CN1918327B - Copper electroplating in microelectronics - Google Patents

Abstract

A method and composition for electroplating copper onto a substrate in the manufacture of microelectronic components of interest, and an electrolytic solution including a source of copper ions and a substituted pyridyl polymer compound for leveling.

Description

Copper Plating in Microelectronics

Technical field:

The present invention relates to methods, compositions and additives for copper electroplating in the field of microelectronics manufacturing.

Background technique:

Copper electroplating is widely used in the field of microelectronics manufacturing to provide electrical interconnections, for example, in the manufacture of components such as semiconductor integrated circuits. Demands for fabricating semiconductor integrated circuit elements such as computer chips with high circuit speeds and high packing densities require ultra large scale integration (ULSI) and very large scale integration (VLSI) structural element size reduction. The trend of decreasing component size and increasing circuit density requires reducing the size of interconnect features. An interconnect feature is a feature such as a via or trench that is formed in a dielectric substrate and then filled with metal to create a conductive interconnect line. Further reductions in interconnect dimensions pose challenges for metal filling.

Copper has been introduced to replace aluminum to form bonding lines and interconnects in semiconductor substrates. Copper has a lower resistivity than aluminum, and for the same resistivity, the thickness of a copper wire is less than that of an aluminum wire. Copper can be deposited on the substrate by electroplating (such as electroless plating and electroplating), sputtering, plasma vapor deposition (PVD) and chemical vapor deposition (CVD). Electrochemical deposition is generally considered the best method for applying copper because it offers high deposition rates and offers low cost of ownership.

Copper plating methods must meet the stringent requirements of the semiconductor industry. For example, copper deposition must be uniform and flawlessly fill the device's small interconnect features such as 100nm (or smaller) openings.

Electrolytic copper systems have been developed that rely on so-called "superfilling" or "bottom-up growth" to deposit copper into high aspect ratio structural elements. Superfilling involves filling structural elements from the bottom up, rather than at the same rate on all their surfaces, to avoid seams and pinch off that can cause voids. Systems including inhibitors and accelerators as additives have been developed for superfilling. As a result of the bottom-up growth momentum, the copper is deposited thicker on the areas where the structural elements are interconnected than on the areas that do not have the structural elements. These areas of overgrowth are often referred to as overplating, mounds, bumps, bumps. Smaller structural elements produce higher overplated bumps due to faster superfill rates. Overplating challenges the subsequent chemical and mechanical polishing processes to planarize the copper surface.

To control overplating, third-party additives called levelers are introduced to create surface "levelling," that is, to reduce the bottom-up growth impulse produced by accelerators and inhibitors. Although the leveler produces a flatter copper plane, it is generally believed that the leveler has a negative effect on the bottom-up growth, especially the high leveler concentration can slow down the superfill growth rate. It is common practice to use the leveler in a narrow concentration window that creates a balance between overplating and superfill performance.

As chip architectures get smaller (interconnects have openings on the order of 100nm through which copper must grow to fill the interconnects), there is a need for increased bottom-up speed. That is, the copper must fill "faster", the growth rate in the vertical direction must be sufficiently greater (eg, 50%, 75% or more) than the growth rate in the horizontal direction, and even larger interconnects than traditional super Padding in a much larger sense. However, the exceptional speed of bottom-up growth on these fine structures produces overplated bumps of larger size, which require more leveler to level. But a further increase in leveler concentration reduces the superfilling speed, which is particularly critical for these fine interconnect structures.

In addition to overfill and overplating issues, micro-defects can form when electroplating copper-filled interconnect features. One defect that may occur is the formation of internal cavities inside the structural elements. As copper is deposited on the structural element sidewalls and structural element top inlets, deposition on the structural element sidewalls and inlets can pinch off, thereby closing off access to the interior of the structural elements, especially for small (e.g. <100nm) and / or structural elements with a high aspect ratio (depth:width). Internal voids may form in the structural element if the copper solution flowing into the structural element is interrupted during the electrolysis process. Internal voids can interfere with the electrical connectivity of the structural elements.

Microvoiding is another defect that forms during or after electrolytic copper deposition due to non-uniform copper growth rates or particulate recrystallization that occurs after copper plating.

On the other hand, some localized areas of the semiconductor substrate, typically where a copper seed layer by physical vapor deposition exists, may not grow copper during electrowinning, resulting in pits or metal-missing defects. These copper vacancies are considered "killer defects" because they reduce the yield of semiconductor manufacturing. Multiple mechanisms lead to the formation of these copper voids, including the semiconductor substrate itself. However, copper plating chemistry has an impact on the occurrence and number of these defects.

Other defects are surface protrusions, which are isolated deposition peaks occurring at localized high current density locations, localized impurity locations, or other locations. Copper plating chemistry has an effect on the generation of such raised defects. Although not considered a defect, copper surface roughness is also important to semiconductor wafer fabrication. In general, a bright copper surface is desired because it reduces swirl patterns that form during wafer entry into the plating bath. The roughness of copper deposits makes it difficult to detect defects by inspection because defects can be hidden by the peaks and valleys of the rough surface. In addition, smooth growth of copper becomes more important for defect filling of fine interconnect structures, since roughness can cause pinch-off of structural elements, thereby closing access to the interior of structural elements. It is generally believed that copper plating chemistry has a strong influence on the roughness of copper deposits through the combined effect of additives, especially levelers. From this point of view, the judicious use of levelers results in a better superfill.

Invention content:

Thus, in brief, the present invention provides a method of electroplating copper onto a substrate in the manufacture of microelectronic components comprising immersing the substrate in a bath containing copper in an amount sufficient to electrodeposit copper onto the substrate and comprising a substituted pyridine A leveler of a polymer compound is added to the electrolyte, and an electric current is supplied to the electrolyte to deposit copper on the substrate.

In another aspect, the present invention provides a composition for electroplating copper onto a substrate in the manufacture of microelectronic components, the composition comprising a source of copper particles and a leveler comprising a substituted pyridine polymer compound.

Other objects and features of the invention will be in part apparent and pointed out in the following sections.

Detailed ways:

According to the invention, additives based on substituted pyridine compounds are integrated into electroplating baths for copper plating in the manufacture of microelectronic components. In one embodiment, an electroplating bath is used to deposit copper onto a semiconductor integrated circuit component substrate, such as a silicon wafer, including copper filling of interconnect structure components.

A clear advantage of the additives of the present invention is that the leveling effect is improved without substantially hindering copper superfilling into high aspect ratio structural elements. That is, since the leveler of the present invention does not substantially interfere with superfilling, the copper bath can be equipped with a combination of accelerator and suppressor additives that provides a growth rate that is much greater than that in the horizontal direction (even greater than that of the interlayer). The growth rate in the vertical direction is much larger than the traditional superfill of the wire. The compositions of the present invention address the risk of buildup that typically occurs with increased superfill rates. The additives also have advantages in reducing defects, improving brightness, minimizing overplating, improving uniformity, and reducing overplating in some large structural elements.

The leveler of the present invention is selected from the group that dissolves in the copper plating bath, maintains its functionality under electrolytic conditions, does not produce harmful by-products under electrolytic conditions (at least not immediately or shortly thereafter), and produces the desired leveling. effect of substituted pyridine compounds. In one embodiment, the leveler is a pyridinium compound, especially a pyridinium quaternary ammonium salt. Pyridinium salt compounds are derived from pyridine in which the pyridine nitrogen atom is protonated. Pyridinium quats are distinct from pyridine and pyridinium quat based polymers are distinct from pyridinium based polymers in that the nitrogen atom of the pyridine ring is quaternized in pyridinium quats and pyridinium quat based polymers. Levelers of the present invention include derivatives of vinylpyridine, such as derivatives of 2-vinylpyridine, and in some preferred embodiments, derivatives of 4-vinylpyridine. The leveler compound polymer of the present invention includes homopolymers of vinylpyridine, copolymers of vinylpyridine, quaternary ammonium salts of vinylpyridine and quaternary ammonium salts of these homopolymers and copolymers. Some specific examples of such compounds include, for example, poly-(4-vinylpyridine), the reaction product of poly-(4-vinylpyridine) and dimethyl sulfate, 4-vinylpyridine and 2-chloroethanol, among others The reaction product of 4-vinylpyridine and benzyl chloride, the reaction product of 4-vinylpyridine and allyl chloride, the reaction product of 4-vinylpyridine and 4-chloromethylpyridine, 4-vinylpyridine The reaction product of pyridine and 1,3-propane sultone, the reaction product of 4-vinylpyridine and methyltosylate, the reaction product of 4-vinylpyridine and chloroacetone, the reaction product of 4-vinylpyridine The reaction product of 2-methoxyethoxymethane chloride, the reaction product of 4-vinylpyridine and 2-chloroethyl ether, the reaction product of 2-vinylpyridine and methyltoluenesulfonyl, the reaction product of 2-vinylpyridine and Reaction product of dimethyl sulfate, reaction product of vinylpyridine with water-soluble initiator, poly(2-methyl-5-enylpyridine) and 1-methyl-4-vinylpyridine trifluoromethanesulfonate . An example of a copolymer is vinylpyridine copolymerized with vinylimidazole.

In one embodiment the substituted pyridine polymer compounds of the present invention have a molecular weight on the order of about 160,000 g/mol or less. While some compounds with higher molecular weight are difficult to dissolve into the plating bath, or remain in solution, other higher molecular weight compounds are soluble due to the increased solvency of the tetrazide cation. The notion of solubility in this context refers to relative solubility, eg, greater than 60% soluble, or some other minimum solubility that is valid in this context. It is not a reference to absolute solubility. The aforementioned preferred value of 160,000 g/mol is not strictly critical in some embodiments. The selected substituted pyridine polymers are soluble in the copper plating bath, retain their functionality under electrolytic conditions, and do not produce harmful by-products immediately thereafter or shortly thereafter under electrolytic conditions.

Poly(4-vinylpyridine) homopolymers are commercially available. Poly(4-vinylpyridine) homopolymers having an average molecular weight ranging from 10,000 to 20,000 with a median value of 16,000 are available from Reilly Industries Inc under the trade name Reilline 410 Solution SOQ. Additionally, poly(4-vinylpyridine) having an average molecular weight ranging from 60,000 to 160,000 is available from Aldrich Chemical Company.

In those embodiments where the leveler compound is a reaction product of vinylpyridine or polyvinylpyridine, by combining vinylpyridine or poly(vinylpyridine) with a Leveler compounds are obtained by reacting with alkylating agents to level effective products of the group. In some embodiments, candidates are selected from reaction products obtained by reacting vinylpyridine or poly(vinylpyridine) with a compound of formula 1 below:

R ₁ -L (1)

wherein _R is alkyl, alkenyl, aralkyl, heteroarylalkyl, substituted alkyl, substituted alkenyl, substituted aralkyl, or substituted heteroarylalkyl; and L is a leaving group.

A leaving group is any group that is removable from a carbon atom. In general, weak bases are good leaving groups. Exemplary leaving groups are halides, methyl sulfate, tosylate, and the like.

In another embodiment, R _is alkyl, substituted alkyl; preferably, _R is substituted or unsubstituted methyl, ethyl, linear, branched or cyclopropyl, butyl, pentyl or hexyl; in one embodiment methyl, hydroxy, acetyl, chloroethoxyethyl or methoxyethoxymethyl.

In a further embodiment, R _is alkyl; preferably, _R is vinyl, propenyl, linear or branched butenyl, linear, branched or cyclic pentenyl, or linear, Branched or cyclic hexenyl; in one embodiment propenyl.

In another embodiment, R _is aralkyl or substituted aralkyl; preferably _R is benzyl or substituted benzyl, naphthylalkyl or substituted naphthylalkyl; in one embodiment benzyl or Naphthylmethyl.

In yet another embodiment, R ₁ is heteroarylalkyl or substituted heteroarylalkyl; preferably, R ₁ is pyridylalkyl; in particular, R ₁ is pyridylmethyl.

In a further embodiment, L is chloride, methyl sulfate (CH ₃ SO ₄ ⁻ ), octyl sulfate (C ₈ H ₁₈ SO ₄ ⁻ ), trifluoromethanesulfonate (CF ₃ SO ₃ ⁻ ) , chloroacetate (CH ₂ ClC(O)O ⁻ ) or tosylate (C ₇ H ₇ SO ₃ ⁻ ); preferably, L is methyl sulfate, chloride or tosylate.

In one such embodiment, the leveler compound is poly(1-methyl-4-vinylpyridine methyl sulfate) obtained by reacting poly(4-vinylpyridine) with dimethyl sulfate, as follows Said:

Water soluble initiators can be used to prepare the vinylpyridine polymers, although they may not be used in the presently preferred embodiments or in the working examples. Exemplary water-soluble initiators are peroxides (e.g., hydrogen peroxide, benzoyl peroxide, perbenzoic acid, etc.), and water-soluble azo initiators such as 4,4'-azobis(4-cyanovaleric acid). agent.

In a further embodiment, the leveler constitutes a component of a mixture of one of the aforementioned polymers and some monomers, eg, pyridine-derived compounds. In one such embodiment, the mixture is obtained by monomers to produce quaternary ammonium salts, which are then self-polymerized. The quaternary ammonium salt does not fully polymerize, instead it produces a mixture of monomers and spontaneously produced polymers. In a presently preferred embodiment, 4-vinylpyridine is quaternized by reaction with dimethyl sulfate, and self-polymerization occurs according to the following equation (45°C-65°C):

This represents the material of Example 4 reacted according to Method 3 of Example 1 below. As the amount of methanol used in the quaternization reaction increased, the monomer fraction increased; ie, the degree of self-polymerization decreased. Although the resulting leveler system is a mixture of polymer and monomer, it initially appears that only the polymer actively performs the leveling function.

The active ingredient of the substituted pyridine polymer compound is incorporated into the plating bath at a concentration of about 0.01 mg/L to about 100 mg/L. In this context, the active ingredients are homopolymers of vinylpyridine, copolymers of vinylpyridine, quaternary ammonium salts of vinylpyridine and/or quaternary ammonium salts of these homopolymers and copolymers. Active ingredients do not include the inactive anions associated with quaternary ammonium salts. In one embodiment, the active ingredient of the compound is present in the tank at a concentration of between about 0.1 mg/L (0.4 micromole/L) and about 25 mg/L (108 micromole/L) or higher.

Although the substituted pyridine polymers of the present invention can be used in many electroplating baths, in one embodiment it is preferred to use them in combination with specific suppressors and accelerators as disclosed in commonly assigned U.S. Patent 6,776,893, which The entire contents of the US patents are hereby incorporated by reference. In such systems, preferred inhibitors are selected from the group consisting of block copolymers of polyoxyethylene and polyoxypropylene, polyol derivatives of polyoxyethylene or polyoxypropylene, and polyoxyethylene and polyoxypropylene polyol derivatives. Mixture of alcohol derivatives. The polyether inhibitor compound is typically at a concentration between about 0.02 and about 2 g/L, more typically at a concentration between about 0.04 and about 1.5 g/L, even more typically between about 0.1 and 1 g/L concentrations are mixed. Particularly preferred inhibitors include polyethers represented by structural formulas 2, 3, and 4.

Formula 4

where x+y+z is 3 to 100, and where e+f+g and h+f+g are 5 to 100, respectively.

A particularly preferred inhibitor is a polyoxyethylene/polyoxypropylene block copolymer of ethylenediamine,

Wherein the molecular weight of polyoxypropylene (hydrophobe) is about 2500-3000, and the molecular weight of polyoxyethylene (hydrophilic substance) is about 2500-3000. The molecular weight of the polymer is about 5500. Such polymers are available from BASF Corporation of Mt. Olive, New Jersey under the tradename 704 get.

Regarding the accelerator, in applicant's current proposed system, the accelerator is a trough-soluble organic divalent sulfur compound corresponding to the formula:

R ₁ -(S) _n RXO ₃ M (5)

in

M can be hydrogen, alkali metal, or ammonium depending on the need to meet the valence;

X is S or P;

R is a hydrocarbon or cyclic olefin having 1 to 8 carbon atoms, an aromatic hydrocarbon or an aliphatic aromatic hydrocarbon having 6 to 12 carbon atoms;

n is 1 to 6; and

R ₁ is selected from the following group:

MO ₃ XR, wherein M, X, and R are as defined above,

Thiocarbamate shown in the following structural formula,

Xanthates shown in the following structural formula:

and aminoimines:

Wherein R ₂ , R ₃ , R ₄ , and R ₅ are respectively hydrogen, an alkyl group having 1 to 4 carbon atoms, a heterocyclic group, or an aromatic group.

Particularly preferred accelerators include soluble organic divalent sulfur compounds corresponding to Formula 5 above, wherein

R ₁ is MO ₃ XR wherein M, X, and R are as defined above or a thiocarbamate shown in the formula

in

R ₂ and R ₃ are independently hydrogen, an alkyl group having 1-4 carbon atoms, a heterocyclic group, or an aromatic group.

A particularly preferred accelerator is 1-propanesulfonic acid 3,3'-disulfide disodium salt according to the formula:

The accelerator is used typically at a concentration of about 0.5-1000 mg/L, more typically between about 5-50 mg/L, even more typically between about 5-30 mg/L.

Alternatively, other leveling compounds such as the reaction product of benzyl chloride and hydroxyethylpolyethyleneimine disclosed in U.S. Patent Publication No. 20030168343, the entire contents of which incorporated herein by reference.

While the combination of inhibitors, accelerators, and leveling compounds is not critical to the efficacy of the compounds of the present invention, it is believed that optimal overall deposition and structural element filling is achieved at this time.

抑制剂的抑制剂、可从Enthone得到的约6ml/L(12ppm)的名称为加速剂的加速剂和从Enthone以名称整平剂得到的约2.5ml/L(4ppm)的整平剂。本发明的取代吡啶基聚合物也可添加到所述电镀槽。A preferred copper deposition tank includes a makeup solution comprising about 40 g/L copper (CuSO ₄ ), about 10 g/L H ₂ SO ₄ and about 50 ppm Cl ⁻ . This preferred total plating bath further includes about 2ml/L (200ppm) available from Enthone as

Inhibitors, about 6ml/L (12ppm) available from Enthone are named Accelerators for Accelerators and Names from Enthone The leveler obtained about 2.5ml/L (4ppm) leveler. The substituted pyridyl polymers of the present invention may also be added to the electroplating bath.

It has been found that the substituted pyridyl polymer compounds of the present invention in the foregoing concentrations and combinations provide enhanced leveling without substantially preventing copper superfilling into high aspect ratio structural elements. The additives have also been shown to have the advantage of reducing defects, improving brightness, minimizing overplating, improving uniformity and reducing underplating in some large structural elements.

An advantage of the substituted pyridyl polymer additives of the present invention is that the occurrence of internal voids is reduced compared to deposits formed from plating baths not containing these compounds. Internal voids are formed by the deposition of copper on the sidewalls of the structural element and the access to the top of the structural element, which causes pinch-off to close access to the interior of the structural element. Such defects are especially visible for structural elements that are small (eg <100 nm) and/or have a high aspect ratio (depth:width, eg >4:1). As the entry of copper into the structural element is inhibited or closed, internal voids may remain in the structural element, preventing electrical connections through the structural element. The compounds of the present invention have been shown to reduce the occurrence of internal voids because the compounds hinder superfilling less than other levelers, thereby reducing the occurrence of closure of high aspect ratio structural elements.

As a general suggestion, leveling can be done more aggressively since there is less hindrance to the superfill. This is especially valuable as chip architectures get smaller, as interconnect sizes shrink to the 100nm (nanometer) level and smaller, requiring much greater vertical deposition rates than required horizontal deposition rates. ratio, requires faster superfill and can exacerbate planarization problems and the need for leveling. The levelers of the present invention allow superfill rates to be accelerated using accelerator/inhibitor combination chemistries that would normally lead to excessive swelling.

Another advantage of the compositions of the present invention is the reduction of copper voids, such as metal-deficient defects, micro-voids, and the like. These defects reduce the yield and reliability of semiconductor integrated circuit elements.

Another advantage of the compositions of the present invention is the reduction of the overall surface roughness of the substrate surface and within the interconnect structure elements. Reducing surface roughness is becoming increasingly important to achieve defect-free filling of fine interconnect structures since rough copper growth can potentially pinch off structural element entrances, leaving internal voids.

Another advantage of the leveler of the present invention is that it reduces the occurrence of surface protrusions, which are isolated deposition peaks at local high current density locations, local impurity locations, or other locations that never contain this The appearance of these bumps is reduced compared to copper deposits formed by electroplating baths of the inventive compound.

Another significant advantage of the compounds of the present invention is due to the reduced size and improved uniformity of overplating, which enables the deposition of thinner copper films to obtain a flat surface, thus having to be removed in post-deposition operations. less material. For example, chemical mechanical polishing (CMP) is used after copper electroplating to reveal underlying structural elements. The higher level deposits of the present invention correspond to a reduction in the amount of metal that must be deposited, thus resulting in a reduction in subsequent removal by CMP. There is a reduction in the amount of metal wasted and, more importantly, a reduction in the time required for the CMP operation. Material removal operations are also less severe, which correlates with a reduced duration, corresponding to a reduction in the tendency of material removal operations to produce defects. In this regard, for many of the embodiments described above, the copper deposition includes the deposition of a copper alloy.

Copper plating baths can vary widely depending on the substrate to be plated and the type of copper deposition desired. The electroplating tank includes an acid tank and an alkali tank. A number of copper electroplating baths are described on pages 183-203 of the book entitled "Modern Electroplating, edited by F.A. Lowenheim, John Reily & Sons, Inc., 1974). Exemplary plating baths include copper fluoroborates, copper pyrophosphates, copper cyanides, copper phosphonates, and other copper metal complexes (eg, methanesulfonic acid, etc.). Most typical copper plating baths include copper sulfate in an acidic solution.

The concentrations of copper and acid may vary widely, for example from about 4-70 g/L copper and from about 2-225 g/L acid. In this regard, the compounds of the present invention are suitable for use in both high acid/low copper systems and low acid/high copper systems. In a high acid/low copper system, the copper ion concentration may be on the order of 4 g/L to 30 g/L, and the acid concentration may be sulfuric acid in an amount greater than about 50-225 g/L. In a high acid/low copper system, the copper ion concentration is approximately 17g/L with _{a H2SO4} concentration of approximately 180g/L. In low-acid/high-copper systems, the copper ion concentration can be on the order of greater than about 30, 40 g/L, or even to the order of 55 g/L (greater than 50 g/L copper corresponds to greater than 200 g/L copper SO ₄ - 5H ₂ O copper sulfate pentahydrate). The acid concentration in these systems is less than 50, 40 g/L, even 30 g/L (H ₂ SO ₄ ), down to about 7 g/L. In an exemplary low acid/high copper system, the copper concentration is approximately 40 g/L and _{the H2SO4} concentration is approximately 10 g/L.

Chloride ions can also be used in the electroplating bath, and its magnitude can be as high as 200 mg/L (preferably about 90 mg/L). The plating bath also preferably contains an organic additive system such as accelerators, suppressors and levelers.

A wide variety of additives are commonly used in electroplating baths to provide the desired surface finish to the copper plated metal. Often, more than one additive is used with each additive to achieve the desired function. These additives are typically used to initiate bottom-up filling of interconnect structure elements, as well as to enhance metallization appearance (brightness), structure and physical properties such as electrical conductivity. Specific additives, often organic, are used for grain refinement, inhibition of dendritic growth, and improved coverage and dispersion. Typical additives used in electroplating are discussed in many of the references listed above including "Modern Electroplating". Particularly desirable additive systems use aromatic or aliphatic quaternary amines, polysulfides and polyethers. Other additives include, for example, selenium, tellurium and sulfur compounds.

Electroplating apparatus for electroplating semiconductor substrates is well known and is described, for example, in US Patent 6,024,856 to Haydu et al. The electroplating apparatus includes an electroplating tank which houses the copper electrolyte and is made of suitable material such as plastic or other material which is chemically inert to the electroplating bath. Particularly for wafer plating, the box may be cylindrical. The cathode is arranged horizontally in the upper part of the box and can be any type of substrate, for example a silicon wafer with openings such as trenches and vias. The wafer substrate is typically coated with a copper or other metal seed layer to initiate electroplating thereon. The copper seed layer can be achieved by chemical vapor deposition (CVD), physical vapor deposition (PVD), or similar methods. The anode is also preferably circular for wafer electroplating, and is arranged horizontally at the lower part of the box to form a space between the anode and the cathode. The anode is typically a soluble anode.

These bath additives are often used in conjunction with film technologies developed by various tool manufacturers. In the system, the anode can be separated from the organic plating bath by a membrane. The purpose of separating the anode and organic bath additives is to minimize organic bath additive oxidation reactions.

The cathode substrate and the anode are respectively electrically connected to a rectifier (power supply) through wires. The cathode substrate for direct or pulsed current has a net negative charge so that copper ions in solution are reduced at the cathode substrate, forming a plated metallic copper on the cathode surface. The oxidation reaction takes place at the anode. Cathodes and anodes can be arranged in the box horizontally or vertically.

During operation of the electroplating system, when the rectifier is energized, metallic copper is plated on the surface of the cathode substrate. Pulse current, direct current, reverse cycle current, or other suitable current may be used. The temperature of the electrolyte may be maintained using a heater/cooler whereby the electrolyte is withdrawn from the holding tank and passed through the heater/cooler before being recirculated to the holding tank.

An optional feature of the process, as described in U.S. Patent 6,024,856, is to control the electroplating system by removing a portion of the electrolyte from the electroplating system when predetermined operating parameters (conditions) are met, and either simultaneously or after removal of the electrolyte has New electrolyte is added to the system in substantially the same amount as the amount of electrolyte removed. The fresh electrolyte is preferably a single liquid containing everything needed to maintain the plating bath and system. The add/remove system keeps the electroplating system in a steady state with enhanced electroplating effects such as constant electroplating properties. Utilizing such systems and methods, the electroplating bath reaches a steady state wherein the electroplating bath components are substantially at steady state values.

Electrolytic conditions such as current concentration, applied voltage, current density, and electrolyte temperature are substantially the same as in conventional electrolytic copper plating methods. For example, the plating bath temperature is typically about room temperature (eg, about 20-27° C.), but can be elevated up to about 40° C. or higher. Current densities are typically as high as 100 amperes per square foot (ASF), and are typically about 2 to 460 ASF. It is preferred to use an anode to cathode ratio of about 1:1, but this can also vary widely, from about 1:4 to 4:1. The process also uses mixing in the electroplating tank, where the mixing is provided by agitation or preferably by circulating electrolyte through the tank. Flow through the plating tank provides a typical residence time of the electrolyte in the tank of less than about 1 minute, more typically less than 30 seconds, eg, 10-20 seconds.

Detailed ways:

The following examples illustrate the invention.

Example 1

resolve resolution

Method 1: The pyridine starting material (0.1 mol) listed below was dissolved in approximately 50 mL of chloroform in a round bottom flask. The reagents listed below (R ₁ L) (0.105 mol) were slowly added to the initial stock solution with stirring. After addition of the reagents (R ₁ L), the mixture was heated to reflux until the reaction was complete. After heating, chloroform was removed by rotary evaporation, and the product was obtained using appropriate methods according to its physical and chemical structural elements. The product was transferred from deionized water to a 100 mL flask. Further dilutions were made to achieve a final concentration of active substance of 750 mg/L.

Method 2: Pyridine starting material (0.1 mol) was added to approximately 50 mL of water in a round bottom flask. Reagent (R ₁ L) (0.105 mol) was slowly added to the initial stock solution with stirring. Based on the alkylating agent, the initial reaction is accompanied by an increase in temperature. After addition of the reagent (R ₁ L) at 35°C, the mixture was heated to reflux for one hour. After heating the product was transferred from deionized water to a 100 mL flask. Further dilutions were made to bring the active substance to a final concentration of 750 mg/L.

Method 3: The pyridine starting material (0.1 mol) was dissolved in approximately 50 mL of anhydrous methanol in a round bottom flask. At a temperature not higher than 35°C, the alkylating agent (0.105 mol) was slowly added to the initial feedstock solution with stirring. After adding the reagent (R ₁ L), about 2 grams of water were added and the mixture was slowly heated to 65-70°C to hydrolyze any residues such as dimethyl sulfate or methyl tosylate. The mixture was heated for several hours until the reaction was considered substantially complete. Methanol was removed by rotary evaporation, but it was acceptable to allow methanol to remain. The product was transferred from deionized water to a 100 mL flask. The method can be used to obtain products that are mixtures of low molecular weight polymers and monomers. Further dilutions were made to achieve a final concentration of active substance of 750 mg/L.

Method 4: Pyridine starting material (0.1 mol) was placed in a round bottom flask. Reagent (R ₁ L) (0.105 mol) was slowly added to the starting material solution with stirring. After addition of the reagents (R ₁ L), the mixture was slowly heated to 105-140°C until the reaction was largely complete. After the reaction, the product was transferred from deionized water to a 100 mL flask. Further dilutions were made to bring the active substance to a final concentration of 750 mg/L.

Method 5: Dissolve pyridine starting material (0.1 mol) in approximately 25 mL of ethylene glycol in a round bottom flask. Reagent (R ₁ L) (0.2 mol) was slowly added to the stock solution with stirring. After addition of the alkylating agent, the mixture was slowly heated to 105°C and then to 130-140°C. The mixture is heated at 130-140°C for several hours until the reaction is substantially complete. Remove as much reagent as possible (R ₁ L) by rotary evaporation. The product was transferred from deionized water to a 100 mL flask. Further dilutions were made to bring the active substance to a final concentration of 750 mg/L.

Polyvinylpyridine polymerization is also disclosed in US Patent Nos. 4,212,764 and 5,824,756.

Example 2-17

The following pyridine starting materials and reagents (R ₁ L) were reacted according to the method described above. Product activity in copper electroplating baths is an indication of the relative ability of the product to produce acceptable copper deposition upon electroplating deposition.

example Pyridine raw material Reagent (R₁L) resolve resolution Product activity in copper bath 2 Poly(4-vinylpyridine) Me₂SO₄ Method 3 very active 3 Poly(4-vinylpyridine) Methyl tosylate Method 3 very active 4 4-vinylpyridine Me₂SO₄ Method 1, 3 Very active; exothermic at room temperature 5 4-vinylpyridine Benzoyl chloride (BzCl) method 1 very active 6 4-vinylpyridine Allyl chloride method 1 very active 7 4-vinylpyridine 2-Chloro-ethanol Method 5 very active 8 4-vinylpyridine Epichlorohydrin method 1 Produces a gel; exothermic when heated 9 4-vinylpyridine 1-Chloromethyl-naphthalene method Insoluble in water 10 4-vinylpyridine 4-Chloromethyl-pyridine method 1 Relatively weak 11 4-vinylpyridine 1,3-propane sultone method 1 Relatively weak; exothermic above room temperature 12 4-vinylpyridine Methyl tosylate Method 2, 3 Very active; exothermic after heating 13 4-vinylpyridine Chloro-acetone method 1 very active

14 4-vinylpyridine Chloro-acetonitrile method 1 Odor of HCN gas 15 4-vinylpyridine 2-Methoxy-ethoxy chloride method 1 very active 16 4-vinylpyridine 2-Chloroethane ether Method 4 active 17 2-vinylpyridine 2-Chloro-ethanol Method 4 active; incomplete reaction 18 2-vinylpyridine Methyl tosylate Method 2, 3 less active 19 2-vinylpyridine Me₂SO₄ Method 1, 3 Relatively weak; exothermic at room temperature 20 4-vinylpyridine 1,3 dichloropropanol Method 5 very active

In Examples 2 and 3, the poly(4-vinylpyridine) starting material had a molecular weight of 16,000. In Examples 4-20, the reaction products were mixtures of polymers and monomers to varying degrees because the products polymerized spontaneously after the quaternization reaction.

Example 21

Deposition from a copper bath containing the reaction product of poly(4-vinylpyridine) and dimethyl sulfate of Example 2

Prepare the following plating baths:

Composition Based on the volume of the plating bath

Copper 40g/l

Sulfuric acid 10g/l

抑制剂                        2ml/l

Inhibitor 2ml/l

Accelerator 9ml/l

poly(4-vinylpyridine) and

Reaction product of dimethyl sulfate 4.5mg/l

Chloride 50mg/L

The plating bath was added to a 267mL Hull cell. The brass Hull cell plate/cathode was plated at 2 amps for 3 minutes. The current density varied in different areas of the Hull cell plate/cathode, from about 2 milliamperes per square centimeter in some areas to about 800 milliamperes per square centimeter in other areas. The electroplating bath produced copper deposits that were very bright and uniform throughout the plating range.

Example 22

Deposition from a copper electroplating bath containing the reaction product of 4-vinylpyridine and 2-chloroethanol of Example 7

Prepare the following plating baths:

Composition Based on the volume of the plating bath

Copper 40g/l

sulfuric acid 10g/l

抑制剂                         2ml/l

Inhibitor 2ml/l

加速剂                         9ml/l

Accelerator 9ml/l

Reaction product of 4-vinylpyridine and 2-chloroethanol 3mg/l

Chloride 50mg/L

The plating bath was added to a 267mL Hull cell. The brass Hull cell plate/cathode was plated at 2 amps for 3 minutes. The current density varied in different areas of the Hull cell plate/cathode, from about 2 milliamperes per square centimeter in some areas to about 800 milliamperes per square centimeter in other areas. The electroplating bath produces a copper deposit that is very bright and uniform over the entire plating range.

Example 23

Deposition from a Copper Plating Bath Containing the Reaction Product of 4-Vinylpyridine and Dimethyl Sulfate of Example 4

Prepare the following plating baths:

Composition Based on the volume of the plating bath

Copper 40g/l

sulfuric acid 10g/l

Inhibitor 2ml/l

加速剂                       9ml/l

Accelerator 9ml/l

Reaction product of 4-vinylpyridine and dimethyl sulfate 12mg/l

Chloride 50mg/L

The plating bath was added to a 267mL Hull cell. The brass Hull cell plate/cathode was plated at 2 amps for 3 minutes. The current density varied in different areas of the Hull cell plate/cathode, from about 2 milliamperes per square centimeter in some areas to about 800 milliamperes per square centimeter in other areas. The electroplating bath produces a copper deposit that is very bright and uniform over the entire plating range.

Example 24

抑制剂(2ml/L)、

加速剂(9ml/L)并且改变整平剂结构元件的溶液中以10mA/cm²电镀15秒。Four patterned test wafers ( _SiO2 with Ta barrier, available under the designation QCD from Sematech) with trenches of 180 nm width as structural elements were prepared in the presence of copper ions (40 g/L), sulfuric acid (10 g/L), chlorine Ions (50mg/L),

Inhibitor (2ml/L),

Accelerator (9ml/L) and change the solution of the leveler structural element to electroplate at 10mA/cm ² for 15 seconds.

Fig. 1 shows the section of the wafer that does not electroplate with leveler; Fig. 2 shows the section of the wafer that utilizes the commercial leveler electroplating of 10ml/L; Fig. 3 shows the wafer that utilizes the leveler electroplating of 10ml/L Section, wherein the leveler constitutes a polymer/monomer mixture prepared according to the protocol of Example 4; Figure 4 shows a section of a wafer plated with 10ml/L of leveler, wherein the leveler is according to Example The polymer prepared by the scheme of 2.

Figure 1 shows the large superfill in 15 seconds without leveler, shown with the position and U-shaped geometry of the growth front within the structural element. This indicates that the bottom growth rate is significantly greater than that of the sidewalls. With the addition of 10ml/L of a commercial leveler (Figure 2), the position of the growth front decreased in the structural elements after 15 seconds, indicating slower overall filling comparable to the leveler's significant hindrance to superfilling. Also, the geometry of the growth front is V-shaped with the leveler, compared to the generally U-shaped profile in Figure 1 without the leveler. Therefore, the leveler hinders superfilling to some extent.

Figures 3 and 4 show even greater superfill in 15 seconds with the two levelers of the invention of Examples 2 and 4. Therefore, these levelers do not substantially interfere with superfill. Advantageously, these also denote a substantially rectangular fill contour with an angle of approximately 90° between the fill base and the side walls through the entire filling process. In contrast, the fill of Figure 2 (commercial leveler) shows that a generally V-shaped fill profile begins to form before the interconnect is 75% full.

Example 25

加速剂(9ml/L)无整平剂的从Novellus得到的Sabre铜镀工具(Sabre Copper Plating Tool)溶液中电镀。Three test wafers (diameter of 200nm; available under the designation QCD from Sematech) with trenches of 180nm width as structural elements were prepared in the presence of copper ions (40g/L), sulfuric acid (10g/L), chloride ions (50mg/L ), Inhibitor (2ml/L),

Accelerator (9ml/L) Plating was performed in a Saber Copper Plating Tool solution from Novellus without leveler.

Figures 5 and 6 show cross-sections of the center (Figure 5) and edge (Figure 5) of a wafer plated at a wafer rotation speed of 30 rpm and a current of 3 A for 33 seconds followed by 18 A for 25 seconds. Figures 7 and 8 show cross-sections of the center (Figure 7) and edge (Figure 8) of wafers plated under these conditions at a wafer rotation speed of 125 rpm and a current of 3 A for 33 seconds followed by 18 A for 25 seconds. Figures 9 and 10 show the center (Figure 9) and edge (Figure 10) of wafers plated under these conditions at a wafer rotation speed of 30 rpm and a current of 1.5 A for 27 seconds followed by 3 A for 27 seconds followed by 12 A for 44 seconds section.

Example 26

抑制剂(2ml/L)、

加速剂(9ml/L)、和6ml/L根据实例4的方案制备的聚合物/单体的整平剂的溶液中电镀。These test wafers (200nm diameter; available under the designation QCD from Sematech) with trenches of 180nm width as structural elements were prepared in the presence of copper ions (40g/L), sulfuric acid (10g/L), chloride ions (50mg/L) ,

Inhibitor (2ml/L),

Accelerator (9ml/L), and 6ml/L polymer/monomer leveling agent prepared according to the scheme of Example 4 were electroplated in the solution.

Figures 11 and 12 show cross-sections of the center (Figure 11) and edge (Figure 12) of a wafer plated at a wafer rotation speed of 30 rpm and a current of 3 A for 33 seconds followed by 18 A for 25 seconds. Figures 13 and 14 show cross-sections of the center (Figure 13) and edge (Figure 14) of wafers plated under these conditions at a wafer rotation speed of 125 rpm and a current of 3 A for 33 seconds followed by 18 A for 25 seconds. Figures 15 and 16 show cross-sections of the center (Figure 15) and edge (Figure 16) of wafers plated under these conditions at a wafer rotation speed of 30 rpm and a current of 3 A for 27 seconds followed by 3 A for 27 seconds followed by 12 A for 44 seconds .

Example 27

加速剂(9ml/L)、和6ml/L根据实例2的方案制备的聚合物/单体的整平剂的溶液中电镀。Three test wafers (diameter of 200nm; available under the designation QCD from Sematech) with trenches of 180nm width as structural elements were prepared in the presence of copper ions (40g/L), sulfuric acid (10g/L), chloride ions (50mg/L ), Inhibitor (2ml/L),

Accelerator (9ml/L), and 6ml/L polymer/monomer leveling agent prepared according to the scheme of Example 2 were electroplated in the solution.

Figures 17 and 18 show cross-sections of the center (Figure 17) and edge (Figure 18) of a wafer plated at a wafer rotation speed of 30 rpm and a current of 3 A for 33 seconds followed by 18 A for 25 seconds. Figures 19 and 20 show cross-sections of the center (Figure 19) and edge (Figure 20) of wafers plated under these conditions at a wafer rotation speed of 125 rpm and a current of 3 A for 33 seconds followed by 18 A for 25 seconds. 21 and 22 show wafer center ( FIG. 21 ) and edge ( FIG. 22 ) sections plated under these conditions at a wafer rotation speed of 30 rpm and a current of 105 A for 27 seconds followed by 3 A for 27 seconds followed by 12 A for 44 seconds.

Comparing the deposits of Figures 5-10 (without leveler) to the deposits of Figures 11-16 (leveler of Example 4) and 17-22 (leveler of Example 2), there was a substantial reduction in doming due to overplating , showing the super-leveled structural element of the present invention. Without a leveling component, a considerable thickness of copper must be deposited to obtain a sufficiently planar surface for subsequent CMP operations, which substantially increases the costs associated with the copper plating and CMP process.

When introducing elements of the invention or its preferred embodiments, the articles "a", "the", and "said" mean that there are one or more of the elements. For example, reference by the foregoing description and appended claims to "an" an interconnect means that there are one or more such interconnects. The words "comprising", "comprising", and "having" are meant to be inclusive and mean that there may be additional elements other than the listed elements.

Various changes could be made in the above without departing from the scope of the invention, it is intended that all matter contained in the above description and which is shown in the accompanying drawings shall be interpreted as illustrative and not restrictive. The scope of the invention is defined by the appended claims and modifications may be made to the above-described embodiments without departing from the scope of the invention.

definition

Unless otherwise specified, the alkyl groups described herein are preferably lower alkyl groups containing one to eight up to 20 carbon atoms in the main chain. They may be linear or branched or cyclic, and include methyl, ethyl, propyl, isopropyl, butyl, hexyl, and the like.

Unless otherwise indicated, the alkenyl groups described herein are preferably lower alkenyl groups comprising from two to eight up to 20 carbon atoms in the principal chain. They may be linear or branched or cyclic, and include vinyl, propenyl, isopropenyl, butenyl, hexenyl, and the like.

Unless otherwise indicated, a "substituted alkyl or substituted alkenyl" moiety as described herein is an alkyl or alkenyl moiety substituted with at least one atom other than a carbon atom, including those in which the carbon chain atoms are replaced by, for example, nitrogen, oxygen, , silicon, phosphorus, boron, or heteroatom-substituted semigroups such as halogen atoms. These substituents include halogen, heterocycle, alkoxy, alkenyloxy, alkynyloxy, hydroxy, protected hydroxy, keto, acyl, acyloxy, nitro, amine, amino, cyano, thiol, Ketals, acetals, esters, ethers.

The terms "aryl" or "aryl" as used herein alone or as part of another group denote optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic, containing 6 to 12 carbon atoms in the ring portion A group such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. Phenyl and substituted phenyl groups are more preferred aromatic groups.

The term "aryl" or "aryl" as used herein by itself or as part of another group denotes an optionally substituted homocyclic aromatic group wherein a carbon atom of the aromatic group is directly attached to a carbon atom of the aryl group, and The aralkyl moiety is attached to the derivative through an aryl group. Aryl and alkyl including aralkyl are defined above.

The terms "halogen" or "halo" as used herein by themselves or as part of another group refer to chlorine, bromine, fluorine, and iodine.

Unless otherwise indicated, the term "heteroarylalkyl" denotes a heteroaryl group as described herein attached to an alkyl group as defined herein serving as a linker group to the remainder of the molecule.

The term "heteroaryl" as used herein by itself or as part of another group denotes an optionally substituted aromatic group having at least one heteroatom in at least one ring and preferably 5 or 6 atoms in each ring. The aromatic heterocyclic group preferably has 1 or 2 oxygen atoms, 1 or 2 sulfur atoms, and/or 1 to 4 nitrogen atoms in the ring, and may be bonded to the rest of the molecule through a carbon or heteroatom. Exemplary heteroarylalkyl groups include thienyl, pyridyl, oxazolyl, pyrrolyl, indole, or isoquinolyl and analogs thereof. Exemplary substituents include one or more of the following groups: hydrocarbyl; substituted hydrocarbyl; keto; protected hydroxy; acyl; acyloxy; alkoxy; alkenyloxy; alkynyloxy; aryloxy; halogen; Amides; amino groups; nitro groups; cyano groups; thiols; ketals; acetals; esters; and ethers.

The term "acyl" as used herein alone or as part of another group denotes a moiety formed by removal of a hydroxyl group from the group -COOH of an organic carboxylic acid, for example, RC(O)-, where R is R ¹ , R ¹ O- , R ¹ R ² N-, or R ¹ S-, R ₁ is hydrocarbyl, heterosubstituted hydrocarbyl, or heterocyclic ring, and R ² is hydrogen, hydrocarbyl, or substituted hydrocarbyl.

The term "acyloxy" as used herein alone or as part of another group denotes an acyl group as described above bonded through an oxygen linkage (--O--), for example RC(O)-, where R is as in conjunction with the term " Acyl" is defined.

Claims (33)

1. A method of electroplating copper onto a substrate with electrically interconnected structural elements in the manufacture of microelectronic components, the method comprising: The substrate is immersed in an electrolytic solution comprising: A source of copper ions in an amount sufficient to electrodeposit copper onto substrates and into electrical interconnection features having openings smaller than 100 nm and having an aspect ratio greater than 4:1; One or more superfiller compositions that promote the deposition of copper in interconnected structural elements, wherein the growth rate of the structural elements is substantially greater in the vertical direction than in the horizontal direction, wherein the superfiller The composition is selected from the group comprising accelerators, inhibitors, and combinations thereof; and Leveling agents, including substituted pyridine polymer compounds, which have a leveling effect that does not interfere with superfill; and Electric current is supplied to the electrolytic solution to deposit copper onto the substrate. 2. The method of claim 1, wherein the substituted pyridine polymer compound is a pyridinium salt compound. 3. The method of claim 1, wherein the substituted pyridine polymer compound is a vinylpyridine derivative. 4. The method of claim 1, wherein the substituted pyridine polymer compound is a derivative of 2-vinylpyridine. 5. The method of claim 1, wherein the substituted pyridine polymer compound is a derivative of 4-vinylpyridine. 6. The method of claim 1, wherein the substituted pyridine polymer compound is a vinylpyridine homopolymer. 7. The method of claim 1, wherein the substituted pyridine polymer compound is a vinylpyridine copolymer. 8. The method of claim 1, wherein the substituted pyridine polymer compound is selected from the group consisting of quaternary ammonium salts of vinylpyridine homopolymers and quaternary ammonium salts of vinylpyridine copolymers. 9. The method of claim 1, wherein the substituted pyridine polymer compound is a reaction product of 4-vinylpyridine. 10. The method of claim 1, wherein the substituted pyridine polymer compound is a reaction product of poly(4-vinylpyridine). 11. The method of claim 1, wherein the substituted pyridine polymer compound is the reaction product of 4-vinylpyridine and dimethyl sulfate. 12. The method of claim 1, wherein the substituted pyridine polymer compound is the reaction product of poly(4-vinylpyridine) and dimethyl sulfate. 13. The method of claim 1, wherein the substituted pyridine polymer compound is a reaction product obtained by reacting 4-vinylpyridine with a compound of the formula: R ₁ -L (1) wherein _R is alkyl, alkenyl, aralkyl, heteroarylalkyl, substituted alkyl, substituted alkenyl, substituted aralkyl, or substituted heteroarylalkyl; and L is a leaving group. 14. The method of claim 1, wherein the substituted pyridine polymer compound is selected from the group comprising the reaction product of poly-(4-vinylpyridine) with dimethyl sulfate, poly-(4- Vinylpyridine) and methyl toluenesulfonate reaction product, 4-vinylpyridine and dimethyl sulfate reaction product, 4-vinylpyridine and methyltoluenesulfonate reaction product, 4-vinylpyridine Reaction product with 2-chloroethanol, reaction product of 4-vinylpyridine with benzyl chloride, reaction product of 4-vinylpyridine with allyl chloride, reaction product of 4-vinylpyridine with 4-chloromethylpyridine Product, reaction product of 4-vinylpyridine and 1,3-propane sultone, reaction product of 4-vinylpyridine and methyltosylate, reaction product of 4-vinylpyridine and chloroacetone, 4- The reaction product of vinylpyridine and 2-methoxyethoxymethane chloride, the reaction product of 4-vinylpyridine and 2-chloroethyl ether, the reaction product of 2-vinylpyridine and methyltosylate, 2- The reaction product of vinylpyridine with dimethyl sulfate, poly(2-methyl-5-vinylpyridine), and 1-methyl-4-vinylpyridine trifluoromethanesulfonate. 15. The method of claim 1, wherein the substituted pyridine polymer compound is a pyridinium quaternary ammonium salt. 16. The method of any one of claims 1-15, wherein the substituted pyridine polymer compound is poly(4-vinylpyridine) and has a molecular weight of 10000 to 20000 g/mol. 17. The method of any one of claims 1-15, wherein the substituted pyridine polymer compound is poly(4-vinylpyridine) and has a molecular weight of 60,000-160,000 g/mol. 18. A method of electroplating copper onto a semiconductor integrated circuit component substrate having electrically interconnected structural elements in the manufacture of microelectronic components, the method comprising: The substrate is immersed in an electrolytic solution comprising: a source of copper ions in an amount sufficient to electrodeposit copper onto substrates and into electrical interconnection features; One or more superfiller compositions that promote the deposition of copper in interconnected structural elements, wherein the growth rate of the structural elements is substantially greater in the vertical direction than in the horizontal direction, wherein the superfiller The composition is selected from the group comprising accelerators, inhibitors, and combinations thereof; and Leveling agents, including substituted pyridine polymer compounds, which have a leveling effect that does not interfere with superfilling, wherein the substituted pyridine polymer compounds are derivatives of 4-vinylpyridine; and Electric current is supplied to the electrolytic solution to deposit copper onto the substrate. 19. The method of claim 18, wherein the substituted pyridine polymer compound is a reaction product of poly(4-vinylpyridine). 20. The method of claim 18, wherein the substituted pyridine polymer compound is the reaction product of 4-vinylpyridine and dimethyl sulfate. 21. The method of claim 18, wherein the substituted pyridine polymer compound is the reaction product of poly(4-vinylpyridine) and dimethyl sulfate. 22. The method of claim 18, wherein the substituted pyridine polymer compound is a reaction product obtained by reacting 4-vinylpyridine with a compound of the formula: R ₁ -L (1) wherein _R is alkyl, alkenyl, aralkyl, heteroarylalkyl, substituted alkyl, substituted alkenyl, substituted aralkyl, or substituted heteroarylalkyl; and L is a leaving group. 23. The method of claim 18, wherein the substituted pyridine polymer compound is selected from the group comprising the reaction product of poly-(4-vinylpyridine) with dimethyl sulfate, poly-(4- Vinylpyridine) and methyl toluenesulfonate reaction product, 4-vinylpyridine and dimethyl sulfate reaction product, 4-vinylpyridine and methyltoluenesulfonate reaction product, 4-vinylpyridine Reaction product with 2-chloroethanol, reaction product of 4-vinylpyridine with benzyl chloride, reaction product of 4-vinylpyridine with allyl chloride, reaction product of 4-vinylpyridine with 4-chloromethylpyridine Product, reaction product of 4-vinylpyridine and 1,3-propane sultone, reaction product of 4-vinylpyridine and methyltosylate, reaction product of 4-vinylpyridine and chloroacetone, 4- The reaction product of vinylpyridine with 2-methoxyethoxymethane chloride, the reaction product of 4-vinylpyridine with 2-chloroethyl ether, and 1-methyl-4-vinylpyridine trifluoromethanesulfonate . 24. The method of claim 18, wherein the substituted pyridine polymer compound is poly(4-vinylpyridine) and has a molecular weight of 10,000 to 20,000 g/mol. 25. The method of claim 18, wherein the substituted pyridine polymer compound is poly(4-vinylpyridine) and has a molecular weight of 60,000-160,000 g/mol. 26. A composition for electroplating copper onto a substrate having electrical interconnect features in the manufacture of microelectronic components, said composition comprising: a source of copper ions in an amount sufficient to electrodeposit copper onto substrates and into electrical interconnection features; and One or more superfiller compositions that promote the deposition of copper in interconnected structural elements, wherein the growth rate of the structural elements is substantially greater in the vertical direction than in the horizontal direction, wherein the superfiller The composition is selected from the group comprising accelerators, inhibitors, and combinations thereof; and The leveling agent includes a substituted pyridine polymer compound, which has a leveling effect that does not interfere with superfilling, wherein the substituted pyridine polymer compound is a derivative of 4-vinylpyridine. 27. The composition of claim 26, wherein the substituted pyridine polymer compound is a reaction product of poly(4-vinylpyridine). 28. The composition of claim 26, wherein the substituted pyridine polymer compound is the reaction product of 4-vinylpyridine and dimethyl sulfate. 29. The composition of claim 26, wherein the substituted pyridine polymer compound is the reaction product of poly(4-vinylpyridine) and dimethyl sulfate. 30. The composition of claim 26, wherein the substituted pyridine polymer compound is a reaction product obtained by reacting 4-vinylpyridine with a compound of the formula: R ₁ -L (1) wherein _R is alkyl, alkenyl, aralkyl, heteroarylalkyl, substituted alkyl, substituted alkenyl, substituted aralkyl, or substituted heteroarylalkyl; and L is a leaving group. 31. The composition of claim 26, wherein the substituted pyridine polymer compound is selected from the group comprising the reaction product of poly-(4-vinylpyridine) with dimethyl sulfate, poly-(4 -vinylpyridine) and methyl toluenesulfonate reaction product, 4-vinylpyridine and dimethyl sulfate reaction product, 4-vinylpyridine and methyl toluenesulfonate reaction product, 4-vinylpyridine The reaction product of pyridine and 2-chloroethanol, the reaction product of 4-vinylpyridine and benzyl chloride, the reaction product of 4-vinylpyridine and allyl chloride, the reaction product of 4-vinylpyridine and 4-chloromethylpyridine Reaction product, reaction product of 4-vinylpyridine and 1,3-propane sultone, reaction product of 4-vinylpyridine and methyltoluenesulfonate, reaction product of 4-vinylpyridine and chloroacetone, 4 - The reaction product of vinylpyridine with 2-methoxyethoxymethane chloride, the reaction product of 4-vinylpyridine with 2-chloroethyl ether, and 1-methyl-4-vinylpyridine trifluoromethanesulfonic acid Salt. 32. The composition of claim 26, wherein the substituted pyridine polymer compound is poly(4-vinylpyridine) and has a molecular weight of 10,000 to 20,000 g/mol. 33. The composition of claim 26, wherein the substituted pyridine polymer compound is poly(4-vinylpyridine) and has a molecular weight of 60,000 to 160,000 g/mol.

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