Metal coating composition containing suppressing agent for void-free filling of submicron surface elements

FIELD: chemistry.

SUBSTANCE: invention relates to electroplating and can be used in producing semiconductors. The composition contains at least one copper source and at least one additive, obtained by reacting a polyatomic alcohol containing at least 5 hydroxyl functional groups with at least a first alkylene oxide and a second alkylene oxide from a mixture of a first alkylene oxide and a second alkylene oxide. The method includes contacting the metal coating composition with a substrate, generating current density in the substrate during a time period sufficient to deposit a metal layer on the substrate.

EFFECT: filling nanometre and micrometre openings without voids and seams.

15 cl, 1 tbl, 7 dwg, 8 ex

 

Fill small surface elements, such as through holes and grooves, by means of electrolytic deposition of copper is an essential part of the manufacturing process of semiconductors. It is well known that the presence of organic substances as additives in an electrolytic bath may play a key role in achieving uniform deposition of metal on the surface of the substrate and in the exclusion of defects, such as voids and seams, inside the copper plating lines.

One class of additives are the so-called surge or immunosuppressive agents. Suppressors are used to provide essentially the rising filling of small surface elements, such as through holes or grooves. The smaller the surface elements, the more advanced should be additive to eliminate voids and seams. A large variety of inhibitory compounds has already been described in the literature. The most widely used class of suppressors are simple polyester compounds such as polyglycols or polyalkylene, such as ethylenebisacrylamide copolymers.

Such polyethers are obtained by reaction of the alcohol used as the starting material containing one or more hydroxyl groups, such as glycol or glycerol, with polyalkyleneglycol.

In the US 2002/0043468 RA is kryvutsa suppressing agents, containing a functional group containing oxygen or nitrogen, localized in the branching of the main chain of the polymer. In General, branched suppressing agents have a molecular weight in the range of about 10,000 or more.

In the US 2004/0217009 A1 as suppressing agents disclosed random polyalkylbenzene copolymers, which may be linear or star-shaped.

In the US 6776893 B1 disclosed immunosuppressive agents selected from block copolymers of polyoxyethylene and polyoxypropylene, polyoxyethylene or polyoxypropylene derivative of a polyhydric alcohol and a mixed polyoxyethylene and polyoxypropylene derivative of a polyhydric alcohol. Examples of polyhydric alcohols are sorbitol, glycerol and mannitol, preferably glycerin. One class of such inhibitory agents contains mixed alkoxygroup, as for example, block copolymers of polyethylene oxide and polypropyleneoxide.

Subsequent reduction of the size of the hole surface features, such as apertures or grooves, to sizes less than 100 nanometers, and even less than 50 nanometers, respectively, filling the interconnect copper is particularly difficult, and also the deposition of the seed layer of copper prior to the electrolytic deposition of copper may not be uniformity and conformity and such about what atom, stronger to reduce the size of the holes, especially on the top holes. Especially difficult to fill holes are serving with the seed particle at the top of the hole or holes of a convex shape, and in this case, require a particularly effective suppression of the growth of copper on the side of the element surface and at the entrance to the hole.

In Fig.3 shows the substrate covered by the seed layer, which is characterized by the influence of seed particles on the inlet surface elements that need to be filled. The seed layer is shown with a layer of light-gray to dark-gray structures. As characterized by the increase in the protrusion of the seed particles with a further decrease in the size of the surface elements, as shown in Fig.3, there is a serious risk of the formation of closed cavities in the upper half of the groove is closer to the inlet, if the suppressor is not completely eliminated the growth of copper on the side wall (2" in Fig.2A-2C). As can be seen, the inlet is reduced to less than half the width without reaching the seed layer effective hole sizes from about 18 nm to 16 nm, respectively. The element of surface is covered by the seed layer has a convex shape.

Therefore, the aim of the present invention is to provide additives for electrolytic what about the deposition of copper, having a good suppressive properties, in particular suppressing agents capable of filling elements of the surface of nanometer and micrometer scale essentially without voids and without joints, with the use of an electrolytic bath for the deposition of metal, preferably an electrolytic bath for the deposition of copper. The next objective of the present invention is to provide additives for electrolytic deposition of copper capable of filling elements of the surface of a convex shape on the merits without voids and without seams.

It has been unexpectedly discovered that the use of polyoxyalkylene polisport having the structure of a random copolymer, and a specific triblock copolymers as additives shows extraordinary properties superpipeline, especially if used to fill surface, having a very small hole sizes and/or high coefficients of proportionality. The present invention provides a new class of highly effective strong suppressive agents, which are able to cope with the bulges of the seed particles and provide for the filling of the grooves is essentially free of defects, despite conformly seed layer of copper.

For this reason, the present invention provides a composition comprising by at least one source of metal ions and at least one polyoxyalkylene polyhydric alcohol, having at least 5 hydroxyl groups. At least one inhibitory agent obtained by the reaction of a polyhydric alcohol containing at least 5 hydroxyl functional groups, with at least the first alkalisation and second alkalisation of a mixture of the first accelerated and second accelerated. Thus is formed a polyhydric alcohol containing a random copolymer of polyoxyalkylene in side chains.

In addition, the present invention provides a composition comprising at least one source of metal ions and at least one additive obtained by the reaction of a polyhydric alcohol containing at least 5 hydroxyl functional groups, with the third alkalization, the second alkalization and the first alkalisation in the specified sequence, and the third accelerated has a longer alkyl chain than the second accelerated, and the second accelerated has a longer alkyl chain than the first accelerated. Thus is formed polyhydric alcohol containing (at least partially) triblock-copolymer polyoxyalkylene in side chains.

The advantage of the additives of the present invention is their overwhelming ability, which leads to a very pronounced increase of copper in the direction of the ascending filled the I, while the growth of copper on the side walls perfectly suppressed, and that, and the other leads to planar front growth, thus ensuring the filling of the grooves and through holes essentially free of defects. The strong suppression of the growth of copper on the side walls in accordance with the present invention enables besposchadnogo filling elements of the surface covered nekonformnyi bare copper layer. Moreover, the present invention provides in General a homogeneous upward filling the neighboring elements of the surface areas densely populated with surface elements.

Suppressing agents according to the present invention are particularly suitable for filling small surface elements, especially with the hole size of 30 nanometers or less.

Supplements in General, are obtained by the reaction of a polyhydric alcohol (also referred to as polisport), containing at least 5 hydroxyl groups, with acceleratedly or of a mixture or in sequence. Thus the hydroxyl group polisport aeriferous education polyoxyalkylene side chains.

In a preferred composition suitable polyalcohol meet the formula (I)

,

where

m is an integer from 5 to 10, preferably from 5 to 6,

X represents the FDS is th m-valent linear or branched aliphatic or cycloaliphatic radical, having 5 to 10 carbon atoms which may be substituted or unsubstituted.

Preferably polysperma is a linear alcohol, give the oxidation of the monosaccharide represented by the formula (II)

,

where n is an integer from 3 to 8.

Examples of appropriate alcohols(II) give the oxidation of the monosaccharide include sorbitol, mannitol, xylitol, ribitol, and their stereoisomers and the like. Particularly preferred alcohol (II), which upon oxidation of the monosaccharide is sorbitol.

Especially preferably polysperma is a cyclic alcohol, give the oxidation of the monosaccharide represented by the formula (III)

,

where o is an integer from 5 to 10.

Examples of appropriate alcohols (III) give the oxidation of the monosaccharide contain Inositol (cyclohexanehexol).

In another composition suitable polyalcohol are monosaccharides and their stereoisomers. The preferred monosaccharide is an aldose monosaccharides of formula (IV)

,

where p is an integer from 4 to 5.

Examples of relevant monosaccharides of aldos (IV) are allose, altrose, galactose, glucose, gulose, idose, mannose, talose, glucoheptonate, mannoheptose and the like. Especially preferred is sustained fashion monosaccharide by alidosi (IV) is glucose.

Especially preferred monosaccharides are the simple sugars ketosis (V)

,

where q and r are integers, and q + r is 3 or 4.

Examples of relevant monosaccharides ketosis (V) are fructose, psicose, sorbose, tagatose, mannoheptulose, sedoheptulose, talegators, alligators and the like. Especially preferred monosaccharide by kyosai (V) is fructose and its derivatives.

In one embodiment, the present invention suitable polyalcohol is selected from disaccharides. Especially preferred disaccharides are sucrose and maltose, and their derivatives.

The additive according to the present invention, in addition, also referred to as polyalkoxysiloxanes a polyalcohol, represent specific products of the reaction of a polyalcohol and alkalisation. Polyalkoxysiloxanes the polyalcohol can be obtained by reaction of Oh groups present in polierte, acceleratedly with the formation of simple terminal polyether groups containing the appropriate oxyalkylene units. Polyalkoxysiloxanes the polyalcohol themselves known in this technical field.

In General, suitable acceleratedly can be C2-C12-alkalinity or stereocity, without restrictions. Examples of appropriate accelerated is to contain ethylene oxide and propylene oxide, 1-buttocked, 2,3-buttocked, 2-methyl-1,2-probenecid (isobutoxide), 1-pentoxide, 2,3-pantanacce, 2-methyl-1,2-buttocked, 3-methyl-1,2-buttocked, 2,3-hexenoic, 3,4-hexenoic, 2-methyl-1,2-pantanacce, 2-ethyl-1,2-buttocked, 3-methyl-1,2-pantanacce, detoxed, 4-methyl-1,2-pentoxide or stimulated.

It is preferable to use accelerated (alkalisation), selected from ethylene oxide, propylene oxide and butilenica or combinations thereof. Preferably, the content of ethylene oxide in the copolymer of ethylene oxide and another accelerated (alkalisation) is from 10 to 90 wt.%, more preferably from 20 to 50 wt.%, most preferably 25 to 40 wt.%.

Preferably the first alkalisation is ethylene oxide, and the second accelerated is selected from propylene oxide and butilenica or combinations thereof. Most preferably the second alkalization is propylene oxide.

Preferably the additive is a random copolymer of ethylene oxide and propylene oxide.

Preferably, in General, apply the highest alkalinity most often in small quantities for fine regulation properties. In General, the number of ethylene oxide and/or propylene oxide, and/or butilenica is at least 80 wt.%, preferably at least 90 wt.%, most predpochtitel is about 100 wt.% the sum of all applied alkalisation.

In the case of the block copolymer third alkalization preferably is butylenes.

Preferably the third accelerated is present in an amount of from 0.1 wt.% up to 10 wt.%, preferably from 0.5 wt.% to 5.0 wt.%.

More preferably accelerated is selected from mixtures of ethylene oxide and propylene oxide. The preferred mass ratio oxyethylene and oxypropylene links in the final product ranges from 10:90 to 90:10, more preferably from 20:80 to 50:50, most preferably from 25:75 to 40:60.

Preferably the molecular weight Mw polyalkoxysiloxanes polyalcohol is from 500 to 30,000 g/mol, more preferably from 1000 to 20000 g/mol, more preferably from 2,000 to 15,000 g/mol and even more preferably from 3000 to 10000 g/mol. Most preferred is a molecular weight of from 4000 to 8000 g/mol.

Medium polyoxyalkylene is from about 10 to about 500, preferably from about 30 to about 400, more preferably from about 50 to about 300, most preferably from about 60 to about 200 alkalinising units on the source substance polisport.

Synthesis of polyoxyalkylene well-known specialists in this field of technology. Detailed description is given, for example, in "Polyoxyalkylenes" in Ullmann''s Encyclopedia of Industrial Chemistry, 6thEdition, Electronic Release.

Preferred is about westline polyoxyalkylene in the presence of standard basic catalysts, for example, hydroxides of alkali metals, preferably potassium hydroxide or alkoxides of alkali metals such as sodium methoxide or trebuchet potassium. Polyalkoxysiloxanes can be carried out in principle in a known manner in the reactor high pressure at a temperature of from 40 to 250°C, preferably from 80 to 200°C and most preferably from 100 to 150°C. When the melting point of polisport higher than the reaction temperature, polisport suspendered in an inert solvent before reaction polyalkoxysiloxanes. Suitable solvents are toluene, xylene, simple polyester and N,N-dimethylformamide.

Polyalkoxysiloxanes the polyalcohol can be functionalized at the next stage of the reaction. Additional functionalization can serve the purposes of modifying the properties polyalkoxysiloxanes polyalcohol. The terminal hydroxyl group alkoxysilane polyalcohol can react with suitable reagents for the functionalization, which are formed group of General formula -(alkoxy)s-Z, where Z is any desired group and s is an integer from 1 to 200. In accordance with functionalities agent the end of the chain may be repelling agent or much more hydrophilization.

The terminal hydroxyl groups can be these inficirovanyh with the formation of esters, for example, under the action of sulphuric acid or its derivatives with the formation of so products with a terminal sulfate groups (sulfation). Similarly, products having a terminal phosphate group, can be obtained by using phosphoric acid, phosphorous acid, polyphosphoric acid, l3or R4O10(phosphatase).

In addition, the terminal Oh groups can also be tarifitsirovana with the formation of such polyalkoxy with simple ether at the end of the General formula -(alkoxy)s-Z, where Z represents alkyl, alkenyl, quinil, alkaryl or aryl group, and s represents an integer from 1 to 200. Preferably Z represents methyl, ethyl, benzyl, acetyl or benzoyl.

The following embodiment of the present invention is the use of an electrolytic bath for the deposition of metal coatings containing composition as described above for the deposition of metal on substrates containing surface elements having a hole size of 30 nanometers or less.

The next object of the present invention is the method of deposition of a metal layer on a substrate, via:

a) contact the electrolytic bath for the deposition of metal coatings containing composition of the present invention, with the substrate, and

b) in order to create current density in the substrate during a period of time, sufficient for the deposition of the metal layer on a substrate.

Preferably, the substrate contains elements of the surface of submicron size, and deposition is carried out with the filling elements of the surface submicron size. Most preferably the surface elements of submicron size are (effective) hole size from 1 to 30 nanometers and/or aspect ratio of 4 or more. More preferably, the surface elements have a hole size of 25 nanometers or less, most preferably 20 nanometers or less.

The size of the opening means according to the present invention, the smallest diameter or gap element surface prior to the electrolytic deposition of the coating, that is, after deposition of the seed layer of copper. The terms "hole" and "inlet" are used herein as synonyms. The convex shape are characteristic of the element surface, with the size of the hole, which is at least 25%, preferably 30%, more preferably 50% less than the large diameter or gap element surface prior to the electrolytic deposition of the coating.

Electrolytic bath for coating according to the present invention, particularly suitable for surface elements having a high coefficient proparts is valinoti - 4 or more 6 or more.

A wide variety of electrolytic baths for the deposition of the metallic coating can be applied according to the present invention. The electrolytic bath for the deposition of metal coatings contain a source of metal ions, an electrolyte and a polymer inhibitory agent.

The source of metal ions may be any compound capable of releasing metal ions, which shall be deposited in the electrolytic bath in sufficient quantity, i.e. a connection which is at least partially soluble in the electrolytic bath. Preferably, the source of metal ions was soluble in the electrolytic bath. Suitable sources of metal ions are metal salts and include, but without limiting to this, the sulfates of metals, halides of metals, acetates, metals, nitrates metals, perborate metals, metal alkyl sulphonates, arylsulfonate metals, sulfamate metals, gluconate metals and the like. Preferably the metal is copper. In addition, the source of metal ions is preferably copper sulfate, copper chloride, copper acetate, copper citrate, copper nitrate, perborate copper methanesulfonate, copper, vinylsulfonate copper and p-toluensulfonate copper. The sulfate pentahydrate m the di and methanesulfonate copper are particularly preferred. Such metal salts, in General, are commercially available and can be used without further purification.

In addition to the electrolytic plating composition may be applied by deposition by the method of chemical recovery layer containing metal. The composition can in particular be used in the deposition of barrier layers containing Ni, Co, Mo, W and/or Re. In this case, in addition to the metal ions of the following elements of groups III and V, in particular, P can be present in compositions for the deposition of chemical recovery and, thus, co-deposited with metals.

The source of metal ions may be used in the present invention in any amount which provides sufficient metal ions to the electrolytic deposition on the substrate. Suitable metal sources of metal ions include, but not limited to, salts of tin, copper salt, and the like. When the metal is copper, salt of copper, usually present in an amount of from about 1 to about 300 g/l of electrolytic solution. It should be appreciated that mixtures of metal salts may be subjected to electrolytic deposition according to the present invention. Thus, alloys, such as alloys of copper and tin, with up to about 2 wt.% tin can predpochtitel is but be applied in the form of a coating according to the present invention. The number of each of the metal salts in such mixtures depends on the specific alloy, which will be applied in the form of a coating, and is well known to specialists in this field of technology.

In General, a source of metal ions and at least one suppressing agent according to the present invention a metal electrolytic compositions according to the present invention preferably include an electrolyte, that is acidic or alkaline electrolyte, one or more sources of metal ions, if necessary, halide ions, and optionally other additives, such as accelerators and/or leveling agents. These baths generally are water. Water may be present in a wide range of quantities. Can be applied to any type of water, such as distilled water, deionized water or tap water.

The electrolytic bath of the present invention can be obtained by combining the components in any order. Preferably, first in the receptacle for bath was added inorganic components, such as metal salts, water, electrolyte, and optionally, a source of halide ions, and then was added to the organic components, such as leveling agents, accelerators, immunosuppressive agents, surfactants and the fact of podobn the E.

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

Suitable electrolytes include such as, but not limited to, sulfuric acid, acetic acid, forborne acid, alkylsulfonate acid, such as methanesulfonate acid, econsultancy acid, propanesulfonic acid and triftormetilfullerenov acid, arylsulfonic acid, such as phenylsulfonyl acid and toluensulfonate acid, sulfamic acid, hydrochloric acid, phosphoric acid, tetraalkylammonium hydroxide, preferably of Tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide and the like. Acid usually present in an amount of from about 1 to about 300 g/l, alkaline electrolyte, usually present in an amount of from about 0.1 to about 20 g/l or to achieve a pH from 8 to 13, respectively, and more typically up to pH values from 9 to 12.

Such electrolytes may optionally contain a source of halide ions such as chloride ions as copper chloride or hydrochloric acid. According to the present invention can be applied to a wide range of concentrations halide is ons such as from about 0 to about 500 parts per million. Typically, the concentration of halide ions is in the range from about 10 to about 100 parts per million from the electrolytic bath. The electrolyte is preferably sulfuric acid or methansulfonate acid, and preferably a mixture of sulfuric acid or methanesulfonic acid and a source of chloride ions. Acid and sources of halide ions, useful according to the present invention, in General, commercially available and can be used without further purification.

Preferably the composition also contains at least one accelerating agent and/or at least one leveling agent.

Any accelerators can preferably be used in the electrolytic bathrooms according to the present invention. Accelerators useful in the present invention include, but without limitation to this, compounds containing one or more sulfur atoms and sulfonic/phosphonic acids or their salts.

In General, the preferred accelerators are of the General structure of the MO3X-R21-(S)n-R22where:

M represents hydrogen or alkali metal (preferably Na or K),

- X represents R or S,

- n is 1-6,

- R21is selected from C1-C8 alkyl group or heteroalkyl group, aryl group or courtesans is an aromatic group. Heteroalkyl groups have one or more heteroatoms (N, S, O) and 1-12 carbon atoms. Carbocyclic aryl groups, as a rule, represent aryl groups such as phenyl, naphthyl. Heteroaromatic groups are also suitable aryl groups and contain one or more atoms of N,O or S and 1-3 separate or paired rings,

- R22is selected from N or (-S-R21'XO3M), and R21' is identical to R21or different from it.

More specifically, useful accelerators include accelerators the following formulas:

MO3S-R21-SH

MO3S-R21-S-S-R21'-SO3M

MO3S-Ar-3-S-Ar-SO3M

and R21defined above, and Ar represents an aryl.

Especially preferred precipitating agents are:

- SPS: bis-(3-sulfopropyl)-disulfide disodium salt

MPS: 3-mercapto-1-propanesulfonic acid, sodium salt

Other examples of accelerators, which are used by themselves or in mixtures, include, but without limitation to this: MES (2-mercaptoethanesulfonate acid, sodium salt); DPS (complex 3-sulfopropyl ether N,N-dimethyldithiocarbamic acid, sodium salt); UPS (3-[(aminoiminomethyl)-thio]-1-propylsulfonyl acid); ZPS (3-(2-benzothiazolylthio)-1-propanesulfonic acid, sodium salt); complex 3-sulfaro the silt ester of 3-mercapto-propylsulfonyl acid; methyl-(ω-sulfopropyl)-disulfide, disodium salt; methyl-(ω-sulfopropyl)-trisulfide, disodium salt.

Such accelerators are generally used in amounts of from about 0.1 parts per million to about 3000 parts per million by weight of the total galvanic baths. Particularly suitable amounts of accelerator, useful according to the present invention are from 1 to 500 parts per million and more preferably from 2 to 100 parts per million.

Any additional inhibitory agent may preferably be used in the present invention. Suppressors, useful according to the present invention, include, but not limited to, polymeric materials, particularly those which have a substituent in the form of a heteroatom and particularly preferably a substituent in the form of an oxygen atom. Preferably overwhelming agent is polyalkylated. Suitable immunosuppressive agents include polietilenglikolya copolymers, especially ethylene glycol-polypropylenglycol copolymers. The location of ethylene oxide and propylene oxide in a suitable immunosuppressive agents may be block, alternating, gradient or random. Polyalkyleneglycol can also contain additional acceleratedly building blocks, such as butylenes. Preferably the average molecular weight under Odesa suppressing agents greater than about 2000 g/mol. Original molecules suitable polyalkyleneglycol can be alkyl alcohols, such as methanol, ethanol, propanol, n-butanol and the like, aryl alcohols, such as phenols and bisphenol, alkaline alcohols such as benzyl alcohol, polyol as one of the original substances such as glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, carbohydrates such as sucrose and the like, amines and oligoamine, such as alkylamines followed, arylamines, such as aniline, triethanolamine, Ethylenediamine and the like, amides, lactams, heterocyclic amines, such as imidazole and carboxylic acids. If necessary polyalkyleneglycols suppressing agents can be functionalized with ionic groups such as sulfate, sulfonate, ammonium, and the like.

When using suppressive agents they are, as a rule, are present in amounts in the range of from about 1 to about 10,000 parts per million by weight of the bath, and preferably from about 5 to about 10,000 parts per million.

Leveling agents may preferably be used in bathrooms for the electrolytic deposition of metallic coatings according to the present invention. The terms "leveling agent" and "equalizer" used in the present invention as synonyms.

Suitable leveling agents include, but without limitation to this, one or the more of polyethylenimine and their derivatives, the stereoselectivity polyethylenimine, polyglycine, poly(allylamine), polyaniline, a polyurea, a polyacrylamide, a copolymer of melamine and formaldehyde reaction products of amines with epichlorohydrin, reaction products of an amine, epichlorohydrin and polyalkylated, reaction products of an amine with polyepoxides, polyvinylpyridine, polyvinylimidazole, polyvinylpyrrolidone or copolymers, nigrosine, pentamethylpiperidine hydrogenogenic, hexamethylpropylene hydrogenogenic, trialkanolamines and their derivatives or compounds containing the functional group of the formula N-R-S, where R is a substituted alkyl, unsubstituted alkyl, substituted aryl or unsubstituted aryl. Typically, the alkyl groups are (C1-C6)alkyl, preferably (C1-C4)alkyl. In General, the aryl group include C6-C20)aryl, preferably (C6-C10)aryl. Such aryl groups can also include heteroatoms, such as sulfur, nitrogen and oxygen. Preferred aryl groups are phenyl or naphthyl. Compounds containing the functional group of the formula N-R-S, in General, well known and generally commercially available and may be used without further purification.

In such compounds containing N-R-S functional group, a sulfur atom ("S") and/or nitrogen atom ("N") can be attached to these compounds through single or d is oinoi communication. When sulfur is attached to these compounds is a single bond, sulfur will have another Deputy, such as, but not limited to, hydrogen, (C1-C12)alkyl, (C2-C12)alkenyl, (C6-C20)aryl, (C1-C12)alkylthio, (C2-C12)alkanity, (C6-C20)aaltio and the like. Similarly, the nitrogen will have one or more substituents, such as, but not limited to, hydrogen, (C1-C12)alkyl, (C2-C12)alkenyl, (C7-C10)aryl, and the like. Functional group N-R-S can be acyclic or cyclic. Compounds containing cyclic functional group N-R-S include containing either a nitrogen atom or a sulfur atom, or a nitrogen atom and a sulfur atom in the ring system.

The term "substituted alkyl" means that one or more hydrogen atoms of the alkyl group substituted by another Deputy, such as, but without limitation to this, cyano, hydroxy-group, halogen, (C1-C6)alkoxy, (C1-C6)alkylthio, thiol, nitro-group and the like. The term "substituted aryl" means that one or more hydrogen atoms of the aryl ring substituted by one or more substituents, such as, but without limitation to this, cyano, hydroxy-group, halogen, (C1-C6)alkoxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C1-C6)alkylthio, thiol, nitro-group and the like. "Aryl" includes carbocyclic and heterocyclic aromatic systems, such as, but without limitation to this, Anil, naphthyl and the like.

Polyalkylene, alkoxysilane polyalkylene, functionalityand polyalkylene, and functionalityand alkoxysilane polyalkylene are particularly preferred levelling agents in the bath for the electrolytic deposition of copper. Such polyalkylene are described in European patent application No. 08172330.6, which is incorporated herein by reference.

Polyalkylene can be obtained by condensation of at least one dialkanolamine General formula N(R11-OH)3(XIa) and/or at least one dialkanolamine General formula R12-N(R11-OH)2(XIb) to produce polyalkylene (XII) (stage A), where each radical R11independently selected from divalent linear or branched aliphatic hydrocarbon radical having from 2 to 6 carbon atoms and each radical R12independently selected from hydrogen and aliphatic, cycloaliphatic and aromatic hydrocarbon radicals, all of which can be linear or branched, having from 1 to 30 carbon atoms.

Alkanolamine can be used as such or, if necessary, can be alkoxycarbonyl, functionalized with getting alkoxysilane of polyamidoamine (XIII), functionalis the level of polyamidoamine (XIV) or functionalized alkoxysilane of polyamidoamine (XV).

Alkoxysilane polyalkylene (XIII) can be obtained by alkoxysilane of polyamidoamine (XII)2-C12-acceleratedly, storelocator, glycidyl alcohol or simple glycidyloxy esters, provided that the average degree of alkoxysilane is from 0.1 to 200 by an Oh group and, when present, secondary amino group (stage b).

Functionalityand polyalkylene (XIV) can be obtained by functionalization of polyamidoamine (XII) appropriate functionalization reagents which are capable of reaction with hydroxyl groups and/or amino groups (stage C).

Functionalityand alkoxysilane polyalkylene (XV) can be obtained by functionalization alkoxysilanes of polyamidoamine (XIII) suitable functionalization reagents which are capable of reaction with hydroxyl groups and/or amino groups (stage D).

Trialkanolamines (XIa) and/or dialkanolamine (XIb) used in stage (A) have the General formula N(R11-OH)3(XIa) and R12-N(R11-OH)2(XIb).

The radicals R11in each case, independently represent a divalent linear or branched aliphatic hydrocarbon radicals having from 2 to 6 carbon atoms, preferably from 2 to 3 carbon atoms. Examples of such radicals include ethane-1,2-diyl, the EN-1,3-diyl, propane-1,2-diyl, 2-methylpropane-1,2-diyl, 2,2-DIMETHYLPROPANE-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl (=1-methylpropan-1,3-diyl), butane-1,2-diyl, butane-2,3-diyl, 2-methylbutane-1.3-diyl, 3-methylbutane-1,3-diyl (=1,1-DIMETHYLPROPANE-1,3-diyl), pentane-1.4-diyl, pentane-1,5-diyl, pentane-2,5-diyl, 2-methylpentan-2,5-diyl (=1,1-dimethylbutan-1,3-diyl) and hexane-1,6-diyl. Radicals are preferably ethane-1,2-diyl, propane-1,3-diyl or propane-1,2-diyl.

The radical R12represents hydrogen and/or linear or branched aliphatic, cycloaliphatic and/or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms and more preferably from 1 to 10 carbon atoms. The aromatic radicals can of course also be aliphatic substituents. R12preferably represents hydrogen or aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms.

Examples of preferred trialkanolamines (XIa) contain triethanolamine, triisopropanolamine and tribute-2-alamin, special preference is given to triethanolamine.

Examples of preferred dialkanolamines (XIb) contain diethanolamine, N-methyldiethanolamine, N,N-bis(2-hydroxypropyl)-N-methylamine, N,N-bis(2-hydroxybutyl)-N-methylamine, N-isopropylacetanilide, N-n-butyldiethanolamine, N-Deut-butyldiethanolamine, N-cyclohexyl the ethanol, N-benzylethanolamine, N-4-tolualdehyde or N,N-bis(2-hydroxyethyl)aniline. Particular preference is given to diethanolamine.

In addition to trialkanolamines (XIa) and/or dialkanolamines (XIb) when necessary the use of additional components (XIc), which has two hydroxyl and/or amino groups for polycondensation.

Polycondensation components (XIa) or (XIb), and optionally (XIc) can be implemented in different ways, in principle, known to experts in the art, when heated components with removal of water. Suitable methods are disclosed, for example, in HER A. It is obvious that in each case it is also possible to use mixtures of different components (XIa), (XIb) or (XIc).

The condensation is generally carried out at temperatures from 120 to 280°C, preferably from 150 to 260°C. and more preferably 180 to 240°C. water Formed preferably Argonauts. The reaction time usually ranges from 1 to 16 hours, preferably from 2 to 8 hours. The degree of condensation can be controlled in a simple way by means of temperature and reaction time.

The polycondensation is preferably carried out in the presence of acid, preferably phosphoric acid (H3RHO3and/or hypophosphorous acid (H3RHO2). The preferred amount is from 0.05 to 2 wt.%, site is preferably from 0.1 to 1 wt.% from components, that are subject to condensation. In addition to the acid may also apply additional catalysts, for example, of the halides of zinc or of aluminum sulfate, optionally in a mixture with acetic acid, as disclosed, for example, in US 4505839.

The viscosity of the obtained polyalkylene (XII) generally is in the range from 1000 to 50000 MPa·s, preferably from 2000 to 20000 MPa·s and more preferably from 3000 to 13000 MPa·s (in each case, measurements were carried out for undiluted product at 20°C).

The average molar mass Mn(Brednikova) received polyalkylene (XII) generally is in the range from 250 to 50,000 g/mol, preferably from 500 to 40000 g/mol, more preferably from 1000 to 20000 g/mol and most preferably from 1000 to 7500 g/mol.

The average molar mass Mw(srednevekovaja) received polyalkylene (XII) generally is in the range from 250 to 50,000 g/mol, preferably from 500 to 30,000 g/mol, more preferably from 1000 to 20000 g/mol.

The resulting polyalkylene (XII) preferably has a polydispersity (Mw/Mnin the interval from 1 to 10, and in particular in the range from 1 to 5.

Polyalkylene (XII) can be alkoxysilane in the second stage (In). At this stage IT group and present any secondary amino groups react with Ala what linkside with the formation of simple terminal polyether groups.

Polyalkylene (XII) can be functionalized at the next stage of the reaction (S). Additional functionalization can help modify the properties of polyalkylene (XII). To this end hydroxyl groups and/or amino groups present in polyamidoamine (XII), converted by suitable agents, which are capable of reacting with hydroxyl groups and/or amino groups. This leads to the formation of functionalized polyalkylene (XIV).

Alkoxysilane polyalkylene (XIII) can be functionalized at the next stage of the reaction (D). Additional functionalization can serve to modify the properties alkoxysilane of polyamidoamine (XIII). To this end hydroxyl groups and/or amino groups present in alkoxysilane polyalkylene (XIII), are transformed by means of suitable agents, which are capable of reacting with hydroxyl groups and/or amino groups. This leads to the formation of functionalized alkoxysilane of polyamidoamine (XV).

In General, the total amount of the leveling agent in the electrolytic bath is from 0.5 parts per million to 10,000 parts per million of the total mass of the electrolytic bath. Leveling agents according to the present invention, as the government is about, apply in a total amount from about 0.1 parts per million to about 1000 parts per million of the total mass of the electrolytic bath and more typically in an amount of from 1 to 100 parts per million, although there may be higher and lower amounts.

The electrolytic bath according to the present invention can include one or more optional additives. Such optional additives include, but without limitation to this, accelerating agents, immunosuppressive agents, surfactants and the like. Such immunosuppressive agents and accelerating agents, in General, known in the art. Experts in the art should be aware of what used immunosuppressive agents and/or accelerating agents, and the quantities in which they are applied.

A large variety of additives may usually be used in the bath to achieve the desired characteristics of the surface of metal by electrolytic copper coating. As a rule, used in more than one additive, with each additive forms a desirable feature. Preferably, the electrolytic bath may contain one or more precipitating agents, leveling agents, sources of halide ions, additives, grinding grain, and mixtures thereof. Most preferably the electrolytic bath contains is as accelerating agent, and leveling agent in addition to the inhibitory agent according to the present invention. Other additives can also be applied appropriately in the electrolytic bathrooms of the present invention.

The present invention is suitable for the deposition of the metal layer, in particular a layer of copper on various substrates, especially substrates having sub-micron and different size holes. For example, the present invention is particularly suitable for the deposition of copper on podarkah for integrated circuits, such as semiconductor device with through-holes of small diameter, grooves or other openings. In one embodiment of the present invention on a semiconductor device is applied to the metal layer in accordance with the present invention. Such semiconductor devices include, but without limiting to this, the plates used in the manufacture of integrated circuits.

In General, the process of electrolytic deposition of copper on a semiconductor substrate for integrated circuits is described with reference to Fig.1 and 2, without limiting the present invention in this manner.

In Fig.1A shows the dielectric substrate 1 covered with the seed copper layer 2A. According Fig.1b, a copper layer 2' is deposited on the dielectric substrate 1 by means of electrolytic deposition.Groove 2 with the substrate 1 are filled, and applied over the copper layer 2b, also referred to as "the covering layer, is formed on the top of all of the structured substrate. During the process, after an optional annealing, the surface copper layer 2b is removed by chemical mechanical planarization (CMP), as shown in Fig.1C.

The key to filling in the grooves 2 of the substrate 1 by means of electrolytic copper deposition is the achievement of a copper layer without defects, especially without voids and seams. This can be achieved through the initiation of growth of copper on the bottom of the groove, and the growth of copper occurs in the direction towards the inlet groove, the suppression of growth of copper on the side walls of the groove. This method of filling the grooves, so-called "super-seeding" or "rising filling, as shown in Fig.2A, is achieved by adding certain additives in an electrolytic bath, namely accelerating agent and suppressing agent. Sensitive interaction between these two additives must be carefully adjusted to achieve the filling of the grooves without any defects.

Rising filling, as shown in Fig.2A, can be achieved through accelerating agent, preferably accumulated and adsorbiruyuschee on the copper base of the groove and, thus, increase the growth of copper 2'", and with potustaronii vast agent on the side walls of the grooves, the vast growth of copper 2". Depending on the chemical structure of the vast agent and, thus, from its overwhelming ability of filling the grooves may be formed according to various ways to the growth fronts of copper 2", as shown in Fig.2A-2C. Excellent working inhibitory agent with full coverage of the side walls and with complete suppression of growth on the side walls 2" shown in Fig.2A. In this case, the growth front 2" is flat with exclusively by the rising growth of copper 2'". Less effective inhibitory agent leads to the growth front copper 2" shown in Fig.2b. Weak growth of copper on the side walls 2 with the prevailing upward growth of copper 2'" leads to an overall growth front U-shape 2"". Weak suppressive agent leads to the growth front V-shaped 2"" due to the significant growth of copper on the side walls 2, as shown in Fig.2C. The growth front copper V-shaped 2"" causes a serious risk of the formation of voids when filling in the grooves. When fully conformal seed layer of copper on the groove of the growth front copper U-shaped 2", as shown in Fig.2b, can provide a satisfactory filling of the grooves. But since there is an increasing projection of the bare particles and/or surface elements of convex shape with a decreasing size of the surface elements, as shown in Fig.3, there is a serious R the SC education of closed cavities in the upper half of the groove, closer to the inlet, if the inhibitory agent is not completely prevent the growth of copper on the side wall 2". The present invention provides a new class of highly effective strong suppressive agents that cope with increasing protrusion of the bare particles and provide for the filling of the grooves without defects, despite conformly seed layer of copper.

The advantage of the present invention is that provided suppressing agents, which lead to a very pronounced increase of copper in the direction of the rising filling with excellent suppression of growth of copper on the side walls, and both leads to planar front growth, thus ensuring the filling of the grooves is essentially free of defects. The strong suppression of the growth of copper on the side walls in accordance with the present invention allows essentially besposchadnogo filling elements of the surface covered nekonformnyi bare copper layer, or elements of the surface of a convex shape. Moreover, the present invention provides in General a homogeneous upward filling the neighboring elements of the surface areas densely populated with surface elements.

The additive of the present invention may also preferably be used for the electrodeposition of copper through silicon to the Apana (TSV). Such valves typically have sizes from a few micrometers to 100 micrometers and large coefficients of proportionality equal to at least 4, sometimes more than 10. In addition, the additive according to the present invention is preferably used in the technology of the Assembly, as, for example, the production of copper pillars with a height and diameter, typically from 50 to 100 micrometers for a process of forming the bar of the conclusions in the technologies of creation of printed circuit boards, such as the production of high density interconnects on printed circuit boards, using technology metallization end-to-end mounting of the micro-holes of printed circuit boards or metallization of the through holes, or other processes in packaging for electronic circuits.

Typically, the electrolytic deposition of the coating on the substrate is carried out by contact of the substrate with an electrolytic EN according to the present invention. Polozka usually acts as the cathode. The electrolytic bath contains an anode, which may be soluble or insoluble. If necessary, the anode and cathode may be separated by a membrane. Potential normally applied to the cathode. Creates a sufficient current density and the electrolytic deposition of the coating is carried out over a period of time sufficient for the deposition of the metal layer, tcog is how the copper layer, having a desired thickness on the substrate. Suitable current density include, but without limiting to this, the interval from 1 to 250 mA/cm2. Typically, the current density is in the range from 1 to 60 mA/cm2when applying for the deposition of copper in the manufacture of integrated circuits. Specific current density depends on the substrate to be coated, the selected leveling agent and the like. The choice of the current density refers to the competence of a person skilled in the art. The applied current may be direct current (DC), pulse current (PC), a pulse reverse current (PRC) or other suitable current.

In General, when the present invention is used for the deposition of metal on a substrate such as a wafer used in the manufacture of integrated circuits, electrolytic baths are mixed during application. A specialist in the art may apply any suitable method of mixing, and such methods are well known in the art. Suitable methods of mixing include, but without limiting to this, the bubbling of inert gas or air, the mixing of the workpiece, the appointment of a jet with a bathtub and the like. Such methods are well known to specialists in this field of technology. When the present invention is used for applying e is actrelationship layer on a substrate for integrated circuits, such as a plate, the plate can rotate at speeds from 1 to 150 rpm, and the electrolytic solution in contact with the rotating plate, as, for example, by injection or spraying. Alternatively, there is no need in the rotation plate when the flow of the electrolytic bath is sufficient to provide the desired deposition of the metal.

Metal, especially copper, is deposited in the holes in accordance with the present invention, essentially without the formation of voids in the deposited layer of metal. The term "essentially without formation of voids" means that 95% covered holes do not contain voids, preferably 98% covered with holes did not contain voids, most preferably, all covered with holes did not contain voids.

Although the method according to the present invention was described with reference to the manufacture of semiconductors, it is obvious that the present invention may be useful in any electrolytic process where it is desirable filling metal small surface elements, essentially, without voids. Such processes include the production of printed circuit boards. For example, the electrolytic bath of the present invention may be useful for coating metal through-holes, pads or tracks on achtnich circuit boards, and for spraying the bar conclusions on the plates. Other suitable processes include Assembly and fabrication of interconnects. Accordingly, suitable substrates include frames with external outputs, interconnects, printed circuit boards and the like.

Electrolytic equipment for electrolytic coating on a semiconductor substrate are well known. Electrolytic equipment contains an electrolytic tank, which contains copper electrolyte, and which is made of a suitable material such as plastic or other material inert to the electrolytic solution for coating. The tank may be cylindrical, especially when the cover plates. The cathode is horizontally located at the top of the tank and may be a substrate of any type, such as a silicon wafer, having holes, such as grooves and through holes. The substrate plate, as a rule, covered by the seed layer of copper or other metal, or a layer containing the metal to initiate the application on its electrolytic coating. The seed layer of copper may be applied by chemical deposition from the vapor (gas) phase (CVD), condensation of the steam (gas) phase (PVD) or the like. The anode is also preferably has a round shape for electrolytic OS the input voltage to the metal layer on the plate and is located horizontally at the bottom of the tank, forming a space between the anode and cathode. The anode typically is soluble anode.

These additives to the bath is useful in combination with membrane technology developed by different manufacturers tools. In this system, the anode may be separated from the organic additives to the bath through the membrane. In order to separate the anode and organic additives to the bath is to minimize the oxidation of organic additives to the bath.

Through wiring substrate, which acts as cathode and anode respectively electrically connected with the rectifier (power supply). The substrate serving as the cathode, at a constant or pulsed current has a resultant negative charge, so that the copper ions in solution are recovered on a substrate serving as a cathode, forming metal, covered with a layer of copper on the cathode surface. The oxidation reaction occurs at the anode. The cathode and anode can be horizontally or vertically arranged in the tank.

Metal, in particular copper, is deposited into the holes in accordance with the present invention, essentially without the formation of voids within the deposited metal. The term "essentially without the formation of voids" means that 95% of the holes, covered with a layer of metal, does not contain voids. Preferably the holes are covered with the e layer of metal, not contain voids.

Although the method according to the present invention was described in relation to the manufacture of semiconductors, it is obvious that the present invention may be useful in any electrolytic process where it is desirable to copper deposition, essentially without the formation of voids. Accordingly, suitable substrates include frames with external outputs, interconnects, printed circuit boards and the like.

All percentages, parts per million or comparable values refer to the weight relative to the total weight of the respective composition, unless otherwise specified. All referenced documents are included in the description of the present invention by reference.

The following examples serve to further illustrate the present invention without limiting the scope of the present invention.

The hydroxyl number is determined in accordance with DIN 53240 by heating the sample in pyridine with acetic anhydride followed by titration with potassium hydroxide.

The distribution of the molecular weight of d was determined using the exclusive chromatography (GPC) using THF as eluent and column PSS SDV as a solid phase.

Examples

Three EO-po copolymer containing polisport as an initial matter, were synthesized by polyalkoxysiloxanes with the setup portion of the original molecule polisport. The composition suppressing agents 1-4 are given in Table 1.

Table 1
The inhibitory agentThe original substancem X(OH)mThe number of SW / number of RO initial substance (theoretical molecular mass [g/mol])LocationThe efficiency of fill
1sorbitol-1BuO644.3/ 78.4 (6500)RO-EO block+
2sorbitol644.3/ 78.4 (6500)random+
3 (comparative example)the pentaerythritol-3.5 SW444.3/ 78.4 (6500)random
4 (comparative example)sorbitol644.3/ 78.4 (6500)SW-RO the Lok

Example 1

Sorbitol (182.2 g), an aqueous solution of sodium hydroxide (concentration: 50 wt.% NaOH; 1.8 g) and water (200 ml) was placed in an autoclave with a volume of 2 liters and heated at a temperature of 120°C and under constant flow of nitrogen (0.5 m3N2/ h) for 1 hour. Then the water was removed at the same temperature in vacuum for 2 hours. After neutralization of nitrogen added butylenes (72.1 g) in parts at 140°C. To complete the reaction provided an opportunity for post-reaction mixture throughout the night. Then added propylene oxide (662.0 g) in portions at 130°C, and again provided an opportunity for post-reaction mixture throughout the night. Added magnesium silicate Ambosol (27.6 g, CAS No. 93616-22-9), media for filtration Hyflow (1.8 g) and water (20 ml) and volatile compounds were removed on a rotary evaporator at 100°C in vacuum. After filtering received a very viscous yellow oil (920.7 g) as an intermediate product.

The intermediate product (203.3 g) and an aqueous solution of cesium hydroxide (concentration: 50 wt. % CsOH; 2.2 g) were placed in the autoclave with a volume of 2 liters and the water was removed at 120°C in vacuum for two hours. After neutralization of nitrogen addition was added propylene oxide (863.2 g) in portions at 130°C. To complete the reaction provided an opportunity for post-reaction mixture during the weekend. Then added an aqueous solution of the hydroxide is the atrium (concentration: 50 wt.% NaOH; 3.0 g) and water (10 ml) and water was removed at 120°C in vacuum for 2 hours. After neutralization of nitrogen added ethylene oxide (433.5 g) in portions at 120°C and provided an opportunity for post-reaction mixture throughout the night. Added Ambosol (44.7 g), Hyflow (3 g) and water (20 ml), and volatile compounds were removed on a rotary evaporator at 100°C in vacuum. After filtering the received light yellow liquid (1491 g). The distribution of molecular weight d 1.04; HE was 49.4 mg/g KOH.

Example 2

A mixture of sorbitol (30 g), water (30 g) and an aqueous solution of cesium hydroxide (concentration: 50 wt.% CsOH; 1.1 g) was stirred overnight. Then this mixture and additional water (20 g) was placed in an autoclave with a volume of 2 liters and the water was removed at 100°C in vacuum (<10 mbar) for 3 hours. After neutralization of nitrogen was added a mixture of ethylene oxide (321.4 g) and propylene oxide (750.1 g) in portions at 130°C for 3 days. After stirring for 1 day, the reaction mixture was treated with nitrogen and volatile compounds were removed in vacuo. The inhibitory agent 2 was obtained in the form of liquid light yellow (1108 g) distribution of molecular weight, d=1.08.

Example 3

A mixture of pentaerythritol-3.5 SW (40 g, from Aldrich, CAS: 30599-15-6), water (10 g) and an aqueous solution of cesium hydroxide (concentration: 50 wt.% CsOH; 2.0 g) was stirred overnight. Then this mixture and additional water (20 g) was placed in an autoclave with a volume of 2 liters and the water was removed at 100°C in vacuum (< 10 mbar) for 2 hours. After neutralization of nitrogen was added a mixture of ethylene oxide (282.9 g) and propylene oxide (660.4 g) in portions at a temperature of 130°C for 4 hours under stirring the reaction mixture for a further 10 hours. Then the reaction mixture was treated with nitrogen and volatile compounds were removed in vacuo. The inhibitory agent 3 was obtained as a yellow liquid (951 g) distribution of molecular weight, d=1.12.

In Fig.3 shows the dimensions of the elements of the surface of the substrate in the form of a plate, covered with a seed layer of copper, which was used for the electrolytic deposition of metal coatings using different electrolytic baths, described next. After deposition of the seed layer of copper grooves had a width of from 15.6 to 17.9 nm at the entrance to the groove width from 34.6 to 36.8 nm at half height of the groove and the depth of 176.4 nanometers.

Example 4

The electrolytic bath was obtained by combining deionized water, 40 g/l copper as copper sulfate, 10 g/l of sulfuric acid, 0.050 g/l chloride ions in the form of HCl, 0.028 g/l of SPS and 3.00 ml/l 4.5 wt. % solution of the vast agent 1 obtained in example 1 in de-ionized water.

The copper layer was deposited by electrolytic deposition on a substrate in the form of a plate with dimensions of surface elements as shown in Fig.3), which is applied for Rabochy the copper layer, by contact of the substrate in the form of a plate with the above-described electrolytic bath at 25°C, applying a constant current of -5 mA/cm2for 3 or 6 seconds, respectively. Received cross-section of such obtained by electrolytic deposition of the copper layer and explored through examination by scanning electron microscope.

In Fig.4A and 4b shows the images obtained with a scanning electron microscope. In Fig.4A shows a partially-filled grooves 3 seconds electrolytic deposition without any voids or seams, and a planar growth front copper can clearly indicate an upward filling, as clearly shown in Fig.2A. The growth of copper on the side walls of the grooves was slightly small, indicating a strong inhibition of the growth of copper on the side walls of the grooves. All input openings of the surface elements still remained open. After 3 seconds the electrolytic deposition of all the grooves were filled completely without defects with an expression of General homogeneous growth front, as shown in Fig.4b.

Example 5

The electrolytic bath was obtained by combining deionized water, 40 g/l copper as copper sulfate, 10 g/l of sulfuric acid, 0.050 g/l chloride ions in the form of HCl, 0.028 g/l of SPS and 2.00 ml/l 5.4 wt. % solution of the vast agent 2 obtained in the example 2, in deionized water.

The copper layer was deposited by electrolytic deposition on a substrate in the form of a plate with dimensions of surface elements, as shown in Fig.3, by contact of the substrate in the form of a plate with the above-described electrolytic bath at 25°C, applying a constant current of -5 mA/cm2for 3 or 6 seconds, respectively. Received cross-section of such obtained by electrolytic deposition of the copper layer and explored through examination by scanning electron microscope.

In Fig.5A and 5b shows the images obtained with a scanning electron microscope. Electrolytic deposition within 3 seconds, as shown in Fig.5A, results in partially filled grooves, showing flat growth front copper with a very small growth of copper on the side walls. The inhibitory effect of the suppressing agent used in this example, a little less in comparison with the overwhelming agent used in example 4, while providing the same fill rate. In any case, the deposition of copper on the bottom of the grooves exceeds the copper deposition on the side walls, providing a surface elements filled without defects, 6 seconds electrolytic deposition as shown in Fig.5b.

Example 6 (comparative)

The electrolytic bath was obtained by the volume of the organisations deionized water, 40 g/l copper as copper sulfate, 10 g/l of sulfuric acid, 0.050 g/l chloride ions in the form of Hcl, 0.028 g/l of SPS and 3.00 ml/l 4.5 wt. % solution of the vast agent 3 obtained in example 3 in deionized water.

The copper layer was deposited by electrolytic deposition on a substrate in the form of a plate with dimensions of surface elements as shown in Fig.3, which is applied to the seed layer of copper, by contact of the substrate in the form of a plate with the above-described electrolytic bath at 25°C, applying a constant current of -5 mA/cm2within 3 seconds or 6 seconds, respectively. Received cross-section of such obtained by electrolytic deposition of the copper layer and explored through examination by scanning electron microscope.

In Fig.6A and 6b shows the image obtained using a scanning electron microscope. The results of electrolytic deposition after 3 seconds, as shown in Fig.6A, already clearly show that the candidate for use as a suppressing agent used in this example, does not have sufficient suppressive efficiency for the rising besposchadnogo filling. In contrast, after 3 seconds the electrolytic deposition of the grooves are partially filled, but with significant copper deposition close to the entrance of the groove, thus leading to education is aniu closed grooves with a large number of voids inside. The result of electrolytic deposition, shown in Fig.6b, confirms the formation of defects, as shown in Fig.6A.

Example 7 (comparative)

A mixture of sorbitol (30 g), water (30 g) and an aqueous solution of cesium hydroxide (concentration: 50 wt.% CsOH; 1.1 g) and additional water (20 g) was placed in an autoclave with a volume of 2 liters and the water was removed at 100°C in vacuum (<10 mbar) for 3 hours. After neutralization of nitrogen was added ethylene oxide (321.4 g) in portions at 130°C for 16 hours to 7 bar. The mixture is then cooled to 80°C and stirred overnight. Then was added propylene oxide (750.1 g) in portions at 130°C for 27 hours up to 7 bar. After 5 hours the reaction mixture was cooled to 80°C, the reaction mixture is treated with nitrogen and volatile compounds were removed in vacuo. After filtering, the inhibitory agent 4 was obtained as a yellow liquid (1102 g) distribution of molecular weight, d=1.03.

Example 8 (comparative)

The electrolytic bath was obtained by combining deionized water, 40 g/l copper as copper sulfate, 10 g/l of sulfuric acid, 0.050 g/l chloride ions in the form of HCl, 0.028 g/l of SPS and 2.00 ml/l 5.4 wt. % solution of the vast agent 4 obtained in example 7, in de-ionized water.

The copper layer was deposited by electrolytic deposition on a substrate in the form of a plate with dimensions of surface elements, as shown in Fig.3, in which the second deposited seed layer of copper, by contact of the substrate in the form of a plate with the above-described electrolytic bath at 25°C, applying a constant current of -5 mA/cm2for 3 or 6 seconds, respectively. Received cross-section of such obtained by electrolytic deposition of the copper layer and explored it through inspection scanning electron microscope at an inclination of 52°.

In Fig.7a and 7b shows the image obtained using a scanning electron microscope. Electrolytic deposition within 3 seconds, as shown in Fig.7a, results in partially filled grooves, showing irregular and uneven growth front copper with obtaining unevenly filled grooves. Fig.7b shows that after 6 seconds electrolytic deposition of some of the grooves are closed with the formation of voids due to insufficient overwhelming effect of applied suppressing agent at the entrance of the groove.

1. Composition for coating metallic coating containing at least one source of copper and at least one additive obtained by the reaction
a) a polyhydric alcohol containing at least 5 hydroxyl functional groups, with
b) at least first alkalisation and second alkalisation of a mixture of the first accelerated and second accelerated.

2. The composition according to p. 1 in which the polyhydric alcohol is selected from compounds of the formula I
,
where
m is an integer from 5 to 10,
X represents a m-valent linear or branched aliphatic or cycloaliphatic radical having from 5 to 10 carbon atoms which may be substituted or unsubstituted.

3. The composition according to p. 1 in which the polyhydric alcohols are linear or cyclic alcohols, give the oxidation of monosaccharides represented by the formula (II) or (III)
,
,
where
n is an integer from 3 to 8, and
o is an integer from 5 to 10.

4. The composition according to p. 3, in which the alcohol that give the oxidation of the monosaccharide is selected from sorbitol, mannitol, xylitol, ribita and Inositol and derivatives thereof.

5. The composition according to p. 1 in which the polyhydric alcohols are monosaccharides of formula (IV) or (V)
,

and their derivatives,
where
p is an integer from 4 to 5, and
q, r are integers, and q+r is 3 or 4.

6. Composition under item 5, in which the monosaccharide is selected from aldos: ellozy, altrose, galactose, glucose, gulose, idose, mannose, talose, glycopeptide, mannoheptose, or ketosis: fructose, psicose, sorbose, tagatose, mannoheptulose, sedoheptulose, talegators, alligators, andtheir derivatives.

7. Composition under item 1, in which the additive is a random copolymer of ethylene oxide and propylene oxide.

8. Composition under item 1, in which the content of the units of the first oxyalkylene in the additive is from 20 to 50 wt.%, preferably from 25 to 40 wt.%.

9. Composition under item 1, in which the molecular mass Mwthe additive is from 3000 to 10000 g/mol, preferably from 4000 to 8000 g/mol.

10. Composition according to any one of paragraphs.1-9, which additionally contains one or more precipitating agents.

11. Composition according to any one of paragraphs.1-9, which additionally contains one or more leveling agents.

12. The use of an electrolytic bath for the deposition of metal coatings containing composition according to any one of paragraphs.1-11, as the electrolytic bath for the deposition of metal on the substrate, containing the elements of the surfaces having a hole size of 30 nanometers or less.

13. The method of applying a metallic coating on a substrate, including:
a) contact the electrolytic bath for the deposition of metal coatings containing composition according to any one of paragraphs.1-11, with the substrate, and
b) creating a current density in the substrate during a period of time sufficient for the deposition of the metallic coating on a substrate.

14. The method according to p. 13, in which the substrate contains elements of the surface of submicron size, and USAID the tion is performed with the filling elements of the surface of micron or submicron size.

15. The method according to p. 14, in which the surface elements of submicron size have a hole size of 1 to 30 nanometers and/or aspect ratio of 4 or more.



 

Same patents:

FIELD: producing copper tracks on insulating substrates.

SUBSTANCE: negative image of track is projected onto copper halide solution layer in organic solvent of substrate with the result that concentric capillary flow occurs in layer which transfers solution to illuminated sections of substrate wherein copper halide tracks remain upon solvent evaporation. These tracks are reduced to copper ones in hydrogen current at temperature sufficient to conduct reducing reaction.

EFFECT: facilitated procedure, reduced cost and copper consumption, improved environmental friendliness due to elimination of wastes.

1 cl, 3 dwg

The invention relates to the field Elektrokhimiya, in particular the production of chrome coatings on semiconductor materials, particularly silicon-n-p type and the silicides of 3d-transition metals

The invention relates to a process for manufacturing electronic equipment and for the application of active dielectric or semiconductor on semiconductor substrate

The invention relates to semiconductor technology and can be used in the manufacture of Schottky field-effect transistors

FIELD: chemistry.

SUBSTANCE: method includes polishing component of copper-containing alloy in electrolyte, used as anode, and synchronous application of copper coating on steel component, used as cathode. Voltage 250-340 V is supplied to cathode and anode with electrolyte temperature 60-90°C. Electrolyte is used in form of water solution, which contains ammonium chloride, ammonium fluoride and mono-, di-, tri-substituted ammonium citrate or their mixture.

EFFECT: polishing of active anode to mirror lustre with synchronous covering of steel cathode surface with copper.

1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of electroplating and can be used for manufacturing semiconductors. Method of precipitating copper on substarte, which contains surface elements of submicrometre size, which have hole diameter 30 nanometres or less, includes: a) contact with substrate of electric bath for precipitation of copper, containing source of copper ions, one or more accelerating agents and one or more inhibiting agents, selected from compounds of formula I where each radical R1 is independently selected from ethylene oxide copolymer and at least one more C3-C4 alkylene oxide, with said copolymer representing random copolymer, each radical R2 is independently selected from R1 or alkyl, X and Y independently represent spacer groups, with X having independent values for each repeating unit, selected from C1-C6 alkylene and Z-(O-Z)m, where each radical Z is independently selected from C2-C6 alkylene, n represents integer number, larger or equal 0, m represents integer number, larger or equal 1, in particular m equals 1-10, and ethylene oxide content in ethylene oxide copolymer and C3-C4 ethylene oxide constitutes from 30 to 70%, and b) creation of current density in substrate for time period sufficient for filling element of submicron size with copper.

EFFECT: obtaining homogeneous coating without voids and seams.

10 cl, 6 ex, 7 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention can be applied in technology of microelectronics, in which layer of copper is to be applied on thin sublayer of cobalt or its alloys (cobalt-phosphorus, cobalt-tungsten-phosphorus) or copper, which is located on the surface of silicic plates. Electro-sedimentation of copper is carried out from electrolyte of copperplating, which contains copper sulfate, ethyl alcohol, ethylenediaminetetraacetic acid (EDTA), ammonium laurylsulphate and ammonia in form of water solution.

EFFECT: electrolyte of copperplating does not contain ions of alkali metals and is suitable for application of copper layers on sublayer of copper, cobalt or its alloys.

4 cl, 4 ex

FIELD: metallurgy.

SUBSTANCE: electrolyte consists of bluestone 105-115 g, ammonium sulphate 220-230 g, polyethylene-polyamine 3-6 g, water solution of ammonia 89-95 ml, bromine-benzo-thyazo 1-3 mmole/l, captax 1-3 mmole/l and water to 1 l.

EFFECT: cathode sediments have fine crystal structure, are smooth, plain, uniform, mirror-bright, well adherent to base and with maximal current output.

3 tbl, 3 ex

FIELD: physics.

SUBSTANCE: invention relates to copper coating on steel backplate without application of intermediate layer; this invention can be used in mechanic engineering, radio engineering and instrument-making industry. Electrolyte contains 30-50 g of copper sulphate, 120-180 g of sodium pyrophosphate, 70-100 g of disubstituted sodium phosphate, 1-5 mmol/l of N-allyldiethylenetriamine chloride, 1-5 mmol/l of pyridine sulphur triethylammonium chloride and water up to 1 litre.

EFFECT: quality improvement of porous-free copper coatings with mirrored surface.

3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: electrolyte contains g/l: copper sulphate 85-150; sulphuric acid 30-50; ammonium oxalate 25-35; tri-ethylene glycol or tetra-ethylene glycol 12-18 and water.

EFFECT: obtaining a high quality, well bonded with the main coating mirror-shiny surface.

1 tbl, 3 ex

FIELD: metallurgy.

SUBSTANCE: invention refers to electrolytic metallurgy and can be used for copper coating on items of various purposes. Electrolyte contains copper (II) from 0.05 to 1.0 moles/l, nitriloti(methylenphosphonic) acid or its soluble compound from 0.1 to 2.0 moles/l, a substance of amines class chosen from the group consisting of monoethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, ethylendiamine, diethylentriamine, triethylene-tetramine from 0.01 to 0.2 moles/l and water to 1.0 l.

EFFECT: producing of fine crystalline coating of high quality and performing of electrolyte in wide range of temperatures and pH values; also expanding range of complex phosphonic electrolytes for copper coating.

4 cl, 4 ex

FIELD: technological process.

SUBSTANCE: invention is related to methods of copper coating of plastics, in particular, polymer composition materials on the basis of carbon fibers and may be used in manufacture of furniture fittings, household appliances and utensils, in automobile and radio industries. Method includes preparation of polymer composition material surface - cleaning, degreasing, immersion and soaking of polymer composition material for 40 - 60 minutes in acid solution of electrolyte with the following composition, g/l: copper sulfate 195 - 235, concentrated sulfuric acid 50 - 60, sodium chloride 0.07 - 0.15 and electrochemical depositing of copper in the same electrolyte at temperature of 20 - 24°C, current density of 5.0 - 6.0 A/dm2 for 5-10 minutes, pH of electrolyte - 1.

EFFECT: allows to increase purity of productivity, to simplify copper coating process, to increase environmental safety and economic efficiency of production.

2 dwg, 2 tbl, 13 ex

FIELD: electroplating processes and equipment, possibly application of copper coatings without use of intermediate sub-layer in machine engineering and instrument making.

SUBSTANCE: electrolyte contains: copper sulfate, 200 -250 g/l; sulfuric acid, 40 - 50 g/l; 2-n-tretbutyloxi-1,3-bis(butyl amino)propane, 1 - 3 mmol/l; and thio-salicylic acid, 1 - 3 mmol/l.

EFFECT: possibility for applying high-quality bright coatings having good cohesion with steel base minimally hydrogen-charged, preparation of electrolyte with high dispersing capability.

3 tbl, 3 ex

FIELD: metallurgy, possibly production of materials with specific structure and special properties, for example in the form of coatings, films or powders containing pentagonal crystallites characterized by high adsorption capability.

SUBSTANCE: method comprises steps of depositing copper from electrolyte where two electrodes are placed. One electrode is made of copper and it is used as anode. As second electrode - cathode - electrically conducting substrate made of material with low heat conductance and roughness is used. Relation of anode surface area to cathode surface area is no less than 1 : 10; deposition is realized at electric current density in range 0.01 - 0.1 A/dm2 for forming nano-size crystals with quinary symmetry on base of non-crystalline seeds.

EFFECT: possibility for depositing copper coatings or films with high adsorption capability.

4 cl, 3 dwg, 1 ex

FIELD: galvanoplastics; manufacture of composite copper foil; manufacture of printed circuit boards.

SUBSTANCE: composite copper foil (10) includes carrier foil (12) electrolitycally precipitated on cathode and provided with cathode side formed in contact with cathode and opposite electrolytic side. Located on electrolytic side of carrier foil (12) is very thin separating layer (14). Thin functional foil (16) formed by precipitation of copper has front side engageable with separating layer (14) and opposite reverse side. Electrolytic side of carrier foil (12) has roughness Rz equal to or lesser than 3.5 mcm. Method of manufacture of such foil includes making carrier foil (12) on cathode by electrolytic precipitation and forming thin separating layer (14) on its electrolytic side; thin functional foil (16) is formed by precipitation of copper; front side of functional foil (16) is engageable with separating layer (14); electrolytic precipitation of carrier foil (12) is made in such way that its electrolytic side has roughness Rz lesser than or equal to 3.5 mcm.

EFFECT: low cost of foil; improved quality of functional foil surface.

26 cl, 9 dwg

FIELD: mechanical engineering; instrument-making industry; galvanization; deposition of the copper coatings on the steel without application of the intermediate sublayer.

SUBSTANCE: the invention is pertaining to galvanization, in particular, to deposition of the copper coatings on the steel without application of the sublayer and may be used in mechanical engineering and instrument-making industry for production of the bright copper coatings. The aqueous electrolyte contains: bluestone - 120-130 g; 70 % ethylene diamine - 115-125 g, sulfuric acid - 55-65 g; dihydrochloride β, β'-dipiperidineisopropyltret-butyl ether - 104-103 mole/l, water - up to 1 liter. The technical result of the invention is production of the qualitative nonporous galvanic deposits with the fine-crystalline structure, the specular surface, the good adhesion, without application of the intermediate layer.

EFFECT: the invention ensures production of the qualitative nonporous galvanic deposits with the fine-crystalline structure, the specular surface, the good adhesive power, without application of the intermediate layer.

3 tbl, 3 ex

FIELD: hydraulic metallurgy of non-ferrous metals, namely electrolytic refining of copper, possibly electroplating metallurgy.

SUBSTANCE: method comprises steps of introducing into electrolyte complex of surface active matters including such as thiocarbomide. The last is preliminarily dissolved in copper sulfate solution at mass relation of ions of copper and sulfur (contained in thiocarbomide) in range 20 - 600 at temperature 40 - 70°C during 10 - 70 h. Initial electrolyte is used as copper sulfate solution for treating thiocarbomide. Invention allows produce smooth cathode copper with high helical elongation characterizing copper capability to rolling.

EFFECT: possibility for producing cathode copper with smooth surface, low content of sulfur, high physical and mechanical properties.

2 cl, 1 tbl, 8 ex

FIELD: electroplating processes, possibly electrochemical copper deposition onto steel surfaces of parts without applying additional sub-layer.

SUBSTANCE: electrolyte contains, mol/l: copper compound, 0.1 - 0.5; alkali metal hydroxide, 1.5 -5.0; potassium or sodium nitrate, 0.2 -0.8; propylene glycol, 0.6 - 2.5; hydroxide of tetraalkyl ammonium, 0.0002 -0.0006. Method comprises steps of preparation of parts and realizing electrolytic deposition of copper from such electrolyte at cathode electric current density 0.5 - 3.0 A/dm2 and temperature of electrolyte 20 - 40°C.

EFFECT: improved micro-hardness, increased cohesion of highly uniform coating with base, protection capability of coating due to its lowered porosity, lowered probability of reduction of copper complexes in electrolyte mass.

5 cl, 3 ex, 1 tbl

FIELD: metallurgy, possibly production of materials with specific structure and special properties, for example in the form of coatings, films or powders containing pentagonal crystallites characterized by high adsorption capability.

SUBSTANCE: method comprises steps of depositing copper from electrolyte where two electrodes are placed. One electrode is made of copper and it is used as anode. As second electrode - cathode - electrically conducting substrate made of material with low heat conductance and roughness is used. Relation of anode surface area to cathode surface area is no less than 1 : 10; deposition is realized at electric current density in range 0.01 - 0.1 A/dm2 for forming nano-size crystals with quinary symmetry on base of non-crystalline seeds.

EFFECT: possibility for depositing copper coatings or films with high adsorption capability.

4 cl, 3 dwg, 1 ex

FIELD: electroplating processes and equipment, possibly application of copper coatings without use of intermediate sub-layer in machine engineering and instrument making.

SUBSTANCE: electrolyte contains: copper sulfate, 200 -250 g/l; sulfuric acid, 40 - 50 g/l; 2-n-tretbutyloxi-1,3-bis(butyl amino)propane, 1 - 3 mmol/l; and thio-salicylic acid, 1 - 3 mmol/l.

EFFECT: possibility for applying high-quality bright coatings having good cohesion with steel base minimally hydrogen-charged, preparation of electrolyte with high dispersing capability.

3 tbl, 3 ex

FIELD: technological process.

SUBSTANCE: invention is related to methods of copper coating of plastics, in particular, polymer composition materials on the basis of carbon fibers and may be used in manufacture of furniture fittings, household appliances and utensils, in automobile and radio industries. Method includes preparation of polymer composition material surface - cleaning, degreasing, immersion and soaking of polymer composition material for 40 - 60 minutes in acid solution of electrolyte with the following composition, g/l: copper sulfate 195 - 235, concentrated sulfuric acid 50 - 60, sodium chloride 0.07 - 0.15 and electrochemical depositing of copper in the same electrolyte at temperature of 20 - 24°C, current density of 5.0 - 6.0 A/dm2 for 5-10 minutes, pH of electrolyte - 1.

EFFECT: allows to increase purity of productivity, to simplify copper coating process, to increase environmental safety and economic efficiency of production.

2 dwg, 2 tbl, 13 ex

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