Copper electrodeposition composition containing polyaminoamide-type leveling agent

Abstract

The present invention relates to a compound comprising copper ions, an acid and a compound of formula L1 [BA-B'-Z] n [YZ] m (L1) and at least one polyaminoamide containing a group represented by the formula:

Description

[Technical field]

[0001] The present invention relates to copper electroplating compositions containing polyaminoamide-type leveling agents, methods of using same, and methods of copper electrodeposition. [Background technology]

[0002] Bumps are formed on the surface of a wafer containing integrated circuits such as LSIs. Such bumps form part of the wiring of the integrated circuit and function as terminals for connection to the circuitry of an external package substrate (or circuit board). The bumps are typically arranged along the periphery of the semiconductor chip (or die) and are connected to the external circuitry by gold wires according to the wire bonding method or by leads according to the TAB method.

[0003] With the recent progress towards higher integration and density of semiconductor devices, the number of bumps for connection to external circuits has increased, creating a need to form bumps over the entire area of ​​the surface of the semiconductor chip. Furthermore, the need for closer wiring spacing has led to the use of a method that involves flipping a semiconductor chip having a large number of bumps formed on its surface and connecting the bumps directly to a circuit board (flip-chip method).

[0004] Electroplating is widely adopted as a method for forming bumps. The process of forming bumps on the surface of a wafer having integrated circuits is one of the most important processes in the final stage of manufacturing a semiconductor device. In this regard, it should be noted that integrated circuits are formed on the wafer by many manufacturing processes. Therefore, the bump formation process performed on a wafer that has passed through all the preceding processes requires a very high reliability. With the progress towards smaller semiconductor chips, the number of bumps for connecting to external circuits is increasing, and the bumps themselves are becoming smaller. Therefore, there is a need to improve the positioning accuracy in bonding semiconductor chips to circuit boards such as package boards. Furthermore, there is a strong demand for no defects in the bonding process in which the bumps melt and solidify.

[0005] Typically, copper bumps are formed on a seed layer of a wafer that electrically connects to an integrated circuit. A resist having openings is formed on the seed layer, and copper is deposited by copper electroplating on the exposed surface of the seed layer in the openings, thereby forming the copper bumps. The seed layer includes a barrier layer, for example, titanium, to prevent copper from diffusing into the insulator. After the resist openings are filled with copper, the resist is removed and the copper bumps are then reflowed.

[0006] The need to fit more functional units into ever smaller spaces drives the integrated circuit industry to bump processes for package connections. The second driving force is to maximize the amount of I / O connections in a given area. With the reduction of bump diameter and inter-bump distance, the connection density can be increased. These arrays are realized by copper bumps or micropillars plated with tin or tin alloy solder caps. To ensure that all bumps make contact across the entire wafer, uniform deposition height is required in addition to void-free deposition and reflow. Furthermore, other packaging techniques such as fan-out technology require redistribution layers (RDLs) made of copper. These RDLs require uniform plating at various line spacings and on pads with various dimensions.

[0007] To achieve this uniform deposition, so-called levellers may be used. In the literature, a variety of different levelling compounds have been described for other electroplating applications. In most cases, the levelling compounds are N-containing, optionally substituted and / or quaternized polymers, such as polyethyleneimine, polyglycine, poly(allylamine), polyaniline (sulfonated), polyurea, polyacrylamide, poly(melamine-co-formaldehyde), reaction products of amines with epichlorohydrin, reaction products of amines, epichlorohydrin and polyalkylene oxides, reaction products of amines with polyepoxides, polyvinylpyridines, polyvinylimidazoles, polyvinylpyrrolidones, polyalkoxylated polyamides and polyalkanolamines.

[0008] US2012 / 292193A discloses leveling agents including polyaminoamides, alkoxylated polyaminoamides, functionalized polyaminoamides, and functionalized and alkoxylated polyaminoamides.US2014 / 097092A discloses aromatic PAAs for use in the application of copper electrodeposition of through-silicon electrodes.WO2014 / 072885 describes polyaminoamides obtainable by reacting at least one diamine with at least one N,N'-bisacrylamide.

[0009] US6425996B1 discloses leveling agents comprising reaction products of polyaminoamides with epihalohydrins, dihalohydrins and 1-halogen-2,3-propanediols, respectively.

[0010] US 2016 / 0076160 A1 discloses an electrolytic plating composition useful for filling submicron features of semiconductor integrated circuit devices or through silicon vias, which contains a leveller comprising a reaction product of an aliphatic di(t-amine) and an alkylating agent.

[0011] Unpublished International Patent Application No. PCT / EP2021 / 057522 discloses copper electroplating compositions comprising a polyaminoamide-type leveling agent preparable from a diamine containing tertiary and primary or secondary amino groups, a diacid and a coupling agent.

[0012] There remains a need in the electronics industry for acid copper electroplating baths that produce bump deposits with good morphology, especially low roughness, combined with improved height uniformity, also known as within-die coplanarity (COP).

[0013] In alkaline zinc or zinc alloys, such as ZnFeCo alloys, cationic polymers specific to the electrodeposition composition are used to improve the luster and uniformity of the alloy part. For example, one of these cationic polymers, disclosed in US 5,435,898, has the formula [ka] The MIRAPOL AD-1. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] US2012 / 292193A [Patent Document 2] US2014 / 097092A [Patent Document 3] WO2014 / 072885 [Patent Document 4] US6425996B1 [Patent Document 5] US2016 / 0076160A1 [Patent Document 6] International Patent Application No. PCT / EP2021 / 057522 [Patent Document 7] US5435898 Summary of the Invention [Problem to be solved by the invention]

[0015] It is an object of the present invention to provide copper electroplating compositions, particularly acid copper electroplating compositions, that provide copper deposits exhibiting good morphology, particularly low surface roughness, and that are capable of filling recessed features on the micrometer scale without substantial formation of defects such as, but not limited to, voids. It is a further object of the present invention to provide copper electroplating baths that provide uniform, planar copper deposits, particularly in recessed features such as bumps that are 500 nanometers to 500 micrometers wide.

[0016] Surprisingly, it has been found that the use of certain cationic aminoamide polymers exhibits surprising leveling properties in copper bump and RDL electroplating. [Means for solving the problem]

[0017] Thus, the present invention relates to a method for preparing a compound having a copper ion, an acid and a compound represented by the formula L1 [BA-B'-Z] n [YZ] m (L1) and at least one polyaminoamide containing a group represented by During the ceremony, B and B' are the same or different, preferably the same, and are represented by the formula L2a

[0018] [ka] or formula L2b [ka] is an amino acid fragment represented by A is the formula L3a [ka] or formula L3b [ka] is a diamine fragment independently selected from D L1 teeth, (a) C1-C optionally substituted with an amino group or interrupted by a double bond or an imino group 20 -Alkanediyl, (b) Formula L2a -(D L10 -O-] o D L10 - (L2c) An ether or polyether group represented by the formula: is a divalent group selected from D L2 teeth, (a) optionally one or more NR L10 or one or more, preferably one or two, groups NR L10 R L11 OR L10 Optionally substituted linear, branched or cyclic C1-C 20 Alkanediyl, or (b)-D L13 -Ar L13 -D L13 -or (c) Formula L2c -(D L10 -O-] o D L10 - (L2c) An ether or polyether group represented by the formula: is a divalent group selected from D L10 is selected from linear or branched C1-C6-alkanediyl, preferably ethanediyl or propanediyl, D L13 is selected from C1-C6-alkanediyl, preferably methanediyl or ethanediyl, Ar L13 is C6~C 10 an aromatic moiety, preferably p-phenylene; D L11 , D L12 teeth, (a) independently selected from linear or branched C1-C6 alkanediyl, or (b) both are part of a 5- or 6-membered aromatic heterocyclic ring system together with the two adjacent N atoms; D L21 , D L22 teeth, (a) independently selected from linear or branched C1-C6 alkanediyl, or (b) both are part of a 5- or 6-membered aromatic heterocyclic ring system together with the two adjacent N atoms; D L23 is C1-C6 alkanediyl, R L1 , R L2 are independently selected from C1 to C6 alkyl; R L3 is selected from H and C1-C6 alkyl; X L2 is N or CR L3 and Y is a comonomer fragment, Z is the formula L4 [ka] is a divalent coupling fragment represented by Z L1 teeth, (a) Straight-chain or branched C1-C alkyl groups, optionally interrupted by one or more O atoms 12 Alkanediyl, preferably C1-C6 alkanediyl optionally interrupted by one or two O atoms, or (b) Divalent group -D L11 -Ar L11 -D L11 - is selected from Z L2 , Z L3 is independently selected from a chemical bond and hydroxyethanediyl; n is an integer from 1 to 400, m is 0 or an integer from 1 to 400, o is an integer from 1 to 100; wherein p and r are independently 0 or 1.

[0019] The leveling agent according to the present invention is particularly useful for filling recessed features having an opening size of 500 nm to 500 μm, especially those having an opening size of 1 to 200 μm. The leveling agent is particularly useful for depositing copper bumps.

[0020] Due to the leveling effect of the leveling agent, a surface with improved coplanarity of the plated copper bumps is obtained. The copper deposits exhibit good morphology, especially low surface roughness. The electroplating composition is capable of filling recessed features at the micrometer scale without substantial formation of defects such as, but not limited to, voids. The electroplating composition ensures uniform plating at various line spacings and on pads with various dimensions, making the composition particularly useful for RDL applications.

[0021] Additionally, the leveling agent according to the present invention provides reduced impurities such as, but not limited to, organics, chlorides, sulfur, nitrogen, or other elements. In particular, when solder is directly plated onto copper, high organic impurity levels lead to significant Kirkendall voids. These voids reduce the reliability of the solder laminate and are therefore less preferred.

[0022] The additives described herein further facilitate high plating speeds and allow plating at elevated temperatures.

[0023] A further advantage of the levelling agents according to the invention is their flexibility in terms of adapting the nitrogen content, hydrophilicity, charge and charge density, inhibition capacity, which makes it easy to adapt them to the very specific requirements of the substrate. In view of the International Patent Application No. PCT / EP2021 / 057522, the levellers according to the invention synthesised from tertiary amino acids, diamines and coupling agents further increase this flexibility, since completely new combinations of building blocks are available.

[0024] The invention further relates to a method of using the aqueous compositions described herein to deposit copper on a substrate comprising recessed features, including conductive feature bottoms and insulating feature sidewalls, wherein the recessed features have an opening size between 500 nm and 500 μm.

[0025] The present invention provides a method for electrodepositing copper on a substrate containing recessed features, the recessed features including conductive feature bottoms and insulating feature sidewalls, the method comprising the steps of: (a) contacting a substrate with a composition described herein; (b) passing an electric current through the substrate for a time sufficient to deposit a copper layer in the recessed feature; wherein the recessed features have an opening size of 500 nm to 500 μm. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] It has been found that quaternized coupled aminoamide polymers can be advantageously used as leveling agents in copper electroplating of bump structures, exhibiting improved leveling performance. Quaternized coupled aminoamide polymers are also referred to herein as "cationic aminoamide polymers," "coupled aminoamide polymers," "coupled aminoamides," "leveling agents," or "levelers."

[0027] As used herein, "accelerator" refers to an organic additive that enhances the plating rate of an electroplating bath. The terms "accelerator" and "accelerating agent" are used interchangeably throughout this specification. In the literature, sometimes accelerator components are also named "brightener" or "brightening agent". "Suppressing agent" or "suppressor" refers to an organic compound that reduces the plating rate of an electroplating bath and ensures that recessed features are filled void-free from bottom to top (so-called "bottom-up fill"). The terms "suppressor" and "suppressing agent" are used interchangeably throughout this specification. "Leveler" refers to an organic compound that is capable of providing a substantially planar metal deposit over areas with a large or small number of recessed features or over various areas of a wafer or die. The terms "leveler", "leveling agent", and "leveling additive" are used interchangeably throughout this specification.

[0028] "Aperture size" according to the present invention means the smallest diameter or free distance of a recessed feature before plating. The terms "width", "diameter", "aperture" and "opening" are used interchangeably herein depending on the shape of the feature (trench, via, etc.). As used herein, "aspect ratio" means the ratio of the depth of a recessed feature to the opening size.

[0029] As used herein, "chemical bond" means that adjacent moieties are bridged such that there is no respective moiety but a direct chemical bond between the adjacent moieties. As an example, in molecule ABC, if moiety B is a chemical bond, then adjacent moieties A and C together form a group AC.

[0030] "C xThe term "C" means that each group contains x number of C atoms. x ~C y The term "alkyl" means an alkyl having x to y number of carbon atoms, and includes unsubstituted straight chain, branched, and cyclic alkyl, unless expressly specified. As used herein, "alkanediyl" refers to a diradical of a straight chain, branched, or cyclic alkane, or combinations thereof.

[0031] As used herein, "aromatic ring" encompasses aryl and heteroaryl groups.

[0032] Leveling agent according to the present invention In addition to copper ions and an acid, the metal electroplating composition comprises a metal complex having Formula I: [BA-B'-Z] n [YZ] m (L1) The polyaminoamide includes at least one polyaminoamide represented by the formula:

[0033] The additives according to formula L1 can generally be obtained by first reacting a diamine compound ([a]) containing two primary or secondary amino groups with an amino acid "b" in a molar ratio of approximately 1:2 to form an aminoamide compound bA-b'. In contrast to the compounds disclosed in US6425996B1, separate monomeric compounds are obtained in this intermediate product.

[0034] This monomeric aminoamide intermediate compound is then reacted with a coupling agent "z" to couple several aminoamide compounds together to form the coupled aminoamide [AB-A'-Z] of the present invention. n get.

[0035] As an example, this reaction scheme shows the preparation of a leveller by starting with 3-aminopropylamine, N,N-dimethylglycine and epichlorohydrin: [ka]

[0036] In the first step, separate aminoamide monomers bA-b' are prepared, which are then coupled with a coupling agent z, where m is 0.

[0037] It is also possible to co-couple the aminoamide compounds with further amine comonomers Y that contain a tertiary amino group and a secondary or tertiary amino group, where m is 1 or greater.

[0038] Fragments A, B, B', Z, and Y are described in more detail below.

[0039] In a first embodiment, the amino acid compound b and "b" are represented by the formula L2a [ka] The resulting product forms two amino acid fragments B and B' represented by the formula:

[0040] In formula L2, the amino acid spacer D L1 (a) C1-C optionally substituted with an amino group or interrupted by a double bond or an imino group; 20 -alkanediyl, or (b) a compound of formula L2a -(D L10 -O-] o D L10 - (L2c) is selected from divalent groups selected from ether or polyether groups represented by the formula: In the formula, D L10 is selected from C1-C6-alkanediyl, preferably from C1-C4-alkanediyl, most preferably from ethanediyl or propanediyl, and o is an integer from 1 to 100, preferably from 1 to 20, most preferably from 1 to 15. In a particular embodiment, o is from 3 to 10, and in another embodiment, o is from 10 to 20.

[0041] In a preferred embodiment, D L1 (i) a straight-chain C2-C alkyl group which may be unsubstituted or substituted by an amino group;10 (ii) an alkanediyl group, (iii) a C2-C3 oxyalkylene group, 12 or (iv) a divalent phenyl or pyridyl group.

[0042] In another preferred embodiment, D L1 is selected from ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, or decanediyl, which may be unsubstituted or substituted by an amino group. Most preferably D L1 is selected from ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, 5-aminopentane-1,5-diyl, and hexane-1,6-diyl.

[0043] In formula L2a, R L1 and R L2 is independently selected from C1 to C6 alkyl, preferably methyl, ethyl or propyl. L3 is selected from H and C1-C6 alkyl, preferably H and methyl.

[0044] In another embodiment, the amino acid compound b and "b" are represented by the formula L2b [ka] The resulting product forms two amino acid fragments B and B' represented by the formula:

[0045] In formula L2b, the divalent group D L11 and D. L12 are independently selected from (a) linear or branched C1-C6 alkanediyl, or (b) both, together with the two adjacent N atoms, are part of a 5- or 6-membered aromatic heterocyclic ring system. L1 R may be the same as defined for formula L2a above. L1 is selected from C1-C6 alkyl, preferably methyl, ethyl or propyl.

[0046] In a first preferred embodiment of formula L2b, D L11 and D. L12 are independently selected from linear or branched C1-C4 alkanediyl. Even more preferably, D L11 and D. L12 is (CH2) g In the formula, g is an integer from 1 to 6, preferably from 1 to 3. Most preferably, D L11 and D. L12 are both ethanediyl or D L11 is methanediyl and D L12 is propanediyl.

[0047] In another preferred embodiment of formula L2b, D L11 and D. L12 forms an imidazole ring together with the two adjacent N atoms.

[0048] Without being limited thereto, tertiary amino acids particularly useful in the preparation of levellers according to the present invention include N,N-dimethylglycine, 3-(dimethylamino)propanoic acid, 4-(dimethyl-amino)-butanoic acid, 5-(dimethyl-amino)pentanoic acid, 1H-imidazole-1-acetic acid, 1H-imidazole-1-propanoic acid, 1H-imidazole-1-butanoic acid, and the amino acids of formula L2d [ka] It is an amino acid represented by the formula:

[0049] The amino acids may be used in the form of the free acid or as carboxylic acid derivatives, such as anhydrides, esters, amides or acid halides, especially chlorides. The use of free amino acids is preferred.

[0050] Since the amino acid fragments B and B' are positively charged, a counterion Y is added to neutralize the overall composition. y- where y is a positive integer. Preferably, such counterions may be selected from halides, especially chloride, methanesulfonate, sulfate or acetate.

[0051] The diamine compound "a" has the formula L3a [ka] or formula L3b [ka] This forms a diamine fragment A represented by the formula:

[0052] Here, a primary or secondary amine functional group of both amine compounds is bonded, respectively, to a carbonyl functional group of an amino acid fragment.

[0053] In a first embodiment of formula L3a, the divalent group D L2 is optionally one or more NR L10 or S may be interposed, or one or more, preferably one or two, radicals NR L10 R L11 OR L10 Optionally substituted linear or branched C1-C 20 alkanediyl, wherein R L10 , R L11 H and C1-C 10 In a particularly preferred embodiment, D is independently selected from alkyl, more preferably H and C1-C4 alkyl, and most preferably H, methyl, or ethyl. L2 is selected from linear or branched C1-C6 alkanediyl. Even more preferably, D L2 (CH2) g In the formula, g is an integer from 1 to 6, preferably from 1 to 3. Most preferably, D L2 is 1,2-ethanediyl or 1,3-propanediyl.

[0054] In a second embodiment of formula L3a, the divalent group D L2 -D L11 -Ar L13 -D L13 wherein D L13is selected from C1-C6-alkanediyl, preferably methanediyl or ethanediyl, Ar L13 is C6~C 10 The aromatic moiety is preferably phenylene, most preferably p-phenylene.

[0055] In a third embodiment of formula L3a, the divalent group D L2 is the formula L2a -(D L10 -O-] o D L10 - (L2a) and wherein the ether or polyether group is selected from the group consisting of In the formula, D L10 is selected from C1-C6-alkanediyl, preferably C1-C4-alkanediyl, most preferably ethanediyl or propanediyl, and o is an integer from 1 to 100, preferably from 1 to 50, most preferably from 1 to 15. In a particular embodiment, o is an integer from 3 to 10, and in another embodiment, o is an integer from 10 to 40.

[0056] In formula L3b, the divalent group D L21 and D. L22 are independently selected from (a) linear or branched C1-C6 alkanediyl, preferably methanediyl, ethanediyl, or propanediyl, or (b) D L21 and D. L22 Both of these, together with the two adjacent N atoms, are part of a 5- or 6-membered aromatic heterocyclic ring system. L23 R may be a C1-C6 alkanediyl, preferably methanediyl, ethanediyl, propanediyl or butanediyl, most preferably methanediyl, ethanediyl or propanediyl. L3 may be selected from H and C1-C6 alkyl, preferably H or methyl, most preferably H. X L2 is N or CR L3, preferably N, CH or C-CH3, and p and r may be the same or different and may be 0 or 1. When p or r is 1, the respective amino acid is bonded to a primary or secondary amine functionality, and when p or r is 0, the respective amino acid is bonded to a secondary amine functionality that is part of a ring system.

[0057] In a first preferred embodiment of formula L3b, D L21 and D. L22 are independently selected from linear or branched C1-C4 alkanediyl. Even more preferably, D L21 and D. L22 is (CH2) g In the formula, g is an integer from 1 to 6, preferably from 1 to 3. Most preferably, D L21 and D. L22 are both ethanediyl or D L21 is methanediyl and D L22 is propanediyl.

[0058] In a second preferred embodiment of formula L3b, D L21 and D. L22 forms an imidazole ring together with the two adjacent N atoms.

[0059] Diamines that are particularly useful in the preparation of levellers according to the invention are propylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,12-diaminododecane, diaminodicyclohexylmethane, isophorone diamine, 3,3'-dimethyl-4,4'-diamino-dicyclo-hexyl-methane, 4,7,10-trioxatridecane-1,13-diamine, xylene diamine, poly(propylene glycol) bis(2-aminopropyl ether) having an average degree of polymerization of 1-50, preferably 2-40, most preferably 1-10, and lysine.

[0060] As used herein, "average degree of polymerization" refers to the average number of repeating monomer units in a polymer.

[0061] The coupling agent "z" is represented by the formula L4 [ka] forming a coupling fragment Z represented by During the ceremony, Z L1 teeth, (a) Straight-chain or branched C1-C alkyl groups, optionally interrupted by one or more O atoms 12 Alkanediyl, preferably C1-C6 alkanediyl optionally interrupted by one or two O atoms, or (b) Divalent group -D L11 -Ar L11 -D L11 - is selected from Z L2 , Z L3 is independently selected from a chemical bond or hydroxyethanediyl.

[0062] In a first preferred embodiment, Z L1 is C1~C 12 In a second preferred embodiment, Z is selected from alkanediyl, preferably C1-C4 alkanediyl, most preferably methanediyl or ethanediyl. L1 is the formula -(D L10 -O-] o D L10 - alkyl or polyalkyl ether groups, in particular bis(2-ethanediyl) ether groups, L10 is selected from C1-C6-alkanediyl, preferably C1-C4-alkanediyl, most preferably ethanediyl or propanediyl, and o is an integer from 1 to 100, preferably from 1 to 20, most preferably from 1 to 10. In a particular embodiment, o is from 1 to 5, and in another embodiment, o is from 5 to 15. In a third preferred embodiment, Z L1 is a divalent group -D L11 -Ar L11 -D L11 -, in particular a biphenyl radical, L11is selected from C1-C6-alkanediyl, preferably methanediyl and ethanediyl, Ar L11 is C6~C 12 The aromatic moiety is preferably phenylene or biphenylene.

[0063] In another preferred embodiment, Z L2 is selected from chemical bonds, Z L3 In yet another preferred embodiment, Z is selected from hydroxyethanediyl. L2 and Z L3 are both selected from chemical bonds.

[0064] Such coupling fragments Z may be derived from coupling agents that contain leaving groups such as, but not limited to, halogens, particularly Cl or Br, and / or epoxy groups.

[0065] Particularly preferred coupling agents "z" are bis(2-chloroethyl)ether, bis(2-chloroethoxy)ethane, epichlorohydrin, 1,ω-dihalo(C 10 ) alkanes, such as, but not limited to, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, and 1,6-dichlorohexane, bis(2-chloroethyl)ethers, di(haloalkyl)aryl groups, such as, but not limited to, xylylene dichloride and 4,4'-bis(bromomethyl)biphenyl. Herein, chloride or bromide may be replaced by other leaving groups, such as, but not limited to, triflate, tosylate, mesylate, and the like.

[0066] In formula L1, n may be an integer from 1 to 400, preferably from 2 to 200, and more preferably from 2 to 150. In certain embodiments, n may be an integer from 2 to 50, and in other embodiments, n may be an integer from 50 to 150.

[0067] In formula L1, m is 0 or, when a comonomer is present, an integer of 1 to 400, preferably 1 to 200, more preferably 2 to 150.

[0068] When a comonomer is used, the ratio of n to m may be from 10:90 to 95:5, preferably from 20:70 to 90:10, more preferably from 30:70 to 70:30.

[0069] Generally, the mass average molecular weight M of the leveling agent is w may be about 450 to about 150,000 g / mol, preferably 1,000 to 80,000 g / mol, and most preferably 1,000 to 50,000 g / mol.

[0070] A first preferred embodiment of the leveller according to the invention is a leveller having the formula L5 [ka] is a coupled amino amide represented by the formula: The general definition is as above. Preferably, D L1 and D. L2 is independently selected from methanediyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, and butane-1,4-diyl. L2 , for example, but not limited to: [ka] or [ka] may be used.

[0071] A second preferred embodiment of the leveller according to the invention is a compound of formula L6 [ka] is a coupled amino amide represented by the formula: The general definition is as above. Preferably, D L1 and D. L2is independently selected from methanediyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, and butane-1,4-diyl; D L11 and D. L12 are selected from (a) methanediyl, ethanediyl and propanediyl, or (b) both, together with the two adjacent N atoms, are part of a 5- or 6-membered aromatic heterocyclic ring system. Particularly preferred levellers are of the formula L6a [ka] It is expressed as follows.

[0072] A third preferred embodiment of the leveller according to the invention is a compound of formula L7 [ka] is a coupled amino amide represented by the formula: The general definition is as above. Preferably, D L1 is selected from methanediyl, ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl and decanediyl; R L3 is selected from methyl, ethyl and propyl, and o is an integer from 2 to 50, preferably from 2 to 40.

[0073] A fourth preferred embodiment of the leveller according to the invention is a compound of formula L8 [ka] is a coupled amino amide represented by the formula: The general definition is as above. Preferably, Ar L13 is phenylene, in particular phenyl-1,4-diyl; D L13 and D. L1 is independently selected from methanediyl, ethanediyl, propanediyl, and butanediyl.

[0074] A fifth preferred embodiment of the leveller according to the invention is a compound of formula L9 [ka] is a coupled amino amide represented by the formula: The general definition is as above. Preferably, D L1 and D. L23 is independently selected from methanediyl, ethanediyl, propanediyl, and butanediyl; D L21 and D. L22 is independently selected from methanediyl, ethanediyl, and propanediyl; R L1 and R L2 is independently selected from methyl, ethyl, propyl, and butyl.

[0075] The aminoamide polymers described herein are typically terminated with a tertiary amine group or partially reacted coupling agent "z."

[0076] Particularly preferred polyaminoamide type levellers are: [ka]

[0077] In an alternative embodiment of formula L1, m is 1 or more and Y is an amine comonomer fragment obtained when an amine comonomer "y" containing at least two tertiary or secondary amino groups is co-coupled with an aminoamide compound. This co-coupling may be carried out in admixture or sequentially in any order. Preferred is the co-coupling from a mixture containing aminoamide and amine comonomer.

[0078] Y may be a fragment of formula L3a or formula L3b. In this case, Y may be the same as or different from A and A'. Alternatively, Y may be any other fragment (with its counterion Cl) disclosed on page 6 of US2016 / 0076160A1, which is incorporated herein by reference. -(independent from

[0079] Particularly preferred fragments Y are those obtained by reaction of 1-(bis(3-dimethylamino)propyl)amino)-2-propanol, 4,4-trimethylenedipiperidine, tetramethyl-1,2 ethylenediamine, tetramethyl-1,3 propanediamine, tetramethyl-1,4 butanediamine, tetramethyl-1,6 hexanediamine, tetramethyl-1,8 octanediamine, tetraethyl-1,3 propanediamine, tetramethylphenylenediamine, bis(dimethylaminoethyl)ether, tetramethyl-2-butene-1,4-diamine, tetramethyl-2,2-dimethyl-1,3 propanediamine. The properties of the additive can be further influenced by using comonomers, for example by increasing or decreasing the nitrogen content, hydrophilicity, charge and charge density, or other chemical or physical properties.

[0080] The condensation of amino acids and diamines is usually carried out by heating the amino acids and diamines to a temperature of, for example, 100 to 250°C, preferably 120 to 200°C, and distilling off the reaction water generated during the condensation. When using the amino acid derivatives, the condensation may be carried out at a temperature lower than the given temperature. The preparation of cationic aminoamide polymers can be carried out without the addition of a catalyst or alternatively using an acidic or basic catalyst. Suitable acidic catalysts are, for example, acids, such as Lewis acids, for example sulfuric acid, p-toluenesulfonic acid, phosphorous acid, hypophosphorous acid, phosphoric acid, methanesulfonic acid, boric acid, aluminum chloride, boron trifluoride, tetraethylorthotitanate, tin dioxide, butyltin dilaurate, or mixtures thereof. Suitable basic catalysts are, for example, alkoxides such as sodium methoxide or sodium ethoxide, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, or lithium hydroxide, alkaline earth metal oxides such as magnesium oxide or calcium oxide, alkali metal and alkaline earth metal carbonates such as sodium, potassium, and calcium carbonate, phosphates such as potassium phosphate, and complex metal hydrides such as sodium borohydride, etc. If used, the catalyst is generally used in an amount of 0.05 to 10% by weight, preferably 0.5 to 1% by weight, based on the total amount of starting materials.

[0081] The reaction can be carried out in a suitable solvent or preferably in the absence of a solvent.When a solvent is used, suitable examples are hydrocarbons such as toluene or xylene, nitriles such as acetonitrile, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, ethers such as diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, etc.The solvent is generally distilled off during the reaction or when the reaction is complete.This distillation can be optionally carried out under protective gas, such as nitrogen or argon.

[0082] Generally, the total amount of leveling agent in the electroplating bath is from 0.05 ppm to 10000 ppm based on the total weight of the plating bath. The leveling agents according to the present invention are typically used in a total amount of from about 0.1 ppm to about 1000 ppm, more typically from 1 to 100 ppm, based on the total weight of the plating bath, although greater or lesser amounts may be used.

[0083] A wide variety of additives may typically be used in the bath to achieve the desired surface finish of the Cu plating metal. Usually, more than one additive is used, with each additive performing a desired function. Advantageously, the electroplating bath may contain one or more of an accelerator, a suppressor, a halide ion source, a refiner, and mixtures thereof. Most preferably, the electroplating bath contains both an accelerator and a suppressor in addition to the leveling agent according to the present invention.

[0084] Other Additives A wide variety of additional additives may typically be used in the bath to achieve the desired surface finish of the Cu plating metal. Usually, more than one additive is used, with each additive performing a desired function. Advantageously, the electroplating bath may contain one or more of an accelerator, a suppressor, a halide ion source, a refiner, and mixtures thereof. Most preferably, the electroplating bath contains both an accelerator and a suppressor in addition to the leveling agent according to the present invention. Other additives may also be suitably used in the electroplating bath of the present invention.

[0085] Accelerator Any accelerator can be advantageously used in the plating bath according to the present invention. As used herein, "accelerator" refers to an organic additive that enhances the plating rate of an electroplating bath. The terms "accelerator" and "accelerating agent" are used interchangeably throughout this specification. In the literature, accelerator components are sometimes also named "brighteners", "brightening agents", or "depolarizers". Accelerators useful in the present invention include, but are not limited to, compounds containing one or more sulfur atoms, and sulfonic / phosphonic acids or salts thereof. Preferably, the composition further comprises at least one accelerator.

[0086] Preferred promoters have the general structure MOY A -X A1 -(S) d R A2 having M is hydrogen or an alkali metal, preferably Na or K; - Y A is P or S, preferably S; - d is an integer from 1 to 6, preferably 2; -X A1 is selected from a C1-C8 alkanediyl or heteroalkanediyl group, a divalent aryl group, or a divalent heteroaromatic group. The heteroalkyl group will have one or more heteroatoms (N, S, O) and 1-12 carbons. Carbocyclic aryl groups are typical aryl groups, such as phenyl or naphthyl. Heteroaromatic groups are also suitable aryl groups, containing one or more N, O, or S atoms and 1-3 separate or fused rings, - R A2 is H or (-SX A1 'Y A O3M), wherein X A1 ' is the group X A1 are independently selected from

[0087] More specifically, useful accelerators include those having the following formula: MO3S-X A1 -SH MO3S-X A1 -SSX A1 '-SO3M MO3S-Ar-SS-Ar-SO3M Examples of the above are represented by the following formula: In the formula, X A1 is as defined above and Ar is aryl.

[0088] Particularly preferred accelerators are - SPS: Bis-(3-sulfopropyl)-disulfide - MPS: 3-mercapto-1-propanesulfonic acid Both are usually applied in the form of their salts, in particular their sodium salts.

[0089] Other examples of accelerators, used alone or in admixture, include, but are not limited to: MES (2-mercaptoethanesulfonic acid, sodium salt), DPS (N,N-dimethyldithiocarbamic acid (3-sulfopropyl ester), sodium salt), UPS (3-[(amino-iminomethyl)-thio]-1-propylsulfonic acid), ZPS (3-(2-benzothiazolylthio)-1-propanesulfonic acid, sodium salt), 3-mercapto-propylsulfonic acid-(3-sulfopropyl)ester, methyl-(ω-sulfopropyl)-disulfide, disodium salt, methyl-(ω-sulfopropyl)-trisulfide, disodium salt.

[0090] Such accelerators are typically used in amounts of from about 0.1 ppm to about 3000 ppm based on the total weight of the plating bath. Particularly suitable amounts of accelerators useful in the present invention are from 1 to 500 ppm, more particularly from 2 to 100 ppm.

[0091] Inhibitor Suppressors may be advantageously used in combination with the leveller according to the invention. As used herein, an "inhibitor" is an additive that increases the overpotential during electrodeposition. The inhibitors described herein are also surface-active substances, so the terms "surfactant" and "inhibitor" are used synonymously. Typically, inhibitors include oxy(C2-C4)alkylene homopolymers or copolymers obtainable by polyoxyalkylation of alcohol or amine starters.

[0092] Particularly useful inhibitors are: (a) Inhibitors obtainable by reacting a mixture of an amine compound containing at least three active amino functional groups with ethylene oxide and at least one compound selected from C3 and C4 alkylene oxides, as described in WO2010 / 115796.

[0093] Preferably, the amine compound is selected from diethylenetriamine, 3-(2-aminoethyl)aminopropylamine, 3,3′-iminodi(propylamine), N,N-bis(3-aminopropyl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetraamine, and N,N′-bis(3-aminopropyl)ethylenediamine.

[0094] (b) inhibitors obtainable by reacting an amine compound containing an active amino functional group with a mixture of ethylene oxide and at least one compound selected from C3 and C4 alkylene oxides, the molecular weight M of which is greater than or equal to 6000 g / mol, as described in WO2010 / 115756; w and the inhibitor is an ethylene C3 and / or C4 alkylene random copolymer.

[0095] (c) inhibitors obtainable by reacting, in a mixture or in succession, an amine compound containing at least three active amino functions with at least one compound selected from ethylene oxide and C3 and C4 alkylene oxides, the molecular weight M of which is greater than or equal to 6000 g / mol, as described in WO 2010 / 115757; w An inhibitor having

[0096] Preferably, the amine compound is selected from ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, neopentanediamine, isophoronediamine, 4,9-dioxadecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, triethyleneglycoldiamine, diethylenetriamine, (3-(2-aminoethyl)aminopropylamine, 3,3′-iminodi(propylamine), N,N-bis(3-aminopropyl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetraamine, and N,N′-bis(3-aminopropyl)ethylenediamine.

[0097] (d) Formula S1 [ka] Inhibitors selected from compounds represented by the formula: S1 radicals are each independently selected from copolymers of ethylene oxide and at least one additional C3-C4 alkylene oxide, said copolymers being random copolymers, R S2 The radical is R S1 or alkyl; S and Y S are independently a spacer group, and X of each repeat unit s S is C2-C6 alkanediyl and Z S -(OZ S ) t wherein Z SInhibitors as described in WO2010 / 115717, wherein the radicals are each independently selected from C2-C6 alkanediyl, s is an integer greater than or equal to 0, and t is an integer greater than or equal to 1.

[0098] Preferably the spacer group X S and Y S are independently, and X of each repeat unit S are independently selected from C2 to C4 alkylene. Most preferably, X S and Y S are independently, and X of each repeating unit s S is independently selected from ethylene (-C2H4-) or propylene (-C3H6-).

[0099] Preferably Z S is selected from C2-C4 alkylene, most preferably ethylene or propylene.

[0100] Preferably, s is an integer of 1 to 10, more preferably 1 to 5, and most preferably 1 to 3. Preferably, t is an integer of 1 to 10, more preferably 1 to 5, and most preferably 1 to 3.

[0101] In another preferred embodiment, the C3-C4 alkylene oxide is selected from propylene oxide (PO), in which case the EO / PO copolymer side chains are produced starting from active amino functional groups.

[0102] The ethylene oxide content in the copolymer of ethylene oxide and a further C3-C4 alkylene oxide can generally be about 5% by mass to about 95% by mass, preferably about 30% by mass to about 70% by mass, and particularly preferably about 35% by mass to about 65% by mass.

[0103] The compound of formula (S1) is prepared by reacting an amine compound with one or more alkylene oxides. Preferably, the amine compound is selected from ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, neopentanediamine, isophoronediamine, 4,9-dioxadecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, triethyleneglycoldiamine, diethylenetriamine, (3-(2-aminoethyl)amino)propylamine, 3,3'-iminodi(propylamine), N,N-bis(3-aminopropyl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetraamine, and N,N'-bis(3-aminopropyl)ethylenediamine.

[0104] Molecular weight M of the inhibitor of formula S1 w The molecular weight M may be from about 500 g / mol to about 30,000 g / mol. w should be about 6000 g / mol or more, preferably about 6000 g / mol to about 20000 g / mol, more preferably about 7000 g / mol to about 19000 g / mol, and most preferably about 9000 g / mol to about 18000 g / mol. The preferred total amount of alkylene oxide units in the inhibitor may be about 120 to about 360, preferably about 140 to about 340, and most preferably about 180 to about 300.

[0105] Typical total amounts of alkylene oxide units in the inhibitor are about 110 ethylene oxide units (EO) and 10 propylene oxide units (PO), about 100EO and 20PO, about 90EO and 30PO, about 80EO and 40PO, about 70EO and 50PO, about 60EO and 60PO, about 50EO and 70PO, about 40EO and 80PO, ​​about 30EO and 90PO, about 100EO and 10 butylene oxide (BO) units, about 90EO and 20BO, about 80EO and 30BO, about 70EO and 40BO, about 60EO and 50BO. 0, or about 40EO and 60BO, to about 330EO and 30PO units, about 300EO and 60PO, about 270EO and 90PO, about 240EO and 120PO, about 210EO and 150PO, about 180EO and 180PO, ​​about 150EO and 210PO, about 120EO and 240PO, about 90EO and 270PO, about 300EO and 30BO units, about 270EO and 60BO, about 240EO and 90BO, about 210EO and 120BO, about 180EO and 150BO, or about 120EO and 180BO.

[0106] (e) Formula (S2)X S (OH) u and at least one alkylene oxide to form a polyhydric alcohol condensate containing a polyoxyalkylene side chain, the polyhydric alcohol condensate being obtained by condensing at least one polyalcohol represented by the formula: S is a u-valent, linear or branched, aliphatic or alicyclic radical having 3 to 10 carbon atoms, which may be substituted or unsubstituted, as described in WO 2011 / 012462.

[0107] Preferred polyalcohol condensates have the formula [ka] wherein Y Sis a u-valent linear or branched aliphatic or alicyclic radical having 1 to 10 carbon atoms, which may be substituted or unsubstituted, a is an integer from 2 to 50, b, which may be the same or different for each polymer arm u, is an integer from 1 to 30, c is an integer from 2 to 3, and u is an integer from 1 to 6. The most preferred polyalcohols are glycerin condensates and / or pentaerythritol condensates.

[0108] (f) Inhibitors as described in WO2011 / 012475, obtainable by reacting a polyhydric alcohol containing at least five hydroxyl functional groups with at least one alkylene oxide to form a polyhydric alcohol containing polyoxyalkylene side chains. Preferred polyalcohols are represented by formula (S3a) or (S3b): HOCH2-(CHOH) v -CH2OH (S3a) (CHOH) w (S3b) is a linear or cyclic monosaccharide alcohol represented by In the formula, v is an integer of 3 to 8, and w is an integer of 5 to 10. Most preferred monosaccharide alcohols are sorbitol, mannitol, xylitol, ribitol, and inositol. Further preferred polyalcohols are those represented by formula (S4a) or (S4b): CHO-(CHOH) x -CH2OH (S4a) CH2OH-(CHOH y -CO-(CHOH) z -CH2OH (S4b) It is a monosaccharide represented by In the formula, x is an integer of 4 to 5, y and z are integers, and y+z is 3 or 4. The most preferred monosaccharide alcohol is selected from aldoses such as allose, altrose, galactose, glucose, gulose, idose, mannose, talose, glucoheptose, and mannoheptose, and ketoses such as fructose, psicose, sorbose, tagatose, mannoheptulose, sedoheptulose, taloheptulose, and alloheptulose.

[0109] (g) Amine-based polyoxyalkylene inhibitors based on cyclic amines, such as those described in WO2018 / 073011, exhibit surprising superfilling properties.

[0110] (h) Polyamine-based or polyhydric alcohol-based inhibitors that are modified by reaction with compounds such as, but not limited to, glycidol or glycerol carbonate, which introduce branching groups into the inhibitor prior to reaction with alkylene oxide, as described in WO2018 / 114985, show surprising superfilling properties.

[0111] When inhibitors are used, they are typically present in an amount within the range of from about 1 to about 10,000 ppm, preferably from about 5 to about 10,000 ppm, based on the weight of the bath.

[0112] Those skilled in the art will recognize that more than one leveling agent may be used. When more than one leveling agent is used, at least one of the leveling agents is a leveling agent according to the present invention or a derivative thereof as described herein. It is preferred to use only one leveling agent in the plating composition.

[0113] Further levelling agents Additional leveling agents can be advantageously used in the copper electroplating baths according to the invention. When two or more leveling agents are used, at least one of the leveling agents is a polyalkoxylated polyalkyleneimine or derivative thereof as described herein. It is preferred to use only one leveling agent in the plating composition which is a polyalkoxylated polyalkylenepolyamine according to the invention.

[0114] Suitable further levelling agents include, but are not limited to, other polyethyleneimines and their derivatives, quaternized polyethyleneimines, polyglycines, poly(allylamine), polyanilines, polyureas, polyacrylamides, poly(melamine-co-formaldehyde), reaction products of amines with epichlorohydrin, reaction products of amines, epichlorohydrin, and polyalkylene oxides, reaction products of amines with polyepoxides, polyvinylpyridines, e.g. polyvinylimidazoles as described in WO 2011 / 151785 A1, polyvinylpyrrolidones, e.g. Examples of suitable compounds include polyaminoamides as described in WO2010 / 064154A2 and WO2014 / 072885A2, or copolymers thereof, nigrosine, pentamethyl-para-rosaniline hydrohalide, hexamethyl-pararosaniline hydrohalide, di- or trialkanolamines and derivatives thereof as described in WO2010 / 069810, biguanides as described in WO2012 / 085811A1, or compounds containing a functional group represented by the formula NRS, where R is substituted alkyl, unsubstituted alkyl, substituted aryl, or unsubstituted aryl. Typically, the alkyl group is a C1-C6 alkyl, preferably a C1-C4 alkyl. In general, the aryl group is a C6-C 20 Aryl, preferably C6-C 10 The aryl group is preferably phenyl or naphthyl. Compounds containing a functional group represented by the formula NRS are generally known, generally commercially available, and can be used without further purification.

[0115] In such compounds containing the NRS functional group, sulfur ("S") and / or nitrogen ("N") may be bonded to such compounds by a single bond or a double bond. When sulfur is bonded to such compounds by a single bond, the sulfur may be bonded to any of a number of groups including, but not limited to, hydrogen, C1-C 12 Alkyl, C2-C 12 Alkenyl, C6-C 20 Aryl, C1-C 12 Alkylthio, C2-C 12Alkenylthio, C6-C 20 Similarly, the nitrogen may have another substituent such as, but not limited to, hydrogen, C1-C 12 Alkyl, C2-C 12 Alkenyl, C7-C 10 The NRS functional group may have one or more substituents such as aryl. The NRS functional group may be acyclic or cyclic. Compounds containing cyclic NRS functional groups include those having either nitrogen or sulfur, or both nitrogen and sulfur, in the ring system.

[0116] Generally, the total amount of leveling agent in the electroplating bath is from 0.5 ppm to 10000 ppm based on the total weight of the plating bath. The leveling agents according to the present invention are typically used in a total amount of from about 0.1 ppm to about 1000 ppm, more typically from 1 to 100 ppm, based on the total weight of the plating bath, although greater or lesser amounts may be used.

[0117] Further details and alternatives are described in WO2018 / 219848, WO2016 / 020216, and WO2010 / 069810, each of which is incorporated herein by reference.

[0118] Generally, the total amount of leveling agent in the electroplating bath is 0.5 ppm to 10000 ppm based on the total weight of the plating bath. The leveling agent according to the present invention is typically used in a total amount of about 100 ppm to about 10000 ppm based on the total weight of the plating bath, although more or less may be used.

[0119] electrolyte The electroplating composition according to the present invention comprises an electrolyte comprising copper ions and an acid.

[0120] Copper ions The copper ion source may be any compound capable of releasing the metal ions to be deposited in sufficient amounts in the electroplating bath, i.e., at least partially soluble in the electroplating bath. The metal ion source is preferably soluble in the plating bath. Suitable metal ion sources are metal salts, including, but not limited to, sulfates, halides, acetates, nitrates, fluoroborates, alkylsulfonates, arylsulfonates, sulfamates, metal gluconates, and the like.

[0121] The metal ion source may be used in the present invention in an amount that provides sufficient metal ions for electroplating on the substrate. When the metal is copper only, it is typically present in an amount ranging from about 1 to about 300 g / L of the plating solution, preferably from about 20 to about 100 g / L, and most preferably from about 40 to about 70 g / L.

[0122] Optionally, the plating bath according to the present invention may contain one or more alloying metal ions in an amount of 10% by weight or less, preferably 5% by weight or less, and most preferably 2% by weight or less. Suitable alloying metals include, but are not limited to, silver, gold, tin, bismuth, indium, zinc, antimony, manganese, and mixtures thereof. Preferred alloying metals are silver, tin, bismuth, indium, and mixtures thereof, more preferably tin. Any bath-soluble salt of the alloying metal may be suitably used as a source of alloying metal ions. Examples of such alloying metal salts include, but are not limited to, metal oxides, metal halides, metal fluoroborates, metal sulfates, metal alkane sulfonates such as metal methane sulfonates, metal ethane sulfonates, and metal propane sulfonates, metal aryl sulfonates such as metal phenyl sulfonates, metal toluene sulfonates, and metal phenol sulfonates, metal carboxylates such as metal gluconates and metal acetates, and the like. Preferred alloying metal salts are metal sulfates, metal alkane sulfonates, and metal aryl sulfonates. When one alloying metal is added to the composition of the present invention, a binary alloy deposit is obtained. When two, three or more different alloying metals are added to the composition of the present invention, a ternary, quaternary, or higher alloy deposit is obtained. The amount of such alloying metals used in the composition of the present invention will depend on the particular tin-alloy desired. The selection of such amounts of alloying metals is within the ability of one skilled in the art. One skilled in the art will recognize that when using a particular alloying metal, such as silver, an additional complexing agent may be required. Such complexing agents (or complexers) are well known in the art and may be used in any suitable amount to obtain the desired tin-alloy composition.

[0123] In a preferred embodiment, the plating solution is essentially free of tin, i.e., the plating solution contains less than 1% by weight tin, more preferably less than 0.1% by weight tin, even more preferably less than 0.01% by weight tin, and even more preferably no tin. In another preferred embodiment, the plating solution is essentially free of any alloying metal, i.e., the plating solution contains less than 1% by weight alloying metal, more preferably less than 0.1% by weight alloying metal, even more preferably less than 0.01% by weight alloying metal, and even more preferably no alloying metal. Most preferably, the metal ions consist of copper ions, i.e., no other ions besides copper.

[0124] The electroplating compositions of the present invention are suitable for depositing copper-containing layers, which may be preferably pure copper layers or alternatively copper alloy layers containing 10% by weight or less, preferably 5% by weight or less, and most preferably 2% by weight or less of alloying metal(s). Exemplary copper alloy layers include, but are not limited to, tin-silver, tin-copper, tin-indium, tin-bismuth, tin-silver-copper, tin-silver-copper-antimony, tin-silver-copper-manganese, tin-silver-bismuth, tin-silver-indium, tin-silver-zinc-copper, and tin-silver-indium-bismuth. Preferably, the electroplating compositions of the present invention deposit pure tin, tin-silver, tin-silver-copper, tin-indium, tin-silver-bismuth, tin-silver-indium, and tin-silver-indium-bismuth, more preferably pure tin, tin-silver, or tin-copper.

[0125] The alloying metal content may be measured by either atomic absorption spectrometry (AAS), X-ray fluorescence (XRF), or inductively coupled plasma mass spectrometry (ICP-MS).

[0126] Generally, in addition to copper ions and at least one leveling agent, the copper electroplating compositions of the present invention preferably include an electrolyte, i.e., an acidic or alkaline electrolyte, optionally halide ions, and optionally other additives such as accelerators and suppressors.

[0127] Such baths are typically aqueous. Generally, as used herein, "aqueous" means that the electroplating compositions of the present invention include a solvent that includes at least 50% water. Preferably, "aqueous" means that the composition is mostly water, more preferably, 90% of the solvent is water, and most preferably, the solvent consists or consists essentially of water. Any type of water may be used, such as distilled water, deionized water, or tap water.

[0128] acid The plating baths of the present invention are acidic, i.e., they have a pH of less than 7. Typically, copper electroplating compositions have a pH of less than 4, preferably less than 3, and most preferably less than 2. The pH depends primarily on the concentration of acid present in the composition.

[0129] Suitable acids include inorganic and organic acids, including but not limited to sulfuric acid, acetic acid, fluoroboric acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and trifluoromethanesulfonic acid, arylsulfonic acids such as phenylsulfonic acid and toluenesulfonic acid, sulfamic acid, hydrochloric acid, and phosphoric acid. Sulfuric acid and methanesulfonic acid are preferred.

[0130] The acid is typically present in an amount within the range of from about 1 to about 300 g / l, preferably from about 60 to about 200 g / l, and most preferably from about 80 to about 140 g / l.

[0131] Such electrolytes may optionally (and preferably) contain a halide ion source, such as a chloride ion source, such as copper chloride or hydrochloric acid. A wide range of halide ion concentrations may be used in the present invention, such as from about 0 to about 500 ppm. Preferably, the halide ion concentration is in the range of from about 10 to about 100 ppm of the plating bath. The electrolyte is sulfuric acid or methanesulfonic acid, preferably a mixture of sulfuric acid or methanesulfonic acid and a chloride ion source. The acids and halide ion sources useful in the present invention are generally commercially available and may be used without further purification.

[0132] process The compositions according to the invention are particularly useful for electrodepositing copper on substrates containing recessed features, including conductive feature bottoms and insulating feature sidewalls, the recessed features having opening sizes between 500 nm and 500 μm. The leveling agents according to the invention are particularly useful for filling recessed features having opening sizes between 1 and 200 μm. The leveling agents are particularly useful for depositing copper bumps.

[0133] Copper is deposited in the recesses by the present invention substantially without forming voids within the metal deposit. The term "substantially without forming voids" means that there are no voids in the metal deposit that are greater than 1000 nm, preferably there are no voids in the metal deposit that are greater than 500 nm, and most preferably there are no voids in the metal deposit that are greater than 100 nm. Most preferably the deposit is free of any defects.

[0134] Due to the leveling effect of the leveling agent, a surface with improved coplanarity of the plated copper bumps is obtained. The copper deposits exhibit good morphology, especially low surface roughness. The electroplating composition is capable of filling recessed features on a micrometer scale without substantially forming defects such as, but not limited to, voids.

[0135] Additionally, the leveling agent according to the present invention provides reduced impurities such as, but not limited to, organics, chlorides, sulfur, nitrogen, or other elements, which exhibit larger grains and improved electrical conductivity, which also facilitates higher plating speeds and allows plating at higher temperatures.

[0136] Generally, when the present invention is used to deposit copper on a substrate, the plating bath is agitated during use. Any suitable agitation method may be used with the present invention, and such methods are well known in the art. Suitable agitation methods include, but are not limited to, inert gas or air sparging, workpiece agitation, impingement, and the like. Such methods are known to those skilled in the art. When the present invention is used to plate an integrated circuit substrate, such as a wafer, the wafer may be rotated, such as at 1-150 RPM, and the plating solution contacts the rotating wafer, such as by pumping or spraying. Alternatively, the wafer need not be rotated if the flow of the plating bath is sufficient to result in the desired metal deposit.

[0137] Plating apparatus for plating semiconductor substrates are well known. The plating apparatus includes an electroplating tank containing a copper electrolyte and made of a suitable material such as plastic or other material that is inert to the electrolytic plating solution. The tank may be cylindrical, particularly for plating wafers. The cathode is placed horizontally on top of the tank and may be any type of substrate, such as a silicon wafer with an opening.

[0138] These additives can be used with soluble and insoluble anodes, with or without a membrane(s) separating the catholyte from the anolyte.

[0139] The cathode substrate and the anode are each electrically connected to a power source by wiring. Because the cathode substrate for direct or pulsed current has a net negative charge, metal ions in the solution are reduced at the cathode substrate to form the plating metal on the cathode surface. The oxidation reaction occurs at the anode. The cathode and anode may be placed horizontally or vertically in the cell.

[0140] Typically, in fabricating copper bumps, a photoresist layer is applied to a semiconductor wafer, followed by standard photolithographic exposure and development techniques to form a patterned photoresist layer (or plating mask) with recessed features or vias. The dimensions of the insulating plating mask (thickness of the plating mask and size of the openings in the pattern) define the size and location of the copper layer that is deposited on the I / O pads and UBM. The diameter of such deposits is typically in the range of 1-300 μm, preferably in the range of 2-100 μm. Usually, the recesses provided by the plating mask are only partially filled, not completely. After the openings in the plating mask are filled with copper, the plating mask is removed and the copper bumps are then typically reflowed.

[0141] Typically, the plating bath of the present invention may be used at any temperature from 10 to 65° C. or higher. It is preferred that the temperature of the plating bath is from 10 to 35° C., more preferably from 15 to 30° C.

[0142] All percentages, ppm, or equivalent values ​​refer to weight based on the total weight of the respective composition unless otherwise indicated. All cited references are incorporated herein by reference.

[0143] The following examples further illustrate the invention without limiting its scope.

[0144] Analysis method The molecular weight of the inhibitor was determined by size exclusion chromatography (SEC). Polystyrene was used as the standard and tetrahydrofuran was used as the eluent. The column temperature was 30°C, the injection volume was 30 μl (microliter), and the flow rate was 1.0 ml / min. The mass average molecular weight (M w ), number average molecular weight (M n ), and polydispersity PDI (M w / M n ) was decided.

[0145] The amine number was determined according to DIN 53176 by titrating a solution of the polymer in acetic acid with perchloric acid.

[0146] The experiments were carried out by using a 300 mm silicon wafer segment (available from IMAT, Inc., Vancouver, WA, USA) with a 120 μm thick patterned photoresist and multiple copper seeded 75 micrometer open vias.

[0147] The electroplated copper was examined by 3D laser scanning microscopy (3D LSM). The height of the deposited copper layer on the bumps was determined visually.

[0148] The non-uniformity was determined from a total of 27 measured bump heights, including 15 bumps in the dense area with a pitch size of 150 μm and 12 bumps with a pitch size of 375 μm.

[0149] Coplanarity, a measure of non-uniformity, is given by the following formula:

number

[0150] Example 1: Preparation of Leveler Example 1.1 The reactants were placed in a 0.5 liter reactor equipped with a stirrer, condenser tube, thermometer, and nitrogen inlet. Poly(propylene glycol) bis(2-aminopropyl ether (n-6), available from BASF, (225.8 g) and hypophosphorous acid (0.3 g) were placed in the reactor under nitrogen atmosphere and heated to 80° C. N,N-dimethylglycine (106.3 g) was then added in portions over 20 minutes. After complete addition of the acid, the reaction mixture was stirred at 120° C. for 1 hour. The temperature was then increased to 150° C. and the reaction mixture was stirred for 8 hours while removing water from the system. The preliminary product was obtained as a brown oil with an amine value of 3.3 mmol / g (yield: 94%).

[0151] The preproduct (85 g) and water (108 g) were placed in a 250 ml flask, heated to 80° C. and stirred for 20 min. Epichlorohydrin (23 g) was then added dropwise over 90 min. To complete the reaction, the mixture was post-reacted for 18.5 h until the Preussmann test was negative. The product (Leveler 1) was obtained as an orange, viscous solution with a chloride value of 1.02 mmol / g (yield: 98%).

[0152] Example 1.2: The reactants were placed in a 0.5 liter reactor equipped with a stirrer, condenser tube, thermometer, and nitrogen inlet. Poly(propylene glycol) bis(2-aminopropyl ether (n-2), available from BASF, (150.0 g) and hypophosphorous acid (0.3 g) were placed in the reactor under nitrogen and heated to 80° C. N,N-dimethylglycine (129.7 g) was then added in portions over 20 minutes. After complete addition of the acid, the reaction mixture was stirred at 120° C. for 1 hour. The temperature was then increased to 150° C. and the reaction mixture was stirred for 8 hours while removing water from the system. The preliminary product was obtained as a brown oil with an amine value of 5.2 mmol / g (yield: 93%).

[0153] The preproduct (85 g) and water (123 g) were placed in a 250 ml flask, heated to 80° C. and stirred for 20 min. Epichlorohydrin (37.9 g) was then added dropwise over 90 min. To complete the reaction, the mixture was post-reacted for 18 h until the Preussmann test was negative. The product (Leveler 2) was obtained as an orange, viscous solution with a chloride value of 1.4 mmol / g (yield: 99%).

[0154] Example 2: Electroplating Experiments Example 2.1 Comparative Example A copper electroplating bath containing 51 g / l Cu ions, 100 g / l sulfuric acid, and 50 ppm chloride was used in the study. In addition, the bath contained the following additives: 50 ppm SPS, and 100 ppm ethylene oxide polymer inhibitor having an average molecular weight of 4000 g / mol.

[0155] The substrate was pre-wetted and electrically contacted before plating. The copper layer was plated by using a bench-top plating fixture available from Yamamoto MS. Electrolyte convection was achieved by a pump and paddle in front of the substrate. The paddle RPM was 50 RPM for all plating conditions. The bath temperature was controlled and set at 25°C and the applied current density was 4 ASD for 340 seconds and 8 ASD for 1875 seconds, resulting in bumps with heights of approximately 50 μm.

[0156] The plated bumps were tested by LSM as detailed above and a coplanarity (COP) of 24.7% was determined.

[0157] Example 2.2 A copper electroplating bath containing 51 g / l Cu ions, 100 g / l sulfuric acid, and 50 ppm chloride was used in the study. In addition, the bath contained the following additives: 50 ppm SPS, 100 ppm ethylene oxide polymer inhibitor having an average molecular weight of 4000 g / mol, and 20 ppm Leveler 1 of Example 1.1.

[0158] The substrate was pre-wetted and electrically contacted before plating. The copper layer was plated by using a bench-top plating fixture available from Yamamoto MS. Electrolyte convection was achieved by a pump and paddle in front of the substrate. The paddle RPM was 50 RPM for all plating conditions. The bath temperature was controlled and set at 25°C and the applied current density was 4 ASD for 340 seconds and 8 ASD for 1875 seconds, resulting in bumps with heights of approximately 50 μm.

[0159] The plated bumps were tested by LSM as detailed above and a coplanarity (COP) of 14.4% was determined.

[0160] The results are summarized in Table 1.

[0161] Example 2.3 A copper electroplating bath containing 51 g / l Cu ions, 100 g / l sulfuric acid, and 50 ppm chloride was used in the study. In addition, the bath contained the following additives: 50 ppm SPS, 100 ppm ethylene oxide polymer inhibitor having an average molecular weight of 4000 g / mol, and 20 ppm Leveler 2 of Example 1.2.

[0162] The substrate was pre-wetted and electrically contacted before plating. The copper layer was plated by using a bench-top plating fixture available from Yamamoto MS. Electrolyte convection was achieved by a pump and paddle in front of the substrate. The paddle RPM was 50 RPM for all plating conditions. The bath temperature was controlled and set at 25°C and the applied current density was 4 ASD for 340 seconds and 8 ASD for 1875 seconds, resulting in bumps with heights of approximately 50 μm.

[0163] The plated bumps were tested by LSM as detailed above and a coplanarity (COP) of 15.6% was determined.

[0164] [Table 1]

[0165] Table 1 shows that all levelers result in copper deposits with very good coplanarity and much better coplanarity compared to Comparative Example 2.1, which does not use a leveller.

Claims

1. Copper ions, an acid, and a compound of formula L1 [B-A-B’-Z] ｎ [Y-Z] ｍ (L1) and at least one polyaminoamide containing a group represented by During the ceremony, B and B' are the same or different, preferably the same, and are represented by the formula L2a 【Chemical 1】 or formula L2b 【Chemistry 2】 is an amino acid fragment represented by A is a compound of formula L3a 【Chemistry 3】 or formula L3b 【Chemistry 4】 are diamine fragments independently selected from D Ｌ１ teeth, (a) optionally substituted with an amino group or interrupted by a double bond or an imino group, C １ ~C ２０ -alkanediyl, (b) Formula L2a -(D Ｌ１０ -O-] ｏ D Ｌ１０ - (L2c) an ether or polyether group represented by is a divalent group selected from D Ｌ２ teeth, (a) optionally one or more NR Ｌ１０ or one or more, preferably one or two groups NR Ｌ１０ R Ｌ１１ OR Ｌ１０ linear, branched or cyclic C optionally substituted with １ ~C ２０ Alkanediyl, or (b)-D Ｌ１３ -Ar Ｌ１３ -D Ｌ１３ - or (c) an ether or polyether group represented by formula L2c is a divalent group selected from D Ｌ１０ is a linear or branched C １ ~C ６ - selected from alkanediyl, preferably ethanediyl or propanediyl, D Ｌ１３ is C １ ~C ６ - selected from alkanediyl, preferably methanediyl or ethanediyl, Ar Ｌ１３ is C ６ ~C １０ an aromatic moiety, preferably p-phenylene; D Ｌ１１ , D Ｌ１２ teeth, (a) Linear or branched C １ ~C ６ alkanediyl; (b) both are part of a 5- or 6-membered aromatic heterocyclic ring system together with the two adjacent N atoms; D Ｌ２１ , D Ｌ２２ teeth, (a) Linear or branched C １ ~C ６ alkanediyl; (b) both are part of a 5- or 6-membered aromatic heterocyclic ring system together with the two adjacent N atoms; D Ｌ２３ is C １ ~C ６ is an alkanediyl, R Ｌ１ , R Ｌ２ is C １ ~C ６ alkyl; R Ｌ３ is H and C １ ~C ６ alkyl, X Ｌ２ is N or CR Ｌ３ and Y is a comonomer fragment, Z is a group of formula L4 【Chemistry 5】 is a divalent coupling fragment represented by Z Ｌ１ teeth, (a) a straight-chain or branched C group optionally interrupted by one or more O atoms; １ ~C １２ Alkanediyl, preferably C optionally interrupted by one or two O atoms １ ~C ６ Alkanediyl, or (b) a divalent group -D Ｌ１１ -Ar Ｌ１１ -D Ｌ１１ - is selected from Z Ｌ２ , Z Ｌ３ are independently selected from a chemical bond and hydroxyethanediyl; n is an integer from 1 to 400, m is 0 or an integer from 1 to 400; o is an integer from 1 to 100; A copper electroplating composition wherein p and r are independently 0 or 1.

2. B and B' are the same or different, preferably the same, and are an amino acid fragment of formula L2a, wherein D Ｌ１ (i) linear C ２ ~C １０ (ii) an alkanediyl group, ２ ~C ３ (iii) a cyclic C ６ ~C １２ 2. The composition of claim 1, wherein the aryl group is selected from (i) an alkanediyl group, or (ii) a divalent phenyl or pyridyl group.

3. B and B' are the same or different, preferably the same, and are a fragment of formula L2b, wherein: (a) D Ｌ１１ and D Ｌ１２ is a linear or branched C １ ~C ４ alkanediyl; or (b) D Ｌ１１ , D Ｌ１２ The composition of claim 1 , wherein: forms an imidazole ring together with two adjacent N atoms.

4. A is a fragment of formula L3a, and D Ｌ２ The composition of any one of claims 1 to 3, wherein is selected from methanediyl, ethanediyl, and 1,3-propanediyl.

5. A is a fragment of formula L3a, and D Ｌ２ is the formula L2a \(D Ｌ１０ ---) ｏ D Ｌ１０ - (,(aa) and wherein the ether or polyether group is selected from the group consisting of: In the formula, D Ｌ１０ is C １ ~C ４ -alkanediyl, and o is an integer from 1 to 50.

6. A is a fragment of formula L3b, wherein D Ｌ２１ , D Ｌ２２ , and D Ｌ２３ The composition of any one of claims 1 to 3, wherein is independently selected from methanediyl, ethanediyl, and propanediyl.

7. A is a fragment of formula L3b, wherein D Ｌ２１ and D Ｌ２２ forms an imidazole ring together with the two adjacent N atoms, and D Ｌ２３ The composition of any one of claims 1 to 3, wherein is independently selected from methanediyl, ethanediyl, propanediyl and butanediyl.

8. Z is C １ ~C １２ 3. The composition according to claim 1, wherein the alkyl group is selected from the group consisting of alkanediyl, bis(2-ethanediyl) ether groups, 2-hydroxypropane-1,3-diyl, and 4,4'-bis(methyl)biphenyl.

9. 3. The composition according to claim 1, wherein n is an integer from 2 to 200, preferably from 2 to 150.

10. 3. The composition according to claim 1, wherein m is 0 or an integer from 1 to 200, preferably 0 or an integer from 2 to 150.

11. The weight average molecular weight M of the polyaminoamide ｗ 3. The composition according to claim 1, wherein the .DELTA.H is from 450 g / mol to 150000 g / mol, preferably from 1000 g / mol to 50000 g / mol.

12. 3. The composition of claim 1 or 2, further comprising one or more accelerators, one or more inhibitors, or a combination thereof.

13. 3. A method of using the copper electroplating composition of claim 1 or 2 to deposit copper on a substrate containing recessed features comprising conductive feature bottoms and insulating feature sidewalls, wherein the recessed features have an opening size of 500 nm to 500 μm.

14. 1. A method for electrodepositing copper on a substrate containing recessed features including conductive feature bottoms and insulating feature sidewalls, comprising: a) contacting the substrate with the composition of claim 1 or 2; b) passing an electric current through the substrate for a time sufficient to deposit a copper layer in the recessed features; wherein the recessed features have an opening size between 500 nm and 500 μm.

15. The method of claim 14, wherein the opening size is between 1 μm and 200 μm.

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