Leveling agent, electroplating solution and application

Abstract

The application discloses a leveling agent, a plating solution and application. The leveling agent comprises a first active component and a second active component. Raw materials of the first active component and the second active component each independently comprise at least one of an epoxy compound and a halogen ether compound, a polyamine compound and raw material (1) or (2). The raw material (1) comprises a cyclic compound or a salt thereof with a general structure shown in formula (I): (I) wherein R is selected from at least one of a hydrogen atom, a C1-C6 alkyl and a C1-C6 heteroalkyl, R substitutes at least one hydrogen atom on any ring-forming carbon atom, n and m are each independently selected from any integer within a range of 1-6; the raw material (2) comprises a tertiary amine compound; the number of primary amine groups in the molecular structure of the polyamine compound is greater than or equal to 2. The small-aperture copper column electroplating is realized by the cooperation of the double active components, and the height uniformity and the copper column height flatness of the electroplated copper columns with different apertures are considered.

Description

Technical Field

[0001] This invention relates to the field of copper electroplating technology, and more particularly to leveling agents, electroplating solutions, and their applications. Background Technology

[0002] As semiconductor packaging technology continues to evolve towards higher density and higher integration, copper pillar plating, as a key interconnect process in advanced packaging, faces increasingly stringent technical requirements. Therefore, while the feature size of copper pillars is decreasing and the pitch is continuously narrowing, chip design places higher demands on the uniformity of copper pillar height and the flatness of the top. Especially under high current density plating conditions, achieving synchronous and uniform filling of copper pillars with different aperture sizes has become a core bottleneck restricting the performance improvement of the plating solution system. Currently, copper pillar plating additive systems typically use single-component leveling agents as the main regulating component. However, a single component only has a single adsorption characteristic and working potential range in its molecular structure. Its inhibition ability during the plating process is sensitive to mass transfer conditions (such as convection intensity and current density). Therefore, when there are copper pillars with various aperture specifications on the same substrate, a single leveling agent cannot adequately address the local mass transfer differences within the micro-regions of different aperture sizes. This easily leads to insufficient filling of small-diameter copper pillars (low protrusion) or excessive growth of large-diameter copper pillars (high protrusion), ultimately causing defects at the top of the copper pillars, or even poor uniformity of the copper pillar height across the entire board. To address this issue, attempts have been made to optimize coating performance by adjusting the leveling agent concentration or by compounding accelerators and inhibitors. However, this has not yet resolved the inherent problem of coordinating and matching leveling capabilities under different aperture sizes. In particular, the contradiction between the flatness of the copper pillar top and the uniformity between different aperture sizes is more prominent under high current densities. Summary of the Invention

[0003] Therefore, it is necessary to provide a leveling agent to improve the flatness of the top of the copper pillar, so as to achieve synchronous and uniform filling of copper pillars with different opening sizes under high current density, and obtain copper pillars with uniform height to meet the performance requirements of advanced packaging.

[0004] In a first aspect, this application provides a leveling agent, comprising a first active ingredient and a second active ingredient:

[0005] The reaction raw materials for the first active ingredient include at least one of epoxy compounds and haloether compounds, polyamine compounds, and heterocyclic compounds or their salts;

[0006] The general structural formula of the heterocyclic compound is shown in formula (I):

[0007]

[0008] (I)

[0009] In the formula, R is selected from at least one of hydrogen atom and C1-C6 alkyl and C1-C6 heteroalkyl, R substitutes at least one hydrogen atom on any cyclic carbon atom, and n and m are each independently selected from any integer in the range of 1-6.

[0010] The reaction raw materials for the second active ingredient include at least one of epoxy compounds and haloether compounds, polyamine compounds, and tertiary amine compounds;

[0011] In the reaction raw materials of the first active ingredient and the second active ingredient, the molecular structure of the polyamine compound contains a primary amine group, and the number of the primary amine groups is independently ≥2.

[0012] In some embodiments, in the general formula shown in equation (I), n and m are each independently selected from any integer in the range of 1-2;

[0013] Optionally, the heterocyclic compound includes at least one of tetrahydrothiazole, thiomorpholine, 2-methyltetrahydrothiazole, and 2,2-dimethyltetrahydrothiazole;

[0014] And / or, the salt includes at least one of hydrochloride, sulfate and nitrate.

[0015] In some embodiments, it has at least one of the following features:

[0016] (1) The epoxy compounds in the reaction raw materials of the first active ingredient and the second active ingredient each independently include at least one of glycidyl ether compounds and epichlorohydrin;

[0017] Optionally, the molecular structure of the glycidyl ether compound includes an epoxy group, and the number of the epoxy groups is ≥2;

[0018] Further optionally, the glycidyl ether compound includes at least one selected from ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, and 1,4-cyclohexanediethanol diglycidyl ether.

[0019] (2) The haloether compounds in the reaction raw materials of the first active ingredient and the second active ingredient each independently include at least one of halooxy ether compounds and halothio ether compounds;

[0020] The general structural formulas of the halothioether compounds are each independently X. 1 -R 1 -SR 2 -Y 1 In the formula X1 and Y 1 Each is independently selected from halogen atoms, R 1 and R 2 Each is independently selected from C1-C8 alkylene or C1-C8 heteroalkylene;

[0021] The general structural formulas of the halooxygen ether compounds are each independently X. 2 -R 3 -OR 4 -Y 2 In the formula X 2 and Y 2 Each is independently selected from halogen atoms, R 3 and R 4 Each is independently selected from C1-C8 alkylene or C1-C8 heteroalkylene;

[0022] Optionally, the halothioether compound includes bis(chloromethyl) sulfide;

[0023] Optionally, the halooxygenated ether compounds include at least one selected from bis(2-chloroethyl) ether, bis(4-chlorobutyl) ether, bis(2-bromoethyl) ether, 1,2-bis(2-chloroethoxy)ethane, 1,2-bis(2-iodoethoxy)ethane, bis[2-[2-(2-chloroethoxy)ethoxy]ethyl] ether, 1-bromo-2-(2-(2-(2-bromoethoxy)ethoxy)ethoxy)ethane, and bis(2-chloroethoxy)methane.

[0024] In some embodiments, the general structural formula of the polyamine compound is H2N-Z-NH2, where Z is selected from C1-C2. 13 Alkylene or C1-C 13 Heteroalkylene;

[0025] Optionally, the C1-C 13 The heteroatom in a heteroalkyl group includes at least one of O, S, and N;

[0026] Optionally, the C1-C 13 The alkyl group is selected from C1-C4 alkyl groups;

[0027] Further optionally, the polyamine compound includes at least one selected from 1,4-butanediamine, diethylenetriamine, ethylenediamine, 4,7,10-trioxo-1,13-tetanediamine, and ethylene glycol di(3-aminopropyl) ether.

[0028] In some embodiments, the tertiary amine compound includes at least one selected from N,N,N',N'-tetramethyl-1,6-hexanediamine, tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N-methyldipropylamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetraethyl-1,3-propanediamine, and N,N,N',N'-tetramethyl-2,2-dimethyl-1,3-propanediamine.

[0029] In some embodiments, the method for preparing the first active ingredient includes: reacting the polyamine compound, the heterocyclic compound or its salt with at least one of the epoxy compound and the haloether compound in a solvent to prepare the first active ingredient;

[0030] and / or,

[0031] The tertiary amine compound is mixed with a solvent to form a first reaction solution; at least one of the epoxy compound and the haloether compound is added to the first reaction solution in batches to form a second reaction solution; the polyamine compound is added to the second reaction solution to react and prepare a second active ingredient.

[0032] Optionally, the reaction temperatures during the preparation of the first active ingredient and the second active ingredient are each independently 70℃-85℃;

[0033] Optionally, the solvents used in the preparation processes of the first active ingredient and the second active ingredient each independently include at least one of an alcohol and water.

[0034] In some embodiments, in the reaction raw materials of the first active ingredient, the molar ratio of at least one of the epoxy compound and the haloether compound, the heterocyclic compound or its salt, and the polyamine compound is independently (1-2):(0.5-1):(0.1-0.5).

[0035] And / or, in the reaction raw materials of the second active ingredient, the molar ratio of at least one of the epoxy compound and the haloether compound, the tertiary amine compound and the polyamine compound is independently (1-2):(0.5-1):(0.1-0.5).

[0036] And / or, the mass ratio of the first active ingredient to the second active ingredient is (3-10):(5-15).

[0037] Secondly, this application also provides an electroplating solution, the functional components of which include copper ions, chloride ions, sulfuric acid, and the leveling agent provided in the first aspect.

[0038] In some embodiments, at least one of the following features (1) to (2) is provided:

[0039] (1) The functional components, based on their content in the electroplating solution, include 150 g / L-170 g / L copper ions, 50 mg / L-70 mg / L chloride ions, 160 g / L-180 g / L sulfuric acid, and 5 mg / L-25 mg / L leveling agent;

[0040] (2) The functional ingredients also include additives, which include at least one of brighteners and inhibitors;

[0041] Optionally, the brightener comprises sodium polydithiopropane sulfonate, and the inhibitor comprises polyethylene glycol;

[0042] Optionally, the additives include brighteners and inhibitors; the amount of brightener added is 12 mg / L-20 mg / L, and the amount of inhibitor added is 200 mg / L-400 mg / L, based on the content in the electroplating solution.

[0043] Thirdly, this application also provides a copper plating process, which uses the electroplating solution provided in the first aspect for electroplating;

[0044] Optionally, the electroplating parameters include: a current density of 4 ADS-10 ADS and an electroplating temperature of 20℃-30℃.

[0045] Compared with traditional technologies, the technical advantages of the present application's technical solution include:

[0046] This application provides a leveling agent comprising a first active ingredient and a second active ingredient. The first active ingredient comprises at least one of an epoxy compound and a haloether compound, a polyamine compound, and a heterocyclic compound or its salt with the general structural formula shown in formula (I). The second active ingredient comprises at least one of an epoxy compound and a haloether compound, a polyamine compound, and a tertiary amine compound. The polyamine compound contains primary amine groups in its molecular structure, and the number of primary amine groups is independently ≥2. This application achieves small-aperture copper pillar electroplating through a dual-active-ingredient synergistic regulation scheme, resulting in highly flat copper pillars. This solves the problem that traditional single-leveling agent systems cannot achieve high uniformity and high flatness of electroplated copper pillars with different apertures. Attached Figure Description

[0047] Figure 1 This is a schematic diagram for calculating the total indication deviation (TIR) ​​of the copper column.

[0048] Figure 2The image shows a copper pillar electroplated using an electroplating solution containing leveling agent No. 1, as shown in Application Example 3.

[0049] Figure 3 High-magnification metallographic micrograph of a copper column electroplated with an electroplating solution containing leveling agent No. 1, as shown in Application Example 3.

[0050] Figure 4 The image shows the top flatness measurement of a copper column (100 μm aperture) electroplated using an electroplating solution containing leveling agent No. 1, as shown in Application Example 3.

[0051] Figure 5 The graph shows the top flatness measurement of a copper column (90 μm aperture) electroplated with an electroplating solution containing leveling agent No. 1, as shown in Application Example 3.

[0052] Figure 6 The graph shows the top flatness measurement of a copper column (60 μm aperture) electroplated with an electroplating solution containing leveling agent No. 1, as shown in Application Example 3.

[0053] Figure 7 High-magnification metallographic micrograph of a copper column electroplated using an electroplating solution containing leveling agent number 9, as shown in Application Example 3.

[0054] Figure 8 The graph shows the top flatness measurement of a copper column (100 μm aperture) electroplated with an electroplating solution containing leveling agent No. 9, as shown in Application Example 3.

[0055] Figure 9 The graph shows the top flatness measurement of a copper column (90 μm aperture) electroplated with an electroplating solution containing leveling agent No. 9, as shown in Application Example 3.

[0056] Figure 10 The image shows a copper pillar electroplated using an electroplating solution containing leveling agent No. 10, as shown in Application Example 3.

[0057] Figure 11 The graph shows the top flatness measurement of a copper column (100 μm aperture) electroplated with an electroplating solution containing leveling agent No. 10, as shown in Application Example 3.

[0058] Figure 12 The image shows the top flatness measurement of a copper column (100 μm aperture) electroplated with an electroplating solution containing leveling agent No. 11, as shown in Application Example 3.

[0059] Figure 13 The image shows the top flatness measurement of a copper column (100 μm aperture) electroplated using an electroplating solution containing leveling agent No. 12, as shown in Application Example 3. Detailed Implementation

[0060] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0061] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0062] The term "alkyl" refers to a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C1-C6 alkyl," refer to alkyl groups containing 1 to 6 carbon atoms, and each time it appears, it can be independently referred to as C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, or C6 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl) 2-Pentyl (-CH(CH3)CH2CH2CH3), 3-Pentyl (-CH(CH2CH3)2), 2-Methyl-2-Butyl (-C(CH3)2CH2CH3), 3-Methyl-2-Butyl (-CH(CH3)CH(CH3)2), 3-Methyl-1-Butyl (-CH2CH2CH(CH3)2), 2-Methyl-1-Butyl (-CH2CH(CH3)CH2CH3), 1-Hexyl (-CH2CH2CH2CH2CH2CH3) and 2-Hexyl (-CH(CH3)CH2CH2CH2CH3).

[0063] The term "alkylene" refers to a divalent group formed by removing two hydrogen atoms from the same carbon atom of an alkane molecule, or by removing one hydrogen atom from each of two different carbon atoms. Phrases containing this term, such as "C1-C6 alkylene," refer to straight-chain or branched divalent saturated hydrocarbon groups containing 1-6 carbon atoms, whose two free valences may be located on the same or different carbon atoms, and which, each time appearing, may independently be C1, C2, C3, C4, C5, or C6 alkylene. Suitable examples include, but are not limited to: methylene (-CH2-), ethylene (-CH2CH2-), 1,2-ethylene (-CH(CH3)-), 1,3-propylene (-CH2CH2CH2-), 1,2-propylene (-CH(CH3)CH2-), and 1,1-propylene (-CH(CH3)CH2-).

[0064] The term "heteroalkyl" refers to an alkyl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, O atom, S atom, etc. For example, if the carbon atom in the alkyl group that is attached to the parent nucleus is replaced by a non-carbon atom, the resulting heteroalkyl group is an alkoxy group (e.g., -OCH3, etc.), an amine (e.g., -NHCH3, -N(CH3)2, etc.), or a thioalkyl group (e.g., -SCH3). If the carbon atom in the alkyl group that is not attached to the parent nucleus is replaced by a non-carbon atom, the resulting heteroalkyl group is an alkyl ether (e.g., -CH2CH2-O-CH3, etc.), an alkylamine (e.g., -CH2NHCH3, -CH2N(CH3)2, etc.), or a thioalkyl ether (e.g., -CH2-S-CH3). If the terminal carbon atom of the alkyl group is replaced by a non-carbon atom, the resulting heteroalkyl group is a hydroxyalkyl group (e.g., -CH2CH2-OH), an aminoalkyl group (e.g., -CH2NH2), or an alkyl mercapto group (e.g., -CH2CH2-SH). Phrases containing this term, such as “C1-C6 heteroalkyl”, refer to heteroalkyl groups containing 1 to 6 carbon atoms, and each time they appear, they can be independently of each other as C1 heteroalkyl, C2 heteroalkyl, C3 heteroalkyl, C4 heteroalkyl, C5 heteroalkyl, or C6 heteroalkyl.

[0065] The term "heteroalkylene" refers to a divalent group formed by replacing at least one carbon atom with a non-carbon atom in an alkylene group (i.e., a divalent group formed by removing two hydrogen atoms from the same carbon atom of an alkane, or removing one hydrogen atom from each of two different carbon atoms). The non-carbon atom can be a nitrogen atom, an oxygen atom, a sulfur atom, etc., and the heteroatom can be an intrachain heteroatom (located between two carbon atoms), a terminal heteroatom (located at the end of the chain, but must meet the divalent linkage requirement), or a linker heteroatom (i.e., the atom connected to the parent nucleus is a non-carbon atom). Examples include divalent groups containing an ether bond (-O-) or a thioether bond (-S-) as a linker (such as -O-CH2-, -S-CH2-, etc.), -CH2-O-CH2- (oxapropylidene), -CH2-NH-CH2- (azapropylidene), -CH2-S-CH2- (thiopropylidene), etc.

[0066] The term "epoxide compounds" refers to organic compounds with a three-membered ring ether structure. Examples include ethylene oxide (ethylene oxide), propylene oxide (propylene oxide), 1,2-epoxybutane (butene oxide), 1,4-epoxybutane (tetrahydrofuran), epichlorohydrin (epiochlorohydrin), and 1,4-dioxane.

[0067] The term "glycidyl ether compounds" refers to a class of organic compounds whose core functional group is glycidyl. Their general structure can be represented as RO-CH2-CH(O)CH2, where R represents different hydrocarbon groups (such as alkyl, aryl, etc.), and the molecule contains at least one highly reactive epoxy group (ethylene oxide ring) at the end.

[0068] The term "halogenated ether compounds" broadly refers to compounds whose molecules contain ether bonds (RER' (E = O or S), where R represents a different hydrocarbon group, and one or more hydrogen atoms on the hydrocarbon group are replaced by halogen atoms (such as fluorine, chlorine, bromine, iodine). When E is selected from O, it indicates a halooxyether compound, in which the ether bond heteroatom in the molecule is oxygen (O), i.e., a compound containing an ROR structure, and the hydrogen on R is replaced by a halogen. When E is selected from S, it indicates a halothioether compound, in which the ether bond heteroatom in the molecule is sulfur (S), i.e., a compound containing an RSR structure, and the hydrogen on R is replaced by a halogen.

[0069] The term "polyamine compounds" refers to a class of compounds whose molecular structure contains two or more amino groups. Based on the number of amino groups in the molecule, they can be classified into diamines, triamines, tetraamines, etc. The amino groups in the molecule include, but are not limited to, primary amines, secondary amines, tertiary amines, or quaternary ammonium groups.

[0070] The term "tertiary amines" refers to a class of organic amines formed when all three hydrogen atoms in an ammonia molecule (NH3) are replaced by hydrocarbon groups (R). Their general formula is R3N (where R represents alkyl, aryl, or other hydrocarbon groups), and their core characteristic is that three hydrocarbon groups are attached to the nitrogen atom, and they no longer contain NH bonds.

[0071] The term "heterocyclic compound" refers to a cycloalkane in which at least one carbon atom is replaced by a non-carbon atom, which can be a nitrogen atom, an oxygen atom, a sulfur atom, etc., and can be a saturated ring or a partially unsaturated ring. Phrases containing this term, such as "C4-C9 heterocyclic compound," refer to heterocyclic compounds containing 4-9 carbon atoms, and each occurrence can independently be a C4 heteroalkane, C6 heteroalkane, C7 heteroalkane, C8 heteroalkane, or C9 heteroalkane. Suitable examples include, but are not limited to, tetrahydrothiazole, thiomorpholine, 2-methyltetrahydrothiazole, and 2,2-dimethyltetrahydrothiazole.

[0072] The term "cyclic tertiary amines" refers to organic compounds whose molecular structure contains a closed cyclic skeleton and whose molecules contain at least one nitrogen atom that conforms to the structural characteristics of tertiary amines (R3N).

[0073] The term "chain-like tertiary amines" refers to tertiary amines in which a nitrogen atom (N) is attached to three hydrocarbon groups in the molecule, and the nitrogen atom itself does not participate in the formation of any cyclic structure (i.e., the nitrogen atom is located on an open-chain aliphatic segment).

[0074] As the requirements for advanced packaging become increasingly stringent, copper pillars are evolving from large-aperture to small-aperture, with increasingly finer spacing. Traditional additives are no longer suitable for achieving "high flatness," especially for copper plating requirements under high current densities. This application therefore requires the design of a specific structure to meet the high uniformity requirements under these refined conditions.

[0075] In a first aspect, this application provides a leveling agent, comprising a first active ingredient and a second active ingredient:

[0076] The reaction raw materials for the first active ingredient include at least one of epoxy compounds and haloether compounds, polyamine compounds, and heterocyclic compounds or their salts;

[0077] The general structural formula of heterocyclic compounds is shown in formula (I):

[0078]

[0079] (I)

[0080] In the formula, R is selected from at least one of hydrogen atom, C1-C6 alkyl and C1-C6 heteroalkane, R substitutes at least one hydrogen atom on any cyclic carbon atom, and n and m are each independently selected from any integer in the range of 1-6.

[0081] The reaction raw materials for the second active ingredient include at least one of epoxy compounds and haloether compounds, polyamine compounds, and tertiary amine compounds;

[0082] In the reaction raw materials of the first and second active ingredients, the molecular structure of the polyamine compounds both contains primary amine groups, and the number of primary amine groups is ≥2 independently.

[0083] This application provides a leveling agent employing a synergistic regulation scheme with two active ingredients. Unlike traditional single-component leveling agent systems, this application uses a compound of two structurally different active ingredients. The first active ingredient is formed through a nucleophilic-electrophilic reaction between a heterocyclic compound containing S and N atoms (as shown in Formula I), with the S and N atoms acting as cyclizing atoms, and at least one of an epoxy compound, a haloether compound, or a polyamine compound. The second active ingredient is formed through a nucleophilic-electrophilic reaction between a tertiary amine compound, at least one of an epoxy compound, a haloether compound, or a polyamine compound. It is understood that the first active ingredient in this application creates a "concave" effect on the top of the electroplated copper pillar, while the second active ingredient creates a "convex" effect. The synergistic effect of the two active ingredients within the same system achieves a leveling effect.

[0084] The first active ingredient is obtained from the above-mentioned reactants via a nucleophilic-electrophilic substitution reaction. Specifically, at least one of an epoxide compound and a haloether compound is used as the electrophile, and a heterocyclic compound and a polyamine compound are used as the nucleophile, forming a polymer with corresponding repeating units through a nucleophilic-electrophilic substitution reaction. It is understood that the first active ingredient includes a quaternary ammonium salt compound, wherein the quaternary ammonium salt compound includes at least a heterocyclic compound of the general structural formula (I). It is understood that the repeating unit formed by the structure shown in Formula I is a cyclic quaternary ammonium.

[0085] The second active ingredient is obtained through a nucleophilic-electrophilic substitution reaction using the above-mentioned reactants. Specifically, at least one of an epoxide compound and a haloether compound is used as the electrophile, and a tertiary amine compound and a polyamine compound are used as the nucleophile, forming a polymer with corresponding repeating units through a nucleophilic-electrophilic substitution reaction. It is understood that the second active ingredient includes a quaternary ammonium salt compound, wherein the quaternary ammonium salt compound includes at least one formed through a tertiary amine compound. It is understood that the repeating units formed by the tertiary amine compound are chain-like quaternary ammonium compounds.

[0086] During the reaction, polyamine compounds, having at least two primary amine groups, can undergo nucleophilic-electrophilic reactions. It is understood that at least two primary amine groups react to form repeating units grafted at both ends.

[0087] This application combines two active ingredients with different structures to achieve synergistic complementarity in the adsorption-desorption kinetics and inhibition capabilities during the copper pillar electroplating process. This enables effective control of the top flatness of small copper pillars (feature size ≤100μm) under high current density, while improving the height uniformity among copper pillars with different aperture sizes.

[0088] In some embodiments, in the general structural formula shown in formula (I), n and m are each independently selected from any integer in the range of 1-2 (exemplarily, n and m are each independently selected from 1 or 2). As a non-limiting example, the heterocyclic compounds of the general structural formula shown in formula (I) include at least one of tetrahydrothiazole, thiomorpholine, 2-methyltetrahydrothiazole, 2,2-dimethyltetrahydrothiazole and their salts.

[0089] In some embodiments, the salts of the heterocyclic compounds of the general structural formula (I) include, but are not limited to, at least one of hydrochloride, sulfate and nitrate.

[0090] In some embodiments, the epoxy compounds in the reaction raw materials of the first and second active ingredients each independently include at least one of glycidyl ether compounds and epichlorohydrin. In the nucleophilic-electrophilic reaction, the epoxy group acts as an electrophile, attacked by the nucleophilic group, and undergoes ring-opening addition.

[0091] In some preferred embodiments, epoxy compounds with ≥2 epoxy groups are preferred. For example, glycidyl ether compounds whose molecular structure includes at least two epoxy groups form repeating unit structures through ring-opening of at least two epoxy groups followed by addition with a nucleophilic reagent. As a non-limiting example, glycidyl ethers include at least one of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, and 1,4-cyclohexanediethanol diglycidyl ether.

[0092] In some embodiments, the haloether compounds in the reaction raw materials of the first active ingredient and the second active ingredient each independently include at least one of halooxyether compounds and halothioether compounds.

[0093] In some embodiments, the general structural formula of each halothioether compound is X. 1 -R 1 -SR 2 -Y 1 In the formula X 1 and Y 1 Each is independently selected from halogen atoms, R 1 and R 2Each is independently selected from C1-C8 alkylene or C1-C8 heteroalkylene. Further, the heteroatom in the C1-C8 heteroalkylene contains an S atom; C1-C... 12 The alkylene groups are selected from C1-C2 alkylene groups, and the C1-C8 heteroalkylene groups are selected from C1-C4 heteroalkylene groups.

[0094] In some embodiments, the general structural formula of each halooxyether compound is X. 2 -R 3 -OR 4 -Y 2 In the formula X 2 and Y 2 Each is independently selected from halogen atoms, R 3 and R 4 Each is independently selected from C1-C8 alkylene or C1-C8 heteroalkylene. Further, the heteroatom in the C1-C8 heteroalkylene contains an O atom; the C1-C8 alkylene is selected from C1-C4 alkylene, and the C1-C8 heteroalkylene is selected from C1-C2 heteroalkylene.

[0095] In some preferred embodiments, the haloether compounds include dihaloether compounds, in which the dihalo groups in the dihaloether compounds all serve as sites attacked by nucleophiles, forming a repeating unit structure.

[0096] As a non-limiting example, halothioether compounds include bis(chloromethyl) sulfides.

[0097] As a non-limiting example, halooxy ether compounds include at least one of bis(2-chloroethyl) ether, bis(4-chlorobutyl) ether, bis(2-bromoethyl) ether, 1,2-bis(2-chloroethoxy)ethane, 1,2-bis(2-iodoethoxy)ethane, bis[2-[2-(2-chloroethoxy)ethoxy]ethyl] ether, 1-bromo-2-(2-(2-(2-bromoethoxy)ethoxy)ethoxy)ethane, and bis(2-chloroethoxy)methane.

[0098] In some embodiments, the general structural formula of polyamine compounds is H2N-Z-NH2, where Z is selected from C1-C2. 13 Alkylene or C1-C 13 Heteroalkylene compounds. The polyamine compounds of this application are chain polyamine compounds with primary amine groups at the end. The primary amine groups act as nucleophiles to attack electrophiles, thereby forming repeating units with -HN-Z-NH-.

[0099] In some embodiments, C1-C 13 The heteroatom in the heteroalkyl group includes at least one of O, S and N.

[0100] In some preferred embodiments, C1-C 13The alkyl group is selected from C1-C4 alkyl groups.

[0101] As a non-limiting example, polyamine compounds include at least one of 1,4-butanediamine, diethylenetriamine, ethylenediamine, 4,7,10-trioxo-1,13-tetanediamine, and ethylene glycol di(3-aminopropyl) ether.

[0102] In some embodiments, the tertiary amine compounds include at least one selected from N,N,N',N'-tetramethyl-1,6-hexanediamine, tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N-methyldipropylamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetraethyl-1,3-propanediamine, and N,N,N',N'-tetramethyl-2,2-dimethyl-1,3-propanediamine.

[0103] In some embodiments, the molar ratio of at least one of the epoxy compound and the haloether compound, the heterocyclic compound or its salt, and the polyamine compound in the reaction raw materials of the first active ingredient is independently (1-2):(0.5-1):(0.1-0.5).

[0104] In some embodiments, the molar ratio of at least one of the epoxy compound and the haloether compound, the tertiary amine compound and the polyamine compound in the reaction raw materials of the second active ingredient is independently (1-2):(0.5-1):(0.1-0.5).

[0105] In some embodiments, the mass ratio of the first active ingredient to the second active ingredient is (3-10):(5-15), including but not limited to 3:5, 3:8, 3:10, 3:15, 5:5, 8:5, 10:5, 8:15, 10:15 or any of the foregoing ranges and values ​​within those ranges.

[0106] In some preferred embodiments, the method for preparing the first active ingredient includes: reacting a polyamine compound, a heterocyclic compound or a salt thereof with at least one of an epoxy compound and a haloether compound in a solvent to prepare the first active ingredient.

[0107] As a non-limiting example, the solvent includes at least one of water and an alcohol. The alcohol is selected from methanol and / or ethanol.

[0108] In some specific embodiments, the reaction temperature is 70°C-85°C.

[0109] In some embodiments, the reaction during the preparation of the first active ingredient may also be carried out under a protective gas atmosphere. As a non-limiting example, the protective gas includes an inert gas, such as nitrogen.

[0110] In some preferred embodiments, the method for preparing the first active ingredient includes:

[0111] A polyamine compound is mixed with a heterocyclic compound or its salt in a solvent to form a reaction solution; at least one of an epoxy compound and the haloether compound is added to the reaction solution in batches to prepare the first active ingredient.

[0112] In some specific embodiments, prior to the step of adding at least one of the epoxy compound and the haloether compound in batches, the step of raising the temperature of the first reaction solution from room temperature to 35°C-45°C is further included.

[0113] In some embodiments, the reaction is carried out in a protective gas atmosphere. As a non-limiting example, the protective gas includes an inert gas, such as nitrogen.

[0114] In some other preferred embodiments, the method for preparing the first active ingredient includes:

[0115] A first active ingredient is prepared by adding at least one of an epoxide compound and a haloether compound in batches to a solvent containing a heterocyclic compound or its salt, followed by adding a polyamine compound to the reaction solution to carry out a second reaction.

[0116] In some specific embodiments, prior to the step of adding at least one of the epoxy compound and the haloether compound in batches, the step of raising the temperature of the solvent containing the heterocyclic compound or its salt from room temperature to 35°C-45°C is further included.

[0117] In some embodiments, both the first and second reactions are carried out in a protective gas atmosphere. As a non-limiting example, the protective gas includes an inert gas, such as nitrogen.

[0118] In some preferred embodiments, the method for preparing the second active ingredient includes:

[0119] A tertiary amine compound is mixed with a solvent to form a first reaction solution; at least one of an epoxy compound and a haloether compound is added to the first reaction solution in batches to form a second reaction solution; a polyamine compound is added to the second reaction solution to react and prepare a second active ingredient.

[0120] In some specific embodiments, the reaction temperature is 70°C-85°C.

[0121] In some specific embodiments, prior to the step of adding at least one of the epoxy compound and the haloether compound in batches, the step of raising the temperature of the first reaction solution from room temperature to 35°C-45°C is further included.

[0122] In some embodiments, the reaction is carried out in a protective gas atmosphere. As a non-limiting example, the protective gas includes an inert gas, such as nitrogen.

[0123] This application utilizes two leveling agents to coordinate leveling, resulting in electroplated copper pillars with good flatness and uniformity. This application employs two active ingredients. The first active ingredient contains sulfur atoms in its molecular structure, exhibiting a strong adsorption capacity for copper ions. The polymer formed from various raw materials has a block structure and simultaneously provides a significant amount of nitrogen. + The cationic structure further enhances adsorption capacity. During electroplating, it is more easily adsorbed in the central region, resulting in faster plating speed at the edges and a concave copper pillar. Specifically, the molecular structure of the first active component contains both S / N heterocycles (S and N atoms together serve as cyclic atoms). During electroplating, this molecule itself forms a heteroatom dual-center synergistic adsorption effect. The plating solution contains trace amounts of Cl... - Cl will preferentially adsorb on the cathode surface. - A negatively charged transition layer is formed. The protonated nitrogen atoms (NH4+) in the molecule... + or N on the quaternary ammonium salt ring + Attracted by electrostatics, the polymer rapidly anchors itself to the cathode surface. Furthermore, the sulfur atoms in the polymer structure possess strong soft-base properties, and their lone pairs of electrons can form extremely strong Cu-S coordination bonds with the copper surface. This makes the adsorption of this molecule on the cathode surface far more robust than that of ordinary nitrogen-containing additives, making it less prone to desorption. Consequently, copper deposition in the central portion is suppressed, while deposition at the edges is faster, ultimately forming a concave state. Simultaneously, the sulfur atoms in the molecule donate electrons, enabling them to interact with the Cu atoms at the interface. + and Cl - This forms a stable ternary coordination intermediate (such as [Cu(I)-S / N-Cl-]). This coordination enhances the efficiency of Cu. + The desolvation energy barrier increases the electrochemical overpotential of copper deposition, significantly refining the coating grains and resulting in denser internal crystallization and lower electrical resistance within the copper pillar. The second active component contains only a relatively large amount of nitrogen in its molecular structure. +During electroplating, cations tend to adsorb at the edges, leading to faster plating speeds in the center and a convex appearance of the copper pillars. Adding both a first and a second active ingredient to the electroplating system creates a synergistic effect, providing excellent inhibition across the entire copper pillar surface, resulting in uniform growth and superior surface smoothness. This application employs a combination of two active ingredients with different structures and complementary electrochemical properties. The synergistic complementarity of adsorption kinetics and inhibition capabilities during copper pillar electroplating enables effective control of the top smoothness of small copper pillars (feature size ≤100 μm) at high current densities, while simultaneously improving the height uniformity among copper pillars of different aperture sizes. This synergistic control strategy for leveling agents provides a novel technical approach to meet the increasingly sophisticated metallized interconnect requirements of advanced packaging.

[0124] Secondly, this application also provides an electroplating solution, the functional components of which include copper ions, chloride ions, sulfuric acid, and the leveling agent provided in the first aspect.

[0125] In some embodiments, the functional components, based on their content in the electroplating solution, include 150 g / L-170 g / L copper ions, 50 mg / L-70 mg / L chloride ions, 160 g / L-180 g / L sulfuric acid, and 5 mg / L-25 mg / L leveling agent.

[0126] In some embodiments, the functional ingredient further includes additives, including at least one of a brightener and an inhibitor. As a non-limiting example, the brightener includes sodium polydithiopropane sulfonate, and the inhibitor includes polyethylene glycol.

[0127] In some preferred embodiments, the additives include brighteners and inhibitors; the amount of brightener added is 12 mg / L-20 mg / L and the amount of inhibitor added is 200 mg / L-400 mg / L, based on the content in the electroplating solution.

[0128] Thirdly, this application also provides a copper plating process, which uses the electroplating solution provided in the first aspect for electroplating.

[0129] In some embodiments, the electroplating parameters include: a current density of 4 ADS-10 ADS and an electroplating temperature of 20°C-30°C.

[0130] For experimental parameters not specified in the following specific embodiments, please refer to the guidelines given in this application document first, or refer to experimental manuals or other experimental methods known in the art, or refer to the experimental conditions recommended by the manufacturer.

[0131] The raw materials and reagents involved in the following specific embodiments can be obtained commercially or prepared by those skilled in the art using known methods.

[0132] Example 1, First Active Ingredient

[0133] This application provides the preparation of the following L1, L1-1, L1-2, L1-3, L1-4, L1-5, and L1-6:

[0134] Synthesis of L1: In a three-necked flask equipped with a thermometer, 30.0 g of ethanol, 5.0 g of thiomorpholine, and 1.0 g of diethylenetriamine were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 30 g of water was added, stirred thoroughly, and the mixture was purged with nitrogen for protection. The temperature was then raised to 80°C and stabilized. 15.0 g of ethylene glycol diglycidyl ether was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 1 hour. After the addition was complete, the temperature was maintained at 80°C for 20 hours, then cooled to room temperature, and the reaction was complete. The product changed from a colorless to a brownish-yellow liquid.

[0135] Synthesis of L1-1: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol, 5.52 g of thiomorpholine, and 0.5 g of diethylenetriamine were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 15.0 g of water was added, stirred thoroughly, and the mixture was purged with nitrogen for protection. The temperature was then raised to 80°C and stabilized. 10.0 g of 1,2-bis(2-chloroethoxy)ethane was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 1 hour. After the addition was complete, the temperature was maintained at 80°C for 30 hours, then cooled to room temperature, and the reaction was complete. The product changed from colorless to a yellow liquid.

[0136] Synthesis of L1-2: In a three-necked flask equipped with a thermometer, 30.0 g of ethanol and 4.1 g of tetrahydrothiazole were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 30 g of water was added, stirred thoroughly, and the mixture was purged with nitrogen for protection. The temperature was then raised to 80°C and stabilized. 15.0 g of ethylene glycol diglycidyl ether was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 1 hour. After the addition was complete, the temperature was maintained at 80°C for 4 hours. Then, 1.2 g of diethylenetriamine was added, and the mixture was kept at this temperature for another 12 hours before cooling to room temperature. The reaction was complete. The product changed from colorless to a brownish-red liquid.

[0137] Synthesis of L1-3: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 6.7 g of 2,2-dimethyltetrahydrothiazole were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 15 g of water was added, stirred thoroughly, and the mixture was purged with nitrogen for protection. The temperature was then raised to 80°C and stabilized. 15.0 g of ethylene glycol diglycidyl ether was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 1 hour. After the addition was complete, the temperature was maintained at 80°C for 4 hours. Then, 1.2 g of diethylenetriamine was added, and the mixture was kept at this temperature for another 12 hours before cooling to room temperature. The reaction was complete. The product changed from colorless to a brownish-red liquid.

[0138] Synthesis of L1-4: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 6.7 g of 2,2-dimethyltetrahydrothiazole were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 15 g of water was added, stirred thoroughly, and the mixture was purged with nitrogen for protection. The temperature was then raised to 80°C and stabilized. 15.0 g of ethylene glycol diglycidyl ether was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 1 hour. After the addition was complete, the temperature was maintained at 80°C for 4 hours. Then, 2.53 g of 4,7,10-trioxo-1,13-tetanediamine was added, and the mixture was kept at this temperature for another 12 hours before cooling to room temperature. The reaction was complete. The product changed from a colorless liquid to a brownish-yellow liquid.

[0139] Synthesis of L1-5: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 4.40 g of 2,2-dimethyltetrahydrothiazole were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 15 g of water was added, stirred thoroughly, and the mixture was purged with nitrogen for protection. The temperature was then raised to 80°C and stabilized. 12.0 g of 1,4-cyclohexanediethanol diglycidyl ether was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 1 hour. After the addition was complete, the temperature was maintained at 80°C for 4 hours. Then, 3.30 g of 4,7,10-trioxo-1,13-tetanediamine was added, and the mixture was kept at this temperature for another 16 hours before cooling to room temperature. The reaction was complete. The product changed from colorless to a yellow liquid.

[0140] Synthesis of L1-6: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 7.16 g of 2,2-dimethyltetrahydrothiazole were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 7.5 g of water was added, stirred thoroughly, and purged with nitrogen for protection. The temperature was then raised to 80°C and stabilized. 8.0 g of bis(chloromethyl)sulfide was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 2 hours. After the addition was complete, the temperature was maintained at 80°C for 6 hours. Then, 2.69 g of 4,7,10-trioxo-1,13-tetanediamine was added, and the mixture was kept at this temperature for another 22 hours before cooling to room temperature. The reaction was complete. The product changed from colorless to a bright yellow liquid.

[0141] Example 2, Second Active Ingredient

[0142] This application provides the preparation of the following L2, L2-1, L2-2, L2-3, and L2-4:

[0143] Synthesis of L2: In a three-necked flask equipped with a thermometer, 20.0 g of ethanol and 10.0 g of N,N,N',N'-tetramethyl-1,3-propanediamine were added at room temperature. After complete dissolution, 20.0 g of water was added, and the temperature was raised to 80°C. Once the temperature was constant, 20.0 g of ethylene glycol diglycidyl ether was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 30 min. After the addition was complete, the temperature was maintained at 80°C for 5 h, and then 1.2 g of diethylenetriamine was added in a single batch. The reaction continued for 10 h, then the temperature was lowered to room temperature, and the reaction was complete. The product changed from colorless to a yellow liquid.

[0144] Synthesis of L2-1: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 10.0 g of N,N,N',N'-tetramethyl-1,3-propanediamine were added at room temperature. After complete dissolution, the temperature was raised to 40°C. Once the temperature stabilized, 15.0 g of water was added, and the mixture was stirred thoroughly. Nitrogen gas was then introduced for protection. The temperature was raised to 80°C, and after stabilization, 14.36 g of 1,2-bis(2-chloroethoxy)ethane was added through a constant-pressure dropping funnel. The dropping rate was controlled, and the addition was completed within 1 hour. After the addition was complete, the reaction was maintained at 80°C for 4 hours. Then, 1.58 g of diethylenetriamine was added, and the reaction continued for 40 hours. Finally, the temperature was lowered to room temperature, and the reaction was complete. The product changed from colorless to a pale yellow liquid.

[0145] Synthesis of L2-2: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 10.56 g of N,N,N',N'-tetramethyl-1,6-hexanediamine were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 15.0 g of water was added, and the mixture was stirred until homogeneous. Nitrogen gas was then introduced for protection. The temperature was raised to 80°C and stabilized. 14.36 g of 1,2-bis(2-chloroethoxy)ethane was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 1 hour. After the addition was complete, the reaction was maintained at 80°C for 4 hours. Then, 1.58 g of diethylenetriamine was added, and the reaction continued for 20 hours. Finally, the temperature was lowered to room temperature, and the reaction was complete. The product changed from colorless to a pale yellow liquid.

[0146] Synthesis of L2-3: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 10.56 g of N,N,N',N'-tetramethyl-1,6-hexanediamine were added at room temperature. After complete dissolution, the temperature was raised to 40°C. Once the temperature stabilized, 15.0 g of water was added, and the mixture was stirred thoroughly. Nitrogen gas was then introduced for protection. The temperature was raised to 80°C, and after stabilization, 14.36 g of 1,2-bis(2-chloroethoxy)ethane was added through a constant-pressure dropping funnel. The dropping rate was controlled, and the addition was completed within 1 hour. After the addition was complete, the reaction was maintained at 80°C for 4 hours. Then, 3.40 g of 4,7,10-trioxo-1,13-tetanediamine was added, and the reaction continued for 20 hours. Finally, the temperature was lowered to room temperature, and the reaction was complete. The product changed from a colorless liquid to a yellow liquid.

[0147] Synthesis of L2-4: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 6.45 g of N,N,N',N'-tetramethyl-1,6-hexanediamine were added at room temperature. After complete dissolution, the temperature was raised to 40°C. Once the temperature stabilized, 15 g of water was added, and the mixture was stirred thoroughly. Nitrogen gas was then introduced for protection. The temperature was then raised to 80°C. After stabilization, 12.0 g of 1,4-cyclohexanediethanol diglycidyl ether was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition within 1 hour. After the addition was complete, the temperature was maintained at 80°C for 4 hours. Then, 1.15 g of 4,7,10-trioxo-1,13-tetanediamine was added, and the mixture was kept at this temperature for another 20 hours before cooling to room temperature. The reaction was complete. The product changed from colorless to a yellow liquid.

[0148] Synthesis of L2-5: In a three-necked flask equipped with a thermometer, 15.0 g of ethanol and 10.52 g of N,N,N',N'-tetramethyl-1,6-hexanediamine were added at room temperature. After complete dissolution, the temperature was raised to 40°C and stabilized. Then, 15 g of water was added, stirred thoroughly, and the mixture was purged with nitrogen for protection. The temperature was then raised to 80°C and stabilized. 12.0 g of bis(chloromethyl)sulfide was added through a constant-pressure dropping funnel, controlling the dropping rate and completing the addition over 2 hours. After the addition was complete, the temperature was maintained at 80°C for 6 hours. Then, 3.0 g of 4,7,10-trioxo-1,13-tetanediamine was added, and the mixture was kept at this temperature for another 40 hours before cooling to room temperature. The reaction was complete. The product changed from a colorless liquid to a brownish-yellow liquid.

[0149] Experimental Example 1: Electroplating of Copper

[0150] This embodiment provides a method for electroplating copper, and the specific electroplating steps are as follows:

[0151] Electroplating equipment: 1.5 L Haring tank, air agitation.

[0152] Electroplated substrate: a substrate with different opening diameters and dry film coating, the substrate material is copper and the dry film thickness is 80μm.

[0153] Electroplating parameters: 1.8 A (plating area is 22.5%, current density is 8ASD based on actual area), electroplating temperature is 30℃, electroplating time is 50 min, and electroplating aperture is 60 μm-100 μm.

[0154] Performance evaluation indicators for copper pillars: as attached Figure 1 As shown, the conventional evaluation criteria for electroplated copper pillars are calculated using the following formula (1) to determine the total indication deviation (TIR) ​​of the copper pillars.

[0155] (1)

[0156] In the formula: H Center H represents the height of the center of the copper pillar. Edge This indicates the height of the side wall of the bronze pillar.

[0157] Understandably, in the actual measurement process, the average value of the TIR calculated through the corresponding two side walls of the copper column is presented as the final result.

[0158] The electroplating solution used in this embodiment consists of: 170 g / L sulfuric acid, 160 g / L copper sulfate, 60 mg / L chloride ions, 300 mg / L PEG 8000, 15 mg / L sodium polydithiopropane sulfonate (SPS), and a leveling agent. The leveling agent has the following composition:

[0159] Number 1: L1 (6 mg / L) + L2 (8 mg / L).

[0160] Number 2: L1 (2 mg / L) + L2-1 (10 mg / L).

[0161] Number 3: L1-1 (3 mg / L) + L2-1 (10 mg / L).

[0162] Number 4: L1-2 (5 mg / L) + L2-2 (10 mg / L).

[0163] Number 5: L1-3 (2 mg / L) + L2-3 (12 mg / L).

[0164] Number 6: L1-4 (2 mg / L) + L2-3 (10 mg / L).

[0165] Number 7: L1-5 (2 mg / L) + L2-4 (8 mg / L).

[0166] Number 8: L1-6 (3 mg / L) + L2-5 (8 mg / L).

[0167] Number 9: L1 (14 mg / L).

[0168] Number 10: L2 (14 mg / L).

[0169] Number 11: L3 (6 mg / L) + L2 (8 mg / L), wherein the preparation method of L3 is similar to that of L1, except that thiomorpholine is replaced with imidazole in equal amounts, and the rest of the composition and preparation method are the same as those of L1.

[0170] Number 12: L4 (6 mg / L) + L2 (8 mg / L), wherein the preparation method of L4 is similar to that of L1, except that diethylenetriamine is replaced with n-propylamine in equal amounts, and the rest of the composition and preparation method are the same as those of L1.

[0171] The copper pillars were electroplated using the above electroplating solution, and the results are shown in Table 1 and Appendix. Figure 2 To be continued Figure 13 As shown, in comparison with the attached document Figure 2 Appendix Figure 3 Appendix Figure 7 Appendix Figure 10 It can be seen that the appendix Figure 2 and attached Figure 3 The top of the copper pillar is significantly flatter than that of the attached pillar. Figure 7 Appendix Figure 10 As can be seen from the top of the copper pillar, the copper pillar electroplated using the leveling agent composed of the first and second active ingredients in this application can achieve a flat top, while using a single active ingredient as a leveling agent cannot electroplat a copper pillar with a flat top. Furthermore, from the attached... Figure 12 To be continued Figure 13 It can be seen that the flatness of the top of the bronze pillar is not as good as that of the attached one. Figure 4 To be continued Figure 6 .

[0172] Table 1: Total Indication Deviation (TIR) ​​Results of Electroplated Copper Pillars

[0173]

[0174] As shown in Table 1, this application achieves high flatness of electroplated copper pillars by using two active ingredients in synergy, and has good uniformity for different pore sizes. The data shows that the total indication deviation (TIR) ​​of the copper pillars numbered 1-8 in the ≤100 μm pore size range is only within 2%, and some active ingredient combinations can achieve less than 1%.

[0175] As for No. 9, it only contains the L1 active ingredient, and the total indicator deviation (TIR) ​​is a large negative value in the ≤100 μm pore size range, indicating that there are many depressions at the top of the copper pillar, which obviously cannot achieve the "flat" technical effect of this application.

[0176] Number 10 contains only the L2 active ingredient. The total indicator deviation (TIR) ​​is a large positive value in the ≤100 μm pore size range, indicating that there are many protrusions at the top of the copper pillar, and it cannot achieve the "flat" technical effect of this application.

[0177] In contrast, number 11 uses L3 instead of L1 and is compounded with L2. The total indication deviation (TIR) ​​is about 7% in the ≤100 μm pore size range. After replacing the monomer containing S / N heterocyclic compound with imidazole, its inhibition ability is greatly reduced, and the copper column cannot achieve excellent flatness, thus failing to achieve the "flatness" technical effect of this application.

[0178] In contrast, the first active ingredient in No. 12 uses a mono-primary amine compound to replace the poly-primary amine, and the copper pillars electroplated with a pore size of <100 μm after compounding cannot achieve the flatness of the copper pillars electroplated in this application.

[0179] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0180] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A leveling agent, characterized in that, Including the first active ingredient and the second active ingredient: The reaction raw materials for the first active ingredient include at least one of epoxy compounds and haloether compounds, polyamine compounds, and heterocyclic compounds or their salts; The general structural formula of the heterocyclic compound is shown in formula (I): （I） In the formula, R is selected from at least one of hydrogen atom, C1-C6 alkyl and C1-C6 heteroalkyl, R substitutes at least one hydrogen atom on any cyclic carbon atom, and n and m are each independently selected from any integer in the range of 1-6. The reaction raw materials for the second active ingredient include at least one of epoxy compounds and haloether compounds, polyamine compounds, and tertiary amine compounds; In the reaction raw materials of the first active ingredient and the second active ingredient, the molecular structure of the polyamine compound contains a primary amine group, and the number of the primary amine groups is independently ≥2.

2. The leveling agent according to claim 1, characterized in that, In the general formula shown in equation (I), n and m are each independently selected from any integer in the range of 1-2; Optionally, the heterocyclic compound includes at least one of tetrahydrothiazole, thiomorpholine, 2-methyltetrahydrothiazole, and 2,2-dimethyltetrahydrothiazole; And / or, the salt includes at least one of hydrochloride, sulfate and nitrate.

3. The leveling agent according to claim 1, characterized in that, It has at least one of the following characteristics: (1) The epoxy compounds in the reaction raw materials of the first active ingredient and the second active ingredient each independently include at least one of glycidyl ether compounds and epichlorohydrin; Optionally, the molecular structure of the glycidyl ether compound includes an epoxy group, and the number of the epoxy groups is ≥2; Further optionally, the glycidyl ether compound includes at least one selected from ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, and 1,4-cyclohexanediethanol diglycidyl ether. (2) The haloether compounds in the reaction raw materials of the first active ingredient and the second active ingredient each independently include at least one of halooxy ether compounds and halothio ether compounds; The general structural formulas of the halothioether compounds are each independently X. 1 -R 1 -SR 2 -Y 1 In the formula X 1 and Y 1 Each is independently selected from halogen atoms, R 1 and R 2 Each is independently selected from C1-C8 alkylene or C1-C8 heteroalkylene; The general structural formulas of the halooxygen ether compounds are each independently X. 2 -R 3 -OR 4 -Y 2 In the formula X 2 and Y 2 Each is independently selected from halogen atoms, R 3 and R 4 Each is independently selected from C1-C8 alkylene or C1-C8 heteroalkylene; Optionally, the halothioether compound includes bis(chloromethyl) sulfide; Optionally, the halooxygenated ether compounds include at least one selected from bis(2-chloroethyl) ether, bis(4-chlorobutyl) ether, bis(2-bromoethyl) ether, 1,2-bis(2-chloroethoxy)ethane, 1,2-bis(2-iodoethoxy)ethane, bis[2-[2-(2-chloroethoxy)ethoxy]ethyl] ether, 1-bromo-2-(2-(2-(2-bromoethoxy)ethoxy)ethoxy)ethane, and bis(2-chloroethoxy)methane.

4. The leveling agent according to claim 1, characterized in that, The general structural formula of the polyamine compounds is H2N-Z-NH2, where Z is selected from C1-C2. 13 Alkylene or C1-C 13 Heteroalkylene; Optionally, the C1-C 13 The heteroatom in a heteroalkyl group includes at least one of O, S, and N; Optionally, the C1-C 13 The alkyl group is selected from C1-C4 alkyl groups; Further optionally, the polyamine compound includes at least one selected from 1,4-butanediamine, diethylenetriamine, ethylenediamine, 4,7,10-trioxo-1,13-tetanediamine, and ethylene glycol di(3-aminopropyl) ether.

5. The leveling agent according to claim 1, characterized in that, The tertiary amine compounds include at least one selected from N,N,N',N'-tetramethyl-1,6-hexanediamine, tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N-methyldipropylamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetraethyl-1,3-propanediamine, and N,N,N',N'-tetramethyl-2,2-dimethyl-1,3-propanediamine.

6. The leveling agent according to claim 1, characterized in that, The preparation method of the first active ingredient includes: reacting the polyamine compound, the heterocyclic compound or its salt with at least one of the epoxy compound and the haloether compound in a solvent to prepare the first active ingredient; and / or, The preparation method of the second active ingredient includes: mixing the tertiary amine compound with a solvent to form a first reaction solution; adding at least one of the epoxy compound and the haloether compound to the first reaction solution in batches to form a second reaction solution; adding the polyamine compound to the second reaction solution to react and prepare the second active ingredient; Optionally, the reaction temperatures during the preparation of the first active ingredient and the second active ingredient are each independently 70℃-85℃; Optionally, the solvents used in the preparation processes of the first active ingredient and the second active ingredient each independently include at least one of an alcohol and water.

7. The leveling agent according to any one of claims 1 to 6, characterized in that, In the reaction raw materials of the first active ingredient, the molar ratio of at least one of the epoxy compound and the haloether compound, the heterocyclic compound or its salt, and the polyamine compound to the three is independently (1-2):(0.5-1):(0.1-0.5). And / or, in the reaction raw materials of the second active ingredient, the molar ratio of at least one of the epoxy compound and the haloether compound, the tertiary amine compound and the polyamine compound is independently (1-2):(0.5-1):(0.1-0.5). And / or, the mass ratio of the first active ingredient to the second active ingredient is (3-10):(5-15).

8. An electroplating solution, characterized in that, The functional ingredients include copper ions, chloride ions, sulfuric acid, and the leveling agent as described in any one of claims 1 to 7.

9. The electroplating solution according to claim 8, characterized in that, It has at least one of the following features (1) to (2): (1) The functional components, based on their content in the electroplating solution, include 150 g / L-170 g / L copper ions, 50 mg / L-70 mg / L chloride ions, 160 g / L-180 g / L sulfuric acid, and 5 mg / L-25 mg / L leveling agent; (2) The functional ingredients also include additives, which include at least one of brighteners and inhibitors; Optionally, the brightener comprises sodium polydithiopropane sulfonate, and the inhibitor comprises polyethylene glycol; Optionally, the additives include brighteners and inhibitors; the amount of brightener added is 12 mg / L-20 mg / L, and the amount of inhibitor added is 200 mg / L-400 mg / L, based on the content in the electroplating solution.

10. A copper plating process, characterized in that, Electroplating is performed using the electroplating solution described in claim 8 or 9; Optionally, the electroplating parameters include: a current density of 4 ADS-10 ADS and an electroplating temperature of 20℃-30℃.

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