Summary of the invention
Lacking present invention aim to address this field a kind of can be achieved, plating property low with defect, coating impurity without cavityThe problem of metal plating compositions of the small effect of good, compact structure, surface roughness, and provide a kind of leveling agent, containing itsMetal plating compositions, preparation method and application.The metal plating compositions are for electroplating printed circuit board and integrated electricityIn the copper-connection electroplating technology of road, it can be achieved that without cavity it is low with defect, coating impurity, plating property good, compact structure, surface roughnessIt is small, there is preferable industrial application value.
The present invention is to solve above-mentioned technical problem by the following technical programs.
First aspect present invention provides a kind of polymer as leveling agent and is preparing the application in metal plating compositions；Wherein, the polymer is made by following methods, and the method includes the following steps：In a second organic solvent, by oneOr multiple RX and one or more compounds with Formulas I structure are reacted；
Wherein, R is carbonyl, C1-C8Alkyl, C3-C8Naphthenic base ,-(CH2)n-O-(CH2)m、-(CH2)y-(O-(CH2)p-O)q-(CH2)z-、-(C3H6)y-(O-(C3H6)p-O)q-(C3H6)z-、Or C6-C10Aryl；
X is halogen；
R1And R2It is identical or different, and it is each independently hydrogen, hydroxyl, C1-C6Alkyl, C1-C6Alkoxy ,-(C1-C6AlkaneBase)-OH ,-(C1-C6Alkyl)-SH or-(C1-C6Alkyl)-NH2；
Described n, m, y, z, p and q respectively stand alone as any integer between 1-12.
The polymer is preparing the application in metal plating compositions as leveling agent, wherein
In the preparation method of the leveling agent, second organic solvent is preferably amide solvent, is more preferably twoMethylformamide.
In the preparation method of the leveling agent, the molar ratio of compound of formula I and RX are preferably 1:1-2:1, more preferably 1:1-1.5:1。
In the preparation method of the leveling agent, the reaction temperature can be conventional for this field, and preferably 70-120 DEG C, moreIt goodly is 90-110 DEG C；The time of the reaction is preferably 12-30 hours, is more preferably 24 hours.
In the preparation method of the leveling agent, when after the reaction was completed, can also including following operation：By the system after reactionFiltering, sediment are washed with ethyl acetate, and the number of the washing is preferably 3-5 times.
In the preparation method of the leveling agent, the preparation method of the compound of formula I includes the following steps：FirstIn organic solvent, under the action of alkali metal hydride, by tetrazole compoundIt is reacted with RX, it is rawAt the compound of formula I；
Wherein, R is as defined above described；R1And R2It is identical or different, and it is each independently hydrogen, hydroxyl, C1-C6Alkyl,C1-C6Alkoxy ,-(C1-C6Alkyl)-OH ,-(C1-C6Alkyl)-SH or-(C1-C6Alkyl)-NH2；It is preferred that：Hydrogen, hydroxyl, methyl,Ethyl, n-propyl, isopropyl, methylol or ethoxy；More preferably：Hydrogen, hydroxyl, methyl or ethyl.
In the preparation method of the compound of formula I, the alkali metal hydride is preferably NaH, KH or LiH, more preferablyGround is NaH.
In the preparation method of the compound of formula I, first organic solvent is preferably anhydrous organic solvent, more preferablyGround is anhydrous ether solvent, is further more preferably anhydrous tetrahydro furan.
In the preparation method of the compound of formula I, tetrazole compoundWith the molar ratio of RXPreferably respectively stand alone as 1:0.1-0.5:5, more preferably respectively stand alone as 1:0.1-0.5:2.
In the preparation method of the compound of formula I, tetrazole compoundAnd metal hydride alkalineThe molar ratio of object preferably respectively stands alone as 10:1-5:1, more preferably respectively stand alone as 9:1-6:1.
The tetrazole compoundMolar ratio be preferably 1:1-1:2, it is more preferably 1:1.5。
It, can be by tetrazole compound in the preparation method of the compound of formula IAnd alkali metalHydride is first dissolved in the first organic solvent, and RX is added at -5 DEG C -5 DEG C and is reacted.
In the preparation method of the compound of formula I, when after the reaction was completed, can also including following operation：After reactingSystem filtering, remove sediment, evaporation remove supernatant in solvent, it is described evaporation preferably using Rotary Evaporators intoRow.
The polymer is preparing the application in metal plating compositions as leveling agent, wherein
R is preferably：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, 2- butyl, 3- butyl,Or phenyl；
R1And R2It is identical or different, preferably, being each independently：Hydrogen, hydroxyl, C1-C4Alkyl ,-(C1-C4Alkyl)-OHOr C1-C4Alkoxy；More preferably, R1And R2It is each independently：Hydrogen, hydroxyl, methyl, ethyl, n-propyl, isopropyl, methylolOr ethoxy；Further more preferably, R1And R2It is each independently：Hydrogen, hydroxyl, methyl or ethyl；
Described n, m, y, z, p and q respectively stand alone as any integer between 1-10；It is any whole between preferably 1-5Number；
X is chlorine, bromine or fluorine, preferably chlorine or bromine, more preferable bromine.
Second aspect of the present invention provides a kind of metal plating compositions, wherein the raw material of the metal plating compositionsIncluding leveling agent described in metal electroplating solution and first aspect present invention；The metal electroplating solution include mantoquita, acidic electrolyte bath,Halogen ion source and water.
The metal plating compositions, wherein
The mantoquita is better selected from：Copper sulphate, copper halide, copper acetate, copper nitrate, cupric fluoborate, alkyl sulfonic acid copper, virtueOne of base sulfonic acid copper, sulfamic acid copper and copper gluconate are a variety of；The alkyl sulfonic acid copper is better selected from LoprazolamOne of copper, ethane sulfonic acid copper and propane sulfonic acid copper are a variety of；The aryl sulfonic acid copper is better selected from phenylbenzimidazole sulfonic acid copper, benzeneOne of copper phenolsulfonate and copper p-toluenesulfonate are a variety of.The molar concentration of copper ion is 0.15- in the mantoquita2.85mol/L。
The acidic electrolyte bath is better selected from：Sulfuric acid, phosphoric acid, acetic acid, fluoboric acid, sulfamic acid, alkyl sulfonic acid, arylOne of sulfonic acid and hydrochloric acid are a variety of；The alkyl sulfonic acid be better selected from Loprazolam, ethane sulfonic acid, propane sulfonic acid andOne of trifluoromethayl sulfonic acid is a variety of；The aryl sulfonic acid is better selected from phenylbenzimidazole sulfonic acid, phenolsulfonic acid and toluenesulfonic acidOne of or it is a variety of.It is the better quality of the acidic electrolyte bath 1-300g in every liter of metal plating compositions.
The preferred chloride-ion source in halogen ion source, the chloride-ion source are better selected from copper chloride, stannic chloride and hydrochloric acidOne of or it is a variety of.In the halogen ion source, the concentration of halogen ion is preferably 0-100ppm, is more preferably 50-100ppm.
In the present invention, the metal electroplating solution is preferably model SYSD2110 electrolytic copper plating solution, it is newly positive by ShanghaiThe production of semiconductor material limited liability company.SYSD2110 preparation can refer to method disclosed in Chinese patent CN100529194CTo prepare.
In the present invention, the raw material of the metal plating compositions may also include accelerator, accelerator (the also referred to as blastAgent) refer to can be improved electroplating bath rate of deposition organic additive, the accelerator can be commonly used in the artAccelerator.The accelerator is better selected from：N, N- dimethyl-disulfide group carbamic acid-(3- sulfopropyl) ester, 3- sulfydryl-the thirdBase sulfonic acid-(3- sulfopropyl) ester, 3- mercapto-propylsulfonic acid sodium salt, carbonic acid disulfide group-o- ethyl ester-s- ester and 3- sulfydryl -1- propaneSulfonic acid potassium salt, double sulfopropyl disulphide, 3- (benzothiazolyl-s- sulfenyl) propyl sulfonic acid sodium salt, pyridylpropyl sulfo group sweet teaDish alkali, 1- sodium -3- thio propane -1- sulphonic acid ester, N, N- dimethyl-disulfide group carbamic acid-(3- sulfoethyl) ester, 3- sulfydryl -Ethyl propyl sulfonic acid-(3- sulfoethyl) ester, 3- Mercapto-Ethyl sulfonate sodium；Carbonic acid-disulfide group-o- ethyl ester-s- ester and 3- mercaptoBase -1- ethane sulfonic acid sylvite, double sulfoethyl disulphide, 3- (benzothiazolyl-s- sulfenyl) ethylsulfonic acid sodium salt, pyridine secondOne of base sulfobetaines and 1- sodium -3- ethane thiol -1- sulphonic acid ester are a variety of.The concentration of the accelerator is preferably0.1ppm-1000ppm。
In the preferred embodiment of the present invention, the product type of the accelerator is UPD3115A, new purchased from ShanghaiPositive Semi Materials Co., Ltd..
In the present invention, the raw material of the metal plating compositions may also include inhibitor, and the inhibitor refers to canInhibit the organic additive of metal plating rate.The inhibitor is better selected from polypropylene glycol copolymers, polyethylene glycol copolymerizationOne of object, epoxy ethane-epoxy propane (EO/PO) copolymer and butanol-ethylene oxide-propylene oxide copolymer are moreKind.The weight average molecular weight of the butanol-ethylene oxide-propylene oxide copolymer is preferably 100-100,000, more preferably for500-10,000.The concentration of the inhibitor is preferably 1-10000ppm, is more preferably 5-10000ppm.
In the preferred embodiment of the present invention, the product type of the inhibitor is UPD3115S, new purchased from ShanghaiPositive Semi Materials Co., Ltd..
In the present invention, the concentration of the leveling agent can be this field normal concentration, preferably 0.01-5000ppm, more preferablyGround is 0.01-500ppm.
In the preferred embodiment of the present invention, the raw material of the metal plating compositions is by the metal electroplating solution, instituteState leveling agent, the accelerator and inhibitor composition.
Those skilled in the art know, when the acidic electrolyte bath exists in form of an aqueous solutions, and acidic electrolyte bathThe addition of aqueous solution is so that each component meets each " preferably " above-mentioned or " more preferably " dosage model in metal plating compositionsWhen enclosing, additional water is not added in the metal plating compositions.
Third aspect present invention provides a kind of preparation side of metal plating compositions as described in respect of the second aspect of the inventionMethod, the preparation method preferably use following steps：Each raw material component is uniformly mixed.
It is electric in printing that fourth aspect present invention provides a kind of metal plating compositions as described in respect of the second aspect of the inventionThe application in plating in the plating of road plate and IC wafer or chip, the application are preferably comprised following steps：
(1) substrate to be electroplated is contacted with aforementioned metal electroplating composition；
(2) apply electric current to be electroplated.
In step (1), the substrate can be any substrate commonly used in the art, preferably printed circuit board or collectionAt the chip or chip of circuit.
In step (2), the current density of the plating can be conventional for this field, preferably 0.1-10ASD, more preferably for0.3-5ASD is further more preferably 0.5-1.5ASD；
In step (2), the time of the plating can be conventional for this field, and preferably 53-110s is more preferably 80-110s；
In step (2), the temperature of the plating can be conventional for this field, and preferably 10-65 DEG C, be more preferably 10-35DEG C, further more preferably it is 20-30 DEG C, may be, for example, 25 DEG C.
In a preferred embodiment in the present invention, the application is preferably carried out using three-step approach：
The current density of the first step be 0.1-0.5ASD, be more preferably 0.3ASD, electroplating time 3-20s, more preferably for10s, electroplating temperature are 10-65 DEG C, are more preferably 10-35 DEG C, are further more preferably 20-30 DEG C, may be, for example, 25 DEG C；
The current density of second step be 0.5-1.5ASD, be more preferably 1.0ASD, electroplating time 20-30s, more preferably for25s, electroplating temperature are 10-65 DEG C, are more preferably 10-35 DEG C, are further more preferably 20-30 DEG C, may be, for example, 25 DEG C；
The current density of third step is 1-10ASD, is more preferably 5ASD, electroplating time 30-60s, goodly is 45s, electricityPlating temperature is 10-65 DEG C, is more preferably 10-35 DEG C, is further more preferably 20-30 DEG C, may be, for example, 25 DEG C.
In the present invention, unless context is separately explicitly indicated, otherwise following abbreviation should be had following meanings：A=amperes；A/dm2=every square decimeter of ampere=ASD；DEG C=degree Celsius；Ppm=parts per million.Unless otherwise noted, otherwise all amounts are allMass percent.All numberical ranges are all inclusive and can combine in any order, it is apparent that this kind of numberical range limitsIn total 100%.
In the present invention, " feature " refers to the geometry on substrate." aperture " refers to the recess including through-hole and blind viasFeature." halide " refers to fluoride, chloride, bromide and iodide.
In the present invention, " ice bath " temperature refers to -5 DEG C -5 DEG C, preferably -5 DEG C -0 DEG C.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present inventionExample.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：
Metal plating compositions of the invention are used comprising by one or more RX and one or more with Formulas I structureCompound reacts resulting reaction product and is used as leveling agent, and the raw material of the metal plating compositions include metal electroplating solution withThe leveling agent.Metal plating compositions of the invention can be used for electroplating printed circuit board and integrated circuit copper interconnecting galvanizer, it can be achieved that, plating property good, compact structure, surface roughness small effect low with defect, coating impurity without cavity in skill；In addition,The metal plating compositions have good thermal reliability and covering power, be able to solve aperture sealing the problem of, have compared withGood industrial application value.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the realityIt applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotientThe selection of product specification.
Prepare the preparation of 1 leveling agent 1 of embodiment
Tetrazolium (100mmol) and sodium hydride (11mmol) are dissolved in 50mL anhydrous tetrahydro furan.Stir mixture simultaneouslyAnd cooling 2 hours in ice bath form hydrogen until stopping.It adds Isosorbide-5-Nitrae-dibromobutane (50mmol) and is stirred at room temperatureMixture 12 hours.After removing sediment, removal solvent obtains bis- (tetrazole radical) butane of Isosorbide-5-Nitrae-.
Bis- (tetrazole radical) butane (10mmol) of Isosorbide-5-Nitrae-and Isosorbide-5-Nitrae-dibromobutane (10mmol) are dissolved in dimethylformamideIn and heat mixture 24 hours at 100 DEG C.Gained sediment (leveling agent 1) is collected by filtration and uses ethyl acetateWashing.Measuring Mn is 4,016, and measuring Mw is 6,506.
Prepare the preparation of 2 leveling agent 2 of embodiment
Methyl tetrazolium (100mmol) and sodium hydride (11mmol) are dissolved in 50mL anhydrous tetrahydro furan.It is stirredObject and hydrogen is formed until stopping in cooling 2 hours in ice bath.It adds Isosorbide-5-Nitrae-dibromobutane (50mmol) and at room temperatureStirring mixture 12 hours.After removing sediment, bis- (methyl tetrazole radical) butane of Isosorbide-5-Nitrae-are obtained by evaporative removal solvent.
By bis- (methyl tetrazole radical) butane (1.16g, 4mmol) of Isosorbide-5-Nitrae-, bis- (tetrazole radical) butane (1.14g, 6mmol) of Isosorbide-5-Nitrae-And Isosorbide-5-Nitrae-dibromobutane is dissolved in dimethylformamide and heats mixture 24 hours at 100 DEG C.Gained sediment(leveling agent 2) is collected by filtration and is washed with ethyl acetate.According to NMR as a result, the methyl tetrazole radical in product 1 compares tetrazoliumThe molar ratio of base is 0.75.Measuring Mn is 4,102, and measuring Mw is 15,304.
Prepare the preparation of 3 leveling agent 3 of embodiment
Methyl tetrazolium (4mmol), tetrazolium (6mmol) and sodium hydride (11mmol) are dissolved in 50mL anhydrous tetrahydro furanIn.It stirs mixture and cooling 2 hours in ice bath forms hydrogen until stopping.Add Isosorbide-5-Nitrae-dibromobutane (50mmol) simultaneouslyAnd mixture is stirred at room temperature 12 hours.After being removed by filtration sediment, 50ml dimethylformamide and 10.8g1 are added,4- dibromobutane (50mmol).It is heated mixture 24 hours at 100 DEG C.Gained sediment (leveling agent 3) is collected by filtrationAnd it is washed with ethyl acetate.According to NMR as a result, methyl tetrazole radical in product 2 than the molar ratio of tetrazole radical is 1.12.It measuresMn is 3,224, and measuring Mw is 11,583.
It prepares 4 metal plating compositions 1-6 of embodiment and compares the preparation of metal plating compositions 1-6
The component and dosage of metal plating compositions 1-6 and comparison metal plating compositions 1-6 are shown in Table 1.Wherein, the goldBelong to ion source and the electrolyte by model SYSD2110 electrolytic copper plating solution provides, and is purchased from Shanghai newly positive semiconductor material shareCo., Ltd.The accelerator of model UPD3115A is purchased from Shanghai Sinyang Semiconductor Materials Co., Ltd.Model UPD3115SInhibitor, be purchased from Shanghai Sinyang Semiconductor Materials Co., Ltd.
Table 1
Application Example 1-6 and comparison Application Example 1-6
This it is bright in, Application Example 1-6 and comparison Application Example 1-6 be respectively adopted metal plating compositions 1-6 andMetal plating compositions 1-6 is compared to carry out.Electroplating technological parameter is carried out according to parameter listed by table 2.
Table 2
Application effect
Application effect is shown in Table 3.Wherein, impurity content is analyzed using the combustion method of elemental analysis, empty situation, plating property,Compact structure, surface roughness use SEM electron microscope observation.
Table 3
It can be seen that from above-mentioned each example and carry out electricity using the metal plating compositions comprising leveling agent prepared by the present inventionPlating is, it can be achieved that plating is low with defect, coating impurity without cavity, the equal small effects of plating property good, compact structure, surface roughness.AndUsing the polymer disclosed in patent CN105705491A containing glyoxaline structure as leveling agent, then it will appear cavity blemish, platingLayer impurity height, the high effect of the poor, short texture of plating property, surface roughness.