TW200825207A - Composition for nonelectrolytic plating and method of forming metallic protection film using the same - Google Patents

Abstract

The present invention provides a composition for nonelectrolytic plating and a method of forming metallic protection film using the same being capable of applying a flat metallic protection film onto a metallic wiring of such as copper formed on a semiconductor substrate, more particularity, the object of the present invention is to provide a composition for nonelectrolytic plating and a method of forming metallic protection film using the same, by which a flat metallic protection film can be formed, especially, the formation of multilayered wiring can be fulfilled effectively, by suppressing the corrosion or elution of copper wiring. The composition comprises a plating metal ion, a reducing agent, a compound from which plating metal ion and complex can be formed, and a compound represented by a general formula (1), (wherein, R<SP>1</SP> and R<SP>2</SP> are respectively independent and represent an alkyl group of carbon atom number 1 to 3, R<SP>3</SP> represents bivalence aliphatic hydrocarbon group of carbon atom number 1 to 6 which may have oxygen atom).

Description

200825207, IX. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a composition for electroless plating and a method for forming a metal protective film. More specifically, the present invention relates to a composition for electroless mineral coating and a method for forming a metal protective film using the same, which is a metal wiring such as copper which can be formed on a semiconductor substrate. The surface forms a protective film. [Prior Art] In order to achieve higher integration and higher performance of the semiconductor device, it is attempted to increase the speed of the device by making the high-density integrated circuit formed on the semiconductor substrate fine or multi-layered. . Based on this month? In the study, the resistivity is used as a wiring material, and a low-valence film having a porosity is used as an interlayer insulating film. The formation of the copper wiring is carried out according to the following means: a predetermined groove is formed on the substrate in advance, and a metal copper or a copper alloy is buried in the σ 卩 by means of a mineral coating or the like, and then chemical mechanical polishing is performed ( Cheuncai Medianieal p〇lishing: (: Mp) removes the surface of the copper and other rain to flatten the surface. After the surface of the substrate is flattened by this CMP or the like, the surface of the wiring such as copper is exposed to the outside to protect the copper. For the purpose of wiring, it has been proposed to form a metal such as a recording material which is stronger in bonding with a wiring material such as copper by means of electroless plating or the like, in particular, a metal alloy film having a low specific resistance. Specifically, for example, a proposal has been proposed. A cobalt-tungsten-phosphorus conductive film is formed as a metal protective film by electroless plating (for example, Patent Document, etc.). However, 319613 200825207 In this method, sodium hypochlorite is used as a reducing agent, and such a metal is used. The salt may contaminate the metal protective film by infiltrating the metal ion to the key coating film, and may cause a problem of adversely affecting the electrical properties of the conductor substrate. Thus, the recent proposal has been electroless plating. In the liquid distortor and the pH adjuster, a metal-free compound is used to solve the above problems, and the plating solution (for example, Patent Documents 2, 3, etc.) is used, but in order to ensure a certain degree of mineral deposit At the speed', ammonia is used to maintain the pH of the ore coating at neutral _, and it is used to reduce the uniformity of the copper wiring. As a result, the copper wiring of the substrate is corroded or dissolved. As a result, the uniformity of the copper wiring is lowered. However, it is impossible to maintain the flatness of (4), especially in the case of multilayering, and there is a problem that the wiring is broken. In this case, it is desired to develop an influence on the electrical properties of the semiconductor without causing metal impurities such as metal. The wiring layer is not affected by the corrosion or dissolution of the copper wiring of the base, and a flat metal protective film electrolytic plating composition can be formed. '"' _ [Patent Document 1] US Patent No. 569581 0 [ [Patent Document 3] Japanese Laid-Open Patent Publication No. 2003-142427 (Patent Document 3) (Problem to be Solved by the Invention) The problem to be solved by the present invention is to provide an electroless plating. group And a method for forming a metal protective film using the composition, wherein the composition for the non-de-plating does not deteriorate the inclusion properties on the semiconductor substrate due to metal impurities such as an alkali metal, and suppresses corrosion of the copper wiring or Disadvantageous effects such as dissolution and 319613 7 200825207 A flat metal protective film can be formed, and in particular, multilayer wiring can be effectively formed. (Means for Solving the Problem) The present invention relates to a composition for electroless plating, which comprises: a plated metal An ion reducing agent, a compound capable of forming a complex with a plated metal ion, and a compound represented by the formula (1) RX 3 N-R3 - OH (1) R2 (wherein R1 and R2 are each independently represented The alkyl group having a carbon number of ii 3 may not have a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms of an oxygen atom). In addition, the present invention is a method for forming a metal film, which is formed by electroless plating of a preform (4), which comprises a metal ion, a reducing agent, and a mineral coating. a compound in which a metal ion forms a complex compound, and a compound represented by the formula (1): RN1 3 N - R3 - OH (1) (wherein R and E are each independently represented; and e carbon number is 1 to 3) The base may not have the carbon number of the oxygen atom ii 6 of the divalent aliphatic group. (Effect of the Invention) The electroless ride (four) composition of the present invention can be applied to a surface of a wiring such as copper on a half (four) substrate by a flat metal protective film (plating film), and by using the above formula (1) The compound shown has a pH adjusted to a predetermined value. It is possible to suppress the copper wiring from being eluted or eluted, and to form a flat metal protective film. = The method for forming the metal protective film of the present invention is advantageous for forming a method for preventing the metal from being twisted. If the compound of the above formula (1) is used, the compound of the above formula (1) is 319613 8 200825207, thereby not only inhibiting the corrosion of the copper wiring as described above or The metal film is eluted, and the adjustment of the I PH is facilitated, and the metal protective film can be formed more easily. [Examples] The alkyl group having 1 to 3 carbon atoms represented by R1 and R2 in the formula (1) may be a straight bond or a branched form, and specific examples thereof include a mercapto group, an ethyl group, and a n-propyl group. , isopropyl, etc., especially sulfhydryl, ethyl is preferred, especially methyl is preferred. The aliphatic hydrocarbon group represented by R3 in the formula (1), which may have an oxygen atom, may have a linear hydrocarbon group, a branched chain or a cyclic group, and specifically, for example, a methylene group (for example, a methylene group) Methyl ene), dimethylene (extended ethyl), decyl methylene, dimethylene, propyl, ethylmethylene, tetramethylene, I-fluorenyldiphenyl, 2 A fluorenyltriazinyl group, an ethylexylethyl group, a 1,1-dimethylexylethyl group, a 1,2-didecylethyl group, a penta-indenyl group, a methyltetramethylene group, a 2-indenyl group Sulfhydryl, 1-ethyltrimethylene, 2-ethyltrimethylene, hydrazine, ι-dimethyltrimethylene, 1,2-dimercaptotrimethylene, 1,3-dimethylamethylene Methyl, 2, 2-indenyldiindolylene, cyclopen tyl ene, hexamethylene, 1-mercapto-5, 2-methylpentamethylene, 3 -methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetradecyl, iota, dimethyl-tetramethylene, 1,2-dimethyltetramethylene, 1,3-Dimethyltetramethylene, 1,4-dimethyltetramethylene, 2,2-dimercaptotetramethylene, 2,3-dimethyltetra Base, cyclohexyl, -(CH2)2〇(CH2)2-yl, -(CH2)2〇(CH2)3-yl, -(CH2)2〇CH2CH(CH3)-yl, -(CH2)2 〇CH(CH3)CH2-yl, -(CH2)3〇(CH2)3-yl, -(CH2)20(CH2)4-yl, -(CH2)2〇(CH2)2〇(CH2)2- , -(CH2)3〇CH2CH(CH3)-yl, -(CH2)2〇(CH2)2CH(CH3)-yl, -(CH2)3〇CH(CH3)CH2-yl, -(CH2)2 〇CH2CH(CH3)CH2-based, 9 319613 200825207, -(CH2)2〇CH(CH3)(CH2)2-based, -(Cfl2)2〇CH2CH(C2H〇-yl, -(CH2)2〇CH (C2H〇CH2-yl, -CH(CH3)CH2()CH2CH(CH3)-yl, ι-CH(CH3)CH2〇CH(CH3)CH2-yl, -(CH2)2〇CH2C(CH3V, • -(CH2)2〇CH(CH3)CH(CH3)-yl...(CH2)2〇C(CH3)2CHr group, -CH2CH(CH3)OCH(CH3)CH2- group, tetrahydroanthracene group, four More preferably, it is a linear or branched divalent aliphatic hydrocarbon group having 2 to 5 carbon atoms of an oxygen atom, and specifically, for example, a dimethylene group (extension) Ethyl), indenyl fluorenyl, trimethylene, propyl, ethylmethylene, tetramethylene, methyltrimethylene, 2-methyltrimethylene, ethylethyl, U Diterpenoid ethyl, U~dimethylexylethyl, pentamethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1-ethyltrientylene, 2-ethyl Triammonium, M-dimethyltrimethylene, 1,2-dimethyltrimethylene, 〗, 3-dimethyltrimethylene, 2,2-dimethyltrimethylene, -(CH2) 2〇(CH2)2-yl, -(CH2)2〇(CH2)3-yl, -(CH2)2〇CH2CH(CH3)-yl,-(CH2)2〇CH(CH3)CH2-yl, wherein In particular, it is preferred to have a methylene group (extended ethyl group), a trimethylene group, a propyl group, a tetramethylene group, a -(CH2)2〇(CH2)2- group, and particularly a trimethylene group. . In the composition for electroless plating of the present invention, the compound represented by the above formula (1) is not particularly limited as long as it is a tertiary amine having the structure of the formula (1), and may be used singly or in combination. A variety. Further, in the compound represented by the above formula (1), particularly, Rlj r2 in the formula (1) is independently a methyl group or an ethyl group, and R3 is a linear chain having a carbon number of 2 to 5 which may have an oxygen atom. The combination of a compound of a divalent month and a divalent hydrocarbon group in the form of a bivalent or branched form is specifically, for example, 2-dimethylaminoethanol, 2 diethylaminoethanol, 319613 10 200825207 2-ethyl group Aminoethanol, 1-dimethylaminoethanol, i-diethylaminoethanol, ethylmethylaminoethanol, 3-dimethylamino-1-propanol, 3-diethylamino-propanol , 3-ethyldecylamino-1-propanol, 1-dimethylamino-2-propanol, 1

Diethylamino-2-propanol, 1-ethyldecylamino-2-polypropanol, 2-diaminoamino-propanol, 2-diethylamino-1-propanol, 2-ethyl Methylamino-1-propanol, 1-dimethylamino-1-propanol, 1-diethylamino-1-propanol, j-ethyldecylamino-1-propanol, 4- Dimethylamino-1-butanol, 4-diethylamino-butanol, 4-ethyldecylamino-1-butanol, 1-diaminoamino-1,3-butanol, j-di Ethylamino 3-butanol, 1-ethylmethylamino-1-butanol, 3-dimethylamino-1-butanol, 3-diethylamino-1-butanol, 3-ethyl Methylamino-1-butanol, 2-methyl-3-dimethylamino-1-propanol, 3-diethylamino-2-methyl-propanol, 3-ethyldecylamine Base-2-mercapto-1-propanol, 1-diaminoamino-2-butanol, j-diethylamino~2-butanol, 1-ethyldecylamino-2-butanol, 2-monodimethylamino-i-butanol, 2-diethylamino-1-butanol, 2-ethylmethylamino-1-butanol, 2-methyl-mono-dimethylamino 2-propanol, 1-diethylamino-2-indolyl-2-propanol, ethylethylamino-2-mercapto-2-propanol, 2-mercapto-2-diamine Base-propanol, 2~diethylamino-2-mercapto-1-propanol, 2-ethyldecylamino-2-2-mercapto-propanol, 3-dimethylamino-2- Butanol, 3-diethylamino-1-butanol 'ethylmethylamino-2-butanol, 5-monoamylamino-p-pentanol, 5-diethylamine-l-pentanol, 5-ethyldecylamino-1-pentanol, diammonium-1,4-pentanol, diethylamino-4-pentanol, 1-ethylmethylamino-4-pentanol, 4~diamine-l-pentanol, 4-diethylamino-1-pentanol, 4-ethylmethylamino-i-pentanol, 2-methyl-1-diaminomethyl-4 -butanol,]diethylamino-2-methyl to 4~butyl alcohol, 1-ethyldecylamino-2-methyl-4-butanol, 2-methyl-4- ® ~Methylamino 319613 11 200825207 ^ &quot;&quot;1 Butanol, 4-diethylamino-2-mercapto-1-butanol, 4-ethylmethylamino-2. Mercapto-1-butanol, 1-dimethylamino-3-pentanol, 1-diethylamino-3-pentanol, 1-ethylmethylamino-3-pentanol, 3-dioxan Amino-1-pentanol, 3-diethylamino-1-pentanol, 3-ethyldecylamino-1-pentanol, 2-ethyl-3-dimethylamino-1-propanol , 2-ethyl-3-diethylamino-1-propanol, 2-ethyl-3-xymethylamino-1-propanol, 3-methyl-1-dimethylamino-3 -butanol, 1-diethylamino-3-mercapto-3-butanol, 1-ethylhydrazinylamino-3-methyl-3-butanol, 3-methyl-3-dimethylamine 1- 1-butanol, 3-diethylamino-3-decyl-1-butanol, 3-monoethylmethylamino-3-mercapto-1-butanol, 2-methyl-1 - dimethylamino-3-butanol, diethylamino-2-methyl-3-butanol, 1-ethyldecylamino-2-methylbutanol, 2-methyl- 3-dimethylamino-1-butanol, 3-diethylamino-1-nonyl-1-butanol, 3-ethylmethylamino-2-mercapto-butanol, 4-12 Amidino-2-pentanol, 4-diethylamino-2-pentanol, 4-ethylmethylamino-2-pentanol, 2, 2,-dimethyl-3-dimethylamino 1-propanol, 3-diethylamino- 2,2-dimethyl Base-1 -propanol, 3-ethylmethylamino- 2,2-dimethyl-i-propanol, 2-[2-mono(-methylamino)ethoxy]ethanol, 2-[2 -(diethylamino)ethoxy]ethanol, 2-[2-(ethylmethylamino)ethoxy]ethanol, 3-mono[2-(diamino)ethoxy]-propanol , 3-[2-(diethylamino)ethoxy] n-propanol, 3-[2-(ethylmethylamino)ethoxy]-n-propanol, 2-[3-(dimethylamine) Base) n-propoxy]ethanol, 2-[3-(diethylamino)-n-propoxy]ethanol, 2-[3_(ethylmethylamino)-n-propoxy]ethanol, 1-methyl 2-1-2[2-(dimethylamino)ethoxy]ethanol 2 [2 (monoethylamino)ethoxy]-l-methylethanol, 2-[2-(ethylmethylamino) Ethoxy]-1-methylethanol, 2-[2-methylethoxy]ethanol, diethylamino)_2 „methylethoxy]) 319613 12 200825207 ^ 2一[2一( Ethylmethylamino)-2-methylethoxy]ethanol, 2-methyl-2-yl[2-dimethylamino)ethoxy]ethanol, 2-[2-(diethylamino)ethyl Oxy] -2- mercaptoethanol, 2-[2-(ethylmethylamino)ethoxy]-2-methyl , 2-[1-methyl-2-(dimethylamino)ethoxy]ethanol, 2-[2-(diethylamino)-methylethyloxy]ethanol, 2-[2-(ethyl Methylamino)-p-methylethoxy]ethanol oxime, wherein 2 - ^-monomethylaminoethanol, 3-dimethylamino-1-propanol, 1-diguanylamino- 2-propanol, 4-Dimethylamino-1butanol and 2-mono[2-(dimethylamino)ethoxy]ethanol are preferred, and among them, 3-dimethylamino-1-indolyl alcohol is particularly preferred. The inventors have found that a flat metal protective film (forged film) can be used for δ by using a compound represented by the above formula (1) instead of the conventional ammonia or the like for use in an electroless mineral coating liquid. In the case of ammonia or the like which has been used until now, it is difficult to apply a flat metal protective film (recording film) because of the corrosion or dissolution of the copper wiring caused by the above, and further studies have been carried out. ) The compound shown, pil m & 腐 或者 or,,,,,,,,,,,,,,,,,, 'Good shirts, and can form a flat metal protective film (plating, in addition, the compound shown in the general formula (1) has the same electroless frosting, Xuan, right fly, and 4c, and is adjusted by two t: In the neutral to the role of the test, and ^ due to the volatilization of the seam and _ higher, so the alkyl saddle will be in the plating from the plating solution Y know the second pa ' ' night volatilization to reduce the pH of the solution In addition, there is no, for example, a low-level pH adjustment to the desired value. The point is not suitable for the electroless r &amp; ',,, and good compounds of the present invention. The metal ion of the bell 彳 f is 319613 13 200825207 1 ion or nickel ion, especially cobalt ion, and the source is cobalt salt such as cobalt sulfate, cobalt nitrate, cobalt chloride or nickel sulfate, nickel nitrate, A nickel salt such as ruthenium chloride. Further, a salt of a cobalt salt or a salt of a nickel salt such as a sulfate salt or a nickel salt may be used as the salt or the salt of the salt. In addition, such a cobalt salt or a nickel salt may be used. A single type can also be used alone or in combination. Since cobalt or nickel ions are used, they are made of cobalt or nickel. Genus protective film (plated film) formed into the protective film of the copper wiring, and ensure the reliability of the wiring.

In the electroless plating composition of the present invention, when the electroless plating is performed, a redox antif is formed in a complex with the plated metal ions, and the metal is wired in a metal such as copper. The precipitation is not limited to a metal sulphide (mine film), and is not particularly limited as long as it is a metal ion other than the metal ion to be plated, but specific examples thereof include: hypophosphorous acid, etc. Phosphate compounds such as methylamine borane, diethylamine borane, tridecylamine borane, hydrazine, hydrazine, barium sulphate, guanidine hydrochloride and cesium carbonate. etc. 合 "combination; especially two? Hydrogen compounds such as amide, diethylamine, and dimethylamine rotten are preferred; among them, dimercaptoamine borane and diethylamine borane are preferred; good. These systems can be used alone or in groups of #; The compound for forming a complex compound with a plated metal ion in the composition for electroless plating of the present invention forms a complex with a plated metal ion, and is f-neutral to miscellaneous electroless plating (four), and has prevention «The role of metal hydroxide precipitation, and as long as it is a metal ion other than the mirror metal ion and can form a complex with the (4) metal ion, there is no 319613 14 200825207 1 , specifically, for example Such as: acetic acid, oxalic acid, malonic acid and other tickic acid 'lactic acid, tartaric acid, citric acid, malic acid and other carboxylic acids; especially =: ip chyle, tartaric acid, citric acid, malic acid; especially F-like acid is particularly good. Further, as the carboxylic acid or the lysine, for example, hydration of a few acids such as hydrazine monohydrate or citric acid monohydrate or a carboxylic acid of several groups may be used. In addition, 'these types can be used alone or in combination, and more appropriate, such as glycine, alanine, etc., and ethylenediaminetetraacetic acid, etc. The compound of the compound has the function of dissolving the copper wiring, and is not used as a compound which can form a complex with the plated metal ion: the use of the above-mentioned reducing agent to form a complex with the ore-coated metal ion In the case where metal ions other than the ore-coated metal ions are not contained, == the electrical properties on the semiconductor substrate are deteriorated by metal impurities such as the above-mentioned alkali metal, so that good plating can be performed. = (4) In the electroless plating of the wire (4), it is preferable to further contain a buffering agent and a metal ion in addition to the above. / or can be co-deposited with the plated metal, the agent has the effect of making the electroless plating solution stable in the pH of the crucible, and as long as it is a buffer of all ions other than the metal ion without the metal ion It is particularly limited, but specifically, acid, carbonic acid, etc., and particularly acid scavenging is preferred. This shrub and squash can also be used in combination. Furthermore, % w糸 can be used alone as an amino acid such as acid (i.e., Bicine), an amine group such as N-parameter or bis(2-hydroxyethyl)glycine, and a copper ion-shaped A Ψ The compound of the group ff- 3 -aminopropyl x complex is not suitable as a buffer because 319613 15 200825207 t has a function of eluting copper wiring. In addition, since the above-mentioned buffering agent is used without using metal ions other than the plated metal ions, the electrical properties on the semiconductor substrate are not deteriorated by the metal impurities such as the above-described metal, so that it can be performed well. Plating. The metal ion which is co-evolved with the plated metal may be, for example, a tungsten ion or a molybdenum ion chain ion, and particularly a crane ion. These metal ions may be used singly or in combination of two or more. The source of the tungsten ion is, for example, a tungsten compound such as tungsten monoxide, tungstic acid, phosphotungstic acid or lanthanum tungstic acid. These crane compounds may be used singly or in combination of two or more. In addition, the source of the molybdenum ion is, for example, a ruthenium compound such as molybdenum trioxide, molybdic acid, phosphomolybdic acid or ruthenium. The platinum compounds may be used singly or in combination of two or more. Further, the source of the chain ion is, for example, a ruthenium compound such as antimony trioxide, and the compound (10) may be used singly or in an appropriate manner. Due to the use of the above-mentioned metal ions which can be co-deposited with the ore-coated metal, for example, cobalt and tungsten, nickel and tungsten, cobalt and molybdenum, nickel and molybdenum, cobalt and yttrium, nickel and chain, etc. The metal of the eutectoid, or a metal protective film (plating film) composed of a metal which can be co-deposited with the ore-coated metal, serves as a protective film for the copper wiring, thereby improving the reliability of the wiring.

The composition for electroless plating of the present invention is usually a solution in which water or the like is used. The pH of the PH system is usually 7 to 11 in order to ensure a certain degree of plating speed, and is usually 8 to 1 〇. It is better to make the mirror speed reach the desired value. In the composition for electroless plating of the present invention, the chemical substance S represented by the above formula (1) is added to a solvent such as water when the plating composition is dissolved, and 319613 16 200825207 t is added thereto to form a solution. The pH in the middle becomes the above pH. Therefore, the amount of use varies depending on the concentration of the coexisting substances. The plating metal ion concentration in the composition for electroless plating of the present invention is such that when the plating composition is dissolved in a solvent such as water, the concentration of the metal ion in the solution is usually 0.001 to lm〇l/ L, and preferably 〇Gog to 0.5 inol/L is preferably from 0.01 to 〇.2 niol/L. The concentration of the reducing agent in the composition for electroless plating of the present invention is such that when the plating composition is dissolved in a solvent such as water, the concentration of the reducing agent in the solution is usually 0.001 to 1 mol/L, and 0.005. It is preferable to use 0 · 01 to 0 · 1 mo 1 / L to 0 5 m 〇 1//L. The concentration of the compound which can form a complex with the plated metal ion in the composition for electroless plating of the present invention, and the plating composition can be combined with the plated metal when the plating composition is dissolved in a solvent such as water The concentration of the compound in which the ion forms a complex compound is usually 〇·01 to 2 mol/L, and preferably 〇·02 to preferably 〇·05 to 〇·5 mol/L. The concentration of the buffer in the composition for electroless plating of the present invention is such that when the plating composition is dissolved in a solvent such as water, the concentration of the buffer in the solution is usually 〇·01 to 2 m〇i. /L, rain is better than 02 to imol/L, and 〇· 05 to 〇·5m〇i/L is preferred. The concentration of the ionic ions in the composition for electroless plating of the present invention which can be co-deposited with the plated metal is such that the composition for dissolving the composition of the mirror is dissolved in a solvent such as water in the 'liquid and plating The concentration of the metal ion coprecipitated metal ion is usually from 0.001 to 1 mol/L, and preferably from 005 to mol·5 mol/L, and preferably from 〇1 to 0.2 mol/L. 319613 17 200825207 In addition to the above-mentioned basic components, the composition for electroless plating of the present invention can be appropriately added as long as it does not impair the effects of the present invention: metal ions other than plated metal ions are not contained. Additives such as plating solution stabilizer, plating accelerator, plating inhibitor, plating smoothing agent, and plating brightener. The plating solution stabilizer may, for example, be thiourea or 2-sulfur-2, 4-anthracene.疋一_(2- let 1〇-2,4-1;111&amp;2〇11(11116(^〇116), 2,2,-biacetidine, 3-iodo-4-hydroxyphenylalanine, etc. Further, the plating accelerator may, for example, be bis(3-stone propyl) disulfide (bis(3 - suifopr〇pyi) disumde), and the plating inhibitor may, for example, be polyethylene glycol. Further, the polyethylene glycol-sintered oxide, etc. Further, the plating smoothing agent may, for example, be gasified 3-diethylaminobis-(4-dimethylaminophenylazo)-5-phenylmorphine Salt (phenaziniuni) = I Further, the plating brightening agent may, for example, be bismuth sulfonate quinone iodide, benzene 〜1, 2-butyne-1,4-diol, etc. Further, the above plating Each of the additives such as the liquid stabilizer may have a single action or a plurality of functions. However, in the respective additives such as the plating stabilizer, it is naturally necessary to select a compound which does not corrode or elute the copper wiring. The plating solution prepared by the composition for electroless plating of the invention, the method for producing the same, and the method for forming the metal protective film (plating film) using the electroless mirror coating composition of the present invention are not particularly limited. As long as it is combined with general electroless metal plating or electroless metal (4), for example, it is necessary to prepare a composition for electroless plating using the helmet of the present invention, which is a kind of electroless plating. , #又/是/谷液', as long as the above-mentioned components - a σ wind knife, combined with the appropriate solvent of the water temple, etc., can be carried out by means of the body, and The plated metal 319613 18 200825207 * ions and can be mixed with the metal ions in the solution to form a complex m, s = b complex pure water, the whole pH, and finally add the reducing agent to adjust the compound In the case of reduction, it is less likely to be precipitated out of the liquid, so it is preferably coated with metal ions. In addition, for example, in the formation of an electroless metal protective film using the present invention (plating film "liquid fox 2 hanging from 40 to (10) c, especially in the case of 5 〇 to ah. ► When forming a composition (4) of the electroless (4) composition film, it is preferred to dissolve the invention: electricity =: _ matter 嶋The ρ Η is appropriately adjusted so that the shovel Iff 5 〇 nm / W is particularly preferably 2 to 1 〇 (10) / is considered to be. The solution temperature and the plating speed of the composition are set to two: = value ', and the film thickness of the metal protective film (plating film) can be easily controlled to the desired film thickness. The ideal film thickness of the metal protective film (plating) applied on the gold-like surface of the high-density integrated circuit is 1 to 5 〇 nm, and preferably 3 to 2 〇 nm. An ideal means for forming a metal protective film (plating film) on the surface of a metal wiring of a high-density integrated circuit formed on a semiconductor substrate by using the composition for electroless-green clock coating of the present invention is 0. The substrate to be formed in the method for forming a metal protective film is formed by providing a fine groove on the surface thereof, and embedding metal copper or a copper alloy in the groove to form a wiring of the high-density integrated circuit (4) wafer Etc. 319613 19 200825207 ^ Semiconductor substrate, etc. • The conductor substrate may have, for example, a groove having a width of 〇·03 to 〇·1/ζπ′ and a clothing degree of about 2 to 2 μm (a groove having an aspect ratio of about 2 to 20). When a copper wiring is formed on the semiconductor substrate, it is in a trench as described above, and is subjected to thermal spraying or chemical vapor deposition (Chemical Vapor).

Depn: CVD) or the like forms a barrier layer selected from titanium, titanium nitride, a group, a nitrided group, etc., and then forms a copper seed crystal as a power supply layer for electrolytic plating by such means. )Floor. Then, metal plating such as copper is applied to the substrate, and a metal is buried in the trench of the semiconductor substrate, and then the metal deposited on the insulating film is removed by (10) or the like, and the metal layer such as copper in the trench is buried. The surface and the surface of the insulating film are substantially uniform in plane. Thereby, a wiring layer composed of a barrier layer, a copper seed layer, and a metal layer such as copper is formed on the semiconductor substrate. Here, the semiconductor substrate in which the copper wiring layer composed of the copper seed layer and the metal tantalum layer such as copper is formed by the above-described means is obtained by dissolving the electroless plating composition of the present invention in a solvent such as water. In the solution, a metal protective film (plating film) can be formed on the surface of the copper wiring by immersing for 1 to 5 minutes at a predetermined temperature as described above and performing electroless mineral coating. (Examples) Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited by the examples. Further, % in the following examples is a weight basis (w/w%) unless otherwise specified. The substrate sample for evaluation is used on a wafer having a side length of 25 sides to form a 319613 20 200825207 thickness of 5 5 0 legs of an insulating layer composed of a dioxide dioxide, and a button having a thickness of 25 nm formed thereon. The barrier layer, a copper substrate on which a copper layer having a thickness of 25 faces is further formed, and the surface of the substrate is further polished by CMp to be planarized. The substrate sample for evaluation was immersed in 2 〇〇 mL of a 3% citric acid aqueous solution which was bubbled with nitrogen gas at room temperature, and then the resulting metal residue or the like was removed by CMP, followed by immersion in 6 〇. The pure water of C was subjected to rinsing for 30 seconds, and a substrate sample for evaluation which had been subjected to pretreatment was prepared. (Reference Example 1) Uniformity test of the surface of the copper layer using 2-dimethylaminoethanol as the compound represented by the general formula (1) The substrate sample for evaluation which has been subjected to the above pretreatment was impregnated at 60 &lt; t The aqueous solution of the following composition (A) was allowed to stand for 3 minutes. Composition (A): citric acid monohydrate 〇·16 mol/L bismuth citrate·16 mol/L 2 dimethylaminoethanol (to add the pH of the aqueous solution to 9.2) pH 9, 2 immersion After the treatment, the substrate sample was rinsed with pure water for 2 sec seconds, and the atomic force microscope, --- ^ w JL , 疋 was used to make the side of the substrate sample 10 Å long. Surface roughness inside. : 疋,, and results are shown in the table. Furthermore, the so-called surface roughness is based on the average roughness (Ra). (Examples 2 to 5) Using the predetermined compound shown in Table 1 as the uniformity test of the surface of the copper layer of the compound shown in Fig. 5 319613 21 200825207 (1), in Reference Examples 2 to 5, except for use κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ κ The compound was adjusted to a pH of 92, and the substrate sample was subjected to impregnation treatment in the same manner as in Reference Example 1 and rinsed, and dried, and the surface roughness was measured for the substrate sample. The measurement results are as shown in the table (Comparative Example υ The use of ammonia instead of the uniformity of the surface of the copper layer of the compound represented by the general formula (1) was tested in Comparative Example 1, except that ammonia was used instead of the composition of Reference Example 1 (Α) = 2-dimethylaminoethanol, and adjusting ρ 成 to 9.2, the substrate sample was subjected to impregnation treatment and rinsing, dry red, and the surface roughness of the substrate sample was measured in the same manner as in Test Example 1. The results of the measurement are shown in Table 1. (Comparative Example 2) The copper layer of the compound represented by the formula (1) was replaced with a 1-stage amine - the uniformity test of the surface 9 In Comparative Example 2, except that the amine of the first order was used. 3-Amino-1-propanol 2 is 2-dimethylaminoethanol in the composition of the test sample 1 (Α), and the pH is adjusted to be 9.2 except that the method is the same as in Reference Example 1. After the substrate sample was processed, rinsed, and dried, the surface roughness was measured for the substrate sample. The measurement results are shown in the table. (Compared to the rutting examples 3 to 4), the second-order amine was used instead of the general formula. (1) Uniformity test of the copper layer surface of the compound shown in Comparative Examples 3 and 4, except that the use as specified in Table 1 was used. 2 22 319613 200825207, the anti-amine oxime in the composition _ i of the composition (A) 2 - dimethylaminoethanol, and: pH: weekly production of 9.2, according to the same method as the reference example After the substrate = product processing, rinsing, and drying, the surface roughness of the substrate sample was measured. The measurement results are shown in Table 1. [Table 1]

As shown in the results of Table 1, when the substrate sample was immersed in the aqueous solution of the compound represented by the general formula (1) in Reference Examples J to 5^3, the value of the surface roughness before the impregnation, and the dip The change in the surface roughness after the collapse treatment was hardly observed, so that it was considered that the etching or the elution of the surface of the copper layer was hardly caused even by the impregnation treatment. On the other hand, when the substrate sample was immersed in the aqueous solution containing ammonia, grading or quaternary amine of Comparative Example 丨 to 4, the surface was red after the immersion treatment before the immersion treatment. The value of I degree is larger, so it is considered that the surface of the copper layer is corroded or eluted by the impregnation treatment. Therefore, it is understood that the compound of 319613 23 200825207 represented by the formula (1) in the amine is used for the impregnation treatment to prevent corrosion or dissolution of the surface of the copper layer. By modulating the electroless plating solution, it is possible to prevent the corrosion of the surface of the layer from being dissolved, and to perform good plating. (Example 1) Test for uniformity of the surface of the metal protective film of the composition for electroless (4) of the present invention (1) The substrate sample for evaluation which is known to be subjected to the above treatment is impregnated into 6 〇 which has the following composition (水溶液) The aqueous solution of the electroless mineral coating composition of the present invention shown in Fig. 3 was electrolessly plated for 3 minutes. Composition (Β): Sulfuric acid heptahydrate Tungstic acid Dimethylamine borane Citric acid monohydrate Boric acid 2-Diamylaminoethanol

之. 02摩尔/L 〇. 024mol / L 〇 · 05mol / L 〇 · 16mol / L 0. 16mol / L appropriate amount (so that the pH of the aqueous solution becomes 9. 2

Method of adding) ρΗ 9· 2 After electroless plating treatment, the substrate sample was rinsed with pure water for 2 sec seconds and dried with nitrogen. Next, the surface roughness in the plane of the single side length of 10/zm of the substrate sample was measured using an atomic force microscope. The measurement results are shown in Table 2. (Sections 2 to 5) The uniformity test (2) to (5) of the surface of the metal protective film using the electroless plating ruthenium composition of the present invention, in Examples 2 to 5, except that the use is as shown in Table 2 The predetermined compound shown is 24 319613 200825207 = the compound of 2-aminoethanol in the composition (8) of Example 1 is used as the compound of y 1), and the pH is adjusted to 9·2 α. The substrate sample was subjected to an electroless plating treatment in the same manner as in Example 1, and the substrate sample was measured for surface degree. The measurement results are shown in Table 2. ^匕车乂例5) The uniformity test of the surface of the metal prism film which replaces the compound of the formula (1) by ammonia production is compared with the composition of the vehicle example 5 except that ammonia is used instead of the embodiment (8): 2, 2 In addition to the pH adjustment to pH 2, the substrate sample was subjected to electroless ore treatment and punched and dried according to the method of Example 1 and k: M4 _ Determination of surface roughness of the substrate sample . The measurement results are shown in Table 2. (Sakisaki 6) The uniformity test of the surface of the metal ruthenium film using a hydrazine amine in place of the compound of the formula (1) was tested in Comparative Example 6 except that the 3-amino group + propanol group Z of the first-grade amine was used. In the same manner as in the example, the substrate sample was subjected to electroless plating treatment, rinsed, and dried, and then the substrate sample was determined. Surface roughness. The measurement results are shown in Table 2. (Comparative Examples 7 to 8) The uniformity test of the surface of the metal protective film using a 2-stage amine in place of the compound of the formula (1) was tested in Comparative Examples 7 and 8, except that a predetermined second-order amine as shown in Table 2 was used instead. In the embodiment! In the same manner as in Example 丨, the sample of 319613 25 200825207 was subjected to electroless plating treatment, rinsed, and dried, in the same manner as in Example 丨, except that 2-dimethylaminoethanol in the composition (8) was adjusted to 9.2. The substrate sample was measured for surface roughness. The measurement results are shown in Table 2. [Table 2]

From the results of Table 2, when using the present invention as shown in Examples i to 5, the composition for electrolytic plating was subjected to a recording alloy ring on the surface of the copper layer 7' because of electroless plating. The value of the surface roughness before the coating treatment and the value of the surface roughness of the surface after the treatment without electricity = almost no change can be observed: / / = alloy handle W coating 'and metal protective film (plating film) : The composition of electrolytic plating for the second time is applied to the surface of the copper layer "after the alloy; before the electroless plating treatment, the electroless plating is larger, and the method is obtained in a series - because No electricity: = at: when compared with the second example: slope 'see, this result T u such Jk class and make the copper layer 319613 26 200825207 t = face or dissolution and become rough, so the metal protective film (clock film) is not As a result of the flattening, the semiconductor piercing of the surface of the metal wiring such as copper formed on the semiconductor substrate by the electroless-ion-coated composition of the present invention is formed, and the film can be expected to be in shape. The layering ingredients make the reliability significantly improved. (Industrial use possibility) It is the residue or dissolution base of the wiring. A gold protective film such as steel formed on the board. A flat metal can be formed on the surface. 319613 27

Claims (2)

200825207, the scope of application for patents: : Two electroless mineral coating composition 'containing: a metal ion, a compound which can form a complex with a plated metal ion, and a compound NR^ represented by the formula (1) OH R2 (1) ^In the main mode, 'R1 and R2 are independent of carbon number! To 3 = 2 valences with a carbon number of oxygen atoms (1) 2. 2. The composition of the item i of the patent range, which contains a buffer or a metal ion which is co-evolved with the plated metal. 3. St. The composition of the first aspect of the invention, wherein the plating metal is a cobalt ion or a nickel ion. 4. = The composition of the item i of the patent application scope, wherein the aforementioned ore-coated metal _ sub-type ionic ion. 5. The composition of claim i, wherein the reducing agent is decanoic acid, dimercaptoamine, diethylamine, tridecylamine, hydrazine, barium sulfate, At least two selected from the group consisting of guanidine hydrochloride and cesium carbonate. The composition of claim 1, wherein the compound capable of forming a complex with the plated metal ion is at least one selected from the group consisting of malonic acid, lactic acid, tartaric acid, citric acid, and malic acid. 7. The composition of claim 1, wherein the compound of the above formula (1) is from 2-dimethylaminoethanol, 3-dimethylamino-1-propanol, 1-di At least one selected from the group consisting of allysyl-.2-propanol, 4-dimethylamino-1-butanol, and 2-[2-(dimethylamino)ethoxy]ethanol. 28 319613 200825207, 8. The composition of claim 2, wherein boric acid. For example, the composition of the second paragraph of the patent application scope, wherein, the person w (7) current month &amp; fish office # metal eutectoid metal ion system from tungsten ion, molybdenum ion and at least one of two . Selection of spider carvings 10. For example, the composition of the scope of patent application i, of which. p«系7至i! 11. The composition of claim i, wherein the plating ion (four) or the nickel ion is from the second. Base amine, diethylamine (tetra), tri-f-amine, hydrazine, acid: at least selected from guanidine hydrochloride and money !! The compound which can form a complex with the cardinic ion is at least one selected from the group consisting of bismuth malonate citrate and malic acid; the former compound is derived from 2-diaminoethanol, 3//1 - dimethylamino-2-propanol, 4-methylamine A, butylated methyl + propanol, ^ 4 monomethylamino-1-butanol and 2-"2-anthracene-methylamino) At least one selected from the group consisting of oxy]ethanol. 12. If you apply for the scope of the patent item u / 忒 魅 ☆ ☆ ☆ you set at least one of the selected from boric acid and / or crane, molybdenum and chain ions 13. A method for forming a metal film, the composition of the basin i. Ί 心 心 专利 专利 14 14 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如For the use of the composition: the temperature is 4G to just c. The implementation of the method according to the 13th paragraph of the Shenqing patent scope, the formation of ancient, soil ^, , Λ 之 , , , , , , The method is carried out in such a manner that the speed becomes 1 to 50 nm/min. 319613 29 200825207 ? 16. The method for forming the metal article according to claim 13 is to make the film thickness of the metal protective film 1 Implemented in the form of 50nm. 30 319613 200825207 ~ VII. Designated representative map·· None (1) The representative representative figure of this case is: (). (2) The symbol of the symbol of this representative figure is simple: 8. If there is a chemical formula in this case Please reveal the chemical formula that best shows the characteristics of the invention: R1 N - R3 - OH (1) / R2 5 319613