JP6637570B2 - Reaction products of amine monomers and polymers containing saturated heterocyclic moieties as additives for electroplating baths - Google Patents

Description

  The present invention is directed to reaction products of amine monomers and polymers containing saturated heterocyclic moieties as additives for electroplating baths. More specifically, the present invention provides a reaction product of an amine monomer and a polymer containing a saturated heterocyclic moiety for an electroplating bath that can be used as a leveler in the electroplating bath to provide good throwing power. set to target.

  Methods for electroplating an article with a metal coating generally involve passing a current between two electrodes in a plating solution, one of the electrodes being the article to be plated. A typical acidic copper plating solution is a sufficient amount of dissolved copper, typically an acidic electrolyte such as sulfuric acid, to provide conductivity to the bath, dissolved copper, typically copper sulfate, a halide source, and plating uniformity and Contains proprietary additives to improve the quality of metal deposition. Such additives include, among others, levelers, accelerators, and inhibitors.

  Electrolytic copper plating solutions are used in various industrial applications, such as decorative and anticorrosive coatings, and in the electronics industry, particularly in the manufacture of printed circuit boards and semiconductors. For circuit board fabrication, copper is typically deposited over selected portions of the surface of the printed circuit board, in blind vias and trenches, and on the walls of through holes that pass between the surfaces of the circuit board preform. Electroplated. The exposed surfaces of the blind vias, trenches, and through holes, ie, the walls and floor, are first made conductive, such as by electroless metallization, before copper is electroplated on the surface of these holes. The plated through holes provide a conductive path from one substrate surface to the other substrate surface. Vias and trenches provide conductive paths between layers within the circuit board. For semiconductor fabrication, copper is electroplated over the surface of a wafer having various features such as vias, trenches, or combinations thereof. Vias and trenches are metallized to provide conductivity between the various layers of the semiconductor device.

  It is well known that in certain areas of plating, such as electroplating of printed circuit boards ("PCBs"), the use of levelers in electroplating baths can be important in achieving uniform metal deposition on the substrate surface. . Electroplating substrates with irregular topography can be difficult. During electroplating, a voltage drop typically occurs in the surface pores, which may result in non-uniform metal deposition between the surface and the pores. The irregularities of electroplating are exacerbated where voltage drops are relatively extreme, ie, where the holes are narrow and long. Thus, depositing a metal layer of substantially uniform thickness is often a difficult step in the manufacture of electronic devices. Leveling agents are often used in copper plating baths to provide a substantially uniform or smooth copper layer in electronic devices.

  The trend of portability, combined with the increased functionality of electronics devices, has driven PCB miniaturization. Conventional multilayer PCBs with through-hole interconnects are not always a practical solution. Alternative approaches for high-density interconnects, such as sequential build-up techniques utilizing blind vias, have been developed. One of the goals in the process of using blind vias is to maximize via filling while minimizing thickness variations in copper deposition between the via and the substrate surface. This is particularly difficult if the PCB has both through holes and blind vias.

  Leveling agents are used in copper plating baths to smooth the deposition over the substrate surface and to improve the throwing power of the electroplating bath. Throwing power is defined as the ratio of the through-hole center copper deposition thickness to its surface thickness. Newer PCBs are being manufactured that have both through holes and blind vias. Current bath additives, especially current leveling agents, do not always result in smooth copper deposition between the substrate surface and filled through holes and blind vias. Via filling is characterized by a height difference between the copper and the surface in the filled via. Thus, there is still a need in the art for a leveling agent for use in metal electroplating baths for PCB production that results in smooth copper deposition while enhancing the throwing power of the bath.

  A reaction product of one or more amine monomers and one or more polymers, wherein the polymer has the formula:

Wherein A is a saturated 5- or 6-membered heterocyclic ring composed of 4 or 5 carbon atoms, and in some of the carbonyl moieties, The ring carbon atoms are independently substituted or unsubstituted; Z is a nitrogen or oxygen atom; and Z ₁ is a carbon or oxygen atom, provided that Z is an oxygen or oxygen atom. A is a 6-membered ring, Z ₁ is a carbon atom, and when Z ₁ is oxygen, A is a 6-membered ring and Z is nitrogen, and R is hydrogen Linear or branched alkyl, linear or branched hydroxyalkyl, linear or branched haloalkyl, linear or branched aminoalkyl, linear or branched vinylalkyl, or _{-CH 2 -O- (R'-O)} d -CH 2 - A substitution comprising Y, wherein R ′ is straight or branched (C ₂ -C ₁₀ ) alkyl, Y is hydroxyl or halogen, and d is an integer from 1 to 10. A reaction product, wherein n is 0 or 1, provided that when n is 0, Z is an oxygen atom.

  A composition comprising one or more metal ion sources, an electrolyte, and one or more compounds of a reaction product of one or more amine monomers and one or more polymers, wherein the polymer has the formula:

Wherein A is a saturated 5- or 6-membered heterocyclic ring composed of 4 or 5 carbon atoms, and in some of the carbonyl moieties, The ring carbon atoms are independently substituted or unsubstituted; Z is a nitrogen or oxygen atom; and Z ₁ is a carbon or oxygen atom, provided that Z is an oxygen or oxygen atom. A is a 6-membered ring, Z ₁ is a carbon atom, and when Z ₁ is oxygen, A is a 6-membered ring and Z is nitrogen, and R is hydrogen Linear or branched alkyl, linear or branched hydroxyalkyl, linear or branched haloalkyl, linear or branched aminoalkyl, linear or branched vinylalkyl, or _{-CH 2 -O- (R'-O)} d -CH 2 - A substitution comprising Y, wherein R ′ is straight or branched (C ₂ -C ₁₀ ) alkyl, Y is hydroxyl or halogen, and d is an integer from 1 to 10. A composition wherein n is 0 or 1, provided that when n is 0, Z is an oxygen atom.

  A composition comprising: providing a substrate; one or more metal ion sources, an electrolyte, and one or more compounds of one or more amine monomers and one or more polymer reaction products. ,formula:

Wherein A is a saturated 5- or 6-membered heterocyclic ring composed of 4 or 5 carbon atoms, and in some of the carbonyl moieties, The ring carbon atoms are independently substituted or unsubstituted; Z is a nitrogen or oxygen atom; and Z ₁ is a carbon or oxygen atom, provided that Z is an oxygen or oxygen atom. A is a 6-membered ring, Z ₁ is a carbon atom, and when Z ₁ is oxygen, A is a 6-membered ring and Z is nitrogen, and R is hydrogen Linear or branched alkyl, linear or branched hydroxyalkyl, linear or branched haloalkyl, linear or branched aminoalkyl, linear or branched vinylalkyl, or _{-CH 2 -O- (R'-O)} d -CH 2 - A substitution comprising Y, wherein R ′ is straight or branched (C ₂ -C ₁₀ ) alkyl, Y is hydroxyl or halogen, and d is an integer from 1 to 10. Providing a composition, wherein n is 0 or 1, provided that when n is 0, Z is an oxygen atom.

  The reaction products may be included in a metal electroplating bath to provide a metal layer having a substantially smooth surface across the substrate, even over substrates having small features and substrates having various feature sizes. The present plating method effectively deposits metal on the substrate and in blind vias and through holes so that the metal plating composition has good throwing power.

As used throughout this specification, the following abbreviations shall have the following meanings, unless the context clearly indicates otherwise. A / dm ² = ampere per square decimeter = ASD, ° C = degrees Celsius, g = gram, mg = milligram, L = liter, ppm = parts per million = mg / L, μm = micron = micrometer, mm = Millimeter, cm = centimeter, DI = deionized, mL = milliliter, mol = mol, mmoles = mmol, Mw = weight average molecular weight, and Mn = number average molecular weight. All numerical ranges are inclusive and combinable in any order, except where it is clear that such numerical ranges are limited to add up to 100%.

  As used throughout this specification, "feature" refers to the shape of a substrate. "Hole" refers to a recessed feature that includes through holes and blind vias. As used throughout this specification, the term "plating" refers to metal electroplating. “Deposition” and “plating” are used interchangeably throughout this specification. "Leveler" refers to an organic compound or salt thereof that is capable of providing a substantially smooth or planar metal layer. The terms "leveler" and "leveling agent" are used interchangeably throughout this specification. "Accelerator" refers to an organic additive that increases the plating rate of an electroplating bath (can be synonymous with brightener). "Inhibitor" refers to an organic additive that suppresses the plating rate of a metal during electroplating. The term "amine monomer" within the scope of the present invention is an organic nitrogen compound that contains at least one primary or secondary amine functionality, and is not a polymer. The term "polymer" refers to a compound of two or more monomers, which may be the same or different, and includes dimers. The term “copolymer” refers to a polymer of two or more different monomers. The term "homopolymer" refers to a polymer of two or more of the same monomer. The terms "printed circuit board" and "printed wiring board" are used interchangeably throughout this specification. The term “moiety” means a part of a molecule or polymer that may contain either all functional groups or a part of a functional group as a partial structure. The terms "moiety" and "group" are used interchangeably throughout this specification. A dashed line "----" in a chemical structure means an arbitrary double bond. The articles "a" and "an" refer to the singular and the plural.

  The compound is a copolymer of the reaction product of one or more amines and one or more polymers, where the polymer can be a copolymer or a homopolymer, and contains two or more imide or anhydride functionalities in a saturated ring. Composed of the reaction products of the monomers, such monomers having the formula:

Wherein A is a saturated 5- or 6-membered heterocyclic ring composed of 4 or 5 carbon atoms, and the carbon atoms of the ring that are not part of the carbonyl moiety are independently Wherein Z is a nitrogen atom or an oxygen atom, and Z ₁ is a carbon atom or an oxygen atom, provided that when Z is oxygen, A is a 6-membered ring Wherein Z ₁ is a carbon atom, and when Z ₁ is oxygen, A is a 6-membered ring, provided that Z is nitrogen; and R is hydrogen, (C ₁ -C ₅ ) alkyl linear or branched alkyl, such as, hydroxy (C 1 _{-C 5)} linear or branched hydroxyalkyl, such as alkyl, halogen chlorine, fluorine, bromine or halo (C ₁ -C iodine, ₅₎ straight-chain, such as Oarukiru or branched Haroa Kill, amino _(C 1 -C ₅₎ linear or branched aminoalkyl such as _{alkyl, (C} 1 -C ₅₎ linear or branched vinyl alkyl such as vinyl alkyl or _-CH 2 -O, - _(R'-O) including d _-CH 2 -Y is a substituent which is not limited to, R 'is a linear or branched _(C 2 _{-C 10)} alkyl, Y is , Hydroxyl, or halogen that is chlorine, fluorine, bromine, or iodine, d is an integer from 1 to 10, and n is 0 or 1, provided that when n is 0, Z is It must be an oxygen atom.

Substituents on ring carbons may be straight-chain or branched (C ₁ -C ₅ ) alkyl, hydroxyl, straight-chain or branched hydroxy (C ₁ -C ₅ ) alkyl, straight-chain or branched Linear carboxy (C ₁ -C ₅ ) alkyl, linear or branched (C ₁ -C ₅ ) alkoxy, linear or branched halo (C ₁ -C ₅ ) alkyl, aryl, linear or Including, but not limited to, branched arylalkyl, and linear or branched, aminoalkyl.

  Preferably, the monomer has the formula:

Wherein the saturated ring having the imide functionality includes an imide functionality, wherein R, n, and Z ₁ are as defined above. Preferably, Z ₁ is a carbon atom and ring A is a 5-membered ring.

  Monomers containing an imide or anhydride functionality in a saturated ring can be reacted together by conventional polymerization methods known in the art, such as condensation or addition reactions. Preferably, monomers containing imide functionality react with each other and monomers containing anhydride functionality react with each other. The formed polymer can be a copolymer or a homopolymer. Such polymers also include dimers. Some polymers are commercially available, such as polysucciimide and bismaleimide.

  Preferred polymers have the formula:

Wherein R ₁ and R ₂ may be the same or different, and R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different and include hydrogen, linear or branched (C ₁ -C ₅ ) alkyl, hydroxyl, linear or branched hydroxy (C ₁ -C ₅ ) alkyl, linear or branched carboxy (C ₁ -C ₅ ) alkyl, linear or Branched (C ₁ -C ₅ ) alkoxy, straight or branched halo (C ₁ -C ₅ ) alkyl, aryl, straight or branched arylalkyl, and straight or branched, Including aminoalkyl, m is an integer of 2 or more, preferably 2 to 12, more preferably 2 to 8. Preferably, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are independently selected from hydrogen and (C ₁ -C ₃ ) alkyl, more preferably, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are hydrogen. Preferably, the polymer has the structure (III) and is a polysuccinimide.

  Dimers have the following general formula:

Wherein A, Z, Z ₁ , and R are as defined above, and R ″ is R ₁₀ or R ₁₅ as defined below.

  Preferred dimers have the following formula:

Wherein R ₁₁ -R ₁₄ , R ₁₇ -R ₂₃ , and R ₂₅ -R ₂₆ are independently hydrogen, linear or branched (C ₁ -C ₅ ) alkyl , Hydroxyl, linear or branched hydroxy (C ₁ -C ₅ ) alkyl, linear or branched carboxy (C ₁ -C ₅ ) alkyl, linear or branched (C ₁ -C ₅₎ ) alkoxy, linear or branched halo (C 1 _{-C 5)} alkyl, aryl, linear or branched arylalkyl, and linear or branched, aminoalkyl, R ₁₅ is _{-CH 2 -O- (R'-O)} d -CH 2 - is a moiety selected from: wherein either R 'and d are as defined above, wherein:

Wherein R ₂₇ and R ₂₈ are independently hydrogen or (C ₁ -C ₃ ) alkyl, p is an integer of 1 to 10, and R ₁₆ is a group represented by the formula ( XII).

  Amine monomers include at least one organic or nitrogen compound having primary or secondary amine functionality that reacts with a polymer containing imide or anhydride functionality to form a polymer reaction product. Such amines have the formula:

Wherein R ₂₉ is hydrogen or linear or branched (C ₁ -C ₅ ) alkyl, and r is an integer from 0 to 8, provided that r is 0 When R ′ is a condition that R ′ is bonded to a nitrogen atom by a covalent bond. Preferably, R ₂₉ is hydrogen. Preferably, r is 1-4.

  R 'is a nitrogen-containing moiety, which may be a linear or branched nitrogen-containing group, an aromatic or non-aromatic heterocyclic group. The linear or branched nitrogen-containing moiety has the general formula:

Wherein R ₃₀ and R ₃₁ are independently hydrogen or linear or branched (C ₁ -C ₅ ) alkyl, and q is It is an integer of 1 to 10, preferably 1 to 4.

  Heterocyclic aromatic and non-aromatic nitrogen-containing moieties include imidazole, triazole, tetrazole, pyrazine, benzimidazole, benzotriazole, purine, piperazine, pyridazine, pyrazole, triazine, tetrazine, pyrimidine, piperidine, benzoxazole, oxazole, pyridine , Morpholine, pyrrolidine, pyrrole, quinoline, isoquinoline, and those derived from heterocyclic nitrogen compounds such as benzothiazole, but are not limited thereto. The heterocyclic nitrogen moiety can have one or more substituents attached to the ring. Such substituents may be linear or branched, substituted or unsubstituted alkyl, hydroxyl, nitro or nitroalkyl, nitroso or nitrosoalkyl, carbonyl, mercapto or mercaptoalkyl, linear or branched hydroxyalkyl, carboxyl, Straight or branched carboxyalkyl, straight or branched alkoxy, substituted or unsubstituted aryl, straight or branched, substituted or unsubstituted arylalkyl, straight or branched, substituted or Includes, but is not limited to, unsubstituted aminoalkyl, substituted or unsubstituted sulfonyl, linear or branched, substituted or unsubstituted amine. Also included are salts of aromatic heterocyclic amines such as halogen salts.

  The heterocyclic nitrogen moiety has the following general structure:

And Q ₁ may be carbon or nitrogen, and Q ₂ -Q ₄ may be nitrogen, oxygen, carbon, or sulfur, provided that one of Q ₂ -Q ₅ Only that it can be oxygen or sulfur in any case. Preferably, the ring has 1 to 3 nitrogen atoms, more preferably 1 to 2 nitrogen atoms. Most preferably, the ring is imidazole. The nitrogen linking the ring to the terminal carbon of formula (XIII) above has a counter anion X ⁻ , wherein X ⁻ is chloride, bromide, iodide, acetate, sulfuric acid, hydroxyl, boron tetrafluoride, Or it may have a positive charge that is nitric acid. Carbon and nitrogen atoms can be substituted or unsubstituted. Substituents on carbon and nitrogen atoms may be straight or branched, substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl, hydroxyl, straight or branched alkoxy, straight or branched. Substituted or unsubstituted hydroxy (C ₁ -C ₁₀ ) alkyl, linear or branched, substituted or unsubstituted alkoxy (C ₁ -C ₁₀ ) alkyl, linear or branched, substituted or unsubstituted carboxy (C ₁ -C ₁₀ ) alkyl, linear or branched, substituted or unsubstituted amino (C ₁ -C ₁₀ ) alkyl, substituted or unsubstituted aryl, linear or branched, substituted or unsubstituted aryl Including but not limited to (C ₁ -C ₁₀ ) alkyl, substituted or unsubstituted sulfonyl, and substituted or unsubstituted amine.

  An aromatic heterocyclic nitrogen moiety having a fused ring has the following general structure:

Can _have, Q 6 _{to Q 11} are carbon, oxygen, nitrogen, or a sulfur, provided at least one of _{Q 6} and _{Q 7,} with the proviso that a nitrogen, _{Q 8} Q ₁₁ may be a carbon or nitrogen atom, provided that only two of Q ₈ -Q ₁₁ may be nitrogen if they are identical. Ring carbon and nitrogen atoms can be substituted or unsubstituted. Substituents may be hydroxyl, linear or branched alkoxy, linear or branched, substituted or unsubstituted hydroxy (C ₁ -C ₁₀ ) alkyl, linear or branched, substituted or unsubstituted alkoxy. (C ₁ -C ₁₀ ) alkyl, linear or branched, substituted or unsubstituted carboxy (C ₁ -C ₁₀ ) alkyl, linear or branched, substituted or unsubstituted amino (C ₁ -C ₁₀₎ ) Includes, but is not limited to, alkyl, substituted or unsubstituted aryl, linear or branched, substituted or unsubstituted aryl (C ₁ -C ₁₀ ) alkyl, substituted or unsubstituted sulfonyl, and substituted or unsubstituted amine Not done. Such moieties are derived from compounds including, but not limited to, benzimidazole, benzotriazole, benzoxazole, benzothiazole, and purine. Preferably, such a compound is benzimidazole.

  The heterocyclic nitrogen moiety also has the general structure:

Wherein Q ₁₂ may be carbon or nitrogen, and Q ₁₃ -Q ₁₇ may be nitrogen, carbon or oxygen, provided that at least one of Q ₁₂ -Q ₁₇ is , Nitrogen, provided that there are less than 4 nitrogen atoms in the ring. The carbon and nitrogen atoms in the ring can be substituted or unsubstituted. Substituents, which may be identical or different, including those substituents described for Q ₁ to Q ₁₁ above, but are not limited to. When Q ₁₂ is nitrogen, the nitrogen may have a positive charge where the counter anion is X ⁻ , where X ⁻ is as defined above. When oxygen is present in the ring, only one of Q ₁₃ -Q ₁₇ is in any case oxygen. The heterocyclic nitrogen compound of structure (XVII) may be an aromatic or non-aromatic heterocyclic nitrogen compound.

  Preferred R 'moieties containing an aromatic heterocyclic nitrogen have the formula:

Wherein R ₃₂ and R ₃₃ are independently hydrogen, (C ₁ -C ₂ ) alkyl, or phenyl;

Wherein R ₃₂ , R ₃₃ , R ₃₄ , and R ₃₅ are independently hydrogen, (C ₁ -C ₂ ) alkyl, or phenyl, and X ⁻ is as defined above;

Wherein R ₃₂ and R ₃₃ are as defined above,

Wherein R ₃₂ , R ₃₃ , R ₃₄ , and R ₃₅ are as defined above,

Wherein R ₃₂ , R ₃₃ , R ₃₄ , and R ₃₅ are as defined above,

Wherein R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ and X ⁻ are as defined above,

Wherein R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and X ⁻ are as defined above, and preferred moieties are also:

Wherein R ₃₂ and R ₃₃ are as defined above,

Wherein R ₃₂ and R ₃₃ are as defined above.

  The order of addition of the reactants to the reaction vessel can vary, but preferably, the one or more polymers are mixed with dimethylformamide (DMF) at room temperature and the one or more Is added dropwise. This is performed under a nitrogen atmosphere. The mixture is stirred for 10-15 hours at room temperature. The amount of each component can vary, but generally, a sufficient amount of each reactant is added to provide a molar ratio of polymer to amine monomer of from 1: 0.05 to 1: 1, based on the molar ratio of reactants. 2, preferably a product ranging from 1: 0.1 to 1: 1.

  Plating compositions and methods that include one or more of the reaction products are useful for providing a substantially smooth plated metal layer on a substrate, such as a printed circuit board or semiconductor chip. Also, the plating compositions and methods are useful for filling holes in a substrate with metal. The metal deposit has good throwing power and good physical reliability for thermal shock stress testing.

  Any substrate on which a metal can be electroplated can be used as a substrate having a metal plating composition containing the reaction product. Such substrates include, but are not limited to, printed wiring boards, integrated circuits, semiconductor packages, lead frames, and interconnects. The integrated circuit substrate may be a wafer used in a dual damascene manufacturing process. Such substrates typically have several features, especially holes having various sizes. The through holes in the PCB may have various diameters, such as a diameter of 50 μm to 350 μm. Such through holes can vary in depth, such as 0.8 mm to 10 mm. PCBs may have blind vias with a wide variety of sizes, such as a maximum diameter of 200 μm and a depth of 150 μm or more. The plating composition can also be used to electroplate on plastic materials that include a conductive polymer or metal seed layer.

  The metal plating composition includes a metal ion source, an electrolyte, and a leveling agent, wherein the leveling agent is a reaction product of one or more amine monomers and one or more polymers containing imide or anhydride functionality. . The metal plating composition may contain a halide ion source, an accelerator, and an inhibitor. Metals that can be electroplated from the composition include, but are not limited to, copper, tin, and tin / copper alloys. Preferably, copper is metal plated.

Suitable sources of copper ions are copper salts, such as copper sulfate, copper halides (such as copper chloride), copper acetate, copper nitrate, copper tetrafluoroborate, copper alkyl sulfonates, copper aryl sulfonates, copper sulfamate, Including but not limited to copper chlorate and copper gluconate. Exemplary copper alkane sulfonates include (C ₁ -C ₆ ) copper alkane sulfonates, more preferably copper (C ₁ -C ₃ ) copper alkane sulfonates. Preferred copper alkane sulfonates are copper methane sulfonate, copper ethane sulfonate, and copper propane sulfonate. Exemplary copper aryl sulfonates include, but are not limited to, copper benzene sulfonate and copper p-toluene sulfonate. Mixtures of copper ion sources may be used. One or more salts of metal ions other than copper ions may be added to the electroplating bath. Typically, the copper salt is present in an amount sufficient to provide from 10 to 400 g / L of copper metal in the plating solution.

  Suitable tin compounds include salts (such as tin halides), tin sulfate, tin alkanesulfonates (such as tin methanesulfonate), tin aryl sulfonates (such as tin benzenesulfonate), and tin p-toluenesulfonate However, it is not limited to these. The amount of tin compound in these electrolyte compositions is typically an amount that results in a tin content in the range of 5 to 150 g / L. Mixtures of tin compounds can be used in the amounts described above.

  Electrolytes useful in the present invention can be alkaline or acidic. Preferably, the electrolyte is acidic. Preferably, the pH of the electrolyte is ≦ 2. Suitable acidic electrolytes include sulfuric acid, acetic acid, fluoroboric acid, alkanesulfonic acids (such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and trifluoromethanesulfonic acid), arylsulfonic acids (benzenesulfonic acid and p-toluenesulfonic acid). Etc.), sulfamic acid, hydrochloric acid, hydrobromic acid, perchloric acid, nitric acid, chromic acid, and phosphoric acid. Mixtures of acids can advantageously be used in the present metal plating baths. Preferred acids include sulfuric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, hydrochloric acid, and mixtures thereof. The acid may be present in an amount ranging from 1 to 400 g / L. Electrolytes are generally commercially available from various sources and can be used without further purification.

  Such an electrolyte may optionally contain a source of halide ions. Typically, chloride ions are used. Exemplary chloride ion sources include copper chloride, tin chloride, sodium chloride, potassium chloride, and hydrochloric acid. A wide range of halide ion concentrations can be used in the present invention. Typically, halide ion concentrations range from 0 to 100 ppm based on the plating bath. Such halide ion sources are generally commercially available and can be used without further purification.

  The plating composition typically contains an accelerator. Any accelerator (also referred to as a brightener) is suitable for use in the present invention. Such accelerators are well-known to those skilled in the art. Accelerators include N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, 3-mercapto-propylsulfonic acid- (3-sulfopropyl) ester, 3-mercapto-propylsulfonic acid sodium salt, 3-mercapto Carbonic acid-dithio-O-ethyl ester-S-ester with 1-propanesulfonic acid potassium salt, bis-sulfopropyl disulfide, bis- (sodium sulfopropyl) -disulfide, 3- (benzothiazolyl-S-thio) propyl sulfone Acid sodium salt, pyridinium propylsulfobetaine, 1-sodium-3-mercaptopropane-1-sulfonate, N, N-dimethyl-dithiocarbamic acid- (3-sulfoethyl) ester, 3-mercapto-ethylpropylsulfonic acid- (3- Sulfo Tyl) ester, 3-mercapto-ethylsulfonic acid sodium salt, carbonic acid-dithio-O-ethylester-S-ester having 3-mercapto-1-ethanesulfonic acid potassium salt, bis-sulfoethyldisulfide, 3- (benzothiazolyl Include, but are not limited to, -S-thio) ethylsulfonic acid sodium salt, pyridinium ethylsulfobetaine, and 1-sodium-3-mercaptoethane-1-sulfonate. Accelerators can be used in various amounts. Generally, accelerators are used in amounts ranging from 0.1 ppm to 1,000 ppm.

  Any compound capable of suppressing the metal plating rate can be used as an inhibitor in the present electroplating composition. Suitable inhibitors include, but are not limited to, polypropylene glycol copolymers and polyethylene glycol copolymers, including ethylene oxide-propylene oxide ("EO / PO") copolymers and butyl alcohol-ethylene oxide-propylene oxide copolymers. Suitable butyl alcohol-ethylene oxide-propylene oxide copolymers are those having a weight average molecular weight of 100 to 100,000, preferably 500 to 10,000. When such inhibitors are used, they are typically present in amounts ranging from 1 to 10,000 ppm, more typically from 5 to 10,000 ppm, based on the weight of the composition. The leveling agents of the present invention may also possess functionality that can act as an inhibitor.

  In general, the reaction product has a number average molecular weight (Mn) of 200 to 100,000, typically 300 to 50,000, preferably 500 to 30,000, but has other Mn values. May be used. Such reaction products may have a weight average molecular weight (Mw) value in the range of 1,000 to 50,000, typically 5,000 to 30,000, although other Mw may be used. .

  The amount of the reaction product (leveling agent) used in the metal electroplating composition depends on the particular leveling agent selected, the concentration of metal ions in the electroplating composition, the particular electrolyte used, the concentration of the electrolyte, And the applied current density. Generally, the total amount of leveling agent in the electroplating composition ranges from 0.01 ppm to 500 ppm, preferably 0.1 ppm to 250 ppm, most preferably 0.5 ppm to 100 ppm, based on the total weight of the plating composition. , Higher or lower amounts may be used.

  The electroplating composition can be prepared by combining the components in any order. An inorganic component such as a metal ion source, water, an electrolyte, and an optional halide ion source is first added to the bath, followed by a leveling agent, an accelerator, an inhibitor, and any other organic components. It is preferable to add the organic constituent of the above.

  The electroplating composition may optionally contain at least one additional leveling agent. Such additional leveling agent may be another leveling agent of the present invention or, alternatively, any conventional leveling agent. Suitable conventional leveling agents that can be used in combination with the present leveling agents are described in US Pat. No. 6,610,192 to Step et al., 7,128,822 to Wang et al., And 7,374,652 to Hayashi et al. And No. 6,800,188 to Hagiwara et al. Such combinations of leveling agents can be used to adjust the properties of the plating bath, including leveling capabilities and throwing power.

  Typically, the plating composition can be used at any temperature from 10 to 65C or higher. Preferably, the temperature of the plating composition is from 10 to 35C, more preferably from 15 to 30C.

  Generally, the metal plating composition is agitated during use. Any suitable stirring method may be used, and such methods are well-known in the art. Suitable agitation methods include, but are not limited to, air sparging, rocking agitation, and impingement.

Typically, the substrate is electroplated by contacting the substrate with a plating composition. The substrate typically functions as a cathode. The plating composition may contain an anode, which may be soluble or insoluble. An electric potential is typically applied to the electrodes. Sufficient current density is applied to deposit a metal layer having the desired thickness on the substrate and to fill blind vias, trenches, and through holes, or to plate conformal through holes. Time, plating is performed. Current density, can range of 0.05~10A / dm ^2, higher or lower current densities may be used. The specific current density depends in part on the substrate to be plated, the composition of the plating bath, and the desired surface metal thickness. Selection of such current densities is within the ability of those skilled in the art.

  An advantage of the present invention is that a substantially smooth metal deposit is obtained on the PCB. The through holes, blind vias, or combinations thereof in the PCB are substantially filled or conformally plated with the desired throwing power where the through holes are desired. A further advantage of the present invention is that a variety of pores and pore sizes can be filled or conformally plated with the desired throwing power.

  Throwing power is defined as the ratio of the average thickness of the metal plated at the center of the through hole compared to the average thickness of the metal plated on the surface of the PCB sample, and is reported as a percentage. The higher the throwing power, the better the plating composition can conformally plate through-holes.

  The compound provides a metal layer having a substantially smooth surface across the substrate, even on substrates having small features and on substrates having various feature sizes. The plating method effectively deposits metal in the through-holes so that the metal plating composition has good throwing power.

  Although the method of the present invention has been generally described with reference to printed circuit board manufacturing, the present invention is directed to the case where essentially smooth or planar metal deposition and filled or conformally plated holes are desired. It is understood that any of the electrolysis steps may be useful. Such steps include, but are not limited to, the fabrication of semiconductor packages and interconnects.

  The following examples are intended to further illustrate the invention but are not intended to limit its scope.

Example 1
Polysuccinimide (2.4 g, 24.7 mmol) and 20 mL of dimethylformamide (DMF) were added to a three-necked round bottom flask. Aminopropylimidazole (3.24 g, 25.9 mmol) in 5 mL of DMF was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove DMF residues and any unreacted aminopropylimidazole. The molecular weight of the crude product was determined such that Mn = 4594 and Mw = 9206.

  Three aqueous acidic copper electroplating baths were prepared as shown in Table 1 below. The reaction product was contained in the bath without purification.

  A 3.2 mm thick test panel having an average through hole diameter of 300 μm was immersed in three aqueous acidic copper electroplating baths. Copper plating was performed at 25 ° C. for 80 minutes. The current density was 2.16 ASD. The copper plated samples were analyzed to determine the throwing power ("TP") of the plating bath and percent cracking according to the following method.

  Throwing power was calculated by determining the ratio of the average thickness of the metal plated at the center of the through hole compared to the average thickness of the metal plated on the surface of the test panel. Throwing power is reported in Table 2 as a percentage.

  The cracking rate was measured according to the IPC-TM-650-2.6.8. Thermal Stress, Plated-Through Holes (published by IPC (Northbrook, Illinois, USA), determined May 2004, Revision E).

  The average surface thickness of the copper plated on the panel was substantially the same for each sample. Through hole thickness was improved in the two baths containing the leveler. Improved throwing power was also observed in the copper plating bath containing the reaction product compared to the copper plating bath containing no reaction product. All of the samples tested had good cracking results. The lower the cracking rate, the better the plating performance. Preferably, cracking was ≦ 10%.

Example 2
The copper electroplating process described above was repeated using the same reaction product in each bath, but with varying amounts. In addition, the amount of brightener added to the copper bath was either 1 ppm or 3 ppm, as shown in the table below. The electroplating conditions were the same as in Example 1 and the type of plated substrate. The results are shown in Table 3.

  All of the precipitates were bright and smooth in appearance. Throwing power was good overall with the best results achieved in samples 6 and 7 at leveler concentrations of 10 ppm and 20 ppm. No cracks were observed. This was consistent with the result of Example 1 described above.

Example 3
To a three neck round bottom flask was added 25 mmol of polysuccinimide and 20 mL of dimethylformamide (DMF). Then the formula in 5 mL DMF:

  Was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove any residues.

  Three aqueous acidic copper electroplating baths were prepared having the formulations disclosed in Table 1 of Example 1, except that the amount of brightener was 1 ppm. The reaction product was contained in the bath without purification. The amount of reaction product or leveler was used in the amounts shown in Table 4 below.

  Samples 2 and 3 achieved acceptable throwing power values, however, Sample 3 had a high cracking rate and the deposit was dull.

Example 4
To a three neck round bottom flask was added 25 mmol of polysuccinimide and 20 mL of dimethylformamide (DMF). Formula in 5 mL DMF:

  Was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove any residues.

  An aqueous acidic copper electroplating bath was prepared having the formulation disclosed in Table 1 of Example 1 except that the amount of brightener was 1 ppm. The reaction product was contained in the bath without purification. The amount of reaction product or leveler was used in the amounts shown in Table 5 below. Plating was performed as described in Example 1 above, using the same type of panel.

  The copper deposition was bright and the throwing power was an acceptable value. No cracks were observed.

Example 5
To a three neck round bottom flask was added 25 mmol of polysuccinimide and 20 mL of dimethylformamide (DMF). Formula in 5 mL DMF:

  Was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove any residues.

  Three aqueous acidic copper electroplating baths were prepared having the formulations disclosed in Table 1 of Example 1, except that the amount of brightener was 1 ppm. The reaction product was contained in the bath without purification. The amount of reaction product or leveler was used in the amounts shown in Table 6 below. Plating was performed as described in Example 1 above, using the same type of panel.

  All samples show good throwing power and all have bright deposits. No crack was observed in any of the precipitates.

Example 6
To a three neck round bottom flask was added 25 mmol of polysuccinimide and 20 mL of dimethylformamide (DMF). Formula in 5 mL DMF:

  Was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove any residues.

  Six aqueous acidic copper electroplating baths having the formulations disclosed in Table 1 of Example 1 were prepared. The amount of brightener in the bath was either 1 ppm or 3 ppm. The reaction product was contained in the bath without purification. The amount of reaction product or leveler was used in the amounts shown in Table 7 below. Plating was performed as described in Example 1 above, using the same type of panel.

  The overall throwing power was very good, however, cracking was a problem in half of the samples analyzed. The precipitation was bright overall.

Example 7
To a three neck round bottom flask was added 25 mmol of polysuccinimide and 20 mL of dimethylformamide (DMF). Formula in 5 mL DMF:

  Was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove any residues.

  Six aqueous acidic copper electroplating baths having the formulations disclosed in Table 1 of Example 1 were prepared. The amount of brightener in the bath was 1 ppm, 2 ppm, or 3 ppm. The reaction product was contained in the bath without purification. The amount of reaction product or leveler was used in the amounts shown in Table 8 below. Plating was performed as described in Example 1 above, using the same type of panel.

  All samples had good throwing power, however, the cracks were extensive.

Example 8
In a three-necked round bottom flask, 25 mmol of polysuccinimide and 20 mL of dimethylformamide (DMF) were added to the three-necked flask. Formula in 5 mL DMF:

  Was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove any residues.

  Three aqueous acidic copper electroplating baths having the formulations disclosed in Table 1 of Example 1 were prepared. The amount of brightener in the bath was 1 ppm or 3 ppm. The reaction product was contained in the bath without purification. The amount of reaction product or leveler was used in the amounts shown in Table 9 below. Plating was performed as described in Example 1 above, using the same type of panel.

  Throwing power was good for all baths. Remarkable cracking was observed only in Sample 2. No cracks were observed in samples 1 and 3. All precipitates were bright.

Example 9
To the round bottom of the three necks was added 25 mmol of polysuccinimide and 20 mL of dimethylformamide (DMF). Formula in 5 mL DMF:

  Was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove any residues.

  Three aqueous acidic copper electroplating baths having the formulations disclosed in Table 1 of Example 1 were prepared. The amount of brightener in the bath was 1 ppm or 3 ppm. The reaction product was contained in the bath without purification. The amount of reaction product or leveler was used in the amounts shown in Table 10 below. Plating was performed as described in Example 1 above, using the same type of panel.

  The throwing power was good for samples 2 and 3. However, significant cracking was observed in samples 1 and 3. All precipitates were bright.

Example 10
To a three neck round bottom flask was added 25 mmol of polysuccinimide and 20 mL of dimethylformamide (DMF). Formula in 5 mL DMF:

  Was added dropwise over 0.5 h with stirring under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 hours. The solvent was then evaporated and the product was washed with acetone to remove any residues.

Three aqueous acidic copper electroplating baths having the formulations disclosed in Table 1 of Example 1 were prepared. The amount of brightener in the bath was 1 ppm, 2 ppm, or 3 ppm. The reaction product was contained in the bath without purification. The amount of reaction product or leveler was used in the amounts shown in Table 11 below. Plating was performed as described in Example 1 above, using the same type of panel.

Except for Sample 4, the throwing power was good, however, cracking was significant.
The appearance of the precipitate was dull.

Claims (2)

An electroplating composition comprising one or more metal ion sources selected from copper salts and tin salts , an electrolyte, and one or more compounds of one or more amine compounds and one or more polymer reaction products. Thus, the polymer has the formula (III) :

Have a, wherein, _{R 1} and _{R 2} are the same or different and are hydrogen, a linear or branched _(C 1 -C ₅₎ alkyl, hydroxyl, straight-chain or branched _{(C 1} —C ₅ ) hydroxyalkyl, straight or branched (C ₁ -C ₅ ) carboxyalkyl, straight or branched (C ₁ -C ₅ ) alkoxy, straight or branched (C ₁₎ -C ₅₎ includes haloalkyl, aryl, linear or branched arylalkyl, and linear or branched, aminoalkyl, m is an integer of 2 or more,
The one or more amine compounds have the formula:

Wherein R ₂₉ is hydrogen or linear or branched (C ₁ -C ₅ ) alkyl, and r is an integer from 0 to 8 with the proviso that r is When 0, R 'is conditioned on being bonded to a nitrogen atom by a covalent bond, and R' is a linear or branched nitrogen-containing moiety, an aromatic or non-aromatic heterocyclic group. object. a) providing a substrate;
b) providing an electroplating composition according to claim 1;
c) contacting the substrate with the composition;
d) applying a current to the substrate and the composition;
e) depositing a metal on said substrate.