogen-containing compound; The structure of the amide compound is shown in Formula I: Formula I; In the formula, x is selected from oxygen or sulfur, each R1 is independently selected from any one of imino, methylene, amide, carbonyl, urea, hydrazide or benzenesulfonamide, R2 is selected from substituted or unsubstituted C1-C12 alkylene or substituted or unsubstituted C1-C12 alkene, and R3 is selected from the aliphatic halogenated hydrocarbon group shown in Formula II or the aromatic halogenated hydrocarbon group shown in Formula III. In the formula, x1 and x2 are independently selected from any one of fluorine, chlorine, bromine or iodine, y is selected from carbonyl or methylene, n is an integer from 1 to 5, and R4 is selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy. The organic nitrogen-containing compounds include aliphatic tertiary amine compounds or aromatic nitrogen heterocyclic compounds.

2. The copper interconnect electroplating leveling agent according to claim 1, characterized in that, The structure of the aliphatic tertiary amine compound is shown in Formula IV: Formula IV; In the formula, R5 is selected from any one of substituted or unsubstituted C1-C20 alkylene or substituted or unsubstituted C1-C20 alkeneoxy groups, and R6, R7, R8, and R9 are independently selected from any one of substituted or unsubstituted C1-C6 alkyl or substituted or unsubstituted C1-C6 alkoxy groups. Preferably, the substituents include methyl or ethyl groups; Preferably, R6, R7, R8, and R9 are independently selected from methyl or ethyl.

3. The copper interconnect electroplating leveling agent according to claim 1 or 2, characterized in that, The structures of the aromatic nitrogen heterocyclic compounds are shown in Formula V and Formula VI: in R represents any one of the following: a heteroaromatic ring, a heteroaromatic fused ring, or a heteroaromatic cyclic ring containing at least one unbonded hydrogen atom and a nitrogen atom. 10 Selected from substituted or unsubstituted C1-C6 alkylene groups, It represents any one of the following: heteroaromatic ring, heteroaromatic ring fused ring, or heteroaromatic ring combined ring, containing at least two unbonded hydrogen atoms and nitrogen atoms.

4. The copper interconnect electroplating leveling agent according to any one of claims 1-3, characterized in that, The organic nitrogen-containing compound includes any one of N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,3-diaminobutane, N,N,N',N'-tetramethyl-p-phenylenediamine, bis(dimethylaminoethyl) ether, 4,4'-bipyridine, 4,4-trimethylenedipyridine, 1,2-bis(4-pyridyl)ethane, 1,3-bis(2-pyridyl)propane, pyrazine, N-methylimidazolium ring, 1-ethylimidazolium, 1-isopropylimidazolium, 1-propylimidazolium, 1,5-naphthidine, quinoxaline, or phenolazine, preferably N,N,N',N'-tetramethyl-1,6-hexanediamine or 4,4'-bipyridine.

5. The copper interconnect electroplating leveling agent according to any one of claims 1-4, characterized in that, The amide compound is obtained by reacting isocyanate halides or isothiocyanate halides with a bis-primary amine compound; Preferably, the isocyanate halide includes aliphatic isocyanate halides or aromatic isocyanate halides; The isothiocyanate halides include aliphatic isothiocyanate halides or aromatic isothiocyanate halides.

6. The copper interconnect electroplating leveling agent according to claim 5, characterized in that, The structure of the aliphatic isocyanate halide or aliphatic isothiocyanate halide is shown in Formula VII: Equation VII; In the formula, x3 is selected from fluorine, chlorine, bromine or iodine, y1 is selected from carbonyl or methylene, z is selected from oxygen or sulfur, and n is an integer from 1 to 5; Preferably, the structure of the aromatic isocyanate halide or aromatic isothiocyanate halide is as shown in Formula VIII: Formula VIII; In the formula, x4 is selected from fluorine, chlorine, bromine or iodine, z1 is selected from oxygen or sulfur, and R 11 Selected from hydrogen, C1-C6 alkyl, or C1-C6 alkoxy; Preferably, the isocyanate halide includes any one of p-chlorophenyl isocyanate, m-chlorophenyl isocyanate, o-chlorophenyl isocyanate, 2-chloroethyl isocyanate, 3-chloropropyl isocyanate, chloroacetyl isocyanate, 6-chlorohexyl isocyanate, p-bromophenyl isocyanate, m-bromophenyl isocyanate or o-bromophenyl isocyanate, preferably 3-chloropropyl isocyanate or chloroacetyl isocyanate; Preferably, the isothiocyanate halide includes any one of 2-chloroethyl isothiocyanate, 2-bromoethyl isothiocyanate, 3-bromopropyl isothiocyanate, 3-chloropropyl isothiocyanate, p-chlorophenyl isothiocyanate, m-chlorophenyl isothiocyanate or o-chlorophenyl isothiocyanate, with 3-chloropropyl isothiocyanate being the most preferred.

7. The copper interconnect electroplating leveling agent according to claim 5 or 6, characterized in that, The structure of the bis-primary amine compound is shown in Formula IX: Formula IX; In the formula, R 12 Selected from C1-C20 substituted or unsubstituted alkylene or C1-C20 substituted or unsubstituted alkeneoxy groups, each R 13 It is independently selected from any one of imino, methylene, amide, carbonyl, ureido, hydrazide or benzenesulfonamide, preferably methylene; Preferably, the bis(primary)amine compound comprises any one of propylenediamine, butanediamine, pentanediamine, hexanediamine, 2,2′-(ethylenedioxy)bis(ethylamine), 1,11-diamino-3,6,9-trioxadecane, 4,7,10-trioxa-1,13-tridecanediamine, polyetheramine, p-phenylenediamine, adipamide, 6-aminohexanoamide, octanoic acid hydrazide, heptane hydrazide, adipic acid hydrazide, 1,3-benzene disulfonamide, or 1,4-benzene disulfonamide, preferably 4,7,10-trioxa-1,13-tridecanediamine or polyetheramine.

8. The copper interconnect plating leveling agent according to any one of claims 1-7, characterized in that, The weight-average molecular weight of the copper interconnect electroplating leveling agent is 200-10000 g / mol, preferably 500-5000 g / mol.

9. An electroplating solution composition, characterized in that, The electroplating solution composition includes water, copper salt, hydrochloric acid, sulfuric acid, inhibitor, accelerator, and copper interconnect electroplating leveling agent as described in any one of claims 1-8; Preferably, the concentration of the copper interconnect electroplating leveling agent is 0.5-100 mg / L.

10. A method for electroplating copper interconnects with a filled open-hole structure, characterized in that, The electroplating method includes the following steps: The cathode substrate and anode, which have an open interconnect structure and are metallized, are immersed in the electroplating solution composition of claim 9, and then plating is applied between the cathode substrate and the anode. Preferably, the cathode substrate comprises any one of a silicon-based wafer, an organic substrate, or a glass substrate; Preferably, in the aperture interconnection structure of the cathode substrate, the aspect ratio is (0.1-4):1.

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