Ammonium salt compound, additive for electrolytic copper plating, electrolytic copper plating solution composition, and electrolytic copper plating method

Abstract

To provide means that allows superior filling of recessed regions of an article to be plated and facilitates formation of a plating film exhibiting high flatness.SOLUTION: Provided is an ammonium salt compound represented by formula (1) below.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an ammonium salt compound, an additive for electrolytic copper plating, an electrolytic copper plating solution composition, and an electrolytic copper plating method. [Background technology]

[0002] In recent years, the increasing complexity of semiconductor circuits has created a demand for highly selective filling of vias and / or trenches in the plating field.To impart selectivity to metal electrodeposition on these uneven surfaces, it is known to use organic compounds called levelers as additives to plating pretreatment solutions or plating solutions.

[0003] Nitrogen-containing organic compounds are commonly used as levelers in copper plating. Known levelers used in copper plating include Janus Green B (JGB), Bismarck Brown Y, and Crystal Violet (Patent Documents 1, 2, 3, 4, and 5). Also known levelers used in copper plating include reaction products of nitrogen-containing organic compounds with compounds having an ether structure, compounds having an alkylene oxide structure, or compounds having an epoxide structure (Patent Documents 3, 6, 7, and 8). Also known levelers used in plating, such as copper plating, include rosarinin, tetramethylpararosarinin hydrochloride, pentamethylpararosarinin hydrochloride, and hexamethylpararosarinin hydrochloride (Patent Documents 2, 4, 9, and 10). Furthermore, as levelers used in plating such as copper plating, there are known oligomers or polymers having a biguanide structure, ionic compounds containing a quaternary ammonium cation, and ionic compounds containing a partial structure derived from an unsaturated heterocyclic compound containing one or more heteroatoms (e.g., nitrogen atoms) (Patent Documents 9 and 11). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-185271 [Patent Document 2] Japanese Patent Application Publication No. 58-27992 [Patent Document 3] Japanese Patent Application Laid-Open No. 2004-360055 [Patent Document 4] Special Publication No. 2015-503033 [Patent Document 5] Japanese Patent Application Publication No. 2018-111863 [Patent Document 6] Special Publication No. 2017-532452 [Patent Document 7] Japanese Patent Application Laid-Open No. 2016-155996 [Patent Document 8] Japanese Patent Application Publication No. 2019-85647 [Patent Document 9] Special Publication No. 2014-505167 [Patent Document 10] US Patent Application Publication No. 2019 / 0100848 [Patent Document 11] Special Publication No. 2018-530675 Summary of the Invention [Problem to be solved by the invention]

[0005] However, with plating solutions using levelers that have been studied in the past, the plating does not sufficiently fill the recesses in the object to be plated, which can result in depressions in the plating film above the recesses in the plated film, making it difficult to form a plating film with a flat surface.

[0006] Therefore, an object of the present invention is to provide a means for forming a plating film that is excellent in filling recesses in an object to be plated and has high flatness. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems, and in the process have found that the above problems can be solved by using a nitrogen-containing organic compound with a specific structure in plating, which has led to the completion of the present invention.

[0008] According to one aspect of the present invention, there is provided an ammonium salt compound represented by the following formula (1):

[0009] [ka]

[0010] In the above formula (1), R 11 , R 12 , R 13 , R 14 , R 21 and R 22 are each independently a methyl group or an ethyl group, R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a cyano group, a nitro group, a fluoro group, a chloro group, a bromo group, an iodo group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)CH3 group, a C(O)OCH3 group, a C(O)NH2 group, or a SO2CH3 group; A is F, Cl, Br or I; X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)CH3 group, a C(O)OCH3 group, a C(O)NH2 group, or a SO2CH3 group; X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 At least one selected from the group consisting of is not a hydrogen atom. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a means for forming a plating film that is excellent in filling recesses in an object to be plated and has high flatness. [Brief explanation of the drawings]

[0012] [Figure 1] 10A and 10B are schematic diagrams for explaining the amount of recession of a via conductor. DETAILED DESCRIPTION OF THE INVENTION

[0013] Preferred embodiments of the present invention are described below. The present invention is not limited to the following embodiments and can be modified in various ways within the scope of the claims. The embodiments described herein can be combined in any way to create other embodiments. In this specification, the term "X to Y" indicates a range, with the numerical values ​​(X and Y) being used to mean "X or more and Y or less," including the lower and upper limits. Unless otherwise specified, operations and measurements of physical properties are performed at room temperature (20-25°C) and a relative humidity of 40-50% RH. In this specification, "A and / or B" refers to A and B, and includes both A and B, as well as combinations thereof.

[0014] <Ammonium salt compounds> One aspect of the present invention relates to an ammonium salt compound represented by the following formula (1):

[0015] [ka]

[0016] In the above formula (1), R 11 , R 12 , R 13 , R 14 , R 21 and R 22 are each independently a methyl group or an ethyl group, R 31 , R 32 , R 33 and R34 are each independently a hydrogen atom, a cyano group (CN group), a nitro group (NO group), a fluoro group, a chloro group, a bromo group, an iodo group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)CH3 group, a C(O)OCH3 group, a C(O)NH2 group, or a SO2CH3 group; A is F, Cl, Br or I; X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)CH3 group, a C(O)OCH3 group, a C(O)NH2 group, or a SO2CH3 group; X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 At least one selected from the group consisting of is not a hydrogen atom.

[0017] The OCF group is a trifluoromethoxy group. The C(O)CH group is also written as C(=O)-CH group, the C(O)OCH group is also written as C(=O)-O-CH group, the C(O)NH group is also written as C(=O)-NH group, and the SOCH group is also written as S(=O)-CH group.

[0018] Throughout this specification, an object to be plated is referred to as a "subject to be plated," and an object that has been plated is referred to as a "plated object."

[0019] The ammonium salt compound represented by the above formula (1) is preferably used in plating, and more preferably in copper plating. In this specification, the term copper plating refers collectively to plating that deposits copper on a substrate and plating that deposits a copper alloy on a substrate. The ammonium salt compound represented by the above formula (1) may be used in plating that forms a copper film or a copper alloy film, but is particularly preferably used in plating that forms a copper film. The elements other than copper contained in the copper alloy film are not particularly limited. Examples of elements other than copper contained in the copper alloy film include metal elements such as aluminum, beryllium, zinc, nickel, tin, and lead, as well as phosphorus.

[0020] In the above formula (1), X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)NH2 group, a C(O)CH3 group, or a SO2CH3 group; X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 Preferably, at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)NH2 group, or a SO2CH3 group, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X18 It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, or an SO2CH3 group, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, a SF5 group, or a SO2CH3 group, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, or an SF5 group, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, an SF5 group, or a cyano group, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom or an SF5 group, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 It is particularly preferred that at least one selected from the group consisting of is not a hydrogen atom.

[0021] In the above formula (1), X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 Preferably, at least two selected from the group consisting of: 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18More preferably, at least six selected from the group consisting of 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 It is more preferred that is not a hydrogen atom.

[0022] In the above formula (1), X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 Preferably, at least one selected from the group consisting of is not a hydrogen atom, and X 11 , X 12 , X 13 and X 14 At least three selected from the group consisting of X are not hydrogen atoms, 15 , X 16 , X 17 and X 18 It is more preferable that at least three selected from the group consisting of are not hydrogen atoms, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 is more preferably not a hydrogen atom.

[0023] In the above general formula (1), X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)NH2 group, a C(O)CH3 group, or a SO2CH3 group; X11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 Preferably, at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)NH2 group, or a SO2CH3 group, and X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, or an SO2CH3 group, and X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, a SF5 group, or a SO2CH3 group, and X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, or an SF5 group, and X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 It is more preferable that at least one selected from the group consisting of X is not a hydrogen atom. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, or an SF5 group, and X 11 , X 12 , X 13 and X 14 At least three selected from the group consisting of X are not hydrogen atoms, 15 , X 16 , X 17 and X 18 It is more preferable that at least three selected from the group consisting of X are not hydrogen atoms. 11 , X12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, an SF5 group, or a cyano group, and X 11 , X 12 , X 13 and X 14 At least three selected from the group consisting of X are not hydrogen atoms, 15 , X 16 , X 17 and X 18 It is more preferable that at least three selected from the group consisting of X are not hydrogen atoms. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 More preferably, X are each independently an SF5 group or a cyano group. 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 is particularly preferably an SF5 group.

[0024] In the above formula (1), R 11 , R 12 , R 13 and R 14 are each preferably independently a methyl group. 11 , R 12 , R 13 and R 14 may be the same or different, but R 11 , R 12 , R 13 and R 14 It is preferable that R 11 , R 12 , R 13 and R 14 is a methyl group, or R11 , R 12 , R 13 and R 14 is preferably an ethyl group, and R 11 , R 12 , R 13 and R 14 is particularly preferably a methyl group.

[0025] In the above formula (1), R 21 and R 22 are each preferably independently a methyl group. 21 and R 22 may be the same or different, but R 21 and R 22 It is preferable that R 21 and R 22 is a methyl group, or R 21 and R 22 is preferably an ethyl group, and R 21 and R 22 is particularly preferably a methyl group.

[0026] In the above formula (1), R 31 , R 32 , R 33 and R 34 are each independently preferably a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)CH3 group, a C(O)OCH3 group, a C(O)NH2 group, or a SO2CH3 group, and more preferably a hydrogen atom. 31 , R 32 , R 33 and R 34 may be the same or different, but R 31 , R 32 , R 33 and R 34 are preferably the same, and R 31 , R 32 , R 33 and R 34 It is particularly preferred that is a hydrogen atom.

[0027] In the above formula (1), A is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I). A is preferably Cl, Br or I, more preferably Cl or Br, and particularly preferably Cl. Therefore, in the above formula (1), A - is the fluoride ion (F - ), chloride ions (Cl - ), bromide ion (Br - ) or iodide ion (I - ) A - is Cl - , Br - or I - Preferably, Cl - or Br - More preferably, Cl - It is particularly preferred that:

[0028] As a preferred embodiment of the ammonium salt compound, there is provided an ammonium salt compound represented by the above general formula (1), 11 , R 12 , R 13 , R 14 , R 21 and R 22 are each independently a methyl group or an ethyl group, and R 31 , R 32 , R 33 and R 34 is a hydrogen atom, A is Cl, Br or I, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)CH3 group, a C(O)NH2 group, or a SO2CH3 group; X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X18 In a more preferred embodiment, the ammonium salt compound is represented by the general formula (1) above, and R 11 , R 12 , R 13 , R 14 , R 21 and R 22 are each independently a methyl group or an ethyl group, and R 31 , R 32 , R 33 and R 34 is a hydrogen atom, A is Cl or Br, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)NH2 group, or a SO2CH3 group, and X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 In a further preferred embodiment, the ammonium salt compound is represented by the general formula (1) above, and R 11 , R 12 , R 13 and R 14 are each independently a methyl group or an ethyl group, and R 21 and R 22 is a methyl group, and R 31 , R 32 , R 33 and R 34 is a hydrogen atom, A is Cl or Br, and X 11 , X 12 , X 13 , X 14 , X 15 , X16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)NH2 group, or a SO2CH3 group, and X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 In a further preferred embodiment, the ammonium salt compound is represented by the general formula (1) above, and R 11 , R 12 , R 13 and R 14 are each independently a methyl group or an ethyl group, and R 21 and R 22 is a methyl group, and R 31 , R 32 , R 33 and R 34 is a hydrogen atom, A is Cl or Br, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, a SF5 group, or a SO2CH3 group, and X 11 , X 12 , X 13 and X 14 At least one selected from the group consisting of X is not a hydrogen atom 15 , X 16 , X 17 and X 18 In a further preferred embodiment, the ammonium salt compound is represented by the general formula (1) above, and R 11 , R 12 , R 13 and R14 are each independently a methyl group or an ethyl group, and R 21 and R 22 is a methyl group, and R 31 , R 32 , R 33 and R 34 is a hydrogen atom, A is Cl, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, or an SF5 group, and X 11 , X 12 , X 13 and X 14 At least three selected from the group consisting of X are not hydrogen atoms, 15 , X 16 , X 17 and X 18 In a further preferred embodiment, the ammonium salt compound is represented by the general formula (1) above, and R 11 , R 12 , R 13 , R 14 , R 21 and R 22 is a methyl group, and R 31 , R 32 , R 33 and R 34 is a hydrogen atom, A is Cl, and X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently an SF5 group or a cyano group.

[0029] Specific preferred examples of the ammonium salt compound represented by the above formula (1) include the following compounds 1 to 9. The ammonium salt compound represented by the above formula (1) is preferably any one of the following compounds 1 to 9. Among these, compounds 1, 2, 3, 4, 5, 7, 8, or 9 are preferred, compounds 1, 2, 3, 4, 5, 8, or 9 are more preferred, compounds 1, 2, 3, 4, 5, or 9 are even more preferred, compounds 1, 2, 3, 4, or 5 are even more preferred, compounds 2, 4, or 5 are even more preferred, and compound 5 is particularly preferred.

[0030] [ka]

[0031] The ammonium salt compound represented by the above formula (1) can be synthesized based on the knowledge of known synthesis methods, but the synthesis method is not particularly limited. The ammonium salt compound according to one embodiment can be synthesized, for example, by the method described in the Examples, or by changing the raw materials, reaction conditions, etc., in the method described in the Examples, adding or excluding some steps, and / or appropriately combining known synthesis methods. For example, compound 1 can be synthesized by the following reaction. In the following reaction, p-toluenesulfonic acid and HCl are Brønsted acids, and PbO2 is an oxidizing agent.

[0032] [ka]

[0033] The method for confirming the structure of the ammonium salt compound represented by the above formula (1) is not particularly limited, and known methods can be used. The structure of the ammonium salt compound represented by the above formula (1) can be confirmed, for example, by the following method: 1 This can be confirmed by H-NMR or the like.

[0034] <Additives for electrolytic copper plating> Another aspect of the present invention relates to an additive for electrolytic copper plating comprising the ammonium salt compound according to the above aspect. The additive for electrolytic copper plating according to one embodiment comprises the ammonium salt compound represented by formula (1) above. The additive for electrolytic copper plating according to a preferred embodiment comprises the ammonium salt compound according to the above preferred embodiment. The additive for electrolytic copper plating according to one embodiment is preferably an additive for a pretreatment solution for electrolytic copper plating and / or an additive for an electrolytic copper plating solution composition, and is particularly preferably an additive for an electrolytic copper plating solution composition. The ammonium salt compound according to the above aspect is preferably a leveler for electrolytic copper plating. In this specification, a leveler refers to an additive that can improve the flatness of a plating film. In this specification, an electrolytic copper plating solution containing two or more substances is also referred to as an "electrolytic copper plating solution composition." An electrolytic copper plating additive comprising a compound selected from the group consisting of the above compounds 1 to 9 is preferred, an electrolytic copper plating additive comprising a compound selected from the group consisting of compounds 1, 2, 3, 4, 5, 7, 8, and 9 is more preferred, an electrolytic copper plating additive comprising a compound selected from the group consisting of compounds 1, 2, 3, 4, 5, 8, and 9 is even more preferred, an electrolytic copper plating additive comprising a compound selected from the group consisting of compounds 1, 2, 3, 4, 5, and 9 is even more preferred, an electrolytic copper plating additive comprising a compound selected from the group consisting of compounds 1, 2, 3, 4, and 5 is even more preferred, an electrolytic copper plating additive comprising a compound selected from the group consisting of compounds 2, 4, and 5 is even more preferred, an electrolytic copper plating additive comprising a compound selected from the group consisting of compounds 2 and 5 is even more preferred, and an electrolytic copper plating additive comprising compound 5 is particularly preferred.

[0035] The electrolytic copper plating additive according to this embodiment may be an additive for electrolytic copper plating that forms a copper film, or an additive for electrolytic copper plating that forms a copper alloy film, but is preferably an additive for electrolytic copper plating that forms a copper film. The elements other than copper contained in the copper alloy film are not particularly limited. Examples of the elements other than copper contained in the copper alloy film include the elements listed above in the description of the copper alloy film.

[0036] <Electrolytic Copper Plating Solution Composition> Another aspect of the present invention relates to an electrolytic copper plating solution composition comprising a copper ion source and the ammonium salt compound according to the above aspect. An electrolytic copper plating solution composition according to one embodiment comprises: a source of copper ions; The ammonium salt compound according to the above embodiment, at least one component selected from the group consisting of accelerators and inhibitors; It is preferred that the compound contains: An electrolytic copper plating solution composition according to one embodiment comprises: a source of copper ions; The ammonium salt compound according to the above embodiment, at least one component selected from the group consisting of accelerators and inhibitors; At least one component selected from the group consisting of a halide ion source other than the ammonium salt compound represented by formula (1) and an acid; Water and More preferably, it further comprises: The electrolytic copper plating solution compositions according to these embodiments preferably contain an accelerator and a suppressor. The electrolytic copper plating solution compositions according to these embodiments preferably contain a halide ion source, an acid, and water. The electrolytic copper plating solution composition according to one embodiment particularly preferably contains a copper ion source, the ammonium salt compound according to the above aspect, an accelerator, a suppressor, a halide ion source, an acid, and water.

[0037] The electrolytic copper plating solution composition according to this embodiment may be an electrolytic copper plating solution composition for forming a copper film or an electrolytic copper plating solution composition for forming a copper alloy film, but is preferably an electrolytic copper plating solution composition for forming a copper film. The elements other than copper contained in the copper alloy film are not particularly limited. Examples of elements other than copper contained in the copper alloy film include the elements listed above in the description of the copper alloy film.

[0038] (Ammonium salt compounds) An electrolytic copper plating solution composition according to one embodiment contains an ammonium salt compound represented by the above formula (1). An electrolytic copper plating solution composition according to a preferred embodiment contains the ammonium salt compound according to the above preferred embodiment. The compound represented by the above formula (1) may be used alone or in combination of two or more. An electrolytic copper plating solution composition according to one embodiment may contain at least one compound selected from the group consisting of the above compounds 1 to 9. The ammonium salt compound according to the above embodiment is preferably a leveler for electrolytic copper plating. The ammonium salt compound according to the above aspect contained in the electrolytic copper plating solution composition according to one embodiment is preferably at least one compound selected from the group consisting of the above-mentioned compounds 1 to 9, more preferably at least one compound selected from the group consisting of compounds 1, 2, 3, 4, 5, 7, 8, and 9, even more preferably at least one compound selected from the group consisting of compounds 1, 2, 3, 4, 5, 8, and 9, still more preferably at least one compound selected from the group consisting of compounds 1, 2, 3, 4, 5, and 9, still more preferably at least one compound selected from the group consisting of compounds 1, 2, 3, 4, and 5, still more preferably at least one compound selected from the group consisting of compounds 2, 4, and 5, still more preferably at least one compound selected from the group consisting of compound 2 and compound 5, and particularly preferably compound 5.

[0039] The concentration of the ammonium salt compound represented by formula (1) in the electrolytic copper plating solution composition (the mass of the ammonium salt compound represented by formula (1) per liter of electrolytic copper plating solution composition) is not particularly limited, but is preferably 0.1 mg / L to 1000 mg / L, more preferably 1 mg / L to 100 mg / L, even more preferably 5 mg / L to 50 mg / L, and particularly preferably 10 mg / L to 20 mg / L. When the electrolytic copper plating solution composition contains two or more ammonium salt compounds represented by formula (1), the concentration of the ammonium salt compound represented by formula (1) in the electrolytic copper plating solution composition refers to the total amount thereof.

[0040] (copper ion source) The copper ion source is not particularly limited, but examples thereof include copper salts. The copper salt is preferably a copper salt that ionizes to generate copper(II) ions. The copper salt is not particularly limited, but examples thereof include copper sulfate, copper halides, copper acetate, copper nitrate, copper tetrafluoroborate, copper alkylsulfonate, copper arylsulfonate, copper sulfamate, copper perchlorate, copper gluconate, and copper citrate. The copper halides are not particularly limited, but examples thereof include copper chloride. The copper alkylsulfonates are not particularly limited, but examples thereof include copper methanesulfonate, copper ethanesulfonate, and copper propanesulfonate. The copper arylsulfonates are not particularly limited, but examples thereof include copper benzenesulfonate and copper p-toluenesulfonate. The copper ion source may be a single type or a combination of two or more types. The copper ion source may include at least one type selected from the group consisting of the compounds exemplified above. The copper ion source is preferably at least one selected from the group consisting of the compounds exemplified above, more preferably a copper salt that ionizes to generate copper (II) ions, and particularly preferably copper sulfate.

[0041] The concentration of the copper ion source in the electrolytic copper plating solution composition (mass of copper ion source per liter of electrolytic copper plating solution composition) is not particularly limited, but is preferably from 1 g / L to 500 g / L, more preferably from 10 g / L to 400 g / L, even more preferably from 50 g / L to 300 g / L, and particularly preferably from 100 g / L to 200 g / L. When the electrolytic copper plating solution composition contains two or more copper ion sources, the concentration of the copper ion source in the electrolytic copper plating solution composition refers to the total amount thereof.

[0042] (accelerator) The electrolytic copper plating solution composition according to this embodiment may or may not further contain an accelerator, but preferably further contains an accelerator. In this specification, the term "accelerator" refers to an additive capable of increasing the plating rate of electrolytic copper plating. The accelerator is a compound other than the ammonium salt compound represented by formula (1) above. Examples of accelerators include, but are not limited to, thiol compounds and disulfide compounds. Specific examples include, but are not limited to, bis(3-sulfopropyl)disulfide, 3-(benzothiazolyl-2-thio)propylsulfonic acid, 3-mercaptopropane-1-sulfonic acid, N,N-dimethyldithiocarbamic acid (3-sulfopropyl)ester, ethylenedithiodipropylsulfonic acid, bis(p-sulfophenyl)disulfide, and salts thereof. The accelerator may be used alone or in combination with two or more. The accelerator may include at least one selected from the group consisting of the compounds exemplified above. The accelerator is preferably at least one selected from the group consisting of the compounds exemplified above, more preferably a disulfide compound, and particularly preferably bis(3-sulfopropyl) disulfide (also known as bis(3-sulfopropyl) persulfide, abbreviated as SPS).

[0043] The concentration of the accelerator in the electrolytic copper plating solution composition (mass of accelerator per 1 L of electrolytic copper plating solution composition) is not particularly limited, but is preferably 0.1 mg / L to 1000 mg / L, more preferably 0.5 mg / L to 100 mg / L, even more preferably 1 mg / L to 50 mg / L, and particularly preferably 5 mg / L to 15 mg / L. When the electrolytic copper plating solution composition contains two or more accelerators, the concentration of the accelerator in the electrolytic copper plating solution composition refers to the total amount thereof.

[0044] (inhibitor) The electrolytic copper plating solution composition according to this embodiment may or may not further contain a suppressor, but preferably further contains a suppressor. In this specification, the term "suppressor" refers to an additive capable of suppressing the plating rate of electrolytic copper plating. The suppressor is a compound other than the ammonium salt compound represented by formula (1) above. Examples of the suppressor include, but are not limited to, polyalkylene glycol, stearic acid polyglycol ester, oleic acid polyglycol ester, stearyl alcohol polyglycol ether, nonylphenol polyglycol ether, and octanol polyalkylene glycol ether. Examples of the polyalkylene glycol include, but are not limited to, polyethylene glycol, polypropylene glycol, and ethylene glycol-propylene glycol copolymer. The suppressor may be used alone or in combination with two or more. The suppressor may include at least one selected from the group consisting of the compounds exemplified above. The inhibitor is preferably at least one selected from the group consisting of the compounds exemplified above, more preferably polyalkylene glycol, still more preferably at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and ethylene glycol-propylene glycol copolymer, and particularly preferably polyethylene glycol.

[0045] The concentration of the suppressor in the electrolytic copper plating solution composition (mass of suppressor per 1 L of the electrolytic copper plating solution composition) is not particularly limited, but is preferably 0.1 mg / L to 1,000 mg / L, more preferably 100 mg / L to 800 mg / L, even more preferably 200 mg / L to 600 mg / L, and particularly preferably 300 mg / L to 400 mg / L. When the electrolytic copper plating solution composition contains two or more suppressors, the concentration of the suppressor in the electrolytic copper plating solution composition refers to the total amount thereof.

[0046] (Halide ion source) The electrolytic copper plating solution composition according to this embodiment may further contain a halide ion source other than the ammonium salt compound represented by the above formula (1), or may not contain a halide ion source other than the ammonium salt compound represented by the above formula (1). However, it is preferable that the composition further contains a halide ion source other than the ammonium salt compound represented by the above formula (1). In this specification, the "halide ion source other than the ammonium salt compound represented by the above formula (1)" is also simply referred to as the "halide ion source." The halide ion source is not particularly limited, but may be, for example, fluoride ions (F - ) source, chloride ions (Cl - ) source, bromide ion (Br - ) source, iodide ion (I -) sources. The halide ion source may be a single source or a combination of two or more sources. The halide ion source may include at least one source selected from the group consisting of a fluoride ion source, a chloride ion source, a bromide ion source, and an iodide ion source. Examples of halide ion sources include, but are not limited to, hydrogen halides and alkali halides. Examples of hydrogen halides include, but are not limited to, hydrochloric acid (hydrogen chloride) and hydrogen bromide. The hydrogen halides may be a single source or a combination of two or more sources. Examples of alkali halides include, but are not limited to, alkali metal chlorides such as sodium chloride and potassium chloride; alkali metal bromides such as sodium bromide and potassium bromide. The alkali halides may be a single source or a combination of two or more sources. The halide ion source may include at least one source selected from the group consisting of the compounds exemplified above. The halide ion source is preferably at least one selected from the group consisting of a fluoride ion source, a chloride ion source, a bromide ion source, and an iodide ion source, more preferably a chloride ion source, even more preferably at least one selected from the group consisting of hydrochloric acid (hydrogen chloride) and an alkali metal chloride, still more preferably an alkali metal chloride, still more preferably at least one selected from the group consisting of sodium chloride and potassium chloride, and particularly preferably sodium chloride.

[0047] The concentration of the halide ion source other than the ammonium salt compound represented by Formula (1) in the electrolytic copper plating solution composition (the mass of the halide ion source other than the ammonium salt compound represented by Formula (1) per liter of the electrolytic copper plating solution composition) is not particularly limited, but is preferably 0.1 mg / L to 1,000 mg / L, more preferably 1 mg / L to 500 mg / L, even more preferably 10 mg / L to 250 mg / L, and particularly preferably 50 mg / L to 100 mg / L. When the electrolytic copper plating solution composition contains two or more halide ion sources other than the ammonium salt compound represented by Formula (1), the concentration of the halide ion source other than the ammonium salt compound represented by Formula (1) in the electrolytic copper plating solution composition refers to the total amount thereof.

[0048] (acid) The electrolytic copper plating solution composition according to this embodiment may or may not contain an acid, but preferably contains an acid. Examples of the acid include, but are not limited to, inorganic acids, alkanesulfonic acids, substituted or unsubstituted alkanesulfonic acids, and substituted or unsubstituted arylsulfonic acids. Examples of the inorganic acid include, but are not limited to, acetic acid, nitric acid, sulfuric acid, hydrochloric acid, fluoroboric acid, hydrobromic acid, perchloric acid, chromic acid, phosphoric acid, and sulfamic acid. Examples of the substituted or unsubstituted alkanesulfonic acids include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and trifluoromethanesulfonic acid. Examples of the substituted or unsubstituted arylsulfonic acids include, but are not limited to, benzenesulfonic acid and p-toluenesulfonic acid. The acid may be used alone or in combination. The acid may include at least one selected from the group consisting of the compounds exemplified above. The acid is preferably an inorganic acid, and particularly preferably sulfuric acid.

[0049] The concentration of the acid in the electrolytic copper plating solution composition (mass of acid per 1 L of the electrolytic copper plating solution composition) is not particularly limited, but is preferably 1 g / L to 500 g / L, more preferably 10 g / L to 400 g / L, even more preferably 50 g / L to 300 g / L, and particularly preferably 100 g / L to 200 g / L. When the electrolytic copper plating solution composition contains two or more acids, the concentration of the acid in the electrolytic copper plating solution composition refers to the total amount thereof.

[0050] (water) The electrolytic copper plating solution composition according to this embodiment may or may not further contain water, but preferably further contains water.

[0051] (Metal ion source other than copper ion source) The electrolytic copper plating solution composition according to this embodiment may further contain a metal ion source other than the copper ion source, or may not contain a metal ion source other than the copper ion source. In this specification, the term "metal ion source other than the copper ion source" refers to a metal ion source other than the copper ion source, and does not fall under the category of the ammonium salt compound represented by Formula (1), copper ion source, halide ion source, accelerator, inhibitor, or acid. The metal ion source other than copper is preferably used in combination with the copper ion source when forming a copper alloy film. The metal ion source other than the copper ion source is not particularly limited, but examples include metal ion sources of the metal elements listed above in the description of the copper alloy film. In one embodiment, the metal ion source other than the copper ion source includes, for example, a tin ion source such as a tin salt. The tin salt is not particularly limited, but examples include tin sulfate, tin alkane sulfonate, and tin aryl sulfonate. The tin ion source may be used alone or in combination. The metal ion source other than the copper ion source may be used alone or in combination. The concentration of the metal ion source other than the copper ion source in the electrolytic copper plating solution composition is not particularly limited, and may be any concentration that allows a desired plating film to be obtained.

[0052] (Other ingredients) The electrolytic copper plating solution composition according to this embodiment may further contain other components in addition to the components listed above, or may not further contain other components.

[0053] (Method of producing electrolytic copper plating solution composition) The method for producing the electrolytic copper plating solution composition according to this embodiment is not particularly limited. The electrolytic copper plating solution composition according to one embodiment can be produced by mixing the components in any order. A preferred production method includes, for example, a method comprising first adding one or more inorganic components to a plating bath, followed by adding one or more organic components to the plating bath. An example of a production method includes mixing multiple inorganic components, including an inorganic copper ion source, an inorganic acid, an inorganic halide ion source other than the ammonium salt compound represented by Formula (1), and water, and then adding multiple organic components, including the ammonium salt compound represented by Formula (1), an organic accelerator, and an organic inhibitor, to the resulting mixture. A preferred example of the production method includes mixing an inorganic copper ion source, an inorganic acid, an inorganic halide ion source other than the ammonium salt compound represented by formula (1), and water, and then adding the ammonium salt compound represented by formula (1), an organic accelerator, and an organic inhibitor to the resulting mixture. The mixing method and conditions are not particularly limited.

[0054] <Electrolytic copper plating method> Another aspect of the present invention relates to an electrolytic copper plating method comprising obtaining a plated article using the electrolytic copper plating solution composition according to the above aspect. The electrolytic copper plating method according to a preferred embodiment comprises forming a via conductor and a wiring pattern on the plated article using the electrolytic copper plating solution composition according to the above aspect. In the electrolytic copper plating method according to this aspect, particularly in the electrolytic copper plating method according to the preferred embodiment, it is preferable to use the electrolytic copper plating solution composition according to the above preferred embodiment.

[0055] The electrolytic copper plating method according to this embodiment may be an electrolytic copper plating method for forming a copper film or an electrolytic copper plating method for forming a copper alloy film, but is preferably an electrolytic copper plating method for forming a copper film. The elements other than copper contained in the copper alloy film are not particularly limited. Examples of elements other than copper contained in the copper alloy film include the elements listed above in the description of the copper alloy film.

[0056] The electrolytic copper plating method is not particularly limited, but is preferably a method comprising contacting an object to be plated with the electrolytic copper plating solution composition according to the above embodiment and applying a current to electroplating copper or a copper alloy onto the object to be plated. The electrolytic copper plating method is not particularly limited, but is more preferably a method comprising contacting an object to be plated with the electrolytic copper plating solution composition according to the above embodiment and applying a current to electroplating copper onto the object to be plated. The method for contacting the object to be plated with the electrolytic copper plating solution composition according to the above embodiment is not particularly limited, but examples include a method of immersing the object to be plated in the electrolytic copper plating solution composition.

[0057] Before plating, the object to be plated may be subjected to cleaning, rinsing and / or pretreatment, etc. Pretreatment is not particularly limited, but examples thereof include acid activation treatment.

[0058] During the plating process, the object to be plated and at least one anode are connected to a current or voltage source. Furthermore, during the plating process, the object to be plated and at least one anode are arranged so as to contact the electrolytic copper plating solution composition according to the above embodiment. Generally, the object to be plated functions as a cathode. The anode may be a soluble anode, such as a copper anode, and / or an insoluble anode. When a current is applied, copper or a copper alloy (preferably copper) is deposited on the object to be plated (at least on a portion of the object to be plated). It is preferable that vias and / or trenches in the object to be plated are filled, thereby forming via conductors and a wiring pattern on the object to be plated. During the plating process, the electrolytic copper plating solution composition is preferably stirred. The stirring method is not particularly limited, and known stirring methods can be used. Examples of stirring methods include, but are not limited to, air sparging, stirring of the workpiece, and collision. The cathode current density is not particularly limited. An example of a cathode current density is 0.05 A / dm 2 More than 10A / dm 2 The following may be mentioned, but the cathode current density is not limited to values ​​within this range. The temperature of the electrolytic copper plating solution composition (the temperature of the plating bath) is not particularly limited, but is preferably in the range of 10°C or more and 65°C or less, more preferably in the range of 10°C or more and 35°C or less, and even more preferably in the range of 15°C or more and 30°C or less. The plating time is not particularly limited, but is preferably in the range of 1 minute or more and 100 hours or less, more preferably in the range of 5 minutes or more and 10 hours or less, and even more preferably in the range of 10 minutes or more and 1 hour or less.

[0059] The object to be plated is not particularly limited. The object to be plated is preferably a substrate, more preferably a substrate having a concave-convex structure such as vias and / or trenches, and even more preferably a substrate having vias. Specific examples of the concave-convex structure are not particularly limited, but include, for example, trenches, blind microvias, through-silicon vias, through-holes, and through-glass vias. The substrate is preferably a substrate selected from the group consisting of printed circuit boards, IC substrates, semiconductor wafers, ceramics, and glass substrates. The substrate may include a conductor layer. Examples of the conductor layer are not particularly limited, but include, for example, a copper film (e.g., a copper plating film) and a copper plate. The substrate may include a resin insulating film. Examples of the resin insulating film are not particularly limited, but include, for example, a polyimide film. The substrate may include a metal seed layer. Examples of the metal seed layer are not particularly limited, but include, for example, a copper seed layer. The constituent material of the substrate is not particularly limited, but preferably includes, for example, a resin, ceramics, glass, or silicon.

[0060] According to each aspect of the present invention described above, there is provided a means for forming a plating film that has excellent flatness and excellent filling ability in recesses of a plating target. According to a preferred embodiment, there is provided a means for forming a plating film that has excellent flatness and excellent filling ability in vias and / or trenches. According to a more preferred embodiment, there is provided a means for forming a plating film that has excellent flatness and excellent filling ability in vias.

[0061] Although the embodiments of the present invention have been described in detail, it is clear that this is for illustrative and exemplary purposes only and not for limitation, and that the scope of the present invention should be interpreted by the appended claims.

[0062] The present invention encompasses the following aspects and configurations: [1] An ammonium salt compound represented by the following formula (1):

[0063] [ka]

[0064] In the above formula (1), R 11 , R 12 , R 13 , R 14 , R 21 and R 22 are each independently a methyl group or an ethyl group, R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a cyano group, a nitro group, a fluoro group, a chloro group, a bromo group, an iodo group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)CH3 group, a C(O)OCH3 group, a C(O)NH2 group, or a SO2CH3 group; A is F, Cl, Br or I; X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)CH3 group, a C(O)OCH3 group, a C(O)NH2 group, or a SO2CH3 group; X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 at least one selected from the group consisting of is not a hydrogen atom; [2] X 11 , the X 12 , the X 13 , the X 14 , the X 15 , the X 16 , the X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, an OCF3 group, an SF5 group, a C(O)NH2 group, or a SO2CH3 group, X11 , the X 12 , the X 13 , the X 14 , the X 15 , the X 16 , the X 17 and X 18 At least one selected from the group consisting of is not a hydrogen atom, the ammonium salt compound according to [1] above; [3] The ammonium salt compound according to [1] or [2], wherein A is Cl or Br; [4] X 11 , the X 12 , the X 13 , the X 14 , the X 15 , the X 16 , the X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, a SF5 group, or a SO2CH3 group, X 11 , the X 12 , the X 13 , the X 14 , the X 15 , the X 16 , the X 17 and X 18 At least one selected from the group consisting of is not a hydrogen atom, The ammonium salt compound according to any one of [1] to [3] above; [5] X 11 , the X 12 , the X 13 , the X 14 , the X 15 , the X 16 , the X 17 and X 18 are each independently a hydrogen atom, a cyano group, a C2F5 group, or an SF5 group, X 11 , the X 12 , the X 13 and X 14 At least three selected from the group consisting of X are not hydrogen atoms, 15 , the X16 , the X 17 and X 18 the ammonium salt compound according to any one of [1] to [4] above, wherein at least three selected from the group consisting of: [6] R 11 , the R 12 , the R 13 and the R 14 The ammonium salt compound according to any one of [1] to [5] above, wherein is a methyl group; [7] R 21 and the R 22 The ammonium salt compound according to any one of [1] to [6] above, wherein is a methyl group; [8] R 31 , the R 32 , the R 33 and the R 34 is a hydrogen atom; the ammonium salt compound according to any one of [1] to [7] above; [9] The ammonium salt compound according to [1] above, which is any one of compounds 1 to 9 above;

[10] An additive for electrolytic copper plating comprising the ammonium salt compound according to any one of [1] to [9] above;

[11] a copper ion source; The ammonium salt compound according to any one of [1] to [9] above, an electrolytic copper plating solution composition comprising:

[12] The electrolytic copper plating solution composition according to

[11] above, further comprising at least one component selected from the group consisting of accelerators and suppressors;

[13] An electrolytic copper plating method, comprising forming a via conductor and a wiring pattern on a plated object using the electrolytic copper plating solution composition according to

[11] or

[12] above. [Example]

[0065] The effects of the present invention will be explained using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. Furthermore, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively.

[0066] <Synthesis of ammonium salt compounds> (Compound 1) 4-(Dimethylamino)benzaldehyde (Compound R1-2 below) (10 mmol), 2-(dimethylamino)benzonitrile (Compound R1-1 below) (40 mmol), p-toluenesulfonic acid (10 mmol), and benzene (20 mL) were placed in a flask equipped with a condenser and reacted at 100 °C for 9 hours. The reaction mixture was diluted with benzene (40 mL) and washed with a 10% sodium bicarbonate solution, followed by saturated saline. After removing the solvent from the resulting mixture, the residue was purified by silica gel column chromatography (eluent: a mixture of hexane and ethyl acetate, hexane:ethyl acetate = 10:1 (volume ratio)) to obtain Compound P1. The yield of Compound P1 in this reaction was 95%, rounded to one decimal place.

[0067] The resulting compound P1 (0.5 mmol) was dissolved in 3 mL of ion-exchanged water, and PbO2 (0.65 mmol) and 15 drops of concentrated HCl (12 N (37% by mass) aqueous HCl solution) were added dropwise. The mixture was stirred overnight at room temperature. The resulting reaction solution was extracted with a mixture of methanol (30 mL), concentrated HCl (12 N (37% by mass) aqueous HCl solution) (3.78 mL), and methylene chloride (20 mL). The extract was concentrated, and the concentrate was purified by silica gel chromatography (eluent: a mixture of methylene chloride and methanol, methylene chloride:methanol = 9:1 (volume ratio)) to obtain compound 1. The yield of compound 1 in this reaction was 100% when rounded to one decimal place.

[0068] [ka]

[0069] The structure of the obtained compound 1 was confirmed by nuclear magnetic resonance ( 1 Identification by H-NMR: 1 H-NMR (300 MHz, CDCl3) σ= 8.10 (s, 1H), 7.29 (s, 1H), 7.19-7.12 (m, 3H), 6.80-6.74 (m, 2H), 6.67-6.60 (m, 1H), 6.20-6.13 (m, 1H), 5.96-5.87 (m, 1H), 3.02 (s, 6H), 3.01 (s, 6H), 0.90 (s, 6H) ppm.

[0070] (Compound 2) Compound 2 was obtained by the same production method as that of Compound 1 in Example 1, except that 2-(dimethylamino)benzonitrile (40 mmol) was replaced with an equimolar amount of (dimethylamino)benzene-1,2,4,5-tetracarbonitrile (Compound R2-1 below).

[0071] [ka]

[0072] The structure of the obtained compound 2 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1 H-NMR (300 MHz, CDCl3) σ= 7.21-7.13 (m, 2H), 6.84-6.73 (m, 2H), 3.03 (s, 6H), 3.00 (s, 6H), 0.94 (s, 6H) ppm.

[0073] (Compound 3) Compound 3 was obtained in the same manner as Compound 1 in Example 1, except that 2-(dimethylamino)benzonitrile (40 mmol) was replaced with an equimolar amount of N,N-dimethyl-2,6-bis(methylsulfonyl)aniline (Compound R3-1 below), and PbO (0.65 mmol) and 15 drops of concentrated HCl (12 N (concentration 37% by mass) aqueous HCl solution) were replaced with PbO (0.65 mmol) and 15 drops of aqueous HBr solution (concentration 47.0 to 49.0% by mass).

[0074] [ka]

[0075] The structure of the obtained compound 3 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1 H-NMR (300 MHz, CDCl3) σ= 8.65 (s, 2H), 7.96 (s, 2H), 7.20-7.11 (m, 2H), 6.84-6.74 (m, 2H), 3.32 (s, 6H), 3.02 (s, 6H), 3.01 (s, 6H), 2.84 (s, 6H), 0.90 (s, 6H) ppm.

[0076] (Compound 4) Compound 4 was obtained by the same production method as that of Compound 1 in Example 1, except that 2-(dimethylamino)benzonitrile (40 mmol) was replaced with an equimolar amount of N,N-diethyl-2,3,6-tris(perfluoroethyl)aniline (Compound R4-1 below).

[0077] [ka]

[0078] The structure of the obtained compound 4 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1H-NMR (300 MHz, CDCl3) σ= 7.81 (s, 1H), 7.21 (s, 1H), 7.19-7.12 (m, 2H), 6.80-6.70 (m, 2H), 4.07 (q, J = 7.1 Hz, 4H), 3.40 (q, J = 7.0 Hz, 4H), 1.41 (t, J = 7.3 Hz, 6H), 1.12 (t, J = 7.3 Hz, 6H), 0.93 (s, 6H) ppm.

[0079] (Compound 5) 2-(Dimethylamino)benzonitrile (40 mmol) was dissolved in an equimolar amount of N,N-dimethyl-2,3,5,6-tetrakis(pentafluoro-λ 6 Compound 5 was obtained in the same manner as in Example 1, except that the compound used was (-sulfanyl)aniline (compound R5-1 below).

[0080] [ka]

[0081] The structure of the obtained compound 5 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1 H-NMR (300 MHz, CDCl3) σ= 7.20-7.12 (m, 2H), 6.86-6.75 (m, 2H), 3.02 (s, 6H), 3.00 (s, 6H), 0.92 (s, 6H) ppm.

[0082] (Compound 6) Compound 6 was obtained in the same manner as Compound 1 in Example 1, except that 2-(dimethylamino)benzonitrile (40 mmol) was replaced with an equimolar amount of methyl 2-(dimethylamino)benzoate (Compound R6-1 below), and PbO (0.65 mmol) and 15 drops of concentrated HCl (12 N (concentration 37 mass%) aqueous HCl solution) were replaced with PbO (0.65 mmol) and 15 drops of aqueous HF solution (concentration 46.0 to 48.0 mass%).

[0083] [ka]

[0084] The structure of the obtained compound 6 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1 H-NMR (300 MHz, CDCl3) σ= 8.50 (s, 1H), 7.37 (s, 1H), 7.24-7.07(m, 3H), 6.89-6.78 (m, 3H), 6.20-6.13 (m, 1H), 5.88-5.70 (m, 1H), 3.95 (s, 3H), 3.71 (s, 3H), 3.00 (s, 6H), 2.93 (s, 6H), 0.88 (s, 6H) ppm.

[0085] (Compound 7) Compound 7 was obtained by the same production method as that of Compound 1 in Example 1, except that 2-(dimethylamino)benzonitrile (40 mmol) was replaced with an equimolar amount of 1,1-(2-(dimethylamino)-1,3-phenylene)bis(ethan-1-one) (Compound R7-1 below), and PbO2 (0.65 mmol) and 15 drops of concentrated HCl (12 N (concentration 37 mass%) aqueous HCl solution) were added dropwise, but instead PbO2 (0.65 mmol) and 15 drops of aqueous HI solution (concentration 55.0 to 58.0 mass%) were used.

[0086] [ka]

[0087] The structure of the obtained compound 7 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1 H-NMR (300 MHz, CDCl3) σ= 8.40 (s, 2H), 7.24 (s, 2H), 7.21-7.10 (m, 2H), 6.79-6.66 (m, 2H), 3.02 (s, 6H), 3.00 (s, 6H), 2.50 (s, 6H), 2.37 (s, 6H) 0.88 (s, 6H) ppm.

[0088] (Compound 8) Compound 8 was obtained by the same production method as that of Compound 1 in Example 1, except that 2-(dimethylamino)benzonitrile (40 mmol) was changed to an equimolar amount of 3-(dimethylamino)benzene-1,2,4-tricarboxyamine (Compound R8-1 below), and 4-(dimethylamino)benzaldehyde (10 mmol) was changed to an equimolar amount of 4-(diethylamino)benzaldehyde (Compound R8-2 below).

[0089] [ka]

[0090] The structure of the obtained compound 8 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1 H-NMR (300 MHz, CDCl3) σ= 8.41 (s, 1H), 7.83-8.02 (m, 12H), 7.27-7.20 (m, 3H), 6.83-6.72 (m, 2H), 3.40 (q, J = 7.0 Hz, 4H), 3.00 (s, 6H), 1.12 (t, J = 7.1 Hz, 6H), 0.90 (s, 6H) ppm.

[0091] (Compound 9) Compound 9 was obtained by the same production method as that of Compound 1 in Example 1, except that 2-(dimethylamino)benzonitrile (40 mmol) was replaced with an equimolar amount of N,N-dimethyl-2,3,5,6-tetrakis(trifluoromethoxy)aniline (Compound R9-1 below).

[0092] [ka]

[0093] The structure of the obtained compound 9 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1H-NMR (300 MHz, CDCl3) σ= 7.25-7.12 (m, 2H), 6.81-6.68 (m, 2H), 3.00 (s, 6H), 2.94 (s, 6H), 0.93 (s, 6H) ppm.

[0094] (Compound C1) Crystal violet manufactured by Tokyo Chemical Industry Co., Ltd. was used as compound C1. Compound C1 has a structure represented by the following formula.

[0095] [ka]

[0096] (Compound C2) Compound C2 was obtained by the same production method as that for Compound 1 in Example 1, except that 2-(dimethylamino)benzonitrile (40 mmol) was replaced with an equimolar amount of N,N-dimethyl-2-(trifluoromethyl)aniline (Compound RC2-1 below).

[0097] [ka]

[0098] The structure of the obtained compound C2 was confirmed by nuclear magnetic resonance spectroscopy ( 1 Identification by H-NMR: 1 H-NMR (300 MHz, CDCl3) σ= 8.10 (s, 1H), 7.29 (s, 1H), 7.23-7.09(m, 2H), 6.85-6.76 (m, 2H), 6.65-6.60 (m, 1H),6.21-6.18 (m, 1H), 5.89-5.87 (m, 1H), 3.02 (s, 6H), 3.01 (s, 6H), 0.90 (s, 6H) ppm.

[0099] <Production of Electrolytic Copper Plating Solution Composition> (Electrolytic copper plating solution composition 1) Electrolytic copper plating solution composition 1 was produced by mixing the components so that the concentrations of each component per 1 L of the produced electrolytic copper plating solution composition were as follows: More specifically, copper sulfate, sulfuric acid, sodium chloride, and water were mixed together, and to the resulting mixture, the above-mentioned compound 1, bis(3-sulfopropyl) disulfide (also known as bis(3-sulfopropyl) persulfide, abbreviated as SPS), and polyethylene glycol were added, thereby producing electrolytic copper plating solution composition 1.

[0100] (Formulation of Electrolytic Copper Plating Solution Composition 1) Compound 1 concentration: 10 mg / L Copper sulfate concentration: 100g / L Sulfuric acid concentration: 100g / L, Concentration of bis(3-sulfopropyl) disulfide: 5 mg / L, Polyethylene glycol concentration: 300 mg / L, Sodium chloride concentration: 50 mg / L, water.

[0101] (Electrolytic Copper Plating Solution Compositions 2 to 9, C1 and C2) In addition, electrolytic copper plating solution compositions 2 to 9, C1 and C2 were obtained in the same manner as the electrolytic copper plating solution composition 1, except that compounds 2 to 9, C1 and C2 were used instead of compound 1.

[0102] <Evaluation> (Electrolytic copper plating process) The substrate to be plated described below was subjected to acid degreasing at 45°C for 3 minutes, washed with warm water at 45°C for 30 seconds, rinsed with water at 25°C for 30 seconds, and then subjected to an acid activation treatment by immersing it in a 10% by mass aqueous sulfuric acid solution at 25°C for 1 minute.

[0103] Next, using electrolytic copper plating solution compositions 1 to 9, C1, and C2, respectively, the acid-activated substrate and anode (manufactured by Yamamoto Plating Tester Co., Ltd., material: titanium iridium, size: length 150 mm, width 50 mm, thickness 2 mm) were immersed in the electrolytic copper plating bath, each connected to a power source, and plating was performed under the plating conditions described below. During the plating process, the electrolytic copper plating bath was agitated by bubbling air. The plated substrate was then rinsed with water at 25°C for 30 seconds and dried to produce substrates with plating films.

[0104] <Plating conditions> Cathode current density: 5.0A / dm 2 Plating bath: Each electrolytic copper plating solution composition obtained above Bath temperature: 30℃ Plating time: 30 minutes Plated object: A substrate with a structure in which a via with a via opening diameter of 90 μm and a depth of 35 μm is formed in a resin insulating film (polyimide film) on a conductor layer (copper film), and a copper sputtered film (0.1 μm) is formed as a seed layer over the entire surface.

[0105] (Via conductor recess amount) The substrate with the plated film obtained above was polished to cut a cross section so that the center of the via was included in the cross section. Using the cross-section method, which is a method of observing a cross section with a scanning electron microscope (SEM), the plating height on the periphery of the via of the plated object and the plating height at the lowest point on the via bottom of the plated object were measured. From the obtained measurement results, the via conductor recession amount (the value obtained by subtracting the plating height at the lowest point on the via bottom of the plated object from the plating height on the periphery of the via of the plated object) was calculated. Figure 1 shows a schematic diagram to explain the via conductor recession amount. In Figure 1, 1 indicates the portion of the substrate with the plated film above the conductor layer. In Figure 1, 2 represents the conductor layer, 3 the resin insulating film, 4 the seed layer, 5 the via, 6 the plating film, 7 the measurement point of the plating height on the via bottom, 8 the measurement point of the via height on the via periphery, 9 the plating height at the lowest point on the via bottom, 10 the plating height on the via periphery, and 11 the amount of via conductor recession. The evaluation results are shown in Table 1.

[0106] <Evaluation Criteria> ◎: The via conductor recess is 2 μm or less. ◯: The via conductor recess amount is more than 2 μm and 5 μm or less. ×: The recession amount of the via conductor exceeds 5 μm.

[0107] [Table 1]

[0108] The results in Table 1 confirm that the use of the ammonium salt compounds of the examples reduces the amount of recession in the via conductor, provides excellent via filling, and forms a plating film with high flatness. On the other hand, the ammonium salt compounds of the comparative examples did not provide sufficient via filling, and did not provide a plating film with high flatness. [Explanation of symbols]

[0109] 1. A portion of a substrate having a plating film above a conductor layer, 2 conductor layers, 3. Resin insulating film, 4 seed layer, 5 vias, 6 plating film, 7 Measurement point of plating height on the via bottom, 8 Via height measurement points on the periphery of the via, 9 The plating height at the lowest point on the via bottom, 10 plating height on the via periphery, 11 Via conductor recess amount.

Claims

1. An ammonium salt compound represented by the following formula (1): 【Chemistry 1】 In the above formula (1), R １１ , R １２ , R １３ , R １４ , R ２１ and R ２２ are each independently a methyl group or an ethyl group, R ３１ , R ３２ , R ３３ and R ３４ are each independently a hydrogen atom, a cyano group, a nitro group, a fluoro group, a chloro group, a bromo group, an iodo group, C ２ F ５ Group, OCF ３ Base, SF ５ group, C(O)CH ３ group, C(O)OCH ３ group, C(O)NH ２ group or SO ２ CH ３ It is the basis, A is F, Cl, Br or I; X １１ , X １２ , X １３ , X １４ , X １５ , X １６ , X １７ and X １８ are each independently a hydrogen atom, a cyano group, or C ２ F ５ Group, OCF ３ Base, SF ５ group, C(O)CH ３ group, C(O)OCH ３ group, C(O)NH ２ group or SO ２ CH ３ It is the basis, X １１ , X １２ , X １３ , X １４ , X １５ , X １６ , X １７ and X １８ At least one selected from the group consisting of is not a hydrogen atom.

2. The X １１ , the X １２ , the X １３ , the X １４ , the X １５ , the X １６ , the X １７ and the X １８ are each independently a hydrogen atom, a cyano group, or C ２ F ５ Group, OCF ３ Base, SF ５ group, C(O)NH ２ group or SO ２ CH ３ It is the basis, The X １１ , the X １２ , the X １３ , the X １４ , the X １５ , the X １６ , the X １７ and the X １８ At least one selected from the group consisting of is not a hydrogen atom, The ammonium salt compound of claim 1.

3. 2. The ammonium salt compound of claim 1, wherein A is Cl or Br.

4. The X １１ , the X １２ , the X １３ , the X １４ , the X １５ , the X １６ , the X １７ and the X １８ are each independently a hydrogen atom, a cyano group, or C ２ F ５ Base, SF ５ group or SO ２ CH ３ It is the basis, The X １１ , the X １２ , the X １３ , the X １４ , the X １５ , the X １６ , the X １７ and the X １８ At least one selected from the group consisting of is not a hydrogen atom, The ammonium salt compound of claim 1.

5. The X １１ , the X １２ , the X １３ , the X １４ , the X １５ , the X １６ , the X １７ and the X １８ are each independently a hydrogen atom, a cyano group, or C ２ F ５ group or SF ５ It is the basis, The X １１ , the X １２ , the X １３ and the X １４ At least three selected from the group consisting of X are not hydrogen atoms, １５ , the X １６ , the X １７ and the X １８ 2. The ammonium salt compound of claim 1, wherein at least three selected from the group consisting of:

6. The R １１ , the R １２ , the R １３ and the R １４ The ammonium salt compound according to claim 1 , wherein is a methyl group.

7. The R ２１ and the R ２２ The ammonium salt compound according to claim 1 , wherein is a methyl group.

8. The R ３１ , the R ３２ , the R ３３ and the R ３４ The ammonium salt compound according to claim 1 , wherein is a hydrogen atom.

9. The ammonium salt compound according to claim 1, which is any one of the following compounds 1 to 9: 【Chemistry 2】

10. An additive for electrolytic copper plating comprising the ammonium salt compound according to any one of claims 1 to 9.

11. a source of copper ions; The ammonium salt compound according to any one of claims 1 to 9, 1. An electrolytic copper plating solution composition comprising:

12. 12. The electrolytic copper plating solution composition according to claim 11, further comprising at least one component selected from the group consisting of accelerators and suppressors.

13. An electrolytic copper plating method comprising forming a via conductor and a wiring pattern on a plated object using the electrolytic copper plating solution composition according to claim 11.

14. An electrolytic copper plating method comprising forming a via conductor and a wiring pattern on a plated object using the electrolytic copper plating solution composition according to claim 12.

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