Use of composition comprising compound of polyaminoamide type for copper nano-twin electrodeposition

Abstract

The present invention provides a novel use of a polyaminoamide comprising a group of formula N1 [B-A-B '-Z] n [Y-Z] m (N1), obtainable by reacting a diamine compound comprising two primary or secondary amino groups with an amino acid in a molar ratio of about 1: 2 to form an aminoamide compound, the aminoamide compound is then reacted with a coupling agent and optionally with a diamine or other comonomer.

Description

Background Art

[0001] The present invention relates to novel uses of copper electroplating compositions containing polyaminoamide-type additives and to copper electrodeposition methods.

[0002] Copper lines are formed by electroplating metal into very thin, high aspect ratio trenches and vias in a method commonly referred to as a "damascene" process (pre-passivation metallization).

[0003] As microelectronic devices advance, there is a continuing need to create smaller and denser interconnect features. One way to achieve this goal is to remove the solder between two separate substrates connecting copper vias, pads, bumps or pillars, which can be done, for example, through a process called Cu-Cu hybrid bonding.

[0004] Nanotwinned copper has attracted attention for use in microelectronics due to a combination of excellent mechanical properties, good electrical conductivity, and a unique structure. Nanotwinned copper (nt-Cu) exhibits excellent mechanical and electrical properties and can be used in a wide variety of applications in wafer-level packaging and advanced packaging designs. Nanotwinned copper refers to ultrafine-grained copper whose grains contain a high density of hierarchical nanotwins separated by coherent twin boundaries.

[0005] Nanotwinned copper can be obtained in several ways, including, for example, sputtering and electrolytic deposition. Direct current electrolytic plating is very compatible with industrial large-scale production. Twinning can occur in materials where two parts of the crystal structure are symmetrically related to each other. In the face-centered cubic (FCC) crystal structure including copper, the coherent twin boundary can be formed as a (111) mirror plane, from which the typical stacking order of the (111) plane is reversed. In other words, adjacent grains are mirrored across the coherent twin boundary in a layered (111)-structure. Twins grow in a layer-by-layer manner extending along the lateral (111) crystal planes, where the twin thickness is on the order of nanometers, hence the term "nano twins".

[0006] Compared with copper with conventional grain boundaries, nanotwinned copper has strong mechanical properties, including high strength and high tensile ductility. Nanotwinned copper also exhibits high electrical conductivity, which can be attributed to the twin boundaries, causing less significant electron scattering compared to grain boundaries. In addition, nanotwinned copper exhibits high thermal stability, which can be attributed to the twin boundaries having excess energy that is an order of magnitude lower than the energy of the grain boundaries. In addition, nanotwinned copper achieves high copper atomic diffusion rates, which is useful for direct bonding of copper to copper. Nanotwinned copper also shows high resistance to electromigration, which may be the result of twin boundaries slowing down electromigration-induced atomic diffusion. Nanotwinned copper exhibits strong resistance to seed etching that may be important in fine line redistribution layer applications. Nanotwinned copper also shows low impurity incorporation, which results in less Kirkendall gaps due to welding reactions with nanotwinned copper. In some embodiments, nanotwinned copper achieves direct copper-copper bonding. This copper-copper bonding can occur at low temperatures, moderate pressures, and lower bonding forces / times. Typically, the deposition of copper structures results in a rough surface. In some embodiments, prior to copper-copper bonding, the electrodeposition of nanotwinned copper can be followed by an electropolishing process to achieve a smooth surface. In the case of a smooth surface, the nanotwinned copper structure can be used for copper-copper bonding with shorter bonding times, lower temperatures, and fewer voids.

[0007] WO 2020 / 092244 and US 2013 / 0270121 A1 describe copper structures with high-density nanotwinned copper deposited on a substrate. It does not describe a specific electrolytic copper plating bath, but rather describes plating conditions like pulsed current, low temperature, etc.

[0008] US 10,566,314 describes how the optimal copper grain structure for Cu-Cu metal-to-metal bonding is a columnar grain microstructure. The copper grain microstructure plated by the disclosed inhibitor-only system produces a columnar grain structure due to the plating of nanotwinned copper.

[0009] US2013 / 0122326 A1 discloses an electrodeposited nano-twinned copper layer and a method for manufacturing the same. At least 50% of the volume of the electrodeposited nano-twinned copper layer comprises a plurality of grains adjacent to each other, wherein the grains are made of stacked twins, and the angle of the stacking direction of the nano-twins between one grain and the adjacent grain is between 0 and 20 degrees. The plating solution comprises copper sulfate, chloride anions and methyl sulfonate, and other surfactants or lattice modifiers (such as BASF Lugalvan) may be added.

[0010] WO 2021 / 197950 discloses a copper electroplating composition comprising a polyaminoamide-type leveling agent preparable from a diamine containing a tertiary amino group and a primary amino group or a secondary amino group, a diacid, and a coupling agent.

[0011] WO 2023 / 052254 discloses a composition comprising copper ions, an acid and at least one polyaminoamide, the polyaminoamide comprising a polyol having the formula [BA-B'-Z] n [YZ] m A group and its use for depositing copper bumps or RDL structures.

[0012] WO 2022 / 47480A1 discloses a copper electroplating solution for depositing nanotwinned columnar copper grains with a high density, the solution comprising a copper salt, a halide ion source, and a linear or branched polyhydroxyl, such as a reaction product between 2,3-epoxy-1-propanol and an amino alcohol or an ammonium alcohol.

[0013] For basic zinc or zinc alloys, such as ZnFeCo alloys, specific cationic polymers are used in electrodeposition compositions to enhance brightness and alloy composition uniformity. For example, one of these cationic polymers disclosed in US 5435898 is MIRAPOL AD-1 having the formula

[0014]

[0015] However, there is still a need in the art for an improved electrolytic copper composition for producing nanotwinned copper deposits. In addition, there is still a need in the art for an improved electrolytic copper composition capable of depositing nanotwinned copper with a (111) orientation and a large number of nanotwins.

[0016] An object of the present invention is to provide an acid copper electroplating composition which provides a copper deposit having nanotwinned copper with a (111) orientation and having a large number of nanotwins. Summary of the invention

[0017] Surprisingly, it has now been found that the use of specific cationic aminoamide polymers enables the formation of nanotwinned copper, in particular (111) oriented nanotwinned copper, having a large number of nanotwins.

[0018] Thus, the present invention provides polyaminoamides comprising groups of formula N1

[0019] [BA-B'-Z] n [YZ] m (N1)

[0020] A novel use in a composition for electrodeposition of nano-twinned copper, wherein

[0021] B, B' are the same or different, preferably the same, and are an amino acid fragment of formula N2a

[0022]

[0023] or an amino acid fragment of formula N2b

[0024]

[0025] or an amino acid fragment of formula N2c

[0026]

[0027] A is a diamine fragment independently selected from formula N3a

[0028]

[0029] or a diamine fragment of formula N3b

[0030]

[0031] D N1 Selected from a divalent group, the divalent group is selected from

[0032] (a) a C1-C2-amino group which may be optionally substituted with an amino group or interrupted with a double bond or an imino group 20 -alkanediyl,

[0033] (b) an ether or polyether group of formula N2c

[0034] -(D N10 -O-] o D N10 - (N2c)

[0035] D N2 is a divalent group selected from

[0036] (a) Straight chain, branched or cyclic C1 to C 20 Alkanediyl, which may be optionally interrupted by one or more NR N10 , or by one or more, preferably 1 or 2, groups NR N10 R N11 OR N10 Replace, or

[0037] (b) -D N13 -Ar N13 -D N13 -;or

[0038] (c) an ether or polyether group of formula N2c

[0039] D N10 Selected from linear or branched C1-C6-alkanediyl, preferably ethanediyl or propanediyl;

[0040] D N13is selected from C1-C6-alkanediyl, preferably selected from methanediyl and ethanediyl;

[0041] Ar N13 C6 to C 10 an aromatic moiety, preferably p-phenylene;

[0042] D N11 , D N12

[0043] (a) independently selected from linear or branched C1 to C6 alkanediyl, or

[0044] (b) both together with the two adjacent N atoms are part of a 5- or 6-membered aromatic heterocyclic ring system;

[0045] D N21 , D N22

[0046] (a) independently selected from linear or branched C1 to C6 alkanediyl, or

[0047] (b) both together with the two adjacent N atoms are part of a 5- or 6-membered aromatic heterocyclic ring system;

[0048] D N23 is C1 to C6 alkanediyl;

[0049] R N1 , R N2 Independently selected from C1 to C6 alkyl;

[0050] R N3 is selected from H and C1 to C6 alkyl;

[0051] R N10 , R N11 Independently selected from H or a linear or branched C1 to C6 alkanediyl group;

[0052] X N2 Is N or CR N3 ;

[0053] Y is a diamine comonomer segment;

[0054] Z is a divalent coupling fragment of formula N4

[0055]

[0056] Z N1 Selected from

[0057] (a) Straight or branched C1 to C2 may be intercalated with one or more oxygen atoms. 12 Alkanediyl, preferably C1 to C6 alkanediyl which may be inserted with 1 or 2 O atoms, or

[0058] (b) Divalent group -D N11 -Ar N11 -D N11 -;

[0059] Z N2 , Z N3 independently selected from a chemical bond and hydroxyethanediyl;

[0060] n is an integer from 1 to 400;

[0061] m is 0 or an integer from 1 to 400;

[0062] o is an integer from 1 to 6; and

[0063] p and r are independently 0 or 1;

[0064] wherein the ratio of n:m is at least 25:75.

[0065] The nanotwin accelerator according to the present invention is particularly useful for depositing nanotwinned copper with a (111) orientation having a large number of nanotwins. In addition, the nanotwin accelerator allows the filling of micron-scale recessed features without substantially forming defects, such as but not limited to voids. The nanotwin accelerator provides a copper electroplating bath that provides uniform and flat copper deposits, particularly in recessed features.

[0066] In addition, nanotwin promoters reduce impurities such as, but not limited to, organics, chlorides, sulfur, nitrogen, or other elements. In particular, when solder is plated directly on copper, higher organic impurity levels result in significant Kirkendall voids. These voids reduce the reliability of the solder stack and are therefore less preferred. The additives described herein also promote high plating rates and allow plating at high temperatures.

[0067] The invention further relates to a composition comprising copper ions, an acid and at least one polyaminoamide as defined in claim 1 comprising groups of formula N1, the composition being free of any sulfur-containing compounds and any polyalkylene oxide compounds.

[0068] The present invention further relates to a method for electrodepositing copper on a substrate comprising a recessed feature, the recessed feature comprising a conductive feature bottom and a dielectric feature sidewall, the method comprising:

[0069] a) contacting a composition comprising a polyaminoamide as described herein, and

[0070] b) applying an electric current to the substrate for a time sufficient to deposit nanotwinned copper on the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1ashows an overview FIB-SAM picture of a nanotwinned copper layer electrodeposited using the composition according to Example 2.1;

[0072] Figure 1b shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.1;

[0073] Figure 2 shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.2;

[0074] Figure 3 shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.3;

[0075] Figure 4 shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.4;

[0076] Figure 5 shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.5;

[0077] Figure 6 shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.6;

[0078] Figure 7 shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.7;

[0079] Figure 8 shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.8;

[0080] Fig. 9 shows a detailed FIB-SAM image of a nanotwinned copper layer electrodeposited using the composition according to Example 2.9; DETAILED DESCRIPTION

[0081] Surprisingly, it has been found that quaternized coupled aminoamide polymers can be advantageously used as nanotwin promoters in copper electrodeposition, i.e., they facilitate the deposition of copper having a columnar (111) orientation. The quaternized coupled aminoamide polymers result in a large number of nanotwins in the deposited copper layer. The quaternized coupled aminoamide polymers are also referred to herein as "cationic aminoamide polymers", "coupled aminoamide polymers", "coupled polyaminoamides", or "nanotwin promoters".

[0082] As used herein, "accelerator" refers to an organic additive that increases the plating rate of an electroplating bath. The terms "accelerator / accelerating agent" are used interchangeably throughout this specification. In the literature, accelerator components are sometimes also referred to as "brighteners / brightening agents". "Suppressors" refer to organic compounds that reduce the plating rate of an electroplating bath and ensure that recessed features are filled from bottom to top without voids (so-called "bottom-up filling"). The terms "suppressor / suppressing agent" are used interchangeably throughout this specification. "Leveling agent" refers to an organic compound that is capable of providing a substantially flat metal deposit on areas with a higher or lower number of recessed features or across different areas of a wafer or die. The terms "leveler / leveling agent" and "leveling additive" are used interchangeably throughout this specification.

[0083] "Aperture size" according to the present invention means the minimum diameter or free distance of a recessed feature before plating. The terms "width", "diameter", "aperture" and "opening" are used synonymously herein, depending on the geometry of the feature (groove, through hole, etc.). As used herein, "aspect ratio" means the ratio of the depth of a recessed feature to the aperture size.

[0084] As used herein, "chemical bond" means that the corresponding moieties do not exist but the adjacent moieties are bridged so as to form a direct chemical bond between these adjacent moieties. For example, if in molecule ABC moiety B is a chemical bond, then adjacent moieties A and C together form a group AC.

[0085] The term "C x " means that the corresponding group contains x number of C atoms. The term "C x To C y "Alkyl" means an alkyl group having a number of x to y carbon atoms, and unless specifically specified otherwise, includes unsubstituted straight chain, branched chain and cyclic alkyl groups. As used herein, "alkanediyl" refers to a diradical of a straight chain, branched chain or cyclic alkane or a combination thereof.

[0086] As used herein, "aromatic ring" covers both aryl and heteroaryl groups.

[0087] As used herein, "high amount of nanotwinning" or "high amount of nanotwins" refers to a copper structure having greater than about 80% nanotwins, and even greater than about 90% nanotwins, as observed using appropriate microscopy techniques.

[0088] Nano twinning accelerator

[0089] In addition to copper ions and an acid, the metal electroplating composition comprises at least one nanotwinning promoter in the form of a cationic polyaminoamide of formula I:

[0090] [BA-B'-Z] n [YZ] m (N1)

[0091] The additive according to formula N1 is generally obtainable by first reacting a diamine compound ('a') comprising two primary or secondary amino groups with an amino acid 'b' in a molar ratio of about 1:2 to form an aminoamide compound bA-b'. In contrast to the compounds disclosed in US 6425996B1, discrete monomeric compounds are obtained in the intermediate product.

[0092] Subsequently, the monomeric aminoamide intermediate compound is reacted with a coupling agent 'z' to connect several aminoamide compounds to each other to form a coupled aminoamide [AB-A'-Z] according to the present invention. n .

[0093] As an example, this reaction scheme shows the preparation of a nanotwinned promoter starting from propane-1,3-diamine, N,N-dimethylglycine and epichlorohydrin:

[0094]

[0095] In the first step, discrete aminoamide monomers bA-b' are prepared and then coupled together with a coupling agent z. In this case, m is zero.

[0096] It is also possible to couple a further comonomer Y comprising at least two amino groups with the aminoamide compound. In this case, m is equal to or greater than 1. The diamine comonomer may comprise tertiary, secondary or primary amino groups, preferably two tertiary amino groups. The advantage of using a comonomer is that a nanotwinned promoter of higher molecular weight is obtained. In this context, "comonomer" means a comonomer that can be coupled with the compound [AB-A'-Z] n Any compound that forms a copolymer; a comonomer can be a monomer as well as a polymer compound.

[0097] Fragments A, B, B', Z and Y are described in more detail below.

[0098] In the first embodiment, amino acid compounds b and 'b' form two amino acid fragments B and B' of formula N2a.

[0099]

[0100] In formula N2a, the amino acid spacer D N1 is selected from a divalent group selected from (a) a C1-C2-C3-C4-C6 ... 20 -alkanediyl, or (b) an ether or polyether group of formula N2a

[0101] -(D N10 -O-] o D N10 -(N2c)

[0102] Where D N10 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 15. In a specific embodiment, o is from 3 to 10, in another embodiment, o is from 10 to 20.

[0103] In a preferred embodiment, D N1 Selected from (i) a linear C2 to C3 residue which may be unsubstituted or substituted with an amino group 10 alkanediyl, (ii) C2 to C3 oxyalkylene, (iii) cyclic C6 to C 12 an alkanediyl group, or (iv) a divalent phenyl group or a pyridyl group.

[0104] In another preferred embodiment, D N1 is selected from ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, or decanediyl, which may be unsubstituted or substituted with amino. Most preferably, D N1 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.

[0105] In formula N2a, R N1 and R N2 R is independently selected from C1 to C6 alkyl, preferably methyl, ethyl or propyl. N3 Selected from H and C1 to C6 alkyl, preferably selected from H and methyl.

[0106] In another embodiment, amino acid compounds b and 'b' form two amino acid fragments B and B' of formula N2b.

[0107]

[0108] In formula N2b, the divalent group D N11 and D N12 Independently selected from linear or branched C1 to C6 alkanediyl groups. N1 R may be the same as defined above for formula N2a. N1 Selected from C1 to C6 alkyl, preferably methyl, ethyl and propyl.

[0109] In a first preferred embodiment of formula N2b, D N11 and D N12 is independently selected from a linear or branched C1 to C4 alkanediyl group. Even more preferably, D N11 and D N12 Selected from (CH2) g , wherein g is an integer from 1 to 6, preferably 1 to 3. Most preferably, D N11 and D N12 Both are ethanediyl, or D N11 is methanediyl and D N12 It is propanediyl.

[0110] In another preferred embodiment of formula N2b, D N11 and D N12 Together with two adjacent N atoms, it forms an imidazole ring.

[0111] In another embodiment, amino acid compounds b and 'b' form two aromatic heterocyclic amino acid fragments B and B' of formula N2c.

[0112]

[0113] In formula N2b, D N1 may be the same as defined above for formula N2a.

[0114] Without limitation, tertiary amino acids particularly useful for preparing the nanotwin promoter according to the present invention are N,N-dimethylglycine, 3-(dimethylamino)propionic acid, 4-(dimethylamino)butyric acid, 5-(dimethyl-amino)pentanoic acid, 1H-imidazole-1-acetic acid, 1H-imidazole-1-propionic acid, 1H-imidazole-1-butyric acid and amino acids of formula N2d

[0115]

[0116] The amino acids can be used in the form of free acids or as carboxylic acid derivatives, such as anhydrides, esters, amides or acid halides, in particular acid chlorides. Preference is given to using free amino acids.

[0117] Since amino acid fragments B and B' are positively charged, counterions Y are required. y- To neutralize the entire composition, wherein y is a positive integer. Preferably, such counterions may be selected from halides, in particular chlorides, methanesulfonates, sulfates or acetates.

[0118] The diamine compound 'a' forms a diamine fragment A of formula N3a

[0119]

[0120] or a diamine fragment of formula N3b

[0121]

[0122] Herein, the primary or secondary amine functional groups of the two amine compounds are respectively combined with the carbonyl functional groups of the amino acid fragments.

[0123] In the first embodiment of formula N3a, the divalent group D N2 Selected from linear or branched C1 to C 20 Alkanediyl, which may be optionally interrupted by one or more NR N10 or S or one or more, preferably 1 or 2, groups NR N10 R N11 OR N10 Substitution, where R N10 , R N11 are independently selected from H and C1-C 10 Alkyl, more preferably selected from H and C1-C4 alkyl, most preferably selected from H, methyl or ethyl. In a particularly preferred embodiment, D N2 is selected from a linear or branched C1 to C6 alkanediyl group. Even more preferably, D N2 Selected from (CH2) g , wherein g is an integer from 1 to 6, preferably 1 to 3. Most preferably, D N2 It is 1,2-ethanediyl or 1,3-propanediyl.

[0124] In the second embodiment of formula N3a, the divalent group D N2 Selected from -D N11 -Ar N13 -D N13 , where D N13 is selected from C1-C6-alkanediyl, preferably methanediyl or ethanediyl, and Ar N13 C6 to C 10 An aromatic moiety, preferably phenylene, most preferably p-phenylene.

[0125] In the third embodiment of formula N3a, the divalent group D N2 An ether or polyether group selected from formula N2a

[0126] -(D N10 -O-] o D N10 -(N2a)

[0127] Where D N10 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 specific embodiment, o is an integer from 3 to 10, in another embodiment, o is an integer from 10 to 40.

[0128] In formula N3b, the divalent group D N21 and D N22 (a) is independently selected from a linear or branched C1 to C6 alkanediyl group, preferably methanediyl, ethanediyl or propanediyl, or (b) D N21 and D N22 Together with the two adjacent N atoms, they are part of a 5- or 6-membered aromatic heterocyclic ring system. N23 It may be a C1 to C6 alkanediyl group, preferably methanediyl, ethanediyl, propanediyl or butanediyl, most preferably methanediyl, ethanediyl or propanediyl. N3 X may be selected from H and C1 to C6 alkyl, preferably H or methyl, most preferably H. N2 Can be N or CR N3 , preferably N, CH or C-CH3; p and r may be identical or different and are 0 or 1. If p or r is 1, the corresponding amino acid is attached to a primary or secondary amine function; if p or r is 0, the corresponding amino acid is attached to a secondary amine function as part of a ring system.

[0129] In a first preferred embodiment of formula N3b, D N21 and D N22 is independently selected from a linear or branched C1 to C4 alkanediyl group. Even more preferably, D N21 and D N22 Selected from (CH2) g , wherein g is an integer from 1 to 6, preferably 1 to 3. Most preferably, D N21 and D N22 Both are ethanediyl, or D N21 is methanediyl and D N22 It is propanediyl.

[0130] In a second preferred embodiment of formula N3b, D N21 and D N22 Together with two adjacent N atoms, it forms an imidazole ring.

[0131] Particularly useful diamines for preparing nanotwinned promoters 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'-diaminodicyclohexylmethane, 4,7,10-trioxatridecane-1,13-diamine, xylene diamine, poly(propylene glycol) bis(2-aminopropyl ether) having an average degree of polymerization of 1 to 50, preferably 2 to 40, most preferably 1 to 10, and lysine.

[0132] As used herein, "average degree of polymerization" means the average number of repeating monomer units in a polymer.

[0133] The coupling agent 'z' forms a coupling fragment Z of formula N4

[0134]

[0135] in

[0136] Z N1 Selected from

[0137] (a) Straight or branched C1 to C2 may be intercalated with one or more oxygen atoms. 12 Alkanediyl, preferably C1 to C6 alkanediyl which may be interrupted by 1 or 2 O atoms; or

[0138] (b) Divalent group -D N11 -Ar N11 -D N11 -;

[0139] Z N2 , Z N3 Independently selected from a chemical bond or hydroxyethanediyl.

[0140] In a first preferred embodiment, Z N1 Select from C1 to C 12 In a second preferred embodiment, Z N1 Selected from formula -(D N10 -O-] o D N10 -alkyl ether or polyalkyl ether radical, in particular bis(2-ethanediyl)ether radical, wherein D N10 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 specific embodiment, o is from 1 to 5, in another embodiment, o is from 5 to 15. In a third preferred embodiment, Z N1Selected from divalent groups -D N11 -Ar N11 -D N11 -, especially biphenyl, wherein D N11 is selected from C1-C6-alkanediyl, preferably methanediyl or ethanediyl, and Ar N11 C6 to C 12 An aromatic moiety, preferably a phenylene or a biphenylene.

[0141] In another preferred embodiment, Z N2 Select from chemical bonds and Z N3 In another preferred embodiment, Z N2 and Z N3 Both are selected from chemical bonds.

[0142] Such coupling fragments Z are derived from coupling agents comprising leaving groups such as, but not limited to, halogens, in particular Cl or Br, and / or epoxy groups.

[0143] Particularly preferred coupling agents 'z' are selected from bis(2-chloroethyl)ether; bis(2-chloroethoxy)ethane; epichlorohydrin, 1,ω-dihalogenated (C2-C 10 ) alkane, such as but not limited to 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane and 1,6-dichlorohexane; bis(2-chloroethyl) ether, di(haloalkyl) aryl, such as but not limited to dichloroxylene and 4,4'-bis(bromomethyl) biphenyl. In this article, chlorine or bromine can be exchanged by other leaving groups, such as but not limited to trifluoromethanesulfonate, tosylate, mesylate.

[0144] In formula N1, n may be an integer from 1 to 400, preferably from 2 to 200, more preferably from 2 to 150. In a specific embodiment, n may be an integer from 2 to 50, and in another embodiment, n is 50 to 150.

[0145] In formula N1, m is 0 or, if comonomers are present, an integer from 1 to 400, preferably from 1 to 200, more preferably from 2 to 150.

[0146] If comonomers are used, the ratio of n to m should be high enough to ensure nanotwin formation. If n is too low, insufficient nanotwins are formed. If n is too high, the molecular weight increase effect of the comonomer is low. Therefore, the ratio of n to m can be from 25:75 to 99.5:0.5, preferably from 30:70 to 90:10 or from 40:60 to 96:4, even more preferably from 30:70 to 70:30, even more preferably from 50:50 to 99.5:0.5, even more preferably from 50:50 to 99:1, even more preferably from 60:40 to 99.5:0.5, even more preferably from 70:30 to 99.5:0.5, most preferably from 80:20 to 99.5:0.5.

[0147] Usually, the mass average molecular weight of the nanotwin accelerator is w It may be from about 450 to about 150,000 g / mol, preferably from about 1,000 to about 80,000 g / mol, most preferably from about 1,000 to about 50,000 g / mol.

[0148] The first preferred embodiment of the nanotwinning promoter is a coupled aminoamide of formula N5

[0149]

[0150] wherein the general definitions are those provided above. Preferably, D N1 and D N2 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, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl. In another embodiment, a cyclic alkanediyl D may be used. N2 , such as but not limited to

[0151]

[0152] or

[0153]

[0154] In addition to diamines, triamines, tetraamines or other polyamines may be used.

[0155] A second preferred embodiment of the nanotwinning promoter is a cyclic coupled aminoamide of formula N6a or N6b

[0156]

[0157] wherein the general definitions are those provided above. Preferably, D N1 and D N2Independently 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.

[0158] A third preferred embodiment of the nanotwinning promoter is a coupled aminoamide of formula N7

[0159]

[0160] wherein the general definitions are those provided above. Preferably, D N1 is selected from the group consisting of methanediyl, ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl and decanediyl; R N3 is selected from H, methyl, ethyl and propyl; and o is an integer from 2 to 50, preferably 2 to 40.

[0161] A fourth preferred embodiment of the nanotwinning promoter is a coupled aminoamide of formula N8

[0162]

[0163] wherein the general definitions are those provided above. Preferably, Ar N13 D is phenylene, especially benzene-1,4-diyl; N13 and D N1 Independently selected from methanediyl, ethanediyl, propanediyl and butanediyl.

[0164] A fifth preferred embodiment of the nanotwinning promoter according to the present invention is a coupled aminoamide of formula N9

[0165]

[0166] wherein the general definitions are those provided above. Preferably, D N1 and D N23 is independently selected from methanediyl, ethanediyl, propanediyl and butanediyl; D N21 and D N22 R is independently selected from methanediyl, ethanediyl and propanediyl; N1 and R N2 Independently selected from methyl, ethyl, propyl and butyl.

[0167] The aminoamide polymers described herein are typically terminated with a tertiary amine group or a partially reacted coupling agent 'z'.

[0168] Particularly preferred polyaminoamide nanotwinning promoters are:

[0169]

[0170]

[0171] In an alternative embodiment of formula N1, m is equal to or greater than 1 and Y is an amine comonomer fragment obtained when an amine comonomer 'y' comprising at least two tertiary or secondary amino groups is co-coupled with an aminoamide compound. The co-coupling can be performed in a mixture or sequentially in any order. Preferred is the co-coupling from a mixture comprising aminoamide and amine comonomers.

[0172] In the following, copolymeric nanotwin promoters with m≥1 are described in more detail.

[0173] In the simplest case, Y may be a fragment of formula N3a or formula N3b. In this case, Y may be the same as or different from A and A'.

[0174] In another embodiment, Y can be other fragments disclosed on page 6 of US2016 / 0076160 A1 (independent of its counterion Cl - ), which is incorporated herein by reference.

[0175] In yet another embodiment, Y can be a fragment of formula M2

[0176]

[0177] in

[0178] Y M21 For each repeating unit l to q is independently selected from nitrogen, an amide group or a urea group;

[0179] X M21 , X M22 Independently selected from C2 to C6 alkanediyl, preferably ethanediyl, propanediyl or butanediyl;

[0180] R M21 , R M23 Independently selected from H and C1 to C6 alkyl, preferably methyl, ethyl, propyl or butyl;

[0181] R M22 is C1 to C6 alkyl, preferably methyl or ethyl;

[0182] p is an integer from 1 to 100, preferably from 3 to 50, most preferably from 5 to 30;

[0183] q is an integer from 0 to 5.

[0184] In a preferred embodiment, Y can be a diamine fragment of formula M3a, M3b or M3c

[0185]

[0186] in

[0187] R M31 , R M32 , R M33 , R M34 and R M31 Independently selected from H and C1 to C6 alkyl, or an adjacent group R M31 , R M32 , R M33 , R M34 or R M31 Two of them together form a C1 to C3 alkanediyl;

[0188] D M31 and D M32 are independently C2 to C6 alkyl, preferably ethanediyl, propanediyl or butanediyl, most preferably ethanediyl or propanediyl;

[0189] t is an integer from 1 to 100, preferably from 3 to 50, more preferably from 5 to 30.

[0190] In another preferred embodiment, Y can also be a polyaminoamide fragment of formula M1

[0191]

[0192] in

[0193] X M11 For each repeating unit l to p, independently selected from a chemical bond or selected from C1-C 20 - a divalent radical of an alkanediyl radical, which may optionally be interrupted (by double bonds and / or imino groups) and / or may optionally be a constituent of one or more saturated or unsaturated carbocyclic 5- to 8-membered rings,

[0194] X M12 , X M13 are independently a linear or branched C1 to C6 alkanediyl group,

[0195] R M1 For each repeating unit 1 to n, independently selected from R M12 、C1-C 20 -alkyl and C1-C 20 -alkenyl, which may be optionally substituted by hydroxy, alkoxy or alkoxycarbonyl;

[0196] R M12 Selected from hydrogen and –(CR M13 R M14 -CR M15 R M16 -O) r -H;

[0197] R M13 , R M14 , R M15 , R M16 Each independently selected from hydrogen, C1-C 10 Alkyl and -CH2-O-alkyl,

[0198] p is an integer from 2 to 150;

[0199] q is an integer from 0 to 5;

[0200] r is the average degree of alkoxylation and is a number from 0.01 to 5.

[0201] Such polyaminoamides are described in more detail in WO 11 / 064154 A2.

[0202] 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-propylenediamine, tetramethyl-1,4-butylenediamine, tetramethyl-1,6-hexanediamine, tetramethyl-1,8-octanediamine, tetraethyl-1,3-propylenediamine, tetramethylphenylenediamine, bis(dimethylaminoethyl)ether, tetramethyl-2-butene-1,4-diamine, tetramethyl-2,2-dimethyl-1,3-propylenediamine. By using comonomers, the properties of the additive can be further influenced, for example by increasing or decreasing the nitrogen content, the hydrophilicity, the charge and charge density or other chemical or physical properties.

[0203] The most preferred nanotwinning promoter is

[0204]

[0205] or

[0206]

[0207] The condensation of amino acids and diamines is usually carried out by heating the amino acids and diamines to a temperature of, for example, from 100°C to 250°C, preferably from 120°C to 200°C, and distilling off the reaction water formed in the condensation. If the amino acid derivative is used, the condensation can also be carried out at a temperature below the given temperature. The preparation of cationic aminoamide polymers can be carried out without adding a catalyst, or alternatively using an acidic or basic catalyst. Suitable acidic catalysts are, for example, acids such as Lewis acids, such as sulfuric acid, p-toluenesulfonic acid, phosphorous acid, hypophosphorous acid, phosphoric acid, methanesulfonic acid, boric acid, aluminum chloride, boron trifluoride, tetraethyl orthotitanate, tin dioxide, butyl dilaurate tin or a mixture 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 carbonate, potassium carbonate and calcium carbonate, phosphates such as potassium phosphate and complex metal hydrides such as sodium borohydride. When used, the catalyst is generally used in an amount of from 0.05 to 10 wt%, preferably 0.5 to 1 wt%, based on the total amount of the starting materials.

[0208] Reaction can be carried out in a suitable solvent or preferably in the absence of a solvent. If a solvent is used, suitable examples are hydrocarbons such as toluene or dimethylbenzene, nitrile such as acetonitrile, acid 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. Usually during the reaction or when the reaction is completed, the solvent is distilled off. This distillation can be carried out alternatively under protective gas (such as nitrogen or argon).

[0209] Typically, the total amount of nanotwin promoter in the electroplating bath is from 0.05 ppm to 10000 ppm based on the total weight of the plating bath. The nanotwin promoter is typically used in a total amount from about 0.1 ppm to about 1000 ppm and more typically from 2 to 250 ppm based on the total weight of the plating bath, although more or less amounts may be used. Most preferably, the nanotwin promoter is used in a total amount from about 5 ppm to about 100 ppm, particularly from about 7.5 ppm to about 50 ppm, based on the total weight of the plating bath.

[0210] Other additives

[0211] Typically a wide variety of additional additives can be used in the bath to provide the desired surface treatment for the Cu plated metal. Typically more than one additive is used, each additive forming a desired function. Advantageously, the electroplating bath may contain one or more of a promoter, an inhibitor, a leveling agent, a halide ion source, a grain refiner, and mixtures thereof. Most preferably, in addition to the nanotwin promoter according to the present invention, the electroplating bath also contains both a promoter and an inhibitor. Other additives may also be suitably used in the electroplating bath of the present invention.

[0212] Accelerator

[0213] Generally, any accelerator can be used in the plating bath according to the present invention. As used herein, "accelerator" refers to an organic additive that increases the plating rate of the electroplating bath. The term "accelerator (accelerator / accelerating agent)" is used interchangeably throughout this specification. In the literature, accelerator components are sometimes also referred to as "brighteners (brightener)", "brightening agents (brightening agent)", or "depolarizers". Accelerators that can be used in the present invention include but are not limited to compounds or salts thereof comprising one or more sulfur atoms and sulfonic acid / phosphonic acid. In one embodiment, the composition further comprises at least one accelerator. In another embodiment, the composition does not contain any sulfur-containing accelerator.

[0214] If present, preferred promoters have the general structure MO3Y A -X A1 -(S) d R A2 ,in:

[0215] - M is hydrogen or an alkali metal, preferably Na or K;

[0216] -Y A is P or S, preferably S;

[0217] - d is an integer from 1 to 6, preferably 2;

[0218] -X A1 Selected from C1-C8 alkanediyl or heteroalkanediyl, divalent aryl or divalent heteroaromatic group. Heteroalkyl will have one or more heteroatoms (N, S, O) and 1-12 carbons. Carbocyclic aryl is typically aryl, such as phenyl or naphthyl. Heteroaromatic group is also suitably aryl and contains one or more N, O or S atoms and 1-3 separate or condensed rings.

[0219] -R A2 Select H or (-SX A1 'Y A O3M), where X A1 ' is independently selected from the group XA1 .

[0220] More specifically, useful accelerators include those of the formula:

[0221] MO3S-X A1 -SH

[0222] MO3S-X A1 -SSX A1 '-SO3M

[0223] MO3S-Ar-SS-Ar-SO3M

[0224] Where X A1 As defined above and Ar is aryl.

[0225] Particularly preferred accelerators are:

[0226] -SPS: bis-(3-sulfopropyl)-disulfide

[0227] -MPS: 3-mercapto-1-propanesulfonic acid.

[0228] Both are usually applied in the form of their salts, especially their sodium salts.

[0229] Other examples of accelerators used alone or in mixtures 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-propanesulfonic acid); ZPS (3-(2-benzothiazolylthio)-1-propanesulfonic acid sodium salt); 3-mercapto-propylsulfonic acid-(3-sulfopropyl) ester; methyl-( -sulfopropyl)-disulfide disodium salt; methyl-( -sulfopropyl)-trisulfide disodium salt.

[0230] If used, such accelerators are typically used in amounts of 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 1 to 500 ppm and more particularly 2 to 100 ppm.

[0231] Inhibitors

[0232] Inhibitors can be used in combination with additives according to the present invention. As used herein, "inhibitors" are additives that increase overpotential during electrodeposition. The terms "surfactant" and "inhibitor" are used synonymously here because the inhibitors described herein are also surface-active substances. Typically, the inhibitor is a polyalkylene oxide containing an oxy (C2 to C4) alkylene homopolymer or copolymer, which is obtainable by polyoxyalkylation of an alcohol or amine starter. In one embodiment, the composition further comprises at least one inhibitor. In another embodiment, the composition does not contain any polyol inhibitor, particularly does not contain any polyalkylene glycol and polyoxyalkylene type inhibitor, most particularly does not contain any polyoxyalkylene type inhibitor.

[0233] Particularly useful inhibitors, if any, are:

[0234] (a) Inhibitors obtainable by reacting an amine compound comprising at least three reactive amino functional groups with a mixture of ethylene oxide and at least one compound selected from C3 and C4 alkylene oxides, as described in WO 2010 / 115796.

[0235] Preferably, the amine compound is selected from diethylenetriamine, 3-(2-aminoethyl)aminopropylamine, 3,3′-iminobis(propylamine), N,N-bis(3-aminopropyl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetramine and N,N′-bis(3-aminopropyl)ethylenediamine.

[0236] (b) an inhibitor obtainable by reacting an amine compound containing a reactive amino functional group with a mixture of ethylene oxide and at least one compound selected from C3 and C4 alkylene oxides to form an ethylene C3 and / or C4 alkylene random copolymer, the inhibitor having a molecular weight M of 6000 g / mol or more w , as described in WO 2010 / 115756.

[0237] (c) an inhibitor obtainable by reacting 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 in mixture or in sequence, the inhibitor having a molecular weight M of 6000 g / mol or more w , as described in WO 2010 / 115757.

[0238] Preferably, the amine compound is selected from ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, neopentyldiamine, isophoronediamine, 4,9-dioxadecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, triethylene glycol diamine, diethylenetriamine, (3-(2-aminoethyl)aminopropylamine, 3,3′-iminobis(propylamine), N,N-bis(3-aminopropyl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetramine and N,N′-bis(3-aminopropyl)ethylenediamine.

[0239] (d) an inhibitor selected from the group consisting of compounds of formula S1

[0240]

[0241] Where R S1 The groups are each independently selected from copolymers of ethylene oxide and at least one additional C3 to C4 alkylene oxide, the copolymers being random copolymers, R S2 The groups are each independently selected from R S1 or alkyl, X S and Y S are independently spacer groups, and for each repeating unit s, X S independently selected from C2 to C6 alkanediyl and Z S -(OZ S ) t , where Z S The groups are each independently selected from C2 to C6 alkanediyl groups, s is an integer equal to or greater than 0, and t is an integer equal to or greater than 1, as described in WO 2010 / 115717.

[0242] Preferably, the spacer group X S and Y S Independently, and for each repeating unit, X S is independently selected from C2 to C4 alkylene. Most preferably, X S and Y S Independently, and for each repeating unit s, X S Independently selected from ethylene (-C2H4-) or propylene (-C3H6-).

[0243] Preferably, Z S Selected from C2 to C4 alkylene, most preferably selected from ethylene or propylene.

[0244] Preferably, s is an integer from 1 to 10, more preferably from 1 to 5, most preferably from 1 to 3. Preferably, t is an integer from 1 to 10, more preferably from 1 to 5, most preferably from 1 to 3.

[0245] In another preferred embodiment, the C3 to C4 alkylene oxide is selected from propylene oxide (PO). In this case, the EO / PO copolymer side chains are generated starting from the active amino functional groups.

[0246] The ethylene oxide content of the copolymer of ethylene oxide and additional C3 to C4 alkylene oxide can generally be from about 5% to about 95% by weight, preferably from about 30% to about 70% by weight, particularly preferably between about 35% to about 65% by weight.

[0247] 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, neopentyldiamine, isophoronediamine, 4,9-dioxadecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, triethylene glycol diamine, diethylenetriamine, (3-(2-aminoethyl)amino)propylamine, 3,3′-iminobis(propylamine), N,N-bis(3-aminopropyl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetramine and N,N′-bis(3-aminopropyl)ethylenediamine.

[0248] The molecular weight M of the inhibitor of formula S1 is w The molecular weight M may be between about 500 g / mol and about 30,000 g / mol. w It should be about 6000 g / mol or greater, preferably from about 6000 g / mol to about 20000 g / mol, more preferably from about 7000 g / mol to about 19000 g / mol and most preferably from about 9000 g / mol to about 18000 g / mol. The preferred total amount of alkylene oxide units in the inhibitor can be from about 120 to about 360, preferably from about 140 to about 340, most preferably from about 180 to about 300.

[0249] A typical total amount of alkylene oxide units in the inhibitor may be about 110 ethylene oxide units (EO) and 10 propylene oxide units (PO), about 100 EO and 20 PO, about 90 EO and 30 PO, about 80 EO and 40 PO, about 70 EO and 50 PO, about 60 EO and 60 PO, about 50 EO and 70 PO, about 40 EO and 80 PO, about 30 EO and 90 PO, about 100 EO and 10 butylene oxide (BO) units, about 90 EO and 20 BO, about 80 EO and 30 BO, about 70 EO and 40 BO, about 60 EO and 50 BO, or about 40 EO and 80 PO. and 60 BO to about 330 EO and 30 PO units, about 300 EO and 60 PO, about 270 EO and 90 PO, about 240 EO and 120 PO, about 210 EO and 150 PO, about 180 EO and 180 PO, about 150 EO and 210 PO, about 120 EO and 240 PO, about 90 EO and 270 PO, about 300 EO and 30 BO units, about 270 EO and 60 BO, about 240 EO and 90 BO, about 210 EO and 120 PO, about 180 EO and 150 BO, or about 120 EO and 180 BO.

[0250] (e) by condensing at least one polyol X derived from formula (S2) S (OH) u An inhibitor obtained by reacting a polyol condensation compound of with at least one alkylene oxide to form a polyol condensate containing a polyoxyalkylene side chain, wherein u is an integer from 3 to 6 and X S is a u-valent straight-chain or branched aliphatic or alicyclic group having from 3 to 10 carbon atoms, which may be substituted or unsubstituted, as described in WO 2011 / 012462.

[0251] Preferred polyol condensates are selected from compounds of the formula

[0252]

[0253]

[0254] where Y S is a u-valent straight or branched aliphatic or alicyclic group having from 1 to 10 carbon atoms which may be substituted or unsubstituted, a is an integer from 2 to 50, b may be the same or different for each polymer arm and 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 polyol is a glycerol condensate and / or a pentaerythritol condensate.

[0255] (f) Inhibitors obtainable by reacting a polyol containing at least 5 hydroxyl functional groups with at least one alkylene oxide to form a polyol containing polyoxyalkylene side chains, as described in WO 2011 / 012475. Preferred polyols are linear or cyclic monosaccharide alcohols represented by formula (S3a) or (S3b)

[0256] HOCH2-(CHOH) v -CH2OH (S3a)

[0257] (CHOH) w (S3b)

[0258] wherein v is an integer from 3 to 8 and w is an integer from 5 to 10. The most preferred monosaccharide alcohols are sorbitol, mannitol, xylitol, ribitol and inositol. Further preferred polyols are monosaccharides of formula (S4a) or (S4b)

[0259] CHO-(CHOH) x -CH2OH(S4a)

[0260] CH2OH-(CHOH y -CO-(CHOH) z -CH2OH(S4b)

[0261] wherein x is an integer from 4 to 5, and y, z are integers and y+z is 3 or 4. The most preferred monosaccharide alcohol is selected from the aldoses allose, altrose, galactose, glucose, gulose, idose, mannose, talose, glucoheptose, mannoheptose, or the ketones fructose, psicose, sorbose, tagatose, mannoheptulose, sedoheptulose, taloheptulose, alloheptulose.

[0262] (g) Amine polyoxyalkylene inhibitors based on cyclic amines show extraordinary superfilling properties as described in WO 2018 / 073011.

[0263] (h) Polyamine-based or polyol-based inhibitors modified by reaction with compounds such as, but not limited to, glycidol or glycerol carbonate that introduce branching groups into the inhibitor prior to reaction with the alkylene oxide show extraordinary superfilling properties, as described in WO 2018 / 114985.

[0264] When inhibitors are used, they are typically present in amounts ranging from about 1 to about 10,000 ppm and preferably from about 5 to about 10,000 ppm based on the weight of the bath.In one embodiment, the composition is free of any of the inhibitors described in this section.

[0265] Leveling agent

[0266] Additional leveling agents may be used in the copper electroplating baths according to the present invention.

[0267] Suitable leveling agents include, but are not limited to, one or more of the following: other polyethyleneimines and their derivatives, quaternized polyethyleneimines, polyglycine, poly(allylamine), polyaniline, 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, polyvinylpyridine, polyvinylimidazoles such as described, for example, in WO 2011 / 151785 A1, polyvinylpyrrolidone, polyaminoamides such as described, for example, in WO 2011 / 064154 A2 and WO 2014 / 072885 A2, or copolymers thereof, nigrosine, pentamethyl-para-magenta hydrohalides, hexamethyl-para-magenta hydrohalides, dialkanolamines or trialkanolamines and their derivatives such as described in WO 2010 / 069810, such as WO 2012 / 085811 The biguanide described in A1, or a compound containing a functional group of formula NRS, wherein R is a substituted alkyl, an unsubstituted alkyl, a substituted aryl or an unsubstituted aryl. Typically, the alkyl is a C1-C6 alkyl and preferably a C1-C4 alkyl. Typically, the aryl includes C6-C 20 Aryl, preferably C6-C 10 Aryl. Preferably, aryl is phenyl or naphthyl. Compounds containing a functional group having the formula NRS are generally known, are generally commercially available and can be used without further purification.

[0268] In such compounds containing NRS functional groups, sulfur ("S") and / or nitrogen ("N") may be attached to such compounds via single bonds or double bonds. When sulfur is attached to such compounds via a single bond, sulfur will have another substituent such as, but not limited to, hydrogen, C1-C 12 Alkyl, C2-C 12 Alkenyl, C6-C 20 Aryl, C1-C 12 Alkylthio, C2-C 12 Thiol, C6-C 20 Likewise, nitrogen will have one or more substituents such as, but not limited to, hydrogen, C1-C 12 Alkyl, C2-C 12 Alkenyl, C7-C 10 Aryl, etc. 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.

[0269] Further details and alternatives are described in WO 2018 / 219848, WO 2016 / 020216 and WO 2010 / 069810, respectively, which are incorporated herein by reference.

[0270] In one embodiment, the composition further comprises at least one leveling agent as disclosed above. In another embodiment, the composition does not contain any leveling agent described in this section.

[0271] If used, 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. Leveling agents according to the present invention are typically used in a total amount of from about 100 ppm to about 10000 ppm based on the total weight of the plating bath, although greater or lesser amounts may be used.

[0272] Electrolytes

[0273] The electroplating composition according to the present invention includes and comprises an electrolyte of copper ions and an acid.

[0274] Copper ions

[0275] The copper ion source can be any compound capable of releasing metal ions in sufficient amounts to be deposited in the electroplating bath (i.e., at least partially soluble in the electroplating bath). It is preferred that the metal ion source is soluble in the plating bath. Suitable metal ion sources are metal salts and include, but are not limited to, sulfates, halides, acetates, nitrates, fluoroborates, alkyl sulfonates, aryl sulfonates, sulfamates, metal gluconates, and the like.

[0276] The copper ion source can be used in the present invention in any amount that provides sufficient metal ions for electroplating on the substrate. Copper is typically present in an amount ranging from about 1 to about 300 g / l, preferably from about 20 to about 100 g / l, and most preferably from about 40 to about 70 g / l of the plating solution.

[0277] In a preferred embodiment, the plating solutions are substantially free of tin, i.e., they contain less than 1% by weight of tin, more preferably less than 0.1% by weight of tin, and still more preferably less than 0.01% by weight of tin, and still more preferably free of tin. In another preferred embodiment, the plating solutions are substantially free of any alloying metals, i.e., they contain less than 1% by weight of alloying metals, more preferably less than 0.1% by weight of alloying metals, even more preferably less than 0.01% by weight of alloying metals, and still more preferably free of alloying metals. Most preferably, the metal ions consist of copper ions, i.e., do not contain any other ions except copper.

[0278] acid

[0279] The plating baths of the present invention are acidic, ie, they have a pH below 7. Typically, the pH of copper electroplating compositions is below 4, preferably below 3, most preferably below 2. The pH depends primarily on the concentration of the acid present in the composition.

[0280] Suitable acids include inorganic and organic acids, such as, 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, aminosulfonic acid, hydrochloric acid and phosphoric acid. Sulfuric acid and methanesulfonic acid are preferred.

[0281] These acids are typically present in amounts ranging from about 1 to about 300 g / l, preferably from about 5 to about 200 g / l, most preferably from about 7.5 to about 50 g / l.

[0282] Such electrolytes may optionally (and preferably) contain a halide source, such as chloride ions in cupric chloride or hydrochloric acid. A wide range of halide concentrations may be used in the present invention, for example from about 0 to about 500 ppm. Preferably, based on the plating bath, the halide concentration is in the range of from about 10 to about 100 ppm. Preferably, the electrolyte is sulfuric acid or methanesulfonic acid, and preferably a mixture of sulfuric acid or methanesulfonic acid and a chloride source. Acids and halide sources that can be used in the present invention are typically commercially available and can be used without further purification.

[0283] Electroplating bath

[0284] The electroplating composition of the present invention is suitable for depositing a copper-containing layer, which may preferably be a pure copper layer.

[0285] Generally, in addition to copper ions and at least one nanotwinned promoter, the copper electroplating composition of the present invention preferably comprises an electrolyte, ie, an acidic or alkaline electrolyte, preferably an acidic electrolyte, optionally halide ions, and optionally other additives such as promoters or suppressors.

[0286] Such baths are typically aqueous. Generally, as used herein, "aqueous" means that the electroplating compositions of the present invention contain a solvent containing at least 50% by weight of water. Preferably, "aqueous" means that the major portion of the composition is water, more preferably 90% by weight of the solvent is water, and most preferably the solvent consists of or essentially consists of water. Any type of water can be used, such as distilled water, deionized water, or tap water. In addition, such baths are typically homogeneous solutions, i.e., they do not contain any particles.

[0287] It has been found that the introduction of other organic electroplating compounds has a negative impact or may even destroy the ability of the nanotwinned accelerator to produce nanotwinned copper. These prohibited compounds include all organic additives commonly present in copper electroplating baths, particularly accelerators, inhibitors, surfactants, and / or leveling agents. Therefore, in a preferred embodiment, the electroplating composition is at least substantially free of any accelerators, inhibitors, surfactants, and / or leveling agents. In another preferred composition, the electroplating composition is at least substantially free of any sulfur-containing compounds (typical accelerators) and polyol compounds, particularly polyalkylene oxide compounds (typical inhibitors).

[0288] In a preferred embodiment, the copper electroplating composition of the present invention comprises:

[0289] a) from about 20 to about 60 g / l, preferably from about 30 to about 50 g / l copper ions;

[0290] b) from about 5 to about 70 g / l, preferably from about 7.5 to about 40 g / l of acid, in particular sulfuric acid;

[0291] c) from about 20 to about 120 mg / l halide ions, preferably from about 30 to about 70 mg / l halide ions, especially chloride ions;

[0292] d) from about 5 to about 250 mg / l, preferably from about 7.5 to about 100 mg / l of a nanotwinning promoter as described herein,

[0293] Wherein the composition does not contain any sulfur-containing accelerators or compounds and does not contain any polyol inhibitors or compounds, particularly polyethylene glycols and polyalkylene oxides.

[0294] As used herein, "substantially free" means that the electroplating composition contains less than 10 ppm, more preferably less than about 5 ppm, and most preferably less than about 2 ppm of any compound that may act as an accelerator, suppressor, or leveling agent.

[0295] In another preferred embodiment, the electroplating composition consists essentially of a copper electroplating composition capable of electrodepositing nanotwinned copper, the electroplating composition consisting essentially of or consisting of:

[0296] a) copper ions;

[0297] b) acids, especially sulfuric acid;

[0298] c) halide ions, in particular chloride ions;

[0299] d) a nanotwinning promoter as described herein.

[0300] In yet another preferred embodiment, the electroplating composition consists essentially of a copper electroplating composition capable of electrodepositing nanotwinned copper, the electroplating composition consisting essentially of or consisting of:

[0301] a) from about 40 to about 60 g / l copper ions;

[0302] b) from about 80 to about 140 g / l of acid, especially sulfuric acid;

[0303] c) from about 30 to about 120 mg / l of halide ions, especially chloride ions;

[0304] d) about 300 to about 500 mg / l of a nanotwinning promoter as described herein.

[0305] In yet another preferred embodiment, the electroplating composition consists essentially of a copper electroplating composition capable of electrodepositing nanotwinned copper, the electroplating composition consisting essentially of or consisting of:

[0306] a) from about 20 to about 60 g / l, preferably from about 30 to about 50 g / l copper ions;

[0307] b) from about 5 to about 70 g / l, preferably from about 7.5 to about 40 g / l of acid, in particular sulfuric acid;

[0308] c) from about 20 to about 120 mg / l halide ions, preferably from about 30 to about 70 mg / l halide ions, especially chloride ions;

[0309] d) about 2 to about 250 mg / l, preferably about 5 to about 100 mg / l, most preferably about 5 to about 50 mg / l of a nanotwinning promoter as described herein.

[0310] method

[0311] The composition comprising the nanotwinning promoter is particularly suitable for electrodepositing nanotwinned copper, preferably in (111) orientation, with a large number of nanotwins, on a substrate, particularly a semiconductor substrate.

[0312] Typically, when the present invention is used to deposit copper on a substrate, the plating bath is stirred during use. Any suitable stirring method can be used for the present invention, and such methods are well known in the art. Suitable stirring methods include but are not limited to inert gas or air bubbling, workpiece stirring and impact (impingement) etc. Such methods are well known to those skilled in the art. When the present invention is used to plate integrated circuit substrates such as wafers, the wafer can be rotated as 1 to 150RPM, and the plating solution contacts the rotating wafer, such as by pumping or spraying. In an alternative, in the case where the flow rate of the plating bath is sufficient to provide the desired metal deposit, the wafer does not need to rotate.

[0313] The plating equipment for plating semiconductor substrates is well known. The plating equipment comprises a plating tank which accommodates a copper electrolyte and is made of suitable materials such as plastics or other materials inert to the plating solution. The tank can be cylindrical, especially for wafer plating. The cathode is horizontally arranged on the top of the tank and can be any type of substrate, such as a silicon wafer with an opening.

[0314] These additives can be used with soluble and insoluble anodes with or without the presence of one or more membranes separating the cathode electrolyte from the anode electrolyte.

[0315] The cathode substrate and the anode are electrically connected by wiring and are electrically connected to a power supply respectively. The cathode substrate for direct current or pulse current has a net negative charge, so that the metal ions in the solution are reduced at the cathode substrate, thereby forming a plated metal on the cathode surface. The oxidation reaction occurs at the anode. The cathode and the anode can be arranged in the tank horizontally or vertically.

[0316] The current density is generally in the range of about 0.01 to about 50 ASD, more preferably about 0.5 to about 20 ASD, and most preferably about 1 to about 10 ASD. In addition, the electroplating solution is preferably stirred, and the electroplating solution is generally mixed at about 1 to about 2,500 rpm, more preferably about 10 to about 1,200 rpm, and most preferably about 50 to about 400 rpm.

[0317] Typically, when preparing copper bumps, a photoresist layer is applied to a semiconductor wafer, followed by standard photolithography exposure and development techniques to form a patterned photoresist layer (or plating mask) with recessed features or through holes. The size of the dielectric plating mask (the thickness of the plating mask and the size of the openings in the pattern) defines the size and position of the copper layer deposited on the I / O pads and UBM. The diameter of such deposits is typically in the range of 1 to 300 μm, preferably in the range of 2 to 100 μm. Typically, the recesses provided by the plating mask are not completely filled but only partially filled. After filling the openings in the plating mask with copper, the plating mask is removed, and then the copper bumps are typically subjected to a reflow process.

[0318] Generally, the substrate to be plated need not have a specific orientation to allow deposition of copper nanotwins. However, it is preferred that the substrate to be plated comprises a substrate having a predominantly <111> Oriented copper seed layer.

[0319] Typically, the plating baths of the present invention may be used at any temperature from 10°C to 65°C or higher. Preferably, the temperature of the plating bath is from 10°C to 35°C and more preferably from 15°C to 30°C.

[0320] Unless otherwise indicated, all percentages, ppm or similar values ​​refer to weight relative to the total weight of the corresponding composition.All cited documents are incorporated herein by reference.

[0321] The following examples shall further illustrate the present invention without limiting the scope of the present invention.

[0322] Analytical methods

[0323] Molecular weight (M w ) was determined by size exclusion chromatography (SEC) using hexafluoroisopropanol containing 0.1% potassium trifluoroacetate as eluent and a hexafluoroisopropanol packed (HFIP) gel column as stationary phase. Polymethyl methacrylate (PMMA) standards were used as standards for determining molecular weight. The column temperature was 35°C, the injection volume was 50 μl (microliters) and the flow rate was 1 mL / min. Determination of weight average molecular weight (M w ), number average molecular weight (M n ) and polydispersity (PDI = M w / M n ).

[0324] The amine number is determined in accordance with DIN 53176 by titrating a solution of the polymer in acetic acid with perchloric acid.

[0325] The substrate is comprised of a main <111> Oriented Cu seed layer coated wafer piece.

[0326] The presence of nanotwinned grain structure may be observed using any suitable microscopy technique, such as electron microscopy.The amount of nanotwinned grain structure in the copper deposit is preferably greater than about 80%, more preferably greater than about 90% nanotwinned columnar copper grains, based on SEM cross-section estimates.

[0327] As explained in the examples below, the nanotwinned copper structure can be characterized by a plurality of (111) oriented crystalline copper grains containing a majority of nanotwins. In some embodiments, the plurality of (111) oriented crystalline copper grains contain a majority of nanotwins.

[0328] The crystal orientation of the crystalline copper grains can be characterized using suitable techniques such as electron backscatter diffraction (EBSD) analysis. In some embodiments, the crystal orientation map can be displayed in an inverse pole figure (IPF) map. According to the present invention, it is preferred that the nanotwinned copper structure contains mainly (111) oriented grains.

[0329] Electroplated copper was studied by FIB-SEM.

[0330] Examples

[0331] Example 1: Preparation of Nano-twinned Accelerator

[0332] Example 1.1

[0333] The reactants were placed in a 0.5 l reactor equipped with a stirrer, condenser tube, thermometer and nitrogen inlet tube. Poly(propylene glycol) bis(2-aminopropyl ether (n is about 2) (150.0 g) and hypophosphoric acid (0.3 g) available from BASF were placed in a reactor under a nitrogen atmosphere and heated to 80 ° C. Then N, N-dimethylglycine (129.7 g) was added portionwise over a period of 20 min. After the acid was completely added, the reaction mixture was stirred at 120 ° C for 1 h. The temperature was then increased to 150 ° C and the reaction mixture was stirred for 8 hours, while the resulting water was removed from the system. A pre-product (yield: 93%) in the form of a brown oil with an amine value of 5.2 mmol / g was obtained.

[0334] The pre-product (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 a period of 90 min. In order to complete the reaction, the mixture was post-reacted for 18 h until the Prosman test was negative. The product (nano twinning promoter 1) was obtained as an orange viscous solution with a chloride value of 1.4 mmol / g (yield: 99%).

[0335] Example 1.2

[0336] The reactant is placed in a 250ml flask equipped with agitator, condenser tube, thermometer and nitrogen inlet tube. Diaminobutane (46g) and hypophosphoric acid (0.1g) are placed in a reactor under a nitrogen atmosphere and heated to 80 ° C. Then N, N-dimethylglycine (108,9g) is added portion by portion over a time period of 45min. After the acid is added completely, the reaction mixture is stirred for 1h at 120 ° C. The temperature is then increased to 150 ° C and the reaction mixture is stirred for 8 hours, while the resulting water is removed from the system. The pre-product (yield: 93%) of a yellow waxy solid with an amine value of 7.8mmol / g is obtained.

[0337] The pre-product (50 g) and water (84 ml) were placed in a 250 ml flask, heated to 80 ° C and stirred for 20 min. Epichlorohydrin (33,6 g) was then added dropwise over a period of 90 min. In order to complete the reaction, the mixture was post-reacted for 19 h until the Prosman test was negative. The product (nano twinning promoter 2) with an orange viscous solution having a chloride value of 2.1 mmol / g was obtained (yield: 97%).

[0338] Example 1.3

[0339] The reactant is placed in a 0.25l reactor equipped with an agitator, a condenser tube, a thermometer and a nitrogen inlet tube. 1,2-propylenediamine (37,06g) and hypophosphoric acid (0.13g) are placed in a reactor under a nitrogen atmosphere and heated to 80 ° C. Then N, N-dimethylglycine (106.31g) is added portionwise over a period of 20min. After the acid is added completely, the reaction mixture is stirred at 120 ° C for 1h. The temperature is then increased to 150 ° C and the reaction mixture is stirred for 8 hours, while the resulting water is removed from the system. The pre-product 3 (yield: 84%) in the form of an orange wax with an amine value of 8.5mmol / g is obtained.

[0340] Pre-product 3 (47 g) and water (81 ml) were placed in a 250 ml flask, heated to 80 ° C and stirred for 20 min. Epichlorohydrin (33.95 g) was then added dropwise over a period of 90 min. In order to complete the reaction, the mixture was post-reacted for 15 h until the Prosman test was negative. The product (nano twinning promoter 3) was obtained as an orange viscous solution with a chloride value of 1.9 mmol / g (yield: 97%).

[0341] Example 1.4

[0342] The reactants were placed in a 250 ml flask equipped with a stirrer, condenser tube, thermometer and nitrogen inlet tube. 1,2-ethylenediamine (30 g) and hypophosphoric acid (0.1 g) were placed in a reactor under a nitrogen atmosphere and heated to 80° C. N,N-dimethylglycine was then added portionwise over a period of 50 min.

[0343] (103.1 g). After the acid was completely added, the reaction mixture was stirred at 120° C. for 1 h. The temperature was then increased to 150° C. and the reaction mixture was stirred for 8 hours while the resulting water was removed from the system. Pre-product 4 was obtained as a brown solid with an amine value of 8.7 mmol / g (yield: 89%).

[0344] Pre-product 4 (50 g) and water (87 ml) were placed in a 250 ml flask, heated to 80 ° C and stirred for 20 min. Epichlorohydrin (37.01 g) was then added dropwise over a period of 90 min. In order to complete the reaction, the mixture was post-reacted for 15 h until the Prosman test was negative. The product (nano twinning promoter 4) was obtained as an orange viscous solution with a chloride value of 2.1 mmol / g (yield: 98%).

[0345] Example 1.5

[0346] Reactant is placed in a 250ml flask equipped with agitator, condenser tube, thermometer and nitrogen inlet tube. 1,6-hexanediamine (46.5g) and hypophosphoric acid (0.04g) are placed in a reactor under a nitrogen atmosphere and heated to 80 ° C. Then N, N-dimethylglycine (85.05g) is added portionwise over a period of 90min. After the acid is added completely, the reaction mixture is stirred at 120 ° C for 1h. The temperature is then increased to 150 ° C and the reaction mixture is stirred for 8 hours, while the resulting water is removed from the system. Pre-product 5 (yield: 95%) in the form of a yellow waxy solid with an amine value of 7.0mmol / g is obtained.

[0347] Pre-product 5 (100 g) and water (160 ml) were placed in a 500 ml flask, heated to 80 ° C and stirred for 20 min. Epichlorohydrin (59,9 g) was then added dropwise over a period of 90 min. In order to complete the reaction, the mixture was post-reacted for 18 h until the Prosman test was negative. The product (nano twinning promoter 5) was obtained as an orange viscous solution with a chloride value of 1.9 mmol / g (yield: 98%).

[0348] Example 1.6

[0349] Reactant is placed in a 500ml flask equipped with agitator, condenser tube, thermometer and nitrogen inlet tube.Diethylenetriamine (72.2g) and hypophosphoric acid (0.12g) are placed in a reactor under a nitrogen atmosphere and heated to 80 ° C. Then N, N-dimethylglycine (144.4g) is added portion by portion over a time period of 20min. After adding acid completely, the reaction mixture is stirred for 1h at 120 ° C. Then the temperature is increased to 150 ° C and the reaction mixture is stirred for 15 hours, while the resulting water is removed from the system. Pre-product 6 (yield: 92%) in the form of a yellow waxy solid with an amine value of 11.0mmol / g is obtained.

[0350] Pre-product 6 (90.9 g) and water (176.2 ml) were placed in a 500 ml flask, heated to 80 ° C and stirred for 20 min. Epichlorohydrin (85.4 g) was then added dropwise over a period of 90 min. In order to complete the reaction, the mixture was post-reacted for 18 h until the Prosman test was negative. The product (nano twinning promoter 6) was obtained as an orange viscous solution with a chloride value of 2.0 mmol / g (yield: 95%).

[0351] Example 1.7

[0352] Reactant is placed in a 500ml flask equipped with agitator, condenser tube, thermometer and nitrogen inlet tube. Dimethylaminopropylamine (111.9g) is placed in a reactor under a nitrogen atmosphere and heated to 80°C. Then dimethyl succinate (80.0g) is added portionwise over a time period of 110min. After complete addition, the reaction mixture is stirred for 1h at 80°C. The temperature is then increased to 100°C and the reaction mixture is stirred for 12 hours, while the resulting methanol is removed from the system. Comonomer 1 (yield: 91%) in the form of a yellow waxy solid with an amine value of 6.8mmol / g is obtained.

[0353] Pre-product 2 (38 g), comonomer 1 (0.2 g) and water (66.3 ml) were placed in a 250 ml flask, heated to 80 ° C and stirred for 20 min. Epichlorohydrin (26.3 g) was then added dropwise over a period of 90 min. In order to complete the reaction, the mixture was post-reacted for 18 h until the Prosman test was negative. The product (nano twinning promoter 7) was obtained as an orange viscous solution with a chloride value of 2.0 mmol / g (yield: 99%).

[0354] Example 1.8

[0355] N, N-bis (3-aminopropyl) methylamine (252g, 1.74mol) was placed in a 2l reactor and stirred under a constant nitrogen flow. Water (67g) was added, resulting in a temperature increase to 45°C. The solution was heated to 85°C and adipic acid (240g, 1.64mol) was added portionwise during 20min. During this period, the temperature was increased to 100°C. The reaction mixture was then stirred at 120°C for 1h, and the color turned orange. Subsequently, the temperature was increased to 170°C and the reaction water was distilled out for 4h. The nitrogen flow was then enhanced to remove residual trace water. The heating was turned off and water (250g) was slowly added when the temperature reached 160°C. After cooling to 80°C, water (1328g) was added again, producing a yellow solution (1987g) of comonomer 2 with an amine value of 0.92mmol / g. The product had an average molecular weight of Mw=42.300g / mol and a polydispersity of Mw / Mn=2.0.

[0356] Pre-product 2 (10 g), comonomer 2 (2.3 g) and water (14.8 ml) were placed in a 100 ml flask, heated to 80 ° C and stirred for 20 min. Epichlorohydrin (6.6 g) was then added dropwise over a period of 90 min. In order to complete the reaction, the mixture was post-reacted for 5 h until the Prosman test was negative. The product (nano twinned promoter 8) with a chloride value of 2.2 mmol / g was obtained as a yellow solution (yield: 91%).

[0357] Example 1.9

[0358] Preproduct 2 (10 g), 3-(dimethylamino)propylamine (10 g) and water (31.5 ml) were placed in a 100 ml flask, heated to 80 ° C and stirred for 20 min. Epichlorohydrin (11.5 g) was then added dropwise over a period of 90 min. To complete the reaction, the mixture was post-reacted for 5 h 40 min until the Prosman test was negative. The product (nano twinning promoter 9) was obtained as an orange solution with a chloride value of 2.0 mmol / g (yield: 94%).

[0359] Example 2: Electroplating experiment

[0360] Example 2.1

[0361] A copper electroplating bath containing 40 g / l Cu ions, 10 g / l sulfuric acid and 50 ppm chloride was used for the investigation. In addition, the bath contained 10 ppm of the nanotwin promoter prepared in Example 1.1.

[0362] The substrates were electrically connected before plating. The copper layer was plated by using an RDE apparatus. Electrolyte convection was achieved by rotating the RDE. The rotation speed in the experiment was 100 RPM. The bath temperature was controlled and set to 25°C. A current density of 1 ASD was applied for 68 min, resulting in a copper layer of approximately 15 μm thickness.

[0363] The grain structure of the plated copper film was examined by FIB-SEM. The thickness of the transition layer was determined by measuring the average distance between the seed layers and the time when the nanotwin layer growth started.

[0364] Figure 1a An overview diagram is shown in Figure 1b A more detailed diagram is shown in . The desired nanotwin formation can be easily seen from the horizontal layered structure. The thickness of the transition layer is shown in Table 1.

[0365] Example 2.2

[0366] Example 2.1 was repeated using 10 ppm of the nanotwin promoter prepared in Example 1.2 and a current density of 0.5 ASD.

[0367] Figure 2 A photograph of the deposited copper is shown in . The desired nanotwin formation can be easily seen from the horizontal layered structure. The thickness of the transition layer is shown in Table 1.

[0368] Example 2.3

[0369] Example 2.2 was repeated using 200 ppm of the nanotwin promoter prepared in Example 1.3.

[0370] Figure 3A photograph of the deposited copper is shown in . The desired nanotwin formation can be easily seen from the horizontal layered structure. The thickness of the transition layer is shown in Table 1.

[0371] Example 2.4

[0372] Example 2.2 was repeated using 10 ppm of the nanotwin promoter prepared in Example 1.4.

[0373] Figure 4 A photograph of the deposited copper is shown in . The desired nanotwin formation can be easily seen from the horizontal layered structure. The thickness of the transition layer is shown in Table 1.

[0374] Example 2.5

[0375] Example 2.2 was repeated using 5 ppm of the nanotwin promoter prepared in Example 1.5.

[0376] Figure 5 A photograph of the deposited copper is shown in . The desired nanotwin formation can be easily seen from the horizontal layered structure. The thickness of the transition layer is shown in Table 1.

[0377] Example 2.6

[0378] Example 2.2 was repeated using 10 ppm of the nanotwin promoter prepared in Example 1.6.

[0379] Figure 6 A photograph of the deposited copper is shown in . The desired nanotwin formation can be easily seen from the horizontal layered structure. The thickness of the transition layer is shown in Table 1.

[0380] Example 2.7

[0381] Example 2.2 was repeated using 10 ppm of the nanotwin promoter prepared in Example 1.7.

[0382] Figure 7 A photograph of the deposited copper is shown in . The desired nanotwin formation can be easily seen from the horizontal layered structure. The thickness of the transition layer is shown in Table 2.

[0383] Example 2.8

[0384] Example 2.2 was repeated using 10 ppm of the nanotwin promoter prepared in Example 1.8.

[0385] Figure 8 A photograph of the deposited copper is shown in . The desired nanotwin formation can be easily seen from the horizontal layered structure. The thickness of the transition layer is shown in Table 2.

[0386] Example 2.9

[0387] Example 2.2 was repeated using 80 ppm of the nanotwin promoter prepared in Example 1.9.

[0388] Fig. 9 A photograph of deposited copper is shown in . Even though the use of higher amounts of comonomer reduces the amount of nanotwins formed during electrodeposition, the expected nanotwin formation can be seen from the horizontal layered structure. The thickness of the transition layer cannot be determined in this case.

[0389] Table 1

[0390]

[0391] *Degree of polymerization is about 2

[0392] Table 2

[0393]

Claims

1. Polyaminoamides containing groups of formula N1 [B-A-B’-Z] n [Y-Z] m (N1) Use in a composition for electrodeposition of nanotwinned copper, in B, B' are the same or different, preferably the same, and are an amino acid fragment of formula N2a or an amino acid fragment of formula N2b or an amino acid fragment of formula N2c A is a diamine fragment independently selected from formula N3a or a diamine fragment of formula N3b D N1 Selected from a divalent group, the divalent group is selected from (a) a C1-C1 residue which may be optionally substituted with an amino group or interrupted with a double bond, an imino group, or one or more amino groups; 20 -Alkanediyl (b) an ether or polyether group of formula N2c -(D N10 -O-] o D N10 -(N2c) D N2 is a divalent group selected from (a) Straight chain, branched or cyclic C1 to C 20 Alkanediyl, which may be optionally interrupted by one or more NR N10 , or by one or more, preferably 1 or 2, groups NR N10 R N11 OR N10 Replace, or (b)-D N13 -Ar N13 -D N13 -;or (c) an ether or polyether group of formula N2c D N10 Selected from linear or branched C1-C6-alkanediyl, preferably ethanediyl or propanediyl; D N13 is selected from C1-C6-alkanediyl, preferably selected from methanediyl and ethanediyl; Ar N13 C6 to C 10 an aromatic moiety, preferably p-phenylene; D N11 、D N12 (a) independently selected from linear or branched C1 to C6 alkanediyl, or (b) both together with the two adjacent N atoms are part of a 5- or 6-membered aromatic heterocyclic ring system; D N21 、D N22 (a) independently selected from linear or branched C1 to C6 alkanediyl, or (b) both together with the two adjacent N atoms are part of a 5- or 6-membered aromatic heterocyclic ring system; D N23 is C1 to C6 alkanediyl; R N1 , R N2 Independently selected from C1 to C6 alkyl; R N3 is selected from H and C1 to C6 alkyl; R N10 , R N11 Independently selected from H and straight or branched C1 to C6 alkanediyl; X N2 Is N or CR N3 ; Y is a diamine comonomer segment; Z is a divalent coupling fragment of formula N4 Z N1 Selected from (a) A straight or branched C1 to C2 chain with one or more oxygen atoms inserted therein 12 Alkanediyl, preferably C1 to C6 alkanediyl which may be inserted with 1 or 2 O atoms, or (b) Divalent group -D N11 -Ar N11 -D N11 -; Z N2 , Z N3 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 6; and p and r are independently 0 or 1; wherein the ratio of n:m is at least 25:

75.

2. The use according to claim 1, wherein B and B' are identical or different, preferably identical and are amino acid fragments of formula N2a, wherein D N1 Selected from (i) linear C2 to C 10 alkanediyl, (ii) C2 to C3 oxyalkylene, (iii) cyclic C6 to C 12 an alkanediyl group, or (iv) a divalent phenyl group or a pyridyl group.

3. The use according to claim 1, wherein B and B' are identical or different, preferably identical and are fragments of formula N2b, wherein (a) D N11 and D N12 independently selected from a linear or branched C1 to C4 alkanediyl group or (b) D N11 and D N12 Together with two adjacent N atoms, it forms an imidazole ring.

4. The use according to any one of claims 1 to 3, wherein A is a fragment of formula N3a, wherein D N2 Selected from methanediyl, ethanediyl and 1,3-propanediyl.

5. The use according to any one of claims 1 to 3, wherein A is a fragment of formula N3a, wherein D N2 An ether or polyether group selected from formula N2a -(D N10 -O-] o D N10 -(N2a) Where D N10 is selected from C1-C4-alkanediyl and o is an integer from 1 to 5.

6. The use according to any one of claims 1 to 3, wherein The polyaminoamide is in D N1 is methanediyl, ethanediyl, propanediyl or butanediyl; R N3 is H, methyl or ethyl, preferably H or methyl; R N32 is H, methyl or ethyl, preferably H or methyl; Z is -CH2-CH(OH)-CH2-.

7. The use according to any one of claims 1 to 3, wherein A is a fragment of formula N3b, wherein D N21 , D N22 and D N23 Independently selected from methanediyl, ethanediyl and propanediyl.

8. The use according to any one of claims 1 to 3, wherein A is a fragment of formula N3b, wherein D N21 and D N22 Together with two adjacent N atoms, they form an imidazole ring, and D N23 Selected from methanediyl, ethanediyl, propanediyl and butanediyl.

9. The use according to any one of the preceding claims, wherein Z is selected from C1 to C 12 alkanediyl, bis(2-ethanediyl)ether group, 2-hydroxypropane-1,3-diyl and 4,4'-bis(methyl)biphenyl.

10. The use according to any one of the preceding claims, wherein n is an integer from 2 to 200, preferably an integer from 2 to 150.

11. The use according to any one of the preceding claims, wherein m is 0 or an integer from 1 to 200, preferably 0 or an integer from 2 to 150.

12. The use according to any one of the preceding claims, wherein The ratio of n:m is at least 50:50, preferably 70:

30.

13. The use according to any one of the preceding claims, wherein The mass average molecular weight M of the polyaminoamide w It is from 450 g / mol to 150 000 g / mol, preferably from 1000 g / mol to 50 000 g / mol.

14. A composition comprising copper ions, an acid and at least one polyaminoamide as defined in claim 1 comprising groups of formula N1, said composition being free of any sulfur-containing compound and any polyalkylene oxide compound.

15. The composition according to claim 14, consisting essentially of copper ions, an acid, halide ions, and at least one polyaminoamide as defined in claim 1 comprising a group of formula N1.

16. A method for electrodepositing copper on a substrate comprising a recessed feature, the recessed feature comprising a conductive feature bottom and a dielectric feature sidewall, the method comprising: a) making a composition comprising a polyaminoamide containing a group of formula N1 [B-A-B’-Z] n [Y-Z] m (N1) or the composition according to claim 14 or 15 is contacted with the substrate, and b) applying an electric current to the substrate for a time sufficient to deposit nanotwinned copper on the substrate, in B, B' are the same or different, preferably the same, and are an amino acid fragment of formula N2a or an amino acid fragment of formula N2b or an amino acid fragment of formula N2c A is a diamine fragment independently selected from formula N3a or a diamine fragment of formula N3b D N1 Selected from a divalent group, the divalent group is selected from (a) a C1-C2-amino group which may be optionally substituted with an amino group or interrupted with a double bond or an imino group 20 -alkanediyl, (b) an ether or polyether group of formula N2c -(D N10 -O-] o D N10 -(N2c) D N2 is a divalent group selected from (a) Straight chain, branched or cyclic C1 to C 20 Alkanediyl, which may be optionally interrupted by one or more NR N10 , or by one or more, preferably 1 or 2, groups NR N10 R N11 OR N10 Replace, or (b)-D N13 -Ar N13 -D N13 -;or (c) an ether or polyether group of formula N2c D N10 Selected from linear or branched C1-C6-alkanediyl, preferably ethanediyl or propanediyl; D N13 is selected from C1-C6-alkanediyl, preferably selected from methanediyl and ethanediyl; Ar N13 C6 to C 10 an aromatic moiety, preferably p-phenylene; D N11 、D N12 (a) independently selected from linear or branched C1 to C6 alkanediyl, or (b) both together with the two adjacent N atoms are part of a 5- or 6-membered aromatic heterocyclic ring system; D N21 、D N22 (a) independently selected from linear or branched C1 to C6 alkanediyl, or (b) both together with the two adjacent N atoms are part of a 5- or 6-membered aromatic heterocyclic ring system; D N23 is C1 to C6 alkanediyl; R N1 , R N2 Independently selected from C1 to C6 alkyl; R N3 is selected from H and C1 to C6 alkyl; R N10 , R N11 Independently selected from H or a linear or branched C1 to C6 alkanediyl group; X N2 Is N or CR N3 ; Y is a comonomer fragment; Z is a divalent coupling fragment of formula N4 Z N1 Selected from (a) A straight or branched C1 to C2 chain with one or more oxygen atoms inserted therein 12 Alkanediyl, preferably C1 to C6 alkanediyl which may be inserted with 1 or 2 O atoms, or (b) Divalent group -D N11 -Ar N11 -D N11 -; Z N2 , Z N3 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 6; and p and r are independently 0 or 1 wherein the ratio of n:m is at least 25:75.

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