TW202117087A - Composition for copper bump electrodeposition comprising a leveling agent - Google Patents

Abstract

A composition comprising copper ions and at least one additive comprising a polyalkyleneimine backbone comprising N-hydrogen atoms, wherein (a) the polyalkyleneimine backbone has a mass average molecular weight MW of from 600 g/mol to 100 000 g/mol, (b) the N-hydrogen atoms are each substituted by a polyoxyalkylene group comprising an oxyethylene and a C₃ to C₆ oxyalkylene unit, and (c) the average number of oxyalkylene units in the polyoxyalkylene groups is of from more than 10 to less than 30 per N-hydrogen atom in the polyalkyleneimine.

Description

Composition containing leveling agent for copper bump electrodeposition

The present invention relates to a copper electroplating composition containing a polyethyleneimine leveling agent, its use and a method for copper bump electrodeposition.

Bumps are formed on the surface of a wafer with integrated circuits (such as LSI). These bumps constitute a part of the interconnection of the integrated circuit and serve as terminals for connecting to the circuit of the external package substrate (or circuit substrate). The bumps are usually arranged along the periphery of the semiconductor chip (or die), and are connected to an external circuit by a gold wire according to the wire bonding method or by a wire according to the TAB method.

With the recent development of higher integration and higher density of semiconductor devices, the number of bumps used to connect to external circuits has increased, resulting in the necessity of forming bumps over the entire area of the surface of the semiconductor wafer. In addition, due to the need for a shorter interconnection pitch, a method (flip-chip method) involving flip-chip mounting of a semiconductor wafer with a large number of bumps formed on the surface and the bumps directly connected to the circuit substrate is used.

Electroplating is widely used as a method of forming bumps. The process of forming bumps on the surface of wafers with integrated circuits is one of the most important processes in the final manufacturing stage of semiconductor devices. In this regard, it should be noted that the integrated circuit is formed on the wafer through multiple processes. Therefore, the bump formation process on the wafer that has passed all the foregoing processes requires extremely high reliability. With the development of the miniaturization of semiconductor chips, the number of bumps used to connect to external circuits is increasing and the size of the bumps themselves is getting smaller and smaller. There is a need to improve the positioning accuracy of the bonding between a semiconductor chip and a circuit substrate such as a package substrate. In addition, there is also a strong demand for defect-free bonding in the bonding process where the bumps are melted and solidified.

Generally speaking, copper bumps are formed on the seed layer of the wafer that is electrically connected to the integrated circuit. A resist with openings is formed on the seed layer, and copper is deposited on the exposed surface of the seed layer in the openings by copper electroplating to thereby form copper bumps. The seed layer includes a barrier layer (for example, made of titanium) to prevent copper from diffusing into the dielectric. After filling the openings in the resist with copper, the resist is removed, and then the copper bumps are reflowed.

The need to install more functional units in smaller and smaller spaces drives the integrated circuit industry to upgrade the packaging and connection process. The second driving factor is to maximize the amount of input/output connections in a given area. As the diameter of the bumps and the spacing between the bumps decrease, the connection density can increase. These arrays are realized by copper bumps or μ pillars plated with tin or tin alloy solder caps. In order to ensure that each bump is in contact across the wafer, in addition to void-free deposition and reflow, a uniform deposition height is required.

Therefore, a copper electroplating bath is required in the electronics industry, which allows bump deposits to have good morphology, especially low roughness, and an improved high degree of uniformity, also known as within the grain coplanarity (COP).

An object of the present invention is to provide a copper electroplating composition that provides copper deposits exhibiting good morphology, especially low roughness, and the copper electroplating composition can fill micron-level recessed components without substantially forming Defects, such as (but not limited to) voids. Another object of the present invention is to provide a copper electroplating bath that provides uniform and flat copper deposits, especially recessed members with a width of 500 nanometers to 500 micrometers.

The present invention provides a composition comprising copper ions and at least one additive containing a polyalkyleneimine backbone, the polyalkyleneimine backbone containing N-hydrogen atoms, wherein (a) preferably, polyalkyleneimine The mass average molecular weight MW of the main chain of alkyleneimine is 600 g/mol to 100 000 g/mol, (b) N-hydrogen atoms are each through a _{polyoxyalkylene group containing oxyethylene and C 3} to C ₆ alkylene oxide units Substituted, the alkylene oxide units may be unsubstituted or substituted by OH; C ₁ to C ₆ alkoxy or C ₆ to C ₁₂ aryl groups, and (c) in polyalkylene imines, polyoxyalkylene groups The average number of alkylene oxide units in each N-hydrogen atom is greater than 10 to less than 30.

The leveling agent according to the present invention is particularly suitable for filling recessed components with an orifice size of 500 nm to 500 μm, especially those with an orifice size of 1 μm to 200 μm. The leveling agent is especially suitable for depositing copper bumps.

Due to the leveling effect of the leveling agent, an improved coplanarity surface with electroplated copper bumps is obtained. The copper deposits exhibit good morphology, especially low roughness. The electroplating composition can fill micron-sized recessed components without substantially forming defects, such as (but not limited to) voids.

In addition, the leveling agent according to the present invention reduces impurities, such as (but not limited to): organic matter, chloride, sulfur, nitrogen or other elements. It exhibits larger particles and improved conductivity. It also promotes high plating rates and allows plating at high temperatures.

The present invention further relates to the use of the aqueous composition as described herein for depositing copper on a substrate containing a recessed member, the recessed member including a bottom of a conductive member and a sidewall of a dielectric member, wherein the hole of the recessed member The mouth size is 500 nm to 500 μm.

The present invention further relates to a method of electrodepositing copper on a substrate including a recessed member, the recessed member including a bottom of a conductive member and a sidewall of a dielectric member, the method comprising: (A) Bring the composition as described herein into contact with the substrate, and (B) applying current to the substrate for a time sufficient to deposit a copper layer into the recessed member, The size of the orifice of the recessed member is 500 nm to 500 μm.

As used herein, “recessed feature” or “feature” refers to geometric shapes on the substrate, such as (but not limited to) grooves and through holes. "Aperture" refers to recessed members such as through holes and grooves. As used herein, unless the context clearly dictates otherwise, the term "plating" refers to copper electroplating. "Deposition" and "Plating" are used interchangeably throughout this manual. The term "alkyl" means C ₁ to C ₂₀ alkyl and includes straight chain, branched chain and cycloalkyl. As used herein, "aryl" includes carbocyclic and heterocyclic aromatic systems such as (but not limited to): phenyl, naphthyl, pyridyl and the like. As used herein, "C _x "refers to a group composed of x carbon atoms. In the case of an aryl group, one or more of the carbon atoms of the aralkyl and alkaryl groups may be substituted with heteroatoms (such as but not limited to O, S, and N) in the aryl moiety (for example, pyridine is where _{A C 6} aryl group substituted by a N atom). As used herein, "arylalkyl" means an alkyl group substituted with a carbocyclic or heterocyclic aromatic ring system, such as (but not limited to): benzyl, phenethyl, naphthylmethyl, pyridine Group methyl and similar groups. As used herein, "alkylaryl" means carbocyclic and heterocyclic aromatic systems substituted with alkyl groups, such as (but not limited to): methylphenyl, dimethylphenyl, ethylphenyl , Methyl naphthyl, methyl pyridyl and similar groups. As used herein, “polymer” generally means any compound containing at least two monomer units, that is, the term polymer includes oligomers such as dimers, trimers, and high molecular weight polymers. Preferably the polymer contains 5 monomer units or more, most preferably 10 monomer units or more.

As used herein, "accelerator" refers to organic additives that increase the plating rate of the electroplating bath. The terms "accelerator" and "accelerating agent" are used interchangeably throughout this specification. In the literature, the accelerator component is sometimes referred to as "brightener/brightening agent". "Suppressor" refers to an organic compound that reduces the plating rate of the electroplating bath and ensures that the recessed components are filled from bottom to top (the so-called "bottom-up filling") without voids. The terms "suppressor" and "suppressing agent" are used interchangeably throughout this specification. "Leveler" refers to an organic compound capable of providing a substantially flat metal layer or a coplanar or uniform deposition height on a recessed member. The terms "leveler/leveling agent" and "leveling additive" are used interchangeably throughout this specification.

According to the present invention, "aperture size" means the minimum diameter or free distance of the recessed member before electroplating. Depending on the geometry of the components (grooves, through holes, etc.), the terms "width", "diameter", "aperture" and "opening" are used synonymously in this article ". As used herein, "aspect ratio" means the ratio of the depth of the recessed member to the size of the orifice. Leveling agent according to the present invention

The present invention is achieved by combining one or more additives capable of providing a substantially flat copper layer and filling members without substantially forming defects (such as but not limited to voids) with a copper electroplating bath.

The additive (also referred to as a leveling agent) according to the present invention can receive a polyalkyleneimine main chain containing N-hydrogen atoms by reacting a polyalkyleneimine backbone with one or more alkylene oxides. Chain leveling agent, wherein (a) preferably, the mass average molecular weight M _W of the polyalkyleneimine main chain is 600 g/mol to 100 000 g/mol, (b) the N-hydrogen The atoms are each _{substituted by a polyoxyalkylene group containing oxyethylene and C 3} to C ₆ oxyalkylene units, and (c) in the polyalkyleneimine, the average number of oxyalkylene units in the polyoxyalkylene group is each There are more than 10 to less than 30 N-hydrogen atoms.

As used herein, "N-hydrogen atom" means a hydrogen atom bonded to a nitrogen atom, which is a part of the polymer backbone of the polyalkyleneimine. It should be emphasized that the term "a/an" in this document covers both the singular and the plural. For example, the polyoxyalkylene group may include one or more oxyethylene and one or more C ₃ to C ₆ oxyalkylene units.

The polyalkyleneimine backbone should be understood to mean a compound composed of a saturated hydrocarbon chain with terminal amine functional groups, and the saturated hydrocarbon chain is interspersed with secondary and tertiary amine groups. Such main chains can be linear or branched. The different polyalkyleneimine main chains can of course be used in the form of a mixture with each other. The mass average molecular weight M _{w of the} leveling agent can be 600 g/mol to 100 000 g/mol. The molecular weight can be determined by size exclusion chromatography such as GPC, using polymethyl methacrylate (PMMA) as a standard and using hexafluoroisopropanol + 0.05% potassium trifluoroacetate as an eluent.

The polyamine backbone may preferably have the general formula L2a:

The main chains before subsequent modification include the first, second, and tertiary amine nitrogen atoms connected ^{by the X L1 "linking" unit.} Except for the terminal groups, the main chain basically contains three types of units, and it should be emphasized that these groups can be distributed along the main chain in any order.

其在改性後具有其經氧化烯單元，較佳氧乙烯單元、氧丙烯單元、氧丁烯單元及其混合物取代之氫原子；以及（c）具有下式之三級胺單元：

其為主要主鏈及二級主鏈之分支點，A^L1 表示藉由分支進行的對鏈結構之延續。此處，藉由分支進行的對鏈結構之延續意謂除末端基團-N(R^L2 )₂ 以外，A^L1 可含有上文所描述之所有一級胺單元、二級胺單元及三級胺單元。分支為q可大於1之原因所在。The unit constituting the main chain of polyalkyleneimine is (a) a one-level unit of the following formula: [H ₂ NX ^L1 ]- and -NH ₂ which end the main main chain and any branched chains, and are modified Then there are two hydrogen atoms each replaced by one or more C ₂ to C ₆ oxyalkylene units, preferably oxyethylene units, oxypropylene units, oxybutylene units, and mixtures thereof; (b) a secondary of the formula Amine unit:

After modification, it has hydrogen atoms substituted by oxyalkylene units, preferably oxyethylene units, oxypropylene units, oxybutylene units, and mixtures thereof; and (c) a tertiary amine unit of the following formula:

It is the branch point of the main main chain and the secondary main chain, and A ^L1 represents the continuation of the chain structure by branching. Here, the continuation of the chain structure by branching means that in addition to the terminal group -N(R ^L2 ) ₂ , A ^L1 may contain all the primary amine units, secondary amine units, and tertiary amines described above unit. The branch is why q can be greater than 1.

If m is 0, the polyethyleneimine main chain is a linear polyethyleneimine main chain. If only the main main chain but no side chain A ^L1 contains any other tertiary amine units, a comb-like main chain structure is formed, and if The side chain A ^L1 contains other tertiary amine units and accepts a highly branched main chain structure. The tertiary unit does not have replaceable hydrogen atoms and is therefore not modified by substitution with polyoxyalkylene units.

During the formation of the polyamine backbone, cyclization may occur, and therefore, a certain amount of cyclic polyamine may be present in the mixture of the parent polyalkyleneimine backbone. Each primary and secondary amine unit of cyclic alkyleneimine is modified by adding polyoxyalkylene units in the same manner as linear and branched polyalkyleneimine.

In the formula L1, the group X ^L1 can be a linear C ₂ -C ₆ alkanediyl group, a branched chain C ₃ -C ₆ alkanediyl group, or a mixture thereof. A preferred branched alkanediyl group is propanediyl. Most preferably, X ^L1 is ethylenediyl or a combination of ethylenediyl and propanediyl. The best polyalkyleneimine backbone contains all groups X ^L1 that are ethylenediyl units.

The lower limit of the weight average molecular weight M _w of the polyalkyleneimine backbone is preferably about 600 g/mol, more preferably about 750 g/mol, even more preferably about 800 g/mol, even more preferably about 900 g/mol , Even more preferably about 1200 g/mol, most preferably about 1500 g/mol. The upper limit of the weight average molecular weight M _w is usually about 100 000 g/mol, preferably 75,000 g/mol, more preferably 25,000 g/mol, and most preferably 10 000 g/mol. Examples of the preferred weight average molecular weight range of the polyethyleneimine backbone are 900 g/mol to 6000 g/mol, preferably 900 g/mol to 5000 g/mol, more preferably 1000 g/mol to 4000 g/mol, The best is 1000 to 3000 g/mol.

The subscripts n, m and o required to achieve a better molecular weight will vary depending on the X ^L1 part of the main chain. n may be 1 or more, preferably 3 or more, most preferably 5 or more. m depends on the branch of the main chain and can be 0 or an integer of 1 or greater. The sum of q, n, m and o is preferably from about 10 to about 2400, more preferably from about 15 to about 1000, even more preferably from about 20 to about 200, even more preferably from about 20 to about 100, most preferably 22 to 70. For example, when X ^L1 is ethylenediyl, the average value of main chain units is 43 g/mol, and when X ^L1 is hexamethylenediyl, the average value of main chain units is 99 g/mol.

The polyalkyleneimine of the present invention can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst (such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.). Specific methods for preparing these polyalkyleneimine backbones are disclosed in U.S. Patent 2,182,306, U.S. Patent 3,033,746, U.S. Patent 2,208,095, U.S. Patent 2,806,839 and U.S. Patent 2,553,696.

In addition, before the polyalkoxylation, the polyalkyleneimine main chain may be partially substituted with the ^{group R L3 by an alkylating agent.} In this case, o in the formula L1 will be 1 or greater. The group R ^{L3 can be} selected from C ₁ to C ₁₂ alkyl, C ₂ to C ₁₂ alkenyl, C ₂ to C ₁₂ alkynyl, C ₆ to C ₂₀ alkaryl, C ₆ to C ₂₀ aralkyl, C ₆ to C ₂₀ aryl. The preferred group R ^{L3 can be} selected from C ₁ to C ₆ alkyl, C ₆ to C ₁₂ alkaryl, C ₆ to C ₁₂ aralkyl, and C ₆ to C ₁₂ aryl. Preferably, the aryl group is phenyl or naphthyl. The substitution by the group R ^L3 will be carried out before the polyalkoxylation of the polyalkyleneimines. Similarly, the terminal groups [H2N-X ^L1 ]- and -NH ₂ can be substituted with the group R ^L3 .

Suitable examples of alkylating agents are organic compounds containing active halogen atoms, such as aralkyl halides, alkyl, alkenyl and alkynyl halides, and the like. In addition, compounds such as alkyl sulfates, alkyl sultones, epoxides, and the like can also be used. Non-limiting examples of corresponding alkylating agents include benzyl chloride, propane sultone, dimethyl sulfate, (3-chloro-2-hydroxypropyl)trimethylammonium chloride or the like. Preferably, dimethyl sulfate and/or benzyl chloride are used.

Preferably, unsubstituted polyalkyleneimines are used before further polyalkoxylation with the group R ^L1. In this case, o in the formula L1 will be zero.

The polyalkyleneimine main chain of the present invention is freely substituted (that is, unsubstituted) with a ^{group R L1} comprising a combination of _{oxyethylene ("EO") and another C 3} to C _{6 alkylene oxide} N-hydrogen atoms (also referred to as "NH units") are polyalkoxylated, and such C ₃ to C ₆ alkanediyl groups can be linear or branched.

The group R ^L1 (also known as "polyalkyleneoxide" or "alkylene oxide copolymer") can generally be represented by the formula -(X ^L11 O) _r (X ^L12 O) _s -R ^L11 description, wherein R ^L11 is ethanediyl and X ^L12 is C ₃ to C ₆ alkanediyl, and wherein R ^L11 may be H or a substituent as described below.

In a preferred embodiment, X ^L12 is selected from propane-1,2-diyl, (2-hydroxymethyl)ethyl-1,2-diyl, but-1,2-diyl, but-2 ,3-Diyl, 2-methyl-prop-1,2-diyl (isobutyl), penta-1,2-diyl, penta-2,3-diyl, 2-methyl-butan -1,2-Diyl, 3-Methyl-But-1,2-Diyl, Hex-2,3-Diyl, Hex-3,4-Diyl, 2-Methyl-Pentane-1,2 -Diyl, 2-ethylbutan-1,2-diyl, 3-methyl-penta-1,2-diyl, decyl-1,2-diyl, 4-methyl-penta-1,2 -Diyl and (2-phenyl)-ethyl-1,2-diyl, and mixtures thereof. Preferably, the C ₃ to C ₆ alkylene oxide is oxypropylene or oxybutylene, most preferably oxypropylene.

Both groups X ^L11 O and X ^L12 O can be arranged in block, random, alternating or gradient order.

As used herein, "random" means that comonomers are polymerized from a mixture and are therefore arranged in a statistical manner depending on their copolymerization parameters.

As used herein, "block" means that comonomers are successively polymerized with each other to form blocks of individual comonomers in any predetermined order. For example, for EO and propylene oxide (PO) comonomers, such blocks can be (but not limited to): -EO _r -PO _s , -PO _s -EO _r , -EO _r1 -PO _s- EOr ₂ , -PO _{s1 -EO r} -PO _s2 and so on. Here, the prefix "-" bond indicates bonding to the polyalkyleneimine main chain.

_{In a preferred embodiment, a -PO s} -EO _r or -EO _r1 -PO _s -EO _r2 block copolymer containing a terminal ethylene oxide block is used, wherein the propylene oxide ("PO") unit can be Another C ₄ to C ₆ alkylene oxide exchange. In this article, the sum of subscripts r1 and r2 is r.

_{In another preferred embodiment, -EO r} -PO _s or -PO _s1 -EO _r -PO _s1 block copolymers containing terminal propylene oxide blocks are used, wherein the PO unit can be another C ₄ to C ₆ Alkylene oxide exchange. The sum of subscripts s1 and s2 in this article is s.

In another preferred embodiment, a random-(EO) _r (PO) _s copolymer with statistically distributed oxyethylene and oxypropylene is used, wherein the PO unit can be another C ₄ to C ₆ alkylene oxide exchange. For reactivity reasons, such random copolymers can start with an EO group before the final copolymerization of EO and PO from the beginning of the mixture.

In all the above specific examples, preferably r or r1+r2 is in the range of 2 to 300, respectively, and s or s1+s2 is in the range of 2 to 300, respectively.

Particularly preferred polyoxyalkylene groups R ^L1 are -EO _r -PO _s and -EO _r1 -PO _s -EO _r2 .

The relative amount s/(s+r) of the C ₃ to C ₆ alkylene oxide units in R ^L1 can generally be about 3% to about 95%, preferably about 5% to about 80%, and even more preferably about 7. % To about 50%, even more preferably from about 8% to about 40%, even more preferably from about 9% to about 30%, most preferably from about 10% to about 20%.

為大於10至小於30之數目的整數。在本文中，p為各別取代基R^L1 中之氧乙烯單元及C₃ 至C₆ 氧化烯單元之總和，亦即r與s之總和。較佳地，平均烷氧基化度為11或更大、較佳12或更大、最佳13或更大。較佳地，平均烷氧基化度為29或更小、更佳28或更小、甚至更佳27或更小、甚至更佳26或更小、甚至更佳25或更小、甚至更佳24或更小、最佳23或更小。在一特定具體實例中，平均烷氧基化度可選自11至28、更佳12至25、最佳13至23之範圍。s and r are selected so that the average degree of alkoxylation, that is, the arithmetic mean number of alkylene oxide units in ^{all polyoxyalkylene groups R L1, 1 to n}

It is an integer from more than 10 to less than 30. In this context, p is the sum of oxyethylene units and C ₃ to C ₆ ^{alkylene oxide units in the respective substituents R L1} , that is, the sum of r and s. Preferably, the average degree of alkoxylation is 11 or more, preferably 12 or more, and most preferably 13 or more. Preferably, the average degree of alkoxylation is 29 or less, more preferably 28 or less, even more preferably 27 or less, even more preferably 26 or less, even more preferably 25 or less, or even better 24 or less, preferably 23 or less. In a specific embodiment, the average degree of alkoxylation can be selected from the range of 11-28, more preferably 12-25, and most preferably 13-23.

Without limitation, the total amount of alkylene oxide units in the leveling agent may be particularly preferably about 27 ethylene oxide units (EO) and about 2 propylene oxide units (PO), about 23 EO and 2 PO, about 18 EO and 2 PO, about 13 EO and 2 PO, about 10 EO and 2 PO, about 9 EO and 2 PO; about 26 EO and 3 PO, about 22 EO and 3 PO, about 17 EO and 3 PO, about 12 EO and 3 PO, about 9 EO and 3 PO, about 8 EO and 3 PO; about 24 EO and 5 One PO, about 20 EO and 5 PO, about 15 EO and 5 PO, about 10 EO and 5 PO, about 7 EO and 5 PO, about 6 EO and 5 PO; about 28 1 EO and 1 PO, about 24 EO and 1 PO, about 19 EO and 1 PO, about 14 EO and 1 PO, about 12 EO and 1 PO, about 10 EO and 1 PO; In this context, PO units can be fully or partially _{exchanged with 1-oxobutene (BO) or other C 4} to C ₆ alkylene oxide units.

In general, polyalkoxylation is performed by reacting individual alkylene oxides with polyethyleneimine. The synthesis of polyalkylene oxide units is known to those skilled in the art. For example, full details are given in the following: Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, "Polyoxyalkylenes" in electronic distribution. When two or more different alkylene oxides are used, the formed polyoxyalkylene group may be a random copolymer, a gradient copolymer or a block copolymer.

The modification of the NH unit in the polymer backbone with alkylene oxide units, for example, by first in an autoclave equipped with a stirrer at a temperature of about 25°C to about 150°C in the presence of up to 80% by weight of water It is carried out by reacting a polymer (preferably polyethyleneimine) with one or more alkylene oxides (preferably ethylene oxide, propylene oxide or a mixture thereof). In the first step of the reaction, alkylene oxide is added in such an amount that almost all hydrogen atoms of the NH unit of the polyalkyleneimine are converted into hydroxyalkyl groups to obtain monoalkoxylated polyalkyleneimine . The water was then removed from the autoclave. With respect to the addition product obtained in the first step of alkoxylation, a basic catalyst such as sodium methoxide, potassium tertiary butoxide, potassium hydroxide, and hydroxide is added in an amount of 0.1% to 15% by weight After sodium, sodium hydride, potassium hydride or alkaline ion exchangers, another amount of alkylene oxide is added to the reaction product of the first step, so that the desired alkylene oxide unit containing the NH unit of each polymer is obtained. Average number of polyalkoxylated polyalkyleneimines. The second step can be performed, for example, at a temperature of about 60°C to about 150°C. The second step of alkoxylation can be carried out in an organic solvent such as xylene or toluene. In order to properly meter the alkylene oxide, the number of polyalkyleneimine primary and secondary amine groups can be reasonably determined before alkoxylation.

The polyalkoxylated polyalkyleneimines may be functionalized with a ^{group R L11} other than H in another reaction step as appropriate. Additional functionalization can be used to modify the properties of polyalkoxylated polyalkyleneimines. For this purpose, the hydroxyl groups present in the polyoxyalkylated polyalkyleneimines are converted by means of suitable reagents capable of reacting with the hydroxyl groups.

The type of functionalization depends on the desired end use. Depending on the functionalizing agent, the chain ends can be hydrophobic or more hydrophilic. However, it is preferred to use alkoxylated polyalkyleneimines without any further functionalization, that is, R ^L11 is H.

The terminal hydroxyl group can be esterified, for example, with sulfuric acid or a derivative thereof, so as to form a product having a terminal sulfate group. Similarly, phosphoric acid, phosphorous acid, polyphosphoric acid, POCl ₃ or P ₄ O _{10 can be used to} obtain products with terminal phosphorus groups.

In addition, the terminal hydroxyl group can also be etherified to form an ether-terminated polyalkoxy group, wherein R ^L11 is selected from C ₁ to C ₁₂ alkyl, C ₂ to C ₁₂ alkenyl, C ₂ to C ₁₂ alkynyl, C ₆ to C ₁₈ aralkyl group, C ₅ to C ₁₂ aryl group. Preferably, R ^L11 may be methyl, ethyl or benzyl.

Finally, the amine matrix present in the polyalkoxylated polyalkyleneimines can be protonated or quaternized by means of a suitable alkylating agent. Examples of suitable alkylating agents are organic compounds containing active halogen atoms, such as aralkyl halides, alkyl, alkenyl and alkynyl halides, and the like. In addition, compounds such as alkyl sulfates, alkyl sultones, epoxides, and the like can also be used. Examples of corresponding alkylating agents include benzyl chloride, propane sultone, dimethyl sulfate, (3-chloro-2-hydroxypropyl)trimethylammonium chloride or the like. Preferably, dimethyl sulfate and/or benzyl chloride are used.

A large number of additives are typically used in the bath to provide the required surface treatment of Cu electroplated metal. Often more than one additive is used, with each additive forming the desired function. Advantageously, the electroplating bath may contain one or more of accelerators, inhibitors, halide ion sources, grain refiners, and mixtures thereof. Most preferably, in addition to the leveling agent according to the present invention, the electroplating bath contains both accelerators and inhibitors. Other additives

A large number of other additives can usually be used in the bath to provide the required surface treatment of Cu electroplated metal. Often more than one additive is used, with each additive forming the desired function. Advantageously, the electroplating bath may contain one or more of accelerators, inhibitors, halide ion sources, grain refiners, and mixtures thereof. Most preferably, in addition to the leveling agent according to the present invention, the electroplating bath also contains both accelerators and inhibitors. Other additives can also be used in the electroplating bath of the present invention in a suitable manner. Accelerator

Any accelerator can be suitably used in the electroplating bath according to the present invention. As used herein, "accelerator" refers to organic additives that increase the plating rate of the electroplating bath. The terms "accelerator" and "accelerating agent" are used interchangeably throughout this specification. In the literature, the accelerator component is sometimes referred to as "brightener/brightening agent" or "depolarizer". Accelerators suitable for use in the present invention include, but are not limited to, compounds containing one or more sulfur atoms and sulfonic acid/phosphonic acid or their salts. Preferably, the composition further contains at least one accelerator.

The preferred accelerator has the general structure MO ₃ Y ^A -X ^A1 -(S) _d R ^A2 , wherein:-M is hydrogen or an alkali metal, preferably Na or K;-Y ^A is P or S, more Preferably it is S;-d is an integer from 1 to 6, preferably 2;-X ^A1 is selected from C ₁ -C ₈ alkanediyl or heteroalkanediyl, divalent aryl or divalent heteroaryl. Heteroalkyl groups will have one or more heteroatoms (N, S, O) and 1-12 carbon atoms. Carbocyclic aryl groups are typically aryl groups, such as phenyl or naphthyl. Heteroaryl groups are also suitable aryl groups and contain one or more N, O or S atoms and 1-3 individual or condensed rings. - R ^A2 is selected from H or _{^{(-SX A1 'Y A O 3}} M), wherein X ^A1' is independently selected from the group X ^A1.

More specific words, suitable accelerators include their accelerator of the ^{_{formula: MO 3 SX A1 -SH MO 3}} SX A1 -SSX A1 '-SO 3 M MO 3 S-Ar-SS-Ar-SO 3 M wherein X ^A1 is as defined above and Ar is an aryl group.

Especially preferred accelerators are: -SPS: Bis(3-sulfopropyl)-disulfide -MPS: 3-mercapto-1-propanesulfonic acid. Both are usually used in the form of their salts, especially their sodium salts.

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

Such accelerators are typically used in an amount of about 0.1 ppm to about 3000 ppm based on the total weight of the electroplating bath. Particularly suitable amounts of accelerators suitable for use in the present invention are 1 ppm to 500 ppm, and more specifically 2 ppm to 100 ppm. Inhibitor

The inhibitor can be suitably used in combination with the leveling agent according to the present invention. As used herein, "inhibitors" are additives that increase the overpotential during electrodeposition. Here, the terms "surfactant" and "inhibitor" are used synonymously, because the inhibitors described herein are also interface active substances.

Particularly suitable inhibitors are: (a) As described in WO 2010/115796, an amine compound containing at least three active amine functional groups and ethylene oxide can be combined with at least one selected from C ₃ and C ₄ An inhibitor obtained by reacting a mixture of alkylene oxide compounds.

Preferably, the amine compound is selected from the group consisting of diethylenetriamine, 3-(2-aminoethyl)aminopropylamine, 3,3'-imine bis(propylamine), N,N-bis(3- Aminopropyl) methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetramine and N,N'-bis(3-aminopropyl)ethylenediamine.

(B) As described in WO 2010/115756, it can be obtained by reacting a mixture of an amine compound containing an active amine functional group with ethylene oxide and at least one compound selected from the group consisting of C ₃ and C ₄ alkylene oxides The inhibitor has a molecular weight M _w of 6000 g/mol or greater, thereby forming an ethylene C ₃ and/or C ₄ alkylene random copolymer.

(C) As described in WO 2010/115757, an amine compound containing at least three active amine functional groups can be mixed with ethylene oxide and at least one compound selected from C ₃ and C ₄ alkylene oxides. Or an inhibitor obtained by a sequential reaction, and the inhibitor has a molecular weight M _w of 6000 g/mol or greater.

Preferably, the amine compound is selected from ethylenediamine, 1,3-diaminopropane, 1,4-butanediamine, 1,5-diaminopentane, 1,6-diaminohexane, Neopentane diamine, isophorone diamine, 4,9-dioxadecan-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, triethyl Glycol diamine, diethylenetriamine, (3-(2-aminoethyl)aminopropylamine, 3,3'-imine bis(propylamine), N,N-bis(3-aminopropyl) Yl)methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetramine and N,N'-bis(3-aminopropyl)ethylenediamine.

其中如WO 2010/115717中所描述，R^S1 基團各自獨立地選自環氧乙烷與至少一種其他C₃ 至C₄ 環氧烷之共聚物，該共聚物為無規共聚物；R^S2 基團各自獨立地選自R^S1 或烷基；X^S 及Y^S 獨立地為間隔基團；且X^s 對於各重複單元獨立地選自C₂ 至C₆ 烷二基及Z^S -(O-Z^S )_t ，其中Z^S 基團各自獨立地選自C₂ 至C₆ 烷二基，s為等於或大於0之整數，且t為等於或大於1之整數。(D) Inhibitors selected from compounds of formula S1

Wherein as described in WO 2010/115717, R ^S1 groups are each independently selected from copolymers of ethylene oxide and at least one other C ₃ to C ₄ alkylene oxide, which is a random copolymer; R ^S2 The groups are each independently selected from R ^S1 or alkyl; X ^S and Y ^{S are} independently spacer groups; and X ^s for each repeating unit is independently selected from C ₂ to C ₆ alkanediyl and Z ^S -(OZ ^S ) _t , wherein the Z ^S groups are each independently selected from C ₂ to C ₆ alkanediyl groups, s is an integer equal to or greater than 0, and t is an integer equal to or greater than 1.

Preferably, the spacer groups X ^S and Y ^{S are} independently, and X ^S is independently selected from C ₂ to C ₄ alkylene for each repeating unit. Most preferably, X ^S and Y ^{S are} independently, and X ^S is independently for each repeating unit, selected from ethylene (-C ₂ H ₄ -) or propylene (-C ₃ H ₆ -).

Preferably, Z ^S is selected from C ₂ to C ₄ alkylene, most preferably selected from ethylene or propylene.

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

In another preferred embodiment, the C ₃ to C ₄ alkylene oxide is selected from propylene oxide (PO). In this case, the side chain of the EO/PO copolymer is generated from the active amine functional group.

The content of ethylene oxide in the copolymer of ethylene oxide and other C ₃ to C ₄ alkylene oxides can generally be about 5 wt% to about 95 wt %, preferably about 30 wt% to about 70 wt% , Especially preferably, it is between about 35% by weight to about 65% by weight.

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-butanediamine, 1,5-diaminopentane, 1,6-diaminohexane, Neopentane diamine, isophorone diamine, 4,9-dioxadecan-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, triethyl Glycol diamine, diethylene triamine, (3-(2-aminoethyl)amino)propylamine, 3,3'-imine bis(propylamine), N,N-bis(3-amino) Propyl) methylamine, bis(3-dimethylaminopropyl)amine, triethylenetetramine and N,N'-bis(3-aminopropyl)ethylenediamine.

The molecular weight M _{w of the} inhibitor of formula S1 may be between about 500 g/mol and about 30,000 g/mol. Preferably, the molecular weight M _w should be about 6000 g/mol or greater, 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, most preferably about 180 to about 300.

The typical total amount of alkylene oxide units in the inhibitor can 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 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 BO, about 180 EO and 150 BO or about 120 EO and 180 BO.

(E) As described in WO 2011/012462, a polyol condensation compound derived from at least one polyol of formula (S2) X ^S (OH) _u by condensation can be formed by reacting at least one alkylene oxide containing An inhibitor obtained from a polyol condensate of a polyoxyalkylene side chain, where u is an integer from 3 to 6, and X ^S is a straight or branched chain aliphatic or cycloaliphatic with 3 to 10 carbon atoms with u valence Group group, which may be substituted or unsubstituted.

其中Y^S 為u價的具有1至10個碳原子之直鏈或分支鏈脂族或環脂族基團，其可經取代或未經取代，a為2至50之整數，b對於各聚合物臂u可為相同或不同的且為1至30之整數，c為2至3之整數，且u為1至6之整數。最佳多元醇為甘油縮合物及/或新戊四醇縮合物。The preferred polyol condensate is selected from compounds of the following formula

Where Y ^S is a straight-chain or branched-chain aliphatic or cycloaliphatic group with 1 to 10 carbon atoms with a valence of u, which may be substituted or unsubstituted, a is an integer from 2 to 50, and b is for each polymerization The object arms u may be the same or different and are an integer from 1 to 30, c is an integer from 2 to 3, and u is an integer from 1 to 6. The best polyol is glycerol condensate and/or neopentylerythritol condensate.

其中v為3至8之整數且w為5至10之整數。最佳單醣醇為山梨糖醇、甘露糖醇、木糖醇、核糖醇及肌醇。更佳多元醇為式（S4a）或（S4b）之單醣

其中x為4至5之整數，且y、z為整數且y+z為3或4。最佳單醣醇係選自醛醣，有阿洛糖（allose）、阿卓糖（altrose）、半乳糖、葡萄糖、古洛糖（gulose）、艾杜糖（idose）、甘露糖、塔羅糖（talose）、葡萄庚糖、甘露庚糖，或酮醣，果糖、阿洛酮糖（psicose）、山梨糖、塔格糖（tagatose）、甘露庚酮糖、景天庚酮糖（sedoheptulose）、塔羅庚酮糖、阿洛庚酮糖。(F) As described in WO 2011/012475, an inhibitor obtained 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. Preferred polyols are linear or cyclic monosaccharide alcohols represented by formula (S3a) or (S3b)

Wherein v is an integer from 3 to 8 and w is an integer from 5 to 10. The best monosaccharide alcohols are sorbitol, mannitol, xylitol, ribitol and inositol. More preferably, the polyol is a monosaccharide of formula (S4a) or (S4b)

Wherein x is an integer from 4 to 5, and y and z are integers and y+z is 3 or 4. The best monosaccharide alcohol is selected from aldose, including allose, altrose, galactose, glucose, gulose, idose, mannose, tarot Sugar (talose), glucoheptose, mannoheptulose, or ketose, fructose, psicose, sorbose, tagatose, mannoheptulose, sedoheptulose , Taloheptulose, alloheptulose.

(G) As described in WO 2018/073011, cyclic amine-based amine-based polyoxyalkylene inhibitors exhibit excellent super-filling properties.

(H) As described in WO 2018/114985, by reacting with a compound (such as (but not limited to) glycidol or glycerol carbonate) that introduces branching groups into the inhibitor before reacting with alkylene oxide The modified polyamine-based or polyol-based inhibitors exhibit excellent super-filling characteristics.

When an inhibitor is used, it is typically present in an amount ranging from about 1 ppm to about 10,000 ppm, and preferably from about 5 ppm to about 10,000 ppm, based on the weight of the bath.

Those skilled in the art should understand that more than one leveling agent can be used. When two or more leveling agents are 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 preferable to use only one leveling agent in the electroplating composition. Other leveling agents

Other leveling agents can be suitably used in the copper electroplating bath according to the present invention. When two or more leveling agents are used, at least one of the leveling agents is a polyalkoxylated polyalkyleneimine or a derivative thereof as described herein. Preferably, only one leveling agent is used in the electroplating composition, that is, the polyalkoxylated polyalkylene polyamine according to the present invention.

Other suitable leveling agents include (but are not limited to) one or more of the following: other polyethyleneimine and its derivatives; quaternary ammonium polyethyleneimine; polyglycine; poly(allylamine); Polyaniline; polyurea; polypropylene amide; poly(melamine-co-formaldehyde); reaction product of amine and epichlorohydrin; reaction product of amine, epichlorohydrin and polyalkylene oxide; of amine and polyepoxide Reaction product; Polyvinylpyridine; Polyvinylimidazole as described in, for example, WO 2011/151785 A1; Polyvinylpyrrolidone; Polyaminoamide as described in, for example, WO 2011/064154 A2 and WO 2014/072885 A2 Or its copolymers; nigrosine; pentamethyl-pararosaniline hydrohalide; hexamethyl-pararosaniline hydrohalide; dialkanolamine or trialkanolamine and others as described in WO 2010/069810 Derivatives; biguanide as described in WO 2012/085811 A1; or compounds containing a functional group of formula NRS, wherein R is substituted alkyl, unsubstituted alkyl, substituted aryl or unsubstituted Aryl. Typically, the alkyl group is a C ₁ -C ₆ alkyl group and preferably a C ₁ -C ₄ alkyl group. Generally speaking, aryl groups include C ₆ -C ₂₀ aryl groups, preferably C ₆ -C ₁₀ aryl groups. Preferably, the aryl group is phenyl or naphthyl. Compounds containing functional groups of formula NRS are generally known, are generally commercially available and can be used without further purification.

In such compounds containing NRS functional groups, sulfur ("S") and/or nitrogen ("N") can be linked to such compounds via single or double bonds. When sulfur is connected to such compounds via a single bond, the sulfur will have another substituent, such as (but not limited to): hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₆ -C ₂₀ Aryl, C ₁ -C ₁₂ alkylthio, C ₂ -C ₁₂ alkenylthio, C ₆ -C ₂₀ arylthio and the like. Likewise, the nitrogen will have one or more substituents, such as (but not limited to): hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₇ -C ₁₀ aryl, and the like. The NRS functional group can be acyclic or cyclic. Compounds containing cyclic NRS functional groups include those compounds having either nitrogen or sulfur or both nitrogen and sulfur in the ring system.

Generally speaking, based on the total weight of the electroplating bath, the total amount of leveling agent in the electroplating bath is 0.5 ppm to 10000 ppm. Based on the total weight of the electroplating bath, the leveling agent according to the present invention is typically used in a total amount of about 0.1 ppm to about 1000 ppm, and more typically 1 ppm to 100 ppm, but more or lesser amounts can be used.

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

Generally speaking, based on the total weight of the electroplating bath, the total amount of leveling agent in the electroplating bath is 0.5 ppm to 10000 ppm. The leveling agent according to the present invention is typically used in a total amount of about 100 ppm to about 10,000 ppm based on the total weight of the electroplating bath, but more or lesser amounts may be used. Electrolyte

The source of copper ions may be any compound capable of releasing metal ions to be deposited in the electroplating bath in a sufficient amount, that is, at least partially soluble in the electroplating bath. Preferably, the metal ion source is soluble in the electroplating bath. Suitable metal ion sources are metal salts and include (but are not limited to): metal sulfates, metal halides, metal acetates, metal nitrates, metal fluoroborates, metal alkyl sulfonates, metal aryl sulfonates , Metal sulfamate, metal gluconate and similar salts.

The metal ion source can provide any amount of metal ions sufficient for electroplating on the substrate for use in the present invention. When the metal is only copper, it is typically present in the electroplating solution in an amount ranging from about 1 g/l to about 300 g/l.

In another preferred embodiment, the electroplating solution is substantially free of tin, that is, it contains 1% by weight of tin, more preferably less than 0.1% by weight, and still more preferably less than 0.01% by weight, and still more preferably free of tin copper. In another preferred embodiment, the electroplating solution is substantially free of any alloy metal, that is, it contains 1% by weight of tin, more preferably less than 0.1% by weight, even more preferably less than 0.01% by weight, and even more Good without tin. The metal is preferably composed of copper.

Optionally, the electroplating bath according to the present invention may contain one or more alloy metal ions in an amount of at most 10% by weight, preferably at most 5% by weight, and most preferably at most 2% by weight. Suitable alloy metals include (but are not limited to): silver, gold, tin, bismuth, indium, zinc, antimony, manganese and mixtures thereof. Preferred alloy metals are silver, tin, bismuth, indium and mixtures thereof, and more preferred is tin. Any bath soluble salt of alloy metal can be used as a source of alloy metal ions. Examples of such alloy metal salts include (but are not limited to): metal oxides; metal halides; metal fluoroborates; metal sulfates; metal alkane sulfonates, such as metal methanesulfonates, metal ethanesulfonates, and Metal propane sulfonate; metal aryl sulfonate, such as metal phenyl sulfonate, metal toluene sulfonate, and metal phenol sulfonate; metal carboxylate, such as metal gluconate and metal acetate; and It is similar to salt. Preferred alloy metal salts are metal sulfate; metal alkane sulfonate; and metal aryl sulfonate. When an alloy metal is added to the composition of the present invention, a binary alloy deposit is obtained. When two, three or more different alloy metals are added to the composition of the present invention, a third-, fourth-, or higher-order alloy deposit is obtained. The amount of such alloy metals used in the composition of the present invention will depend on the specific tin alloy required. The selection of such amounts of alloy metal is within the abilities of those having ordinary knowledge in the relevant technical field. Those skilled in the art should understand that when certain alloy metals such as silver are used, additional complexing agents may be required. Such complexing agents (or complexes) are well known in the art and can be used in any suitable amount to obtain the desired tin alloy composition.

The electroplating composition of the present invention is suitable for depositing a copper-containing layer, which may preferably be a pure copper layer or alternatively include copper of one or more alloyed metals at most 10% by weight, preferably at most 5% by weight, and most preferably at most 2% by weight Alloy layer. 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-coated silver-zinc-copper and tin-silver-indium-bismuth. Preferably, the electroplating composition of the present invention deposits pure tin, tin-silver, tin-silver-copper, tin-indium, tin-silver-bismuth, tin-silver-indium, and tin-silver-indium-bismuth, and more It is best to deposit pure tin, tin-silver or tin-copper.

Alloy metal content can be measured by atomic absorption spectroscopy (AAS), X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS) Measurement.

Generally speaking, in addition to at least one of the copper ion and the leveling agent, the copper electroplating composition of the present invention preferably includes an electrolyte, that is, an acidic or alkaline electrolyte, optionally a halide ion, and optionally includes other additives , Such as accelerators and inhibitors. Such baths are typically aqueous.

Generally speaking, as used herein, "aqueous" means that the electroplating composition of the present invention contains a solvent containing at least 50% water. Preferably, "aqueous" means that the main part of the composition is water, more preferably 90% of the solvent is water, and the best solvent consists of water or consists essentially of water. Any type of water can be used, such as distilled, deionized or tap water.

Preferably, the electroplating bath of the present invention is acidic, that is, its pH is lower than 7. Typically, the pH of the copper electroplating composition is lower than 4, preferably lower than 3, and most preferably lower than 2.

The electroplating bath of the present invention can be prepared by combining the components in any order. Preferably, first add inorganic components such as metal salts, water, electrolytes and optionally halide ion sources to the bath container, and then add organic components such as accelerators, inhibitors, leveling agents and the like. Components.

Suitable electrolytes include, but are not limited to: sulfuric acid; acetic acid; fluoroboric acid; alkyl sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and trifluoromethanesulfonic acid; arylsulfonic acids, such as benzenesulfonic acid Acid and toluenesulfonic acid; amine sulfonic acid; hydrochloric acid; phosphoric acid; tetraalkylammonium hydroxide, preferably tetramethylammonium hydroxide; sodium hydroxide; potassium hydroxide and the like. The acid is typically present in an amount ranging from about 1 g/l to about 300 g/l. In a specific example, the at least one additive comprises a counter ion Y ^o- selected from methane sulfonate, sulfate, or acetate, where o is a positive integer.

Such electrolytes may optionally (and preferably) contain a source of halide ions, such as chloride ions in copper chloride or hydrochloric acid. A wide range of halide ion concentrations can be used in the present invention, such as about 0 to about 500 ppm. Preferably, based on the electroplating bath, the halide ion concentration is in the range of about 10 ppm 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 chlorine ion source. Sources of acids and halide ions suitable for use in the present invention are generally commercially available and can be used without further purification. method

The composition according to the present invention is particularly suitable for electrodepositing copper on a substrate containing a recessed member, the recessed member including a bottom of a conductive member and a sidewall of a dielectric member, wherein the size of the orifice of the recessed member is 500 nm to 500 μm. The leveling agent according to the present invention is particularly suitable for filling recessed components with an orifice size of 1 μm to 200 μm. The leveling agent is especially suitable for depositing copper bumps.

According to the present invention, copper is deposited in the recesses without substantially forming voids in the metal deposit. The term "without substantially forming void" means that there is no void larger than 1000 nm in the metal deposit, preferably no void larger than 500 nm in the metal deposit, and no void larger than 500 nm in the optimal metal deposit. The gap is greater than 100 nm. Optimally, the deposit does not contain any defects.

Due to the leveling effect of the leveling agent, an improved coplanarity surface with electroplated copper bumps is obtained. The copper deposits exhibit good morphology, especially low roughness. The electroplating composition can fill micron-sized recessed components without substantially forming defects, such as (but not limited to) voids.

In addition, the leveling agent according to the present invention reduces impurities, such as (but not limited to): organic matter, chloride, sulfur, nitrogen or other elements. It exhibits larger particles and improved conductivity. It also promotes high plating rates and allows plating at high temperatures.

Generally speaking, when the present invention is used to deposit copper on a substrate, the electroplating bath is agitated during use. Any suitable agitation method can 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 bubbling, workpiece agitation, impingement and similar methods. Such methods are known to those with ordinary knowledge in the relevant technical field. When the present invention is used for electroplating an integrated circuit substrate (such as a wafer), the wafer can be rotated such as 1 RPM to 150 RPM and the electroplating solution can contact the rotating wafer such as by pumping or spraying. In the alternative, when the electroplating bath flow is sufficient to provide the required metal deposits, the wafer does not need to be rotated.

Electroplating equipment for electroplating semiconductor substrates is well known. The electroplating equipment includes an electroplating tank, which contains a copper electrolyte, and is made of a suitable material (such as plastic or other materials that are inert to the electrolytic plating solution). The groove may be cylindrical, especially for wafer plating. The cathode is horizontally arranged at the upper part of the groove, and can be any type of substrate, such as a silicon wafer with openings.

These additives can be used with soluble and insoluble anodes in the presence or absence of one or more membranes that separate the catholyte from the anolyte.

The cathode substrate and the anode are electrically connected by wiring and are respectively electrically connected to a power source. The cathode substrate used for direct current or pulsed current has a net negative charge, so that the metal ions in the solution are reduced at the cathode substrate, thereby forming electroplated metal on the surface of the cathode. The oxidation reaction takes place at the anode. The cathode and anode can be placed in the tank horizontally or vertically.

Generally speaking, when preparing copper bumps, a photoresist layer is coated on a semiconductor wafer, followed by standard photolithography exposure and development techniques to form a patterned photoresist layer with recessed members or through holes (or Electroplating mask). The size of the dielectric plating mask (the thickness of the plating mask and the size of the opening in the pattern) defines the size and location of the copper layer deposited on the I/O pads and UBM. The diameter of such deposits is typically in the range of 1 μm to 300 μm, preferably in the range of 2 μm to 100 μm. Generally, the recesses provided by the electroplating mask are not complete but only partially filled. After filling the openings in the electroplating mask with copper, the electroplating mask is removed, and then the copper bumps are usually reflowed.

Typically, the electroplating bath of the present invention can be used at any temperature from 10°C to 65°C or higher. Preferably, the temperature of the electroplating bath is 10°C to 35°C, and more preferably 15°C to 30°C.

Unless otherwise specified, all percentages, ppm or similar values refer to the weight relative to the total weight of the respective composition. All cited documents are incorporated herein by reference.

The following examples will further illustrate the present invention without limiting the scope of the present invention. Analytical method

The molecular weight of the leveling agent is determined by size-exclusion chromatography (SEC). Polystyrene was used as the standard and tetrahydrofuran was used as the effluent. The temperature of the column is 30°C, the injection volume is 30 microliters (μl), and the flow rate is 1.0 ml/min. Determine the weight average molecular weight (M _w ), number average molecular weight (M _n ) and polydispersity PDI (M _w /M _n ) of the inhibitor.

The amine value is determined according to DIN 53176 by titrating a solution of the polymer in acetic acid with perchloric acid.

The experiment was performed using a 300 mm silicon wafer (available from IMAT Corporation, Vancouver, WA, USA) with a patterned photoresist of 120 μm thickness and a plurality of copper inoculated through holes of 75 μm.

The electroplated copper is studied by 3D laser scanning microscope (3D laser scanning microscope; 3D LSM). Visually observe the height of the deposited copper layer in the bump.

The unevenness is measured by the height of a total of 27 measuring bumps. Among them, 15 bumps with a distance of 150 μm between the dense line (dense) area and 12 bumps with a distance of 375 μm are measured.

其中 「單線凸塊高度平均值（bump height average iso）」及「密線凸塊高度平均值（bump height average dense）」為各區域之算術平均值。「平均高度（mean height）」係藉由「單線凸塊高度平均值」與「密線凸塊高度平均值」之總和除以2來計算。 實施例 實施例1：調平劑製備 中間化合物A之合成Calculate the coplanarity (indicator of non-uniformity) from the height by using the following formula:

Among them, "bump height average iso" and "bump height average dense" are the arithmetic averages of each area. The "mean height" is calculated by dividing the sum of the "average height of single-line bumps" and the "average height of dense-line bumps" by 2. Examples Example 1: Preparation of leveling agent. Synthesis of intermediate compound A

Polyethyleneimine (Lupasol G20 from BASF) (430.4 g) was placed in a 3.5 l autoclave at 80°C and the reactor was purged with nitrogen three times under 1.5 bar. Subsequently, ethylene oxide (440.5 g) was added in portions over a period of 10 hours at 100°C to a maximum pressure of 5 bar. In order to complete the reaction, the mixture was post-reacted at 100°C under a pressure of 2 bar for 6 hours. Subsequently, the temperature was lowered to 80°C and the volatile compounds were removed in vacuum at 80°C. A brown viscous liquid (769.2 g) was observed with an amine value of 538.7 mg/g. Synthesis of intermediate compound B

Polyethyleneimine (Lupasol PR8515 from BASF) (1677 g) was placed in a 5 l autoclave at 80°C and the reactor was purged with nitrogen three times under 1.5 bar. Subsequently, ethylene oxide (1717.9 g) was added in portions over a period of 10 hours at 100°C to a maximum pressure of 5 bar. In order to complete the reaction, the mixture was post-reacted at 100°C under a pressure of 2 bar for 6 hours. Subsequently, the temperature was lowered to 80°C and the volatile compounds were removed in vacuum at 80°C. A brown viscous liquid (3314.9 g) was observed with an amine value of 640.7 mg/g. Synthesis of Intermediate Compound C

Polyethyleneimine (Lupasol FG from BASF) (430.4 g) was placed in a 3.5 l autoclave at 80°C and the reactor was purged with nitrogen three times under 1.5 bar. Subsequently, ethylene oxide (440.5 g) was added in portions over a period of 10 hours at 100°C to a maximum pressure of 5 bar. In order to complete the reaction, the mixture was post-reacted at 100°C under a pressure of 2 bar for 6 hours. Subsequently, the temperature was lowered to 80°C and the volatile compounds were removed in vacuum at 80°C. A brown viscous liquid (753.8 g) was observed with an amine value of 654.7 mg/g. Comparative Example 1.1

Intermediate compound A (125 g) and potassium tert-butoxide (0.9 g) were placed in a 3.5 l autoclave at 80°C and the reactor was purged with nitrogen three times under 1.5 bar. Subsequently, ethylene oxide (475.7 g) was added in portions over a period of 10 hours at 100°C to a maximum pressure of 5 bar. In order to complete the reaction, the mixture was post-reacted at 100°C under a pressure of 2 bar for 6 hours. Subsequently, the temperature was lowered to 80°C and the volatile compounds were removed in vacuum at 80°C. A brown viscous liquid (576.2 g) was observed, with an amine value of 118.5 mg/g. Comparative Example 1.2

Intermediate compound A (104.2 g) and potassium tert-butoxide (1.08 g) were placed in a 3.5 l autoclave at 80°C and the reactor was purged with nitrogen three times at 1.5 bar. Subsequently, ethylene oxide (616.7 g) was added in portions over a period of 10 hours at 100°C to a maximum pressure of 5 bar. In order to complete the reaction, the mixture was post-reacted at 100°C under a pressure of 2 bar for 6 hours. Subsequently, the temperature was lowered to 80°C and the volatile compounds were removed in vacuum at 80°C. A brown viscous liquid (703.2 g) was observed with an amine value of 78.8 mg/g. Example 1.3:

Intermediate compound A (100 g) and potassium tert-butoxide (1.3 g) were placed in a 2 l autoclave at 80°C and the reactor was purged with nitrogen three times at 1.5 bar. Subsequently, ethylene oxide (607.3 g) was added in portions over a period of 10 hours at 130°C to reach a maximum pressure of 5 bar. The mixture was post-reacted for 6 hours. Propylene oxide (133.4 g) was then added at 130°C over a period of 10 hours to reach a maximum pressure of 5 bar. The mixture was post-reacted for 6 hours. Subsequently, the temperature was lowered to 80°C and the volatile compounds were removed in vacuum at 80°C. A brown viscous liquid (819.3 g) with an amine value of 77.3 mg/g was obtained. Example 1.4:

Intermediate compound B (87.1 g) and potassium tert-butoxide (1.1 g) were placed in a 3.5 l autoclave at 80°C and the reactor was purged with nitrogen three times at 1.5 bar. Subsequently, ethylene oxide (528.6 g) was added in portions over a period of 10 hours at 100°C to a maximum pressure of 5 bar. Propylene oxide (116.2 g) was then added at 130°C over a period of 10 hours to reach a maximum pressure of 5 bar. The mixture was post-reacted for 6 hours. Subsequently, the temperature was lowered to 80°C and the volatile compounds were removed in vacuum at 80°C. A brown viscous liquid (679.7 g) was observed with an amine value of 79.4 mg/g. Example 1.5:

Intermediate compound C (87.1 g) and potassium tert-butoxide (1.1 g) were placed in a 3.5 l autoclave at 80°C and the reactor was purged with nitrogen three times at 1.5 bar. Subsequently, ethylene oxide (528.6 g) and propylene oxide (116.2 g) were added in portions over a period of 10 hours at 100°C to reach a maximum pressure of 5 bar. Propylene oxide (116.2 g) was then added at 130°C over a period of 10 hours to reach a maximum pressure of 5 bar. The mixture was post-reacted for 6 hours. Subsequently, the temperature was lowered to 80°C and the volatile compounds were removed in vacuum at 80°C. A brown viscous liquid (695.5 g) was observed with an amine value of 79.9 mg/g. Comparative Example 2.1

A copper electroplating bath containing 51 g/l Cu ions, 100 g/l sulfuric acid and 50 ppm chloride has been used for research. In addition, the bath contains the following additives: 50 ppm SPS, 100 ppm of ethylene oxide polymer with an average molecular weight of 4000 g/mol, and 20 ppm of Comparative Example 1.1.

The substrate is pre-wetted and electrically contacted before electroplating. The copper layer was electroplated by using a benchtop electroplating tool purchased from Yamamoto MS. Electrolyte convection is realized by the pump and paddle in front of the substrate. The RPM of the paddle for all plating conditions is 50 RPM. The bath temperature was controlled and set to 25°C, and the applied current density was 4 ASD (340 seconds) and 8 ASD (1875 seconds), resulting in bumps with a height of about 50 μm.

The plated bumps were inspected with LSM as described in detail above. The degree of coplanarity (COP) was determined to be 11.5%.

The results are summarized in Table 1. Comparative Example 2.2

A copper electroplating bath containing 51 g/l Cu ions, 100 g/l sulfuric acid and 50 ppm chloride has been used for research. In addition, the bath contains the following additives: 50 ppm SPS, 100 ppm of ethylene oxide polymer inhibitor with an average molecular weight of 4000 g/mol, and 20 ppm of the compound of Comparative Example 1.2.

The substrate is pre-wetted and electrically contacted before electroplating. The copper layer was electroplated by using a benchtop electroplating tool purchased from Yamamoto MS. Electrolyte convection is realized by the pump and paddle in front of the substrate. The RPM of the paddle for all plating conditions is 50 RPM. The bath temperature was controlled and set to 25°C, and the applied current density was 4 ASD (340 seconds) and 8 ASD (1875 seconds), resulting in bumps with a height of about 50 μm.

The plated bumps were inspected with LSM as described in detail above. The degree of coplanarity (COP) was determined to be 9.0%.

The results are summarized in Table 1. Example 2.3

A copper electroplating bath containing 51 g/l Cu ions, 100 g/l sulfuric acid and 50 ppm chloride has been used for research. In addition, the bath contains the following additives: 50 ppm SPS, 100 ppm of ethylene oxide polymer inhibitor with an average molecular weight of 4000 g/mol, and 20 ppm of the compound of Example 1.3.

The substrate is pre-wetted and electrically contacted before electroplating. The copper layer was electroplated by using a benchtop electroplating tool purchased from Yamamoto MS. Electrolyte convection is realized by the pump and paddle in front of the substrate. The RPM of the paddle for all plating conditions is 50 RPM. The bath temperature was controlled and set to 25°C, and the applied current density was 4 ASD (340 seconds) and 8 ASD (1875 seconds), resulting in bumps with a height of about 50 μm.

The plated bumps were inspected with LSM as described in detail above. The degree of coplanarity (COP) was determined to be 6.8%.

The results are summarized in Table 1. Table 1 Example M _w [g/mol]* EO unit PO unit COP [%] Comparative Example 2.1 1 300 10 0 11.5 Comparative Example 2.2 1 300 15 0 9.0 2.3 1 300 13 2 6.8 *For the PEI main chain

Comparing the results from Examples 2.1, 2.2 and 2.3 with the same polyethyleneimine backbone as the starting material, when compared with the leveling agent of Examples 2.1 and 2.2 when using the leveling agent of Example 2.3 containing oxypropylene , Copper electroplating produces significantly better coplanarity. Example 2.4

A copper electroplating bath containing 51 g/l Cu ions, 100 g/l sulfuric acid and 50 ppm chloride has been used for research. In addition, the bath contains the following additives: 50 ppm SPS, 100 ppm of ethylene oxide polymer inhibitor with an average molecular weight of 4000 g/mol, and 20 ppm of Example 1.4.

The substrate is pre-wetted and electrically contacted before electroplating. The copper layer was electroplated by using a benchtop electroplating tool purchased from Yamamoto MS. Electrolyte convection is realized by the pump and paddle in front of the substrate. The RPM of the paddle for all plating conditions is 50 RPM. The bath temperature was controlled and set to 25°C, and the applied current density was 4 ASD (340 seconds) and 8 ASD (1875 seconds), resulting in bumps with a height of about 50 μm.

The plated bumps were inspected with LSM as described in detail above. The degree of coplanarity (COP) was determined to be 7.0%.

The results are summarized in Table 2. Example 2.5

A copper electroplating bath containing 51 g/l Cu ions, 100 g/l sulfuric acid and 50 ppm chloride has been used for research. In addition, the bath contains the following additives: 50 ppm SPS, 100 ppm of ethylene oxide polymer inhibitor with an average molecular weight of 4000 g/mol, and 20 ppm of Example 1.5.

The substrate is pre-wetted and electrically contacted before electroplating. The copper layer was electroplated by using a benchtop electroplating tool purchased from Yamamoto MS. Electrolyte convection is realized by the pump and paddle in front of the substrate. The RPM of the paddle for all plating conditions is 50 RPM. The bath temperature was controlled and set to 25°C, and the applied current density was 4 ASD (340 seconds) and 8 ASD (1875 seconds), resulting in bumps with a height of about 50 μm.

The plated bumps were inspected with LSM as described in detail above. The degree of coplanarity (COP) was determined to be 9.1%.

The results are summarized in Table 2. Table 2 Example Mw [g/mol] EO unit PO unit COP [%] 2.4 2 000 13 2 7.0 2.5 800 13 2 9.1

Table 2 shows that both leveling agents exhibit excellent coplanarity significantly below 10.

no

no

Claims (15)

A composition comprising copper ions and at least one additive containing a polyalkyleneimine main chain, the polyalkyleneimine main chain containing N-hydrogen atoms, wherein (a) the polyalkyleneimine main chain The mass average molecular weight M _W of the chain is 600 g/mol to 100 000 g/mol, (b) the N-hydrogen atoms are each substituted with a polyoxyalkylene group _{containing oxyethylene and C 3} to C _{6 alkylene oxide units, and} (C) In the polyalkyleneimine, the average number of oxyalkylene units in the polyoxyalkylene groups is greater than 10 to less than 30 per N-hydrogen atom. The composition of claim 1, wherein the average number of oxyalkylene units in the polyoxyalkylene group is 11 to 28 per N-hydrogen atom. The composition of claim 1 or 2, wherein the at least one additive is a polyalkyleneimine of formula L1

Or its derivatives obtained by protonation or quaternary ammonium, wherein X ^{L1 is} independently selected from linear C ₂ -C ₆ alkanediyl, branched C ₃ -C ₆ alkanediyl and mixtures thereof; A ^L1 is the continuation of the polyalkyleneimine main chain by branching; R ^L1 is a polyoxyalkylene unit of formula -(X ^L11 O) _r (X ^L12 O) _s -R ^{L11 ; R L2} is selected From R ^L1 and R ^L3 ; R ^L3 is selected from C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ alkenyl, C ₁ to C ₁₂ alkynyl, C ₆ to C ₂₀ alkaryl, C ₆ to C ₂₀ Aralkyl and C ₆ to C ₂₀ aryl; X ^L11 is ethylenediyl; For each n, X ^{L12 is} independently selected from C ₃ to C ₆ alkanediyl, preferably prop-1,2-diyl, ( 2-Hydroxymethyl) ethyl-1,2-diyl, but-1,2-diyl, but-2,3-diyl, 2-methyl-prop-1,2-diyl (isobutyl Base), pentyl-1,2-diyl, pentyl-2,3-diyl, 2-methyl-but-1,2-diyl, 3-methyl-but-1,2-diyl, hexyl -2,3-diyl, hex-3,4-diyl, 2-methyl-pentan-1,2-diyl, 2-ethylbut-1,2-diyl, 3-methyl-pentyl -1,2-diyl, decyl-1,2-diyl, 4-methyl-pentyl-1,2-diyl and (2-phenyl)-ethyl-1,2-diyl, and mixtures thereof ; R ^{L11 is} each independently hydrogen, C ₁ to C ₁₂ alkyl, C ₂ to C ₁₂ alkenyl, C ₂ to C ₁₂ alkynyl, C ₆ to C ₁₈ aralkyl, C ₅ to C ₁₂ aryl, C ₂ to C ₁₂ alkylcarbonyl and mixtures thereof; s and r are selected so that the arithmetic mean of the alkylene oxide units in the ^{R L1 groups is 1 to n}

It is an integer greater than 10 to less than 30, where p is the sum of r and s; and q, n, m, and o are integers, the restriction conditions are (q + n + m + o) is 10 to 24000 and n Is 1 or greater. Such as the composition of any one of claim 3, wherein X ^L1 is selected from the group consisting of ethylenediyl, 1,3-propanediyl and 1,4-butanediyl. Such as the composition of any one of claim 3 or 4, wherein the relative amount s/(s+r) of the C ₃ to C ₆ ^{alkylene oxide units in R L1 is 7% to 50%.} The composition according to any one of claims 3 to 5, wherein the C ₃ to C ₆ alkylene oxide is oxypropylene. Such as the composition of any one of claims 3 to 6, wherein p is selected so that the arithmetic mean of the alkylene oxide units in the ^{R L1 groups is 1 to n}

The number is from 11 to 28, especially from 13 to 25. Such as the composition of any one of claims 3 to 7, wherein q + n + m + o is 15 to 10,000, especially 20 to 5,000. Such as the composition of any one of claims 3 to 7, wherein q + n + m + o is 25 to 65 or 1000 to 1800. Such as the composition of any one of claims 3 to 9, wherein o is 0. The composition according to any one of the preceding claims, wherein the average number of oxyalkylene units in the polyoxyalkylene group is 12 to 25 per N-hydrogen atom, preferably 13 to 23 per N-hydrogen atom . The composition according to any one of the preceding claims, which further comprises one or more accelerators, one or more inhibitors or a combination thereof. A use of the composition of any one of the preceding claims for depositing copper on a substrate containing a recessed member, the recessed member including a bottom of a conductive member and a side wall of a dielectric member, wherein the orifice of the recessed member The size is 500 nm to 500 μm. A method of electrodepositing copper on a substrate containing a recessed member, the recessed member including a bottom of a conductive member and a sidewall of a dielectric member, the method comprising: a) Bring the composition of any one of claims 1 to 12 into contact with the substrate, and b) applying current to the substrate for a time sufficient to deposit a copper layer into the recessed member, The size of the orifice of the recessed member is 500 nm to 500 μm. Such as the method of claim 14, wherein the size of the orifice is 1 μm to 200 μm.