CN1918327B - Copper electrodeposition in microelectronics - Google Patents
Copper electrodeposition in microelectronics Download PDFInfo
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- CN1918327B CN1918327B CN2004800418981A CN200480041898A CN1918327B CN 1918327 B CN1918327 B CN 1918327B CN 2004800418981 A CN2004800418981 A CN 2004800418981A CN 200480041898 A CN200480041898 A CN 200480041898A CN 1918327 B CN1918327 B CN 1918327B
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Abstract
A method and composition for electroplating Cu onto a substrate in the manufacture of a microelectronic device involving and electrolytic solution containing a source of Cu ions and a substituted pyridyl polymer compound for leveling.
Description
Technical field:
The present invention relates to copper electric plating method, composition and additive in the field of microelectronic fabrication.
Background technology:
Copper is electroplated and to be widely used in the field of microelectronic fabrication so that electrical interconnection to be provided, and for instance, is used for making at for example semiconductor integrated circuit element.As the requirement of semiconductor integrated circuit elements such as computer chip the structural element size of imperial scale integrated (ULSI) and ultra-large integrated (VLSI) is reduced Production Example with high circuit speed and high packaging density.The trend that component size reduces to increase with current densities requires to reduce the size of interconnection structure element (interconnect features).The interconnection structure element is that for example through hole or groove etc. are formed in the dielectric substrate, follow with metal filled to produce the structural element of conductive interconnection line.Further the reducing of interconnect dimensions challenged to metal filled.
Having introduced copper replaces aluminium to form wire and interconnection in semiconductor substrate.Copper has the resistivity lower than aluminium, and for same resistivity, the thickness of copper cash is less than the thickness of aluminum steel.Copper can be deposited on the substrate by electroplating (for example chemical plating and plating), spraying plating, plasma gas phase deposition (PVD) and chemical vapor deposition (CVD).It has been generally acknowledged that electrochemical deposition is the best approach of using copper,, and provide the low cost that has because it can provide high sedimentation velocity.
The copper electroplating method must satisfy the strict demand of semi-conductor industry.For example, copper deposition must be uniformly, and little interconnection structure element 100nm (or littler) opening for example of packing elements perfectly.
Developed and depended on so-called " super filling " or " growth " from bottom to top copper is deposited the into electrolytic copper system of high-aspect-ratio structure element.Super filling comprises interstitital texture element from bottom to top, rather than on its all surface with identical speed interstitital texture element, with suture (seam) and the pinch off (pinch off) of avoiding causing the hole.Developed the system of comprising that is used for super filling as the inhibitor and the accelerator of additive.As the result of the impulse force of growing from bottom to top (momentum), copper is deposited on the zone of interconnection structure element than thick on the zone that does not have structural element.The zone of these overgrowths is commonly called excessive plating, mound, projection, protuberance.The small construction element produces higher excessive galvanized protuberance owing to super filling speed faster.Excessively electroplate chemistry and the mechanical polishing process that made the copper surface planarization afterwards caused challenge.
In order to control excessive plating, introduce the third party's additive that is called leveling agent (leveler), to produce surface " leveling ", promptly reduce the impulse force of growth from bottom to top that accelerator and inhibitor produce.Although leveling agent produces more smooth copper plane, it has been generally acknowledged that leveling agent has negative effect to growth from bottom to top, particularly high leveling agent concentration can be slowed down super intussusception growth speed.Usually practice is to cause in the narrow and small concentration window of equilibrated to use leveling agent between to excessive plating and super filling properties.
Along with chip architecture diminishes (interconnection line has the opening about 100nm, and copper must pass the opening growth to fill interconnection line) gradually, need to improve speed from bottom to top.That is, copper must " quickly " be filled, and the speed of growth in vertical direction must be sufficiently more than the speed of growth on (for example 50%, 75% or higher) horizontal direction, and even the traditional super filling of bigger interconnection line on the much bigger meaning.Yet the abnormal speed of the growth from bottom to top on these fine structures produces the excessive galvanized protuberance of large-size, and this requires more leveling agent to flatten.But further the leveling agent concentration that improves has reduced for the crucial especially super filling speed of these meticulous interconnection structures.
Except super filling and excessive plating problem, may when filling the interconnection structure element, electro-coppering form microdefect.A defective that may occur is hole in the inner formation of structural element.Because copper is deposited on structural element sidewall and the structural element top inlet, so deposition possibility pinch off on structural element sidewall and inlet, thereby be closed to the inlet of structural element inside, particularly less (for example＜100nm) and/or have a high aspect ratio (degree of depth: structural element width).Cut off during electrolysis process if flow into the copper solutions of structural element, then in structural element, can form interior hole.Interior hole can hinder the electrical connectivity of structural element.
Microcavities is during the electrolytic copper depostion or the another kind of defective that forms of the particulate recrystallize that takes place after thereafter owing to the uneven copper speed of growth or copper facing.
On the other hand, some regional areas of semiconductor substrate are generally the zone that exists by the copper seed layer of physical vapor deposition, and the copper of may not growing during electrolytic deposition causes pit or metal disappearance defective.These copper holes are considered to " killer's defective ", because they have reduced the output that semi-conductor is made.A plurality of mechanism cause the formation in these copper holes, comprise semiconductor substrate self.Yet the copper electroplating chemical is influential to these generation of defects and quantity.
Other defective is a rat, described projection be in local high current density position, the isolated deposition peak that occurs of local impurity position or other position.The copper facing chemistry is influential to so protruding generation of defects.Although do not think defective, the roughened copper surface degree also is important for the semiconductor wafer manufacturing.Usually,, bright copper surface energy enters the vortex pattern that forms during the electroplate liquid, so want the copper surface of becoming clear because reducing wafer.The sedimentary roughness of copper makes and is difficult to detect defective by checking, because defective may be hidden by the peak of uneven surface and paddy.In addition, the smooth growth of copper is filled for the thing defective of meticulous interconnection structure and is become more important, because roughness can cause the pinch off of structural element, thereby is closed to the inlet of structural element inside.It has been generally acknowledged that by the additive combined effect of leveling agent particularly, the copper facing chemistry has a significant impact the sedimentary roughness of copper.From this viewpoint, the wisdom of leveling agent is used can form better super filling effect.
Summary of the invention:
Therefore, in brief, the invention provides a kind of method that in the manufacturing of microelectronic element, copper is electroplated onto on the substrate, comprise substrate is immersed in the electrolytic solution that comprises the leveling agent that has the copper that is enough to the amount of acid copper to the substrate and comprise the substituted pyridines polymer compound, give electrolytic solution with the supply electric current, to deposit copper on the substrate.
On the other hand, the invention provides a kind of being used in the manufacturing of microelectronic element copper to be electroplated onto composition on the substrate, described composition comprises the shot copper component and comprises the leveling agent of substituted pyridines polymer compound.
Other target of the present invention and characteristic will partly become obviously, and point out in following part.
Embodiment:
According to the present invention, in the manufacturing of microelectronic element, be integrated into electroplating bath for the copper plating based on the additive of substituted pyridine compound. In one embodiment, electroplating bath is used for depositing copper to such as semiconductor integrated circuit device substrates such as silicon wafers, comprises that the copper of interconnection structure element is filled.
The obvious advantage of additive of the present invention is to have improved the leveling effect, and does not substantially hinder in the super structural detail that is filled into high aspect ratio of copper. Namely because leveling agent of the present invention does not hinder super filling substantially, so the copper groove can be equipped with the combination of accelerator and inhibitor additive, described combination provides than the speed of growth on the vertical direction of the speed of growth much larger (even more much larger than the traditional super filling of large interconnection line) in the horizontal direction. Composition of the present invention has solved the danger that mounds along with the raising of super filling speed of common generation. Described additive also at reduce injection defect, improve brightness, make plating excessively minimize, improve the uniformity and reduce plating in some macrostructure elements and have advantage aspect excessive.
Leveling agent of the present invention is the substituted pyridine compound that is selected from can dissolves in copper plating groove, keep that it is functional, do not produce harmful side product under electrolytic condition under electrolytic condition the leveling effect that (be not at least immediately or soon afterwards) and generation want. In one embodiment, leveling agent is pyridiniujm compound, particularly pyridine quaternary ammonium salt. The pyridiniujm compound is from protonated pyridine derived of the nitrogen-atoms of pyridine wherein. Pyridine quaternary ammonium salt is different from pyridine and the pyridine quaternary ammonium salt based polyalcohol is different with the pyridine radicals polymer, because the nitrogen-atoms of pyridine ring is quaternized in pyridine quaternary ammonium salt and pyridine quaternary ammonium salt based polyalcohol. Leveling agent of the present invention comprises the derivative of vinylpyridine, and for example the derivative of 2-vinylpyridine in some preferred embodiments, is the derivative of 4-vinylpridine. Leveling agent compound polymer of the present invention comprises the homopolymers of vinylpyridine, copolymer, vinylpyridine quaternary ammonium salt and these homopolymers of vinylpyridine, the quaternary ammonium salt of copolymer. Some instantiations of such compound especially comprise poly--(4-vinylpridine) for instance, the product of poly--(4-vinylpridine) and dimethyl suflfate, the product of 4-vinylpridine and ethylene chlorhydrin, the product of 4-vinylpridine and benzyl chloride, the product of 4-vinylpridine and allyl chloride, the product of 4-vinylpridine and 4-PMC, the product of 4-vinylpridine and PS, the product of 4-vinylpridine and methyl tosyl (methyltosylate), the product of 4-vinylpridine and chlroacetone, the product of 4-vinylpridine and 2-methoxy ethoxy chloromethanes, the product of 4-vinylpridine and 2-dichloroethyl ether, the product of 2-vinylpyridine and methyl tosyl, the product of 2-vinylpyridine and dimethyl suflfate, the product of vinylpyridine and water-soluble initator, poly-(2-methyl-5-thiazolinyl pyridine) and 1-methyl-4-vinylpridine trifluoromethyl sulfonic acid. The example of copolymer is the vinylpyridine with the vinyl imidazole copolymerization.
The molecular weight of substituted pyridines polymer compound of the present invention is about 160 in one embodiment, 000g/mol or less magnitude. Although some compounds with higher molecular weight are difficult to dissolve electroplating bath, or remain in the solution, because the solvability of four azonias that increase, the compound of other higher molecular weight is soluble. The concept of solubility refers to relatively soluble in this context, for example, greater than 60% solvable, or under this environment effective a certain other minimum solubility. It is not the reference to absolute solubility. Aforementioned preferred value 160 in certain embodiments, 000g/mol is not strict critical. Selected substituted pyridines polymer solubilized in copper plating groove keeps it functional under electrolytic condition, and just after or under electrolytic condition, do not produce soon afterwards harmful side product.
Poly-(4-vinylpridine) homopolymer is available on market.The intermediate value of molecular-weight average from 10,000 to 20,000 is that poly-(4-vinylpridine) homopolymer of 16,000 can obtain with trade name Reilline410Solution SOQ from Reilly Industrial Co., Ltd (Reilly Industries Inc).In addition, poly-(4-vinylpridine) of molecular-weight average from 60,000 to 160,000 can obtain from Aldrich chemical company (Aldrich Chemical Company).
At the leveling agent compound is among those embodiment of reaction product of vinyl pyridine or polyvinylpyridine, by make vinyl pyridine or poly-(vinyl pyridine) be selected from can produce soluble, groove is compatible, react the leveling agent compound of acquisition for the alkylating agent of the group that flattens effective product.In certain embodiments, candidate target is selected from by making vinyl pyridine or poly-(vinyl pyridine) and the compound of following formula 1 react the reaction product that obtains:
R
1-L (1)
R wherein
1Be alkyl, thiazolinyl, aralkyl, heteroarylalkyl, substituted alkyl, substituted alkenyl, substituted aralkyl or substituted heteroaryl alkyl; And L is a leavings group.
Leavings group is can be from any group of carbon atom removal.Generally speaking, weak base is good leavings group.Exemplary leavings group is halogenide, methyl sulfate, tosylate etc.
In another embodiment, R
1Be alkyl, substituted alkyl; Preferably, R
1For replacing or unsubstituted methyl, ethyl, straight chain, side chain or cyclopropyl, butyl, amyl group or hexyl; Be methyl, hydroxyl, ethanoyl, chloroethoxy ethyl or methoxy ethoxy methyl in one embodiment.
In a further embodiment, R
1Be alkyl; Preferably, R
1Be vinyl, propenyl, straight or branched butenyl, straight chain, side chain or ring-type pentenyl or straight chain, side chain or ring-type hexenyl; Be propenyl in one embodiment.
In another embodiment, R
1Be aralkyl or substituted aralkyl; Preferred R
1Be benzyl or substituted benzyl, naphthyl alkyl or substituted naphthyl alkyl; Be benzyl or naphthyl methyl in one embodiment.
In another embodiment, R
1Be heteroarylalkyl or substituted heteroaryl alkyl; Preferably, R
1Be pyridyl alkyl; Especially, R
1Be pyridylmethyl.
In a further embodiment, L is muriate, methyl sulfate (CH
3SO
4 -), sulfuric acid monooctyl ester (C
8H
18SO
4 -), three fluoro methane sulfonates (CF
3SO
3 -), chloroacetate (CH
2ClC (O) O
-) or tosylate (C
7H
7SO
3 -); Preferably, L is methyl sulfate, muriate or tosylate.
In such embodiment, poly-(the 1-methyl-4-vinylpridine methyl sulfate) that the leveling agent compound obtains for poly-by making (4-vinylpridine) and methyl-sulfate reaction, as described below:
Water-soluble initiator can be used for preparing vinylpyridine polymer, certainly, also can not use them in currently preferred embodiments or in working example.Exemplary water-soluble initiator is superoxide (for example, hydrogen peroxide, benzoyl peroxide, peroxybenzoic acid etc.) and for example 4,4 '-azo two water-soluble azo initiators such as (4-cyanovaleric acids).
In a further embodiment, leveling agent constitutes the ingredients of a mixture of one of them and some monomer (for example, being pyridine derivative compound) of above-mentioned polymkeric substance.In such embodiment, mixture obtains by monomer, and to produce quaternary ammonium salt, described quaternary ammonium salt then carries out autohemagglutination.Quaternary ammonium salt does not have complete polymerization, and on the contrary, it produces the mixture of polymers of monomer and spontaneous generation.In currently preferred embodiments, 4-vinylpridine is by quaternized with the methyl-sulfate reaction, and autohemagglutination according to following reaction formula (45 ℃-65 ℃) takes place:
This has represented the material according to the example 4 of method 3 reactions of following example 1.Along with the increase of the amount of the methyl alcohol that uses in the quaterisation, monomeric fraction increases; That is, the autohemagglutination degree reduces.Although formed leveling agent system is polymkeric substance and monomeric mixture, its prima facie, only polymkeric substance is actively carried out the leveling function.
The active ingredient of substituted pyridines polymer compound is integrated in the plating tank to the concentration of about 100mg/L with about 0.01mg/L.Thus, active ingredient is the homopolymer of vinyl pyridine, the multipolymer of vinyl pyridine, the quaternary ammonium salt of vinyl pyridine and/or the quaternary ammonium salt of these homopolymer and multipolymer.Active ingredient does not comprise the nonactive negatively charged ion relevant with quaternary ammonium salt.In one embodiment, the active ingredient of compound with between about 0.1mg/L (0.4micromole/L) and about 25mg/L (108micromole/L) or higher concentration be present in the groove.
Although substituted pyridines polymkeric substance of the present invention can be used in many plating tanks, but in one embodiment, preferably with they with as at commonly assigned United States Patent (USP) 6,776, the special inhibitor and the accelerator that disclose in 893 are used in combination, and the full content of this United States Patent (USP) is hereby expressly incorporated by reference.In such system, preferred inhibitors is the polyol derivative that is selected from the segmented copolymer, polyoxyethylene or the polyoxypropylene that comprise polyoxyethylene and polyoxypropylene, the mixture that reaches the polyol derivative of polyoxyethylene and polyoxypropylene.The polyethers inhibitor compound typically with about 0.02 and about 2g/L between concentration, more typically with about 0.04 and about 1.5g/L between concentration, even more typically about 0.1 and 1g/L between concentration mixed.Particularly preferred inhibitor comprises the polyethers of representing with structural formula 2,3 and 4.
Structural formula 4
Wherein x+y+z is 3 to 100, and wherein e+f+g and h+f+g are respectively 5 to 100.
A kind of particularly preferred inhibitor is the polyoxyethylene/polyoxypropylene block copolymers of quadrol,
Wherein the molecular weight of polyoxypropylene (hydrophobic materials) is about 2500-3000, and the molecular weight of polyoxyethylene (hydrophile) is about 2500-3000.The molecular weight of polymkeric substance is about 5500.Described polymkeric substance can (BASF Corporation of Mt.Olive be NewJersey) with trade name from the BASF AG on Olive mountain, New Jersey
704 obtain.
For accelerator, in the system of the current proposition of applicant, accelerator is corresponding to the solvable organic divalent sulfur compound of the groove of following formula:
R
1-(S)
nRXO
3M (5)
Wherein
M can be hydrogen, basic metal or ammonium according to satisfying valent needs;
X is S or P;
R is hydrocarbon or the cycloolefin with 1 to 8 carbon atom, the aromatic hydrocarbon that contains 6 to 12 carbon atoms or aliphatic aromatic hydrocarbon;
N is 1 to 6; And
R
1Be selected from following group:
MO
3XR, wherein M, X and R as defined above,
Thiocarbamate shown in the following structural formula,
Xanthate shown in the following structural formula:
And amido imide:
R wherein
2, R
3, R
4, R
5Be respectively hydrogen, have alkyl, heterocyclic radical or the aromatic base of 1 to 4 carbon atom.
Particularly preferred accelerator comprises corresponding to the solvable organic divalent sulfur compound of the groove of said structure formula 5, wherein
R
1Be M, X and R MO as defined above wherein
3Thiocarbamate shown in XR or the structural formula
Wherein
R
2And R
3Be respectively hydrogen, have alkyl, heterocyclic radical or the aromatic group of 1-4 carbon atom.
Preferred especially accelerator is the 1-propanesulfonic acid 3 according to following structural formula, 3 '-disulfide group disodium salt:
The concentration of used accelerator is typically about 0.5-1000mg/L, more typically in the concentration between about 5-30mg/L between about 5-50mg/L even more typically.
Alternatively, other leveling compound can be incorporated in the plating tank as the benzyl chloride that discloses in U.S. Patent Publication No. No.20030168343 and reaction product of hydroxyethyl polymine etc., and the full content of this piece patent is hereby expressly incorporated by reference.
Although the combination of described inhibitor, accelerator and leveling compound is not crucial for compound efficacy of the present invention, think to obtain best overall deposition and structural element filling this moment.
A kind of preferred copper sedimentation tank comprises the copper (CuSO that comprises about 40g/L
4), the H of about 10g/L
2SO
4Cl with about 50ppm
-Additional liquid.This preferred total plating tank further comprises being called of about 2ml/L (200ppm) that can obtain from Enthone
The name of the inhibitor of inhibitor, about 6ml/L (12ppm) that can obtain from Enthone is called
The accelerator of accelerator and from Enthone with title
The leveling agent of about 2.5ml/L (4ppm) that leveling agent obtains.Substituted pyridines based polyalcohol of the present invention also can add described plating tank to.
Have been found that the substituted pyridinyl polymer compound of the present invention with aforementioned concentration and combination can provide the leveling effect of raising, and do not hinder substantially in the super structural element that is filled into high aspect ratio of copper.Described additive also demonstrates to be had the defective of minimizing, improve brightness, minimizes excessive plating, improves uniformity coefficient and reduces the advantage of invading (underplating) in the end in some macrostructure elements.
The advantage of substituted pyridinyl polymeric additive of the present invention is, compares with the settling that the plating tank that never comprises these compounds forms, and reduced the appearance of inner cavity.Inner cavity is by the formation of deposits of copper at structural element sidewall and structural element top inlet, thereby it causes pinch off to be closed to the inlet of structural element inside.This defective especially for less (for example,＜100nm) and/or the structural element with high aspect ratio (degree of depth: width, for example〉4:1) especially as seen.Because the inlet that copper enters structural element is suppressed or closes, thus inner cavity can stay in the structural element, thereby hinder electrical connection by structural element.Compound exhibits of the present invention can reduce the appearance of internal cavity, because compound less hinders super filling than other leveling agent, thereby has reduced the generation of closing of high-aspect-ratio structure element.
As general recommendation, because existence is to the less obstruction of super filling, so can flatten more energetically.More and more littler this is just valuable especially along with chip architecture becomes, because along with interconnect dimensions reduces to 100nm (nanometer) level and littler, just comparing much bigger vertical deposition speed with the level deposition speed that requires compares, require super faster filling, and can aggravate planarization problem and needs flattening.Leveling agent of the present invention allows to use the accelerator/inhibitor combinatorial chemistry product that causes usually excessively swelling to quicken super filling speed.
Another advantage of composition of the present invention is to reduce copper hole, for example metal disappearance defective and microcavities etc.These defectives have reduced the output and the reliability of semiconductor integrated circuit element.
Another advantage of composition of the present invention is the total surface roughness that has reduced in substrate surface and the interconnection structure element.Because coarse copper growth is pinch off structural element inlet potentially, stays inner cavity, becomes more and more important so the minimizing surfaceness fills to become for the zero defect of realizing meticulous interconnection structure.
Another advantage of leveling agent of the present invention is the appearance that has reduced rat, described rat be in local high current density position, the copper sediment-filled phase ratio that forms of isolated deposition peak that local impurity position or other position occur and the plating tank that never comprises compound of the present invention, the appearance of these projectioies reduces.
The tangible advantage of another of compound of the present invention causes owing to excessive galvanized size reduces to improve with uniformity coefficient, and this has realized thin copper layer deposition, obtaining smooth surface, thereby must remove less material in the electroless copper deposition operation of back.For example, the structural element below use chemically machinery polished (CMP) appears after copper is electroplated.More level deposition of the present invention (leveldeposit) therefore causes to be removed by CMP afterwards and reduces corresponding to the minimizing of the amount of metal that must be deposited.There is the minimizing of depleted amount of metal, more importantly, reduces CMP operation required time.It also is more not serious that material is removed operation, and this is related with the time length that reduces, and removes the minimizing that operation produces the trend of defective corresponding to material.Thus, for a lot of embodiment among above-mentioned numerous embodiment, the copper deposition comprises the deposition of copper alloy.
Copper plating tank can be according to being altered a great deal by galvanized substrate and the copper of wanting sedimentation type.Described plating tank comprises acid tank and alkali groove.By name " the modern plating (and ModernElectroplating, F.A.Lowenheim edits, John Reily ﹠amp; Sons, Inc., 1974) " books in the 183-203 page or leaf a lot of copper plating tanks have been described.Exemplary plating tank comprises copper fluoroborate, copper pyrophosphate salt, copper prussiate, copper phosphonate and other copper metal complex (for example methylsulfonic acid etc.).The typical copper plating tank of great majority comprises the copper sulfate in the acidic solution.
The concentration of copper and acid can change in very wide scope, for example from the copper of about 4-70g/L with from the acid of about 2-225g/L.Thus, compound of the present invention is suitable for being used in peracid/low copper system and the low acid/high-copper system.In peracid/low copper system, the magnitude that copper ion concentration can be from the magnitude of 4g/L to 30g/L, and acid concentration can be at the sulfuric acid greater than the amount of about 50-225g/L.In a kind of peracid/low copper system, copper ion concentration is about 17g/L, wherein H
2SO
4Concentration is about 180g/L.In low acid/high-copper system, copper ion concentration can be greater than magnitude about 30,40g/L, in addition to the magnitude of 55g/L (greater than 50g/L copper corresponding to copper SO greater than 200g/L
4-5H
2The O cupric sulfate pentahydrate).Acid concentration in these systems less than 50,40g/L, even be 30g/L (H
2SO
4), low to about 7g/L.In an exemplary low acid/high-copper system, copper concentration is about 40g/L, H
2SO
4Concentration is about 10g/L.
Chlorion also can be used in the plating tank, and its magnitude can be up to 200mg/L's (preferably being about 90mg/L).Described plating tank also preferably comprises for example organic additive systems such as accelerator, inhibitor and leveling agent.
A variety of additives can be used in the plating tank usually, so that the surface finish to the expection of copper facing metal to be provided.Usually, use with the every kind of additive that is used to form the function of wanting more than a kind of additive.These additives are generally used for initiating the filling from bottom to top of interconnection structure element, and are used to improve physical attributes such as metal-plated outward appearance (brightness), structure and for example electroconductibility.Specific additive (usually being organic additive) is used for grain refining, suppresses dendritic growth and improve to cover and dispersive ability.Be used in a lot of reference that comprise " ModernElectroplating " that the typical additive in the plating enumerates in the above and discussed.Special ideal additive system uses aromatic series or aliphatics quaternary amine, polysulphide and polyethers.Other additive comprises for example selenium, tellurium and sulphur compound.
The electroplating device that is used for the electroplating of semiconductor substrate is known, and is described in people's such as Haydu United States Patent (USP) 6,024,856 for instance.Electroplating device comprises plating vat, its ccontaining copper electrolyte, and by for example plastics or other for the chemically inert material of electroplate liquid etc. suitably material make.For wafer electroplating, described case can be a cylindricality especially.Negative electrode is horizontally set on upper box part, and can be the substrate of any kind, for example has the silicon wafer such as openings such as groove and through holes.Wafer substrate typically applies with copper or other metal seed layer, electroplates to cause thereon.Copper seed layer can pass through chemical vapor deposition (CVD), physical vapor deposition (PVD) or similar approach to be realized.Also be preferably circle for the wafer electroplating anode, and be horizontally set on lower box part, between anode and negative electrode, form a space.Anode typically is soluble anode.
These plating tank additives usually use in conjunction with the membrane technique of various tool manufacturers exploitation.In described system, anode can be isolated by film and organic plating tank.The purpose of separating anode and organic plating tank additive is that organic plating tank additive oxidizing reaction is minimized.
Cathode base and anode are electrically connected to rectifier (power supply) by lead respectively.The cathode base that is used for direct current or pulsed current has net negative charge, thereby the cupric ion in the solution reduces at the cathode base place, forms electroplated metal copper on cathode surface.Oxidizing reaction occurs in the anode place.Negative electrode and anode can levels or are vertically set in the case.
In the operating period of electroplating system, when rectifier was energized, metallic copper was plated on the surface of cathode base.Can adopt pulsed current, direct current, reversal periods electric current or other electric current that is fit to.Can use heater/cooler to keep the temperature of electrolytic solution, electrolytic solution is taken out from storage box thus, and the heater/cooler of flowing through, and then is recycled to storage box.
The optional attribute of described technology is, as United States Patent (USP) 6,024, described in 856, when satisfying predetermined work parameter (condition), by removing the part control electroplating system of electrolytic solution from electroplating system, and simultaneously or the new electrolytic solution that after removing electrolytic solution, has an amount identical with the electrolyte content cardinal principle of removing be added to described system.New electrolytic solution preferably comprises the single liquid of keeping the needed all substances of plating bath and system.Interpolation/removal system makes the electroplating system of the electroplating effect with raisings such as for example constant plating attributes keep stable state constant.Utilize this system and method, plating bath reaches stable state, and wherein the plating tank component is steady-state value substantially.
For example identical substantially in electrolytic conditions such as current concentration, applied voltage, current density and electrolyte temperature and the traditional electrolytic copper electroplating method.For example, the plating tank temperature is about room temperature (for example, about 20-27 ℃) usually, but also up to about 40 ℃ or higher high temperature.Current density is about 2 to 460ASF usually usually up to 100 amperes every square feet (ASF).Preferably use to be about the anode of 1:1 and the ratio of negative electrode, but this also can alter a great deal, from about 1:4 to 4:1.Described technology is also used the mixing in plating vat, wherein by stirring or preferably providing described mixing by circular electrolyte is circulated by case.The plating vat of flowing through provides the typical residence time of electrolytic solution in case less than about 1 minute, more typically less than 30 seconds, for example, 10-20 second.
Embodiment:
Following example illustrates the present invention.
Example 1
Synthetic method
Method 1: the pyridine initial feed of listing below (0.1mol) is dissolved in the chloroform of about 50mL in the round-bottomed flask.Reagent (the R that lists below
1L) (0.105mol) under agitation added at leisure in the initial feed solution.Adding reagent (R
1L) after, heated mixt makes backflow, finishes up to reaction.After heating, remove chloroform by rotary evaporation, and utilize proper method to obtain product according to its physics and chemical structure element.Described product is transferred in the flask of 100mL by deionized water.Further dilution is so that active substance reaches the ultimate density of 750mg/L.
Method 2: (0.1mol) adds in the water of about 50mL in the round-bottomed flask with the pyridine initial feed.Reagent (R
1L) (0.105mol) under agitation added at leisure in the initial feed solution.Based on alkylating agent, initial reaction is attended by temperature and raises.Adding reagent (R with 35 ℃
1L) after, mixture is heated to reflux one hour.Described product is transferred in the 100mL flask by deionized water after heating.Further dilution is so that active substance reaches the ultimate density of 750mg/L.
Method 3: (0.1mol) is dissolved in the anhydrous methanol of about 50mL in the round-bottomed flask with the pyridine initial feed.When temperature is not higher than 35 ℃, alkylating agent (0.105mol) stirring is added in the initial feed solution down at leisure.Adding reagent (R
1L) after, add the water of about 2 grams, and mixture slowly is heated to 65-70 ℃, with any residue of hydrolysis, for example methyl-sulfate or methyl tosylate.With the mixture heating up several hrs, finish substantially up to thinking to react.Remove methyl alcohol by rotary evaporation, but it also is acceptable allowing methyl alcohol to stay.Described product is transferred in the flask of 100mL by deionized water.Described method can be used for obtaining the product into low-molecular weight polymer and monomeric mixture.Further dilution is so that active substance reaches the ultimate density of 750mg/L.
Method 4: (0.1mol) is placed in the round-bottomed flask with the pyridine initial feed.With reagent (R
1L) (0.105mol) stirring is added in the starting material solution down at leisure.Adding reagent (R
1L) after, mixture slowly is heated to 105-140 ℃, finishes substantially up to reaction.After reaction, described product is transferred in the 100mL flask by deionized water.Further dilution is so that active substance reaches the ultimate density of 750mg/L.
Method 5: (0.1mol) is dissolved in the ethylene glycol of about 25mL in the round-bottomed flask with the pyridine initial feed.With reagent (R
1L) (0.2mol) stirring is added in the material solution down at leisure.After adding alkylating agent, mixture slowly is heated to 105 ℃, then be heated to 130-140 ℃.130-140 ℃ with the mixture heating up several hrs, up to the reaction finish substantially.Remove reagent (R as much as possible by rotary evaporation
1L).Described product is transferred in the 100mL flask by deionized water.Further dilution is so that active substance reaches the ultimate density of 750mg/L.
U.S. Patent No. 4,212,764 and 5,824,756 have also disclosed polyvinyl arsenic pyridine polymerization.
Example 2-17
Make following pyridine raw material and reagent (R
1L) react according to aforesaid method.Its lytic activity in the copper electroplating bath shows that product produces the sedimentary relative capacity of acceptable copper when electroplating deposition.
| Example | The pyridine starting material | Reagent (R 1L) | Synthetic method | Its lytic activity during copper is bathed |
| 2 | Poly-(4-vinylpridine) | Me 2SO 4 | Method 3 | Activity is very strong |
| 3 | Poly-(4-vinylpridine) | The methyl tosylate | Method 3 | Activity is very strong |
| 4 | 4-vinylpridine | Me 2SO 4 | Method 1,3 | Activity is very strong; The room temperature heat release |
| 5 | 4-vinylpridine | Benzoyl chloride (BzCl) | Method 1 | Activity is very strong |
| 6 | 4-vinylpridine | Chlorallylene | Method 1 | Activity is very strong |
| 7 | 4-vinylpridine | 2-chloro-ethanol | Method 5 | Activity is very strong |
| 8 | 4-vinylpridine | Epicholorohydrin | Method 1 | Produce gel; Heating back heat release |
| 9 | 4-vinylpridine | 1-chloromethyl-naphthalene | Method | Water insoluble |
| 10 | 4-vinylpridine | 4-chloromethyl-pyridine | Method 1 | A little less than the relative reactivity |
| 11 | 4-vinylpridine | 1,3-propane sultone | Method 1 | A little less than the relative reactivity; Be higher than the room temperature heat release |
| 12 | 4-vinylpridine | The methyl tosylate | Method 2,3 | Activity is very strong; Heating back heat release |
| 13 | 4-vinylpridine | Chloro-acetone | Method 1 | Activity is very strong |
| 14 | 4-vinylpridine | The chloro-acetonitrile | Method 1 | The smell of HCN gas |
| 15 | 4-vinylpridine | 2-methoxyl group-oxyethyl group muriate | Method 1 | Activity is very strong |
| 16 | 4-vinylpridine | 2-monochloroethane ether | Method 4 | Activity is arranged |
| 17 | The 2-vinyl pyridine | 2-chloro-ethanol | Method 4 | Activity is arranged; Incomplete reaction |
| 18 | The 2-vinyl pyridine | The methyl tosylate | Method 2,3 | Activity is not stronger |
| 19 | The 2-vinyl pyridine | Me 2SO 4 | Method 1,3 | A little less than the relative reactivity; The room temperature heat release |
| 20 | 4-vinylpridine | 1,3 dichlorohydrine | Method 5 | Activity is very strong |
In example 2 and 3, the molecular weight of poly-(4-vinylpridine) raw material is 16,000.In example 4-20, because the reaction of quaterisation after product spontaneous polymerization, so reaction product is in various degree polymkeric substance and monomer mixture.
Example 21
Deposition from the copper groove of the reaction product of poly-(4-vinylpridine) that comprise example 2 and methyl-sulfate
Prepare following plating bath:
Composition is based on the amount of plating tank
Copper 40g/l
Sulfuric acid 10g/l
Accelerator 9ml/l
Poly-(4-vinylpridine) and
The reaction product 4.5mg/l of methyl-sulfate
Chlorion 50mg/L
Plating tank is added to the Hull cell of 267mL.At 2 amperes brass Hull cell plate/negative electrode was electroplated 3 minutes.Current density changes in the different zones of Hull cell plate/negative electrode, from about 2 milliamperes every square centimeter to about 800 milliamperes every square centimeter in other zone in some zones.It is very bright and uniform that described plating tank generation copper is deposited on the interior copper deposition of whole plating scope.
Example 22
Deposition from the copper plating tank of the reaction product of the 4-vinylpridine that comprises example 7 and ethylene chlorhydrin
Prepare following plating bath:
Composition is based on the amount of plating tank
Copper 40g/l
Sulfuric acid 10g/l
The reaction product 3mg/l of 4-vinylpridine and ethylene chlorhydrin
Chlorion 50mg/L
Plating tank is added to the Hull cell of 267mL.At 2 amperes brass Hull cell plate/negative electrode was electroplated 3 minutes.Current density changes in the different zones of Hull cell plate/negative electrode, from about 2 milliamperes every square centimeter to about 800 milliamperes every square centimeter in other zone in some zones.It is very bright and even that described plating tank generation copper is deposited on the interior this copper deposition of whole plating scope.
Example 23
Deposition from the copper plating tank of the reaction product of the 4-vinylpridine that comprises example 4 and methyl-sulfate
Prepare following plating bath:
Composition is based on the amount of plating tank
Copper 40g/l
Sulfuric acid 10g/l
Inhibitor 2ml/l
The reaction product 12mg/l of 4-vinylpridine and methyl-sulfate
Chlorion 50mg/L
Plating tank is added to the Hull cell of 267mL.At 2 amperes brass Hull cell plate/negative electrode was electroplated 3 minutes.Current density changes in the different zones of Hull cell plate/negative electrode, from about 2 milliamperes every square centimeter to about 800 milliamperes every square centimeter in other zone in some zones.It is very bright and uniform that described plating tank generation copper is deposited on the interior this copper deposition of whole spraying plating scope.
Example 24
Groove with the 180nm width is four graphics test wafer (SiO with Ta barrier of structural element
2, can obtain with title QCD from Sematech) respectively comprise cupric ion (40g/L), sulfuric acid (10g/L), chlorion (50mg/L),
Inhibitor (2ml/L),
Accelerator (9ml/L) and changing in the solution of leveling agent structural element with 10mA/cm
2Electroplated 15 seconds.
Fig. 1 illustrates the cross section of the galvanized wafer of leveling agent of no use; Fig. 2 illustrates the cross section of the galvanized wafer of commercial leveling agent that utilizes 10ml/L; Fig. 3 illustrates the cross section of the galvanized wafer of leveling agent that utilizes 10ml/L, and wherein said leveling agent constitutes the polymer/monomer mixture according to the scheme preparation of example 4; Fig. 4 illustrates the cross section with the galvanized wafer of leveling agent of 10ml/L, and wherein said leveling agent is the polymkeric substance according to the scheme preparation of example 2.
Fig. 1 illustrates without the big super loading level of leveling agent in 15 seconds, illustrates with growth forward position and U-shaped geometrical shape in the structural element.This expression bottom speed of growth is obviously big a lot of than the sidewall growth.Add the commercial leveling agent (Fig. 2) of 10ml/L, the growth forward position reduces in structural element after 15 seconds, represents that slower integral-filled and leveling agent is suitable to the great obstruction degree of super filling.And, with among Fig. 1 without the cardinal principle U-shaped profile phase ratio of leveling agent, growth forward geometrical shape is utilized the leveling agent forming V-shape.Therefore, leveling agent hinders super filling to a certain extent.
Fig. 3 and 4 illustrate utilize example 2 and 4 two kinds of leveling agents of the present invention in 15 seconds even bigger super loading level.Therefore, these leveling agents do not disturb super filling substantially.Advantageously, these represent that also having the orthogonal that is roughly that is roughly 90 ° of angles by whole fill process between filling bottom and sidewall fills profile.On the contrary, the ST Stuffing Table of Fig. 2 (commercial leveling agent) is shown in and is interconnected in the 75% filling profile that is roughly V-arrangement before being full of and begins to form.
Example 25
Groove with the 180nm width is three testing wafer (diameters of 200nm of structural element; Obtain with title QCD from Sematech) respectively comprise cupric ion (40g/L), sulfuric acid (10g/L), chlorion (50mg/L),
Inhibitor (2ml/L),
From Sabre copper plating instrument (the Sabre Copper Plating Tool) solution that Novellus obtains, electroplating of the no leveling agent of accelerator (9ml/L).
Fig. 5 and 6 illustrates with the wafer speed of rotation of 30rpm and 33 seconds 3A succeeded by the center (Fig. 5) of the galvanized wafer of electric current of 25 seconds 18A and the cross section of edge (Fig. 5).Fig. 7 and 8 illustrates under these conditions with the wafer speed of rotation of 125rpm and 33 seconds 3A succeeded by the center (Fig. 7) of the galvanized wafer of electric current of 25 seconds 18A and the cross section of edge (Fig. 8).Fig. 9 and 10 illustrates under these conditions with the wafer speed of rotation of 30rpm and 27 seconds 1.5A succeeded by 27 seconds 3A succeeded by the center (Fig. 9) of the galvanized wafer of electric current of 44 seconds 12A and the cross section of edge (Figure 10).
Example 26
Testing wafer (the diameter of 200nm that these grooves with the 180nm width are structural element; Obtain with title QCD from Sematech) respectively comprise cupric ion (40g/L), sulfuric acid (10g/L), chlorion (50mg/L),
Inhibitor (2ml/L),
Electroplate in accelerator (9ml/L) and 6ml/L the solution according to the leveling agent of the polymer/monomer of the scheme preparation of example 4.
Figure 11 and 12 illustrates with the wafer speed of rotation of 30rpm and 33 seconds 3A succeeded by the center (Figure 11) of the galvanized wafer of electric current of 25 seconds 18A and the cross section of edge (Figure 12).Figure 13 and 14 illustrates under these conditions with the wafer speed of rotation of 125rpm and 33 seconds 3A succeeded by the center (Figure 13) of the galvanized wafer of electric current of 25 seconds 18A and the cross section of edge (Figure 14).Figure 15 and 16 illustrates under these conditions the cross section succeeded by 27 seconds 3A succeeded by the galvanized center wafer of the electric current of 44 seconds 12A (Figure 15) and edge (Figure 16) with the wafer speed of rotation of 30rpm and 27 seconds 3A.
Example 27
Groove with the 180nm width is three testing wafer (diameters of 200nm of structural element; Obtain with title QCD from Sematech) respectively comprise cupric ion (40g/L), sulfuric acid (10g/L), chlorion (50mg/L),
Inhibitor (2ml/L),
Electroplate in accelerator (9ml/L) and 6ml/L the solution according to the leveling agent of the polymer/monomer of the scheme preparation of example 2.
Figure 17 and 18 illustrates with the wafer speed of rotation of 30rpm and 33 seconds 3A succeeded by the center (Figure 17) of the galvanized wafer of electric current of 25 seconds 18A and the cross section of edge (Figure 18).Figure 19 and 20 illustrates under these conditions with the wafer speed of rotation of 125rpm and 33 seconds 3A succeeded by the center (Figure 19) of the galvanized wafer of electric current of 25 seconds 18A and the cross section of edge (Figure 20).Figure 21 and 22 illustrates under these conditions with the wafer speed of rotation of 30rpm and 27 seconds 105A succeeded by 27 seconds 3A succeeded by galvanized center wafer of the electric current of 44 seconds 12A (Figure 21) and cross section, edge (Figure 22).
With the deposition of Fig. 5-10 (not having leveling agent) and the sediment-filled phase ratio of Figure 11-16 (leveling agent of example 4) and 17-22 (leveling agent of example 2),, show super leveling structural element of the present invention owing to excessively electroplate and protuberance minimizing substantially.Do not flatten composition, the necessary sizable copper of deposit thickness, to obtain to be used for the abundant smooth surface of CMP operation subsequently, this has improved in fact and copper plating and CMP technology cost related.
When introducing the key element of the present invention or its preferred embodiment, article " ", " being somebody's turn to do ", " described " are meant and have one or more key element.For example, the description of front and appending claims are quoted " one " interconnection and are meant one or more such interconnection of existence.Speech " comprises ", " comprising " and " having " be meant open comprising, means to have the other key element different with listed key element.
Can make various changes to above-mentioned, and not depart from scope of the present invention, the objective of the invention is, comprise and should be understood that exemplary with all substances illustrated in the accompanying drawings in the superincumbent description, but not determinate.Scope of the present invention is limited by appended claims, and can make the modification that does not depart from scope of the present invention to the foregoing description.
Definition
Unless otherwise noted, otherwise alkyl described herein be preferably and comprise one to eight low alkyl group in the main chain up to 20 carbon atoms.They can be straight or branched or ring-type, and comprise methyl, ethyl, propyl group, sec.-propyl, butyl, hexyl etc.
Unless otherwise noted, otherwise thiazolinyl described herein be preferably and comprise two to eight low thiazolinyls in the main chain up to 20 carbon atoms.They can be straight or branched or ring-type, and comprise vinyl, propenyl, pseudoallyl, butenyl, hexenyl etc.
Unless otherwise noted, otherwise " substituted alkyl or substituted alkenyl " described herein half family uses and at least one is different from alkyl or alkenyl half family that the atom of carbon atom replaces, and comprises half family that carbochain atom wherein replaces with heteroatomss such as for example nitrogen, oxygen, silicon, phosphorus, boron or halogen atoms.These substituents comprise halogen, heterocycle, alkoxyl group, alkenyloxy, alkynyloxy group, hydroxyl, protection hydroxyl, ketone group, acyl group, acyloxy, nitro, amido, amino, cyano group, mercaptan, ketone acetal, acetal, ester, ether.
Here use separately or as the term " aromatic base " of the part of another base or the homocyclic ring aromatic group of the optional replacement of " aryl " expression, be preferably the monocycle or the bicyclic group that comprise 6 to 12 carbon atoms in the loop section, for example phenyl, biphenyl, naphthyl, substituted-phenyl, substituted biphenyl or substituted naphthyl.Phenyl and substituted-phenyl are preferred aromatic bases.
Here use separately or as the term " aromatic base " of the part of another base or the homocyclic ring aromatic group of the optional replacement of " aryl " expression, wherein the carbon atom of aromatic group is connected directly to the carbon atom of aromatic base, and aralkyl half family is connected to derivative by aromatic base.Aromatic base and comprise that the alkyl of aralkyl defines in the above.
Here use separately or be meant chlorine, bromine, fluorine and iodine as term " halogen " or " (halo) of halogen " of the part of another base.
Unless otherwise noted, otherwise term " heteroarylalkyl " expression be connected to as definition here as the alkyl of the chain group (linker group) of the rest part of molecule as heteroaryl described herein.
Here use separately or be illustrated in and have the optional replacement aromatic group that preferably has 5 or 6 atoms at least one heteroatoms and each ring at least one ring as the term " heteroaryl " of the part of another base.Fragrant heterocyclic radical preferably has 1 or 2 Sauerstoffatom, 1 or 2 sulphur atom and/or 1 to 4 nitrogen-atoms in ring, and can be connected to the rest part of molecule by carbon or heteroatomic bond.Exemplary heteroarylalkyl comprises thienyl, pyridyl, oh azoles base, pyrryl, indoles or its isoquinolyl and analogue.Exemplary substituent comprises the one or more of following base: alkyl; Substituted hydrocarbon radical; Ketone group; The protection hydroxyl; Acyl group; Acyloxy; Alkoxyl group; Alkenyloxy; Alkynyloxy group; Aryloxy; Halogen; Amide group; Amino; Nitro; Cyano group; Mercaptan; Ketal; Acetal; Ester; And ether.
Here use separately or remove half family that hydroxyl forms by base-COOH from organic carboxyl acid as term " acyl group " expression of the part of another base, for example, RC (O)-, wherein R is R
1, R
1O-, R
1R
2N-or R
1S-, R
1Be alkyl, assorted substituted hydrocarbon radical or heterocycle, and R
2Be hydrogen, alkyl or substituted hydrocarbon radical.
Here use separately or as term " acyloxy " expression of the part of another base by oxygen connect (--O--) the aforesaid acyl group of keyed jointing, for example RC (O)-, wherein R is as defining in conjunction with term " acyl group ".
Claims (33)
1. method that in the microelectronic element manufacturing, copper is electroplated onto on the substrate with electric interconnection structure element, described method comprises:
Described substrate immersion is comprised in the electrolytic solution of following compositions:
Copper ion source, its amount enough with copper electrodeposition to the substrate and in the electric interconnection structure element, wherein, the opening of described electric interconnection structure element is less than 100nm, and its aspect ratio was greater than 4: 1;
One or more super bulking agent compositions, it promotes the deposition of copper in the interconnection structure element, wherein the structural element speed of growth in vertical direction is more much bigger than the speed of growth in the horizontal direction, and wherein said super bulking agent compositions is selected from the group that comprises accelerator, inhibitor and combination thereof; And
Leveling agent comprises the substituted pyridines polymer compound, and it has the leveling effect that does not hinder super filling; And
With the current supply electrolytic solution, to deposit copper on the substrate.
2. method according to claim 1, wherein said substituted pyridines polymer compound is the pyridinium salt compound.
3. method according to claim 1, wherein said substituted pyridines polymer compound is the vinylpyridine piperidine derivatives.
4. method according to claim 1, wherein said substituted pyridines polymer compound are the derivatives of 2-vinyl pyridine.
5. method according to claim 1, wherein said substituted pyridines polymer compound are the derivatives of 4-vinylpridine.
6. method according to claim 1, wherein said substituted pyridines polymer compound is the vinyl pyridine homopolymer.
7. method according to claim 1, wherein said substituted pyridines polymer compound is a vinylpyridine copolymer.
8. method according to claim 1, wherein said substituted pyridines polymer compound is selected from the quaternary ammonium salt of vinyl pyridine homopolymer and the quaternary ammonium salt of vinylpyridine copolymer.
9. method according to claim 1, wherein said substituted pyridines polymer compound are the reaction product of 4-vinylpridine.
10. method according to claim 1, wherein said substituted pyridines polymer compound are the reaction product of poly-(4-vinylpridine).
11. method according to claim 1, wherein said substituted pyridines polymer compound are the reaction product of 4-vinylpridine and methyl-sulfate.
12. method according to claim 1, wherein said substituted pyridines polymer compound are the reaction product of poly-(4-vinylpridine) and methyl-sulfate.
13. method according to claim 1, wherein said substituted pyridines polymer compound are 4-vinylpridine and chemical formula is the reaction product that following compound reaction obtains:
R
1-L (1)
R wherein
1Be alkyl, thiazolinyl, aralkyl, heteroarylalkyl, substituted alkyl, substituted alkenyl, substituted aralkyl or substituted heteroaryl alkyl; And
L is a leavings group.
14. method according to claim 1, wherein said substituted pyridines polymer compound is selected from and comprises following group: the reaction product of poly--(4-vinylpridine) and methyl-sulfate, the reaction product of poly--(4-vinylpridine) and methyl tosylate, the reaction product of 4-vinylpridine and methyl-sulfate, the reaction product of 4-vinylpridine and methyl tosylate, the reaction product of 4-vinylpridine and ethylene chlorhydrin, the reaction product of 4-vinylpridine and benzyl chloride, the reaction product of 4-vinylpridine and chlorallylene, the reaction product of 4-vinylpridine and 4-chloromethylpyridine, 4-vinylpridine and 1, the reaction product of 3-propane sultone, the reaction product of 4-vinylpridine and methyl tosylate, the reaction product of 4-vinylpridine and monochloroacetone, the reaction product of 4-vinylpridine and 2-methoxy ethoxy methyl chloride, the reaction product of 4-vinylpridine and 2-chlorethyl ether, the reaction product of 2-vinyl pyridine and methyl tosylate, the reaction product of 2-vinyl pyridine and methyl-sulfate, poly-(2-methyl-5-vinylpyrine), with 1-methyl-4-vinylpridine trifluoromethyl sulfonic acid.
15. method according to claim 1, wherein said substituted pyridines polymer compound is a pyridine quaternary ammonium salt.
16. according to arbitrary described method among the claim 1-15, wherein said substituted pyridines polymer compound is poly-(4-vinylpridine), and its molecular weight is 10000 to 20000g/mol.
17. according to arbitrary described method among the claim 1-15, wherein said substituted pyridines polymer compound is poly-(4-vinylpridine), and its molecular weight is 60000-160000g/mol.
18. a method that in the manufacturing of microelectronic element copper is electroplated onto on the semiconductor integrated circuit device substrate with electric interconnection structure element, described method comprises:
Described substrate immersion is comprised in the electrolytic solution of following compositions:
Copper ion source, its amount enough with copper electrodeposition to the substrate and in the electric interconnection structure element;
One or more super bulking agent compositions, it promotes the deposition of copper in the interconnection structure element, wherein the structural element speed of growth in vertical direction is more much bigger than the speed of growth in the horizontal direction, and wherein said super bulking agent compositions is selected from the group that comprises accelerator, inhibitor and combination thereof; And
Leveling agent comprises the substituted pyridines polymer compound, and it has the leveling effect that does not hinder super filling, and wherein said substituted pyridines polymer compound is the derivative of 4-vinylpridine; And
With the current supply electrolytic solution, to deposit copper on the substrate.
19. method according to claim 18, wherein said substituted pyridines polymer compound are the reaction product of poly-(4-vinylpridine).
20. method according to claim 18, wherein said substituted pyridines polymer compound are the reaction product of 4-vinylpridine and methyl-sulfate.
21. method according to claim 18, wherein said substituted pyridines polymer compound are the reaction product of poly-(4-vinylpridine) and methyl-sulfate.
22. method according to claim 18, wherein said substituted pyridines polymer compound are 4-vinylpridine and chemical formula is the reaction product that following compound reaction obtains:
R
1-L (1)
R wherein
1Be alkyl, thiazolinyl, aralkyl, heteroarylalkyl, substituted alkyl, substituted alkenyl, substituted aralkyl or substituted heteroaryl alkyl; And
L is a leavings group.
23. method according to claim 18, wherein said substituted pyridines polymer compound is selected from and comprises following group: the reaction product of poly--(4-vinylpridine) and methyl-sulfate, the reaction product of poly--(4-vinylpridine) and methyl tosylate, the reaction product of 4-vinylpridine and methyl-sulfate, the reaction product of 4-vinylpridine and methyl tosylate, the reaction product of 4-vinylpridine and ethylene chlorhydrin, the reaction product of 4-vinylpridine and benzyl chloride, the reaction product of 4-vinylpridine and chlorallylene, the reaction product of 4-vinylpridine and 4-chloromethylpyridine, 4-vinylpridine and 1, the reaction product of 3-propane sultone, the reaction product of 4-vinylpridine and methyl tosylate, the reaction product of 4-vinylpridine and monochloroacetone, the reaction product of 4-vinylpridine and 2-methoxy ethoxy methyl chloride, the reaction product of 4-vinylpridine and 2-chlorethyl ether, with 1-methyl-4-vinylpridine trifluoromethyl sulfonic acid.
24. method according to claim 18, wherein said substituted pyridines polymer compound are poly-(4-vinylpridines), and its molecular weight is 10000 to 20000g/mol.
25. method according to claim 18, wherein said substituted pyridines polymer compound are poly-(4-vinylpridines), and its molecular weight is 60000-160000g/mol.
26. a manufacturing that is used at microelectronic element is electroplated onto copper the composition on the substrate with electric interconnection structure element, described composition comprises:
Copper ion source, its amount enough with copper electrodeposition to the substrate and in the electric interconnection structure element; And
One or more super bulking agent compositions, it promotes the deposition of copper in the interconnection structure element, wherein the structural element speed of growth in vertical direction is more much bigger than the speed of growth in the horizontal direction, and wherein said super bulking agent compositions is selected from the group that comprises accelerator, inhibitor and combination thereof; And
Leveling agent comprises the substituted pyridines polymer compound, and it has the leveling effect that does not hinder super filling, and wherein said substituted pyridines polymer compound is the derivative of 4-vinylpridine.
27. composition according to claim 26, wherein said substituted pyridines polymer compound are the reaction product of poly-(4-vinylpridine).
28. composition according to claim 26, wherein said substituted pyridines polymer compound are the reaction product of 4-vinylpridine and methyl-sulfate.
29. composition according to claim 26, wherein said substituted pyridines polymer compound are the reaction product of poly-(4-vinylpridine) and methyl-sulfate.
30. composition according to claim 26, wherein said substituted pyridines polymer compound are that to make 4-vinylpridine and chemical formula be the reaction product that the reaction of following compound obtains:
R
1-L (1)
R wherein
1Be alkyl, thiazolinyl, aralkyl, heteroarylalkyl, substituted alkyl, substituted alkenyl, substituted aralkyl or substituted heteroaryl alkyl; And
L is a leavings group.
31. composition according to claim 26, wherein said substituted pyridines polymer compound is selected from and comprises following group: the reaction product of poly--(4-vinylpridine) and methyl-sulfate, the reaction product of poly--(4-vinylpridine) and methyl tosylate, the reaction product of 4-vinylpridine and methyl-sulfate, the reaction product of 4-vinylpridine and methyl tosylate, the reaction product of 4-vinylpridine and ethylene chlorhydrin, the reaction product of 4-vinylpridine and benzyl chloride, the reaction product of 4-vinylpridine and chlorallylene, the reaction product of 4-vinylpridine and 4-chloromethylpyridine, 4-vinylpridine and 1, the reaction product of 3-propane sultone, the reaction product of 4-vinylpridine and methyl tosylate, the reaction product of 4-vinylpridine and monochloroacetone, the reaction product of 4-vinylpridine and 2-methoxy ethoxy methyl chloride, the reaction product of 4-vinylpridine and 2-chlorethyl ether, with 1-methyl-4-vinylpridine trifluoromethyl sulfonic acid.
32. composition according to claim 26, wherein said substituted pyridines polymer compound are poly-(4-vinylpridines), and its molecular weight is 10000 to 20000g/mol.
33. composition according to claim 26, wherein said substituted pyridines polymer compound are poly-(4-vinylpridines), and its molecular weight is 60000 to 160000g/mol.
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| US10/963,369 | 2004-10-12 | ||
| US10/963,369 US8002962B2 (en) | 2002-03-05 | 2004-10-12 | Copper electrodeposition in microelectronics |
| PCT/US2004/041620 WO2005066391A1 (en) | 2003-12-22 | 2004-12-13 | Copper electrodeposition in microelectronics |
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| CN103601651A (en) * | 2013-11-25 | 2014-02-26 | 华东理工大学 | Multi-dendritic quaternary ammonium compound, and preparation and use thereof |
| CN105441994B (en) * | 2015-12-30 | 2017-09-19 | 上海新阳半导体材料股份有限公司 | A kind of electroplating liquid composition that can be used to improve salient point coplanarity |
| CN105887144B (en) * | 2016-06-21 | 2018-09-21 | 广东光华科技股份有限公司 | Copper electrolyte and its copper plating process is electroplated |
| US11124888B2 (en) | 2016-09-22 | 2021-09-21 | Macdermid Enthone Inc. | Copper deposition in wafer level packaging of integrated circuits |
| CN113278104A (en) * | 2021-05-10 | 2021-08-20 | 江苏理工学院 | Quaternary ammonium salt surfactant and preparation method thereof |
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| US3940320A (en) * | 1972-12-14 | 1976-02-24 | M & T Chemicals Inc. | Electrodeposition of copper |
| US4009087A (en) * | 1974-11-21 | 1977-02-22 | M&T Chemicals Inc. | Electrodeposition of copper |
| US20020036145A1 (en) * | 2000-04-27 | 2002-03-28 | Valery Dubin | Electroplating bath composition and method of using |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3940320A (en) * | 1972-12-14 | 1976-02-24 | M & T Chemicals Inc. | Electrodeposition of copper |
| US4009087A (en) * | 1974-11-21 | 1977-02-22 | M&T Chemicals Inc. | Electrodeposition of copper |
| US20020036145A1 (en) * | 2000-04-27 | 2002-03-28 | Valery Dubin | Electroplating bath composition and method of using |
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