TWI359880B - Method to electrodeposit metals using ionic liquid - Google Patents

Abstract

The present invention pertains to the use of an additive selected from the group consisting of amorphous silica, graphite powder, and a mixture thereof in a process to electroplate or electropolish a metal on a substrate using an ionic liquid as the electrolyte to increase metal layer thickness. It furthermore pertains to a method to electroplate or electropolish a metal on a metal substrate wherein an ionic liquid is employed as electrolyte, wherein a metal salt added to said ionic liquid or a metal anode is employed as metal source, and wherein said ionic liquid comprises said additive.

Description

1359880 * I* IX. Description of the Invention: [Technical Field of the Invention] An ionic liquid as a method for using the present invention relates to a method for electrodepositing a metal on a substrate by using an electrolyte in the presence of an additive, an additive To increase the layer thickness of the deposited metal layer. [Prior Art]

Ionic liquid system is a salt in a bean that is not coordinated with T A /, T ethyl ion, which causes such a

The solvent is lower than the temperature of HTC (the temperature of HTC. Many of the towels are liquid even at room temperature. At least one ion in the ionic liquid has a non-local charge and a group of organic substances, which prevents stable lattice The ionic liquid has a very low vapor pressure, and therefore, it does not substantially generate harmful vapors with respect to many conventional solvents. In general, ionic liquids are known to be used in many applications, for example, as a reaction solvent, Extraction of solvents, batteries and electrolytes in electrodeposition, catalysts, heat exchange fluids, additives in coatings. Well-known systems include systems formed from halogenated alkyl pyrenes with mono-aluminum halides or dialkylimidazolium halides. 'and systems based on choline chloride and a (hydrated) metal salt such as chromium (III) chloride. These systems have been used as electrolytes in electroplating' for example ΕΡ 0 4〇4 188 and ΕΡ 1 322 Further described in 591. WO 2002/026381 discloses the use of vaporized choline and a (hydrated) metal salt such as ionic liquid (eutectic mixture) of chromium (III) chloride and its use in electrodeposition and electropolishing. The The mixture is composed of vaporized choline and the (hydrated) metal salt in a ratio of ammonium to metal ions between 1:1 and 1:2.5 and is said to be particularly suitable for use on a metal substrate. Depositing chromium, cobalt, zinc or silver.] 33195.doc 1359880 » ,, In addition, pcT/ep/2G()7/()51329 describes a method of electroforming or electropolishing-metal on a substrate, in which An ionic liquid selected from the group consisting of n+RiR2ra χ_ ' or N+R5R6R7Rs γ• as an electrolyte, and adding a metal salt to the ionic liquid as a metal source or using a metal ruthenium as a metal source' Wherein R, to any of - independently represents hydrogen, cyclyl, cycloalkyl, aryl or aralkyl, selected from the group consisting of ruthenium, alpha, alpha, fluoro, fluorene, phenyl, νη2, CN, Ν. 〇2, C00R9, CH〇, c〇Rg or 基R9 is substituted by a group φ group, at least one of R5 to Rs is a fatty alkyl chain, and one or more of the cores may be (poly)oxyalkylene a group wherein the alkyl group is alkyl and the total number of oxygen alkyl units may be from i to 5 units of an oxygen alkyl unit, and at least one of & to Rs is c To C4 alkyl chain, R9 alkyl or cycloalkyl, χ_ has an anion of Ν-mercaptosulfonimide anion (_c〇_N._s〇2_), γ system and N+mRs ammonium cation Compatible anions such as halide anions, carboxylate anions, sulfates (both organic and inorganic sulfates), sulfonates, carbonates, nitrates 'nitrites, thiocyanates, hydroxides or sulfoniums Imino anions. The use of ionic liquids as electrolytes in electrodeposition processes has several advantages. For example, conventional chromic acid plating processes are extremely dangerous because they rely primarily on highly toxic and carcinogenic hexavalent chromium. On the other hand, ionic liquids eliminate the need to use hexavalent chromium and allow the use of trivalent chromium which is considered to be of little risk. In addition, conventional chromium plating baths require the use of strong acids which can cause serious disposal problems, and the use of ionic liquids generally minimizes or even eliminates such handling difficulties. In addition, ionic liquids are non-volatile and therefore do not cause atmospheric pollution. The disadvantages of prior art electrodeposition processes using an ionic liquid as the electrolyte are that it is difficult or even impossible to deposit a metal layer thicker than some of the metals of (10). For some applications, such as decorative plating, thin metal layers are acceptable. For applications where the metal layer needs to provide protection against wear or grind, or to increase hardness (functionalized ore), a metal layer that is much thicker than 200 nm is required. More specifically; in other words, layers of several micrometers or even tens of micrometers are required.

Thus, there is a need for an improved ion-based electrodeposition system for depositing a metal layer of increased thickness. SUMMARY OF THE INVENTION It has been surprisingly found that a thicker metal can be deposited by adding an additive to the plasma liquid based plating bath. More specifically, the present invention relates to the use of an amorphous cerium oxide, graphite powder or a mixture thereof as an additive for reading or f-polishing on a substrate, and using an ionic liquid as an electrolyte to increase the thickness of the metal layer. . For the right stem cause, the additive has been added to the ionic liquid containing the electrolyte. For example, δ 'us 7'196'221 discloses a brightener during the metal plating and electropolishing process, and in particular, the chrome-plated material is improved by the use of a brightener to improve the appearance of the coating obtained in the ionic liquid solvent/electrolyte. Contains sulfur veins, saccharin, vanillin, propyl urea, #acid, _acid, gelatin, 2-mercaptobenzopyrene, tetraethylammonium fluoride dihydrate or tetradecylammonium chloride pentoxide. However, @, these additives have an adverse effect on the deposition of the deposited layer, or have no effect at all. W〇2〇〇6/〇74523 relates to a method for recovering a family of metals, 133195.doc 9880 -, including ionic liquid electricity from which a gasification reducing agent, a binder, a conductivity enhancer may be present A platinum group metal is deposited. US 6,552,843 relates to a device for controlling the reflectivity and/or transmission of electromagnetic radiation, such as an adjustable mirror, a smart window, an optical attenuator and a display, which discloses a reversible electrodeposition optics using an ionic liquid electrolyte Modulation device "The ionic liquid electrolyte is composed of a mixture of an ionic organic compound and an electrode of an electrodepositable metal. The ionic organic compound comprises a heterocyclic cation such as N-alkylpyrrole, pyrrole ingot, b-alkyl-3-methylimidazole rust, N-alkylpyridinium, 2·alkylpyrroline quinone, 1·alkane Imidazole rust. The electrodepositable metal is silver, copper, tin, zinc, palladium, iridium, cadmium, mercury, indium, lead, antimony, bismuth and alloys thereof. It is mentioned that the ionic liquid electrolyte can be made more viscous, semi-solid or solid by the addition of an organic or inorganic gelling agent. An inorganic or organic substance including suspended carbon and a dissolved dye may be added to the electrolyte to impart a desired color or to reduce background reflection. None of these documents teaches how to obtain a thicker metal layer in an electrodeposition process using an ionic liquid containing an electrolyte. The term electrodeposition in this application is to be understood to include both electroplating and electropolishing. The so-called electroplating refers to a process of applying a metal layer to a conductive object by using a current. The preferred result is that a thin, smooth and uniform coating of the metal on the object is mainly applied to deposit a certain desired property (for example, anti- The metal layer of abrasion and abrasion, corrosion resistance, lubricity, aesthetic quality, etc.) is on a surface lacking such characteristics. Another application uses electroplating to increase the thickness on undersized components. By electropolishing is meant that a previously rough or uneven metal surface is coated with a relatively thin metal layer 133195.doc 1359880 to smooth it and into its appearance β. According to the invention, the thickness of the deposited metal layer is increased. The additive is amorphous - cerium oxide, graphite powder, or a mixture thereof. • The term amorphous oxygen cut means that it contains any form of colloidal stone. 彳', towel, such colloidal stone particles (also known as Shixi sol) can be sourced from, for example, precipitated vermiculite , tannin extract, pyrolysis vermiculite (smoke vermiculite), micro vermiculite (micro-powder powder) or a mixture thereof. The colloidal vermiculite according to the present invention may be modified and may contain other elements such as amines, imitations and/or sheds which may be present in particulate and/or continuous phases. The colloidal stone particles can be dispersed in a substantially aqueous solvent, suitably in the presence of a stable cation such as an organic cation, first, second, third and fourth amines, and mixtures thereof The sputum forms a water-based sol sol. However, a dispersion containing an organic solvent such as low carbon _, acetone or a mixture thereof (also referred to as an organic sol sol) may also be used. Preferably, the content of the Shishi stone in the sol is from about 5 to about 8 weight percent. • Aqueous sol-gel systems suitable for use in accordance with the present invention, for example, are commercially available from Akzo. Suitable organic sol-gel systems are commercially available, for example, from Nissan Chemical Industries. The term "graphite powder" means fine-grained carbon powder or carbon. The additive is preferably used in at least the amount based on the total weight of the electrolyte, more preferably at least G.G5 wt%, and optimally up to "%". It is preferred to use no more than 5 wt% of the additive based on the total weight of the detoxification, more preferably more than the domain, and most preferably no more than ...%. It should be noted that the term electrolyte system, 133195.doc 135988, refers to the entire electrolyte mixture, and also contains dissolved metal salts and additives. By the present invention, that is, by adding the additive by the mash, the layer thickness can be increased by at least μ times, preferably at least 20 times, and optimally at least 4 times, when compared with electrodeposition without the additive. .

The ionic liquid used as the electrolyte is preferably selected from the group consisting of N+RiR2r3R4 χ-, N+R5R6R7R8Y_, and mixtures thereof, each of which independently represents an argon, a hospital, a ring-based, an aryl or a Fangyuan. Base, which can be selected from OH'CM'Br'F,! a group substituted with a group of phenyl, NH2, cn N〇2, c〇〇R9, CHO, CORA〇R9, at least one of which is a fatty alkyl chain branched as appropriate, wherein I may be π". )-N+R,6R17R,8 (wherein ~~ are respectively similar to Hangu: Ruler 3, R4), or CjC4 alkyl chain, and wherein & one or more can be (poly)oxyalkylene a group, wherein the alkyl group is 丨. 4 alkyl and the number of oxygen alkyl units can be from 1 to 50 oxygen alkyl units, and wherein & a fluorenyl chain, wherein R9(tetra)yl or cycloalkyl, wherein X is an anion compatible with N+RlR2R3R4, such as a complex anion, a m-acid anion, a sulfate (both organic and inorganic sulfate), a citrate, a carbonate, a nitrate, a nitrite, a thiocyanate, a hydroxide, a saccharinate anion or a sulfonium imine anion, and wherein the oxime has an sulfonimide anion or a sulfonium sulfoximine An anion (_c〇_n__ s〇2_) functional anion. In an embodiment _, X · is selected from the group of F-, C1-, Br-, j-; R 〇 coo · anion group , Wherein Ri0 may be a hydrogen, a hydrazine, an alkenyl or an aryl group; a group of an RnS〇4. anion, wherein R|1 may be absent (in the 133195.doc, the cation is divalent), A group of R^SO3 anions, wherein Riz may be absent (in this case, the cation is divalent), hydrogen, (:1 to (:22 alkane). Base, alkenyl or aryl;

a RuC〇3 anion group in which the anion may be absent (in this case, the cation is divalent), hydrogen, 4 to (:22 alkyl, alkenyl or aryl; and Rl4_N-SCVR5 anion a group, wherein and/or Ri5 may independently be hydrogen, C| to C22 alkyl, alkenyl or aryl, and Rm may be bonded to the nitrogen atom by a carbonyl group. The fatty alkyl chain means saturated and Or unsaturated chain and comprising from 8 to 22 carbon atoms; preferably, it contains from 1 to 22 carbon atoms, most preferably from 12 to 2 carbon atoms. In another embodiment, the chemical formula N + is used An ionic liquid, wherein R, R3 and & are as described above and I is (C2 to C6 alkyl) n + r16r17r a. Preferably, R16, Ri7 and Ri8 are respectively at R|, ^ and R4 The same, wherein at least one of them depends on the fatty alkyl chain of the branch, resulting in a double sub-star structure (ie, a symmetric di-tetraammonium compound). In another embodiment, the 'gamma system is based on A compound known as a sweetener. In another embodiment, 'N+mi^-amine, wherein the group 5 to I is hydrogen or an alkyl or ring optionally substituted with 0H or C1 More preferably, at least three of the alkyl groups are more preferably c 1 to c 4 alkyl groups. In a preferred embodiment, the ionic liquid system is selected from any of the following: biliary saccharate, gall Alkali acesulfonamide, gasified cetyl trimethyl sulphate, gasified octadecyltrimethylammonium, gasified coconut trimethylammonium, gasified cow 133195.doc 12 1359880 lipid trimethylammonium , Hydrogenated hydrogenated tallow trimethyl ammonium, hydrogenated palmitized palm trimethyl sulphate, gasified oil diluted trimethyl ammonium, gasified soybean trimethyl record, chlorinated benzyl monomethyl, chlorinated C12-16 - mercaptobenzyl dimethyl record, gasified hydrogenated tallow benzyl decyl ammonium, dioctyl dimethyl ammonium chloride, dimercaptodimethylammonium chloride, dicocodimethylammonium nitrite, Dicobalt diammonium chloride, gasified di(hydrogenated tallow) decyl ammonium, chlorinated di(hydrogenated tallow) benzyl ammonium, chlorinated ditallow diammonium chloride, di-octadecyl chloride Dimethylammonium chloride, gasified hydrogenated tallow (2-ethylhexyl) dimethyl ammonium, hydrogenated hydrogenated oxol (2·ethylhexyl) dimethyl ammonium, gasified tris-hexadecyl base , octadecyl chloride, f-based (2-ethyl), dinitromethane di(2-ethyl)methylammonium, gasified coconut bis(2-hydroxyethyl)methylammonium, gasification Coconut bis(2.hydroxyethyl)benzylammonium, gasified oleyl bis(2-hydroxyethyl)methylammonium, gasified coconut [polyoxy-extended ethyl (1 5)]-f-ammonium, A Sulfate-based coconut [polyoxy-extended ethyl (15)] methyl ammonium, chlorinated coconut [polyoxy-extended ethyl (17)] methyl ammonium, octadecyl chloride [polyoxy-extended ethyl (15)] Methylammonium, gasified hydrogenated tallow [polyoxy-extended ethyl (15)] decyl ammonium, tris(2-hydroxyethyl) ammonium taurate, di-gasified tallow _ 1, 3-propanol pentamethyl dim . Many of the ionic liquids suitable for use in accordance with the present invention as described above may be prepared by a simple salt reaction, for example, by metathesis of choline chloride with sodium saccharinate (ethionine) to form a saccharin acid. (Ethyl sulfonamide) biliary ionic liquid, or by the fourth ammoniumation of the corresponding amine. The ammonium cation of the ionic liquid is preferably between 1, 〇〇〇:1 and the molar of the metal cation derived from the dissolved salt or the metal salt from the metal anode. More preferably, the ammonium cation of the ionic liquid and the metal cation of the metal salt are 133195.doc 13 1359880 The molar ratio is between 500:1 and 5··, and the optimal molar ratio is between 1〇〇·ι and Between 7:1, this provides a good quality metal layer, a good balance between the excellent dissolution of the metal in the ionic liquid and the cost of the process and the appearance of the plated substrate product. Preferably, one of the metals chromium, aluminum, titanium, rhodium or copper, or an alloy thereof is deposited. More preferred is the deposition of chromium or aluminum, the best chromium. This metal deposition can be carried out from a metal salt dissolved in the electrolyte, which is, for example, a metal halide, preferably Φ (non-limiting) metal chloride. It can also be carried out using a pure metal (i.e., chromium, ig, titanium, zinc or copper anode) applied as an anode. In embodiments in which a metal anode is used, the anode can be in the form of a metal plate, a metal block, a metal sheet, or any other suitable form known to those skilled in the art. The substrate which may be electroplated or electropolished according to the present invention may be any electrically conductive object, preferably a solid metal object, such as a carbon steel object, or • it comprises a conductive element such as a composite object. The invention relates to a method for electroplating or electropolishing a metal on a metal & plate, wherein the ionic liquid system is selected from the group consisting of N+R^m x-, N+Rshl^R8 Υ· and mixtures thereof a group, wherein Ri to any of them, independently represents hydrogen, alkyl, cycloalkyl, aryl or aralkyl, which may be selected from the group consisting of OH, Cb Br 'F, I, phenyl, Nh2 Substituting a group of CN, N〇2, c〇()R9, CHO, COR9 or OR9, wherein at least one of the centroids is a fatty alkyl chain branched as appropriate, wherein I can be (C2 to alkyl b) N+R16R17R18 (wherein r16, Rl7, and Ri8 are respectively similar to samarium, I, R〇, or (: 丨 to (: 4 alkyl chain, and one or more of the centers to the size 8 may be (poly)) Oxyalkylene, wherein the alkyl group (to the alkyl group and the oxygen alkyl unit 133195.doc • 14- may be a total of 丨 to "oxyalkylene units" and wherein 1 At least one is a C 丨 to c 4 alkyl chain ' wherein 尺 9 is an alkyl or cycloalkyl group, wherein the oxime is an anion compatible with the N + mt ammonium cation, such as a toothing anion, a carboxylate anion, a sulfate ( Organic and none Both sulfates), sulfonate, carbonate, nitrate, nitrite, thiocyanate, hydroxide, saccharinate anion or sulfonium imine anion, and wherein γ_ has sulfonimide anion or An anion of a Ν-mercaptosulfonimide anion (_c〇_N-_s〇2_), wherein a metal salt or a metal anode added to the ionic liquid is used as a metal source, and the total weight based on the electrolyte Ionic liquids include at least 〇〇1

The Wt〇/Q is selected from the group consisting of amorphous cerium oxide, graphite powder, and mixtures thereof. The additive is preferably used in the amounts described above. Electrodeposition is preferably below 90. (At the temperature, and more preferably at room temperature 'implemented in an open electrodeposition vessel, but electrodeposition is not limited to such conditions. [Embodiment] The method according to the present invention is further exemplified by the following examples Clarification. Example Comparison Example 1 - Chlorinated Coconut Alkylmethylhydrazine without Additives Polyoxyethyl Ethyl Ethyl (15) Ammonium t From CrCl3 Hexahydrate Salt Electroplating Chromium on Carbon Steel to Calcine Chromium (III The hexahydrate salt is added to a vaporized coconut alkyl fluorenyl [polyoxyethyl (15)] ammonium ionic liquid containing 0.2 wt% water at a temperature of about 133195.doc -15·1359880 at about 50 °C. The mixture is agitated until the solid salt is dissolved. In the prepared solution, the concentration of chromium (III) hexahydrate vaporized is 75 g/kge. About 250 ml of the solution is poured into a thin film battery provided with an electric heating element (Hull In the cell, it has a length of 65 mm on the anode side and a length of 102 mm on the cathode side, a shortest distance of the anode-cathode of 48 mm, an anode-cathode maximum distance of 127 mm, and a depth of 65 mm. The battery is heated and will The temperature is maintained at about 80 ° C ^ The top-extending impeller is stirred in the center. The plated titanium plate is used as the anode and is connected to the positive terminal of a DC power source. At the same time, a carbon steel plate is used as a cathode (substrate) and connected to the negative terminal. The substrate is introduced before being introduced into the groove. The film is first cleaned with a commercial scouring powder, washed in demineralized water, in acetone and then in ethanol, and finally in an aqueous solution of 4 Μ·Ηα. When both plates are connected and introduced into the battery, the voltage difference Set to 30 V. Monitor the current on a series connected meter. After plating for a few hours, separate the cathode from the power supply and remove it from the battery. Wash the plate in water and acetone and then dry. By combining χ-ray scattering Scanning electron microscopy (SEM/EDX) performed chemical analysis on the substrate, which confirmed the deposition of chromium on carbon steel. The thickness of the deposited layer was measured using a thickness measuring device obtained from Fischer, Germany. The thickness was determined to be less than 〇5 μm. Example 2 - Adding 〇·2 Wt% Amorphous Cerium Oxide to Gasified Coconut Methyl Methyl [Polyoxyethyl (15)] Ammonium: 丨3 hexahydrate salt to chrome on carbon steelThe chromium chloride (ruthenium) hexahydrate salt prepared as described in Example 1 is dissolved in a solution of gasified coconut alkylmethyl [polyoxyethyl (15)] ionic liquid to contain 8 Wt % of the active compound of the amorphous oxidized rock hydrate aqueous colloid 133195.doc 16 1359880 liquid: the concentration of the amorphous cerium oxide in the preparation solution, expressed as the amount of the active compound, is 1.6 g / kg. About 250 ml of the solution Pour into the thin film battery described in the example. The battery was heated to a temperature of about 8 ° C. The same pretreatment of the carbon steel substrate (cathode) was carried out as in the example, and the plated titanium plate was again applied. As an anode. Set the potential difference to 3〇 v. The liquid system utilizes a top-mounted impeller _ disposed in the center. The current between the electrodes is monitored on a meter connected in series. After the current has flowed for several hours, the cathode is separated from the power source and taken out of the battery. The plate was washed in water and acetonitrile and then dried. Chemical analysis of the substrate by scanning electron microscopy (SEM/EDX) combined with X-ray scattering confirmed that chromium was deposited on the carbon steel sheet. It has been determined that the thickness of the deposited layer measured by a thickness measuring device (Fischer, Germany) is as high as μηη in a specific region of the substrate, which is significantly thicker than when no additive is used. As is typical for thin-film battery experiments, the layer thickness varies with the position on the substrate—in this case, 1 μΓη to 8 _. To confirm 'these measurements, cross-section metallographic analysis was also performed. A sample of the substrate was embedded in the epoxy resin and the deposit was evaluated under a microscope. The layer thickness measured in this way is consistent with the results of the thickness measuring device. Example 3_ Gasification of a 0.4 〇/〇 amorphous oxidized gas by gasification of a methylene group [polyoxy-extension ethyl (15)] recorded from Cra3 hexahydrate salt chrome on a carbon steel in a solid m The gasified chromium (10) hexahydrate salt prepared in the above is dissolved in a solution of a gasified coconut alkyl sulfhydryl [polyoxyethyl (15)] ammonium ionic liquid, and the active compound containing 8 Wt 〇 / 0 is added. Amorphous oxidized oxide aqueous colloidal solution. The concentration of the amorphous oxidized oxide in the prepared solution is expressed as the amount of active compound 133195.doc • 17-1359880, which is 4 g/kg » about 250 ml of the solution is poured into the film described in Example i battery_. The battery was heated to a temperature of about 80 °C. The same pretreatment as in Example 1 A carbon steel substrate (cathode) was carried out and a platinized titanium plate was again applied as an anode. Set the potential difference to 3 〇 V. The liquid system utilizes a top-extending leaf (four) that is placed in the center. The current between the electrodes is monitored on a meter connected in series. After a few hours of current flow, the cathode was separated from the power source and removed from the t-cell. The plate was washed in water and acetone and then dried. Chemical analysis of the electron microscopy (SEM/EDX) of the substrate by X-ray scattering confirmed that chromium was deposited on the carbon steel sheet. The thickness of the deposited layer measured by the thickness measuring device (Fischer, Germany) and by cross-section metallographic analysis was measured to be in the range of 1 to 9 μm. Example 4 - Electroplating of chromium onto carbon steel from CrCh hexahydrate II in a gasified coconut alkylmethyl hydrazine polyoxyethylidene (15) 1 ammonium with 1 wt% carbon black added as described in Example 1. The prepared vaporized chromium (III) hexahydrate salt is dissolved in a solution of chlorinated coconut alkyl sulfonyl [polyoxyethyl (15)] ammonium ionic liquid to add carbon black. The concentration of carbon black in the prepared mixture was 10 g/kg. About 250 ml of this mixture was poured into the film cell described in the example. The battery was heated to about 7 Torr. The temperature of 〇. The same pretreatment as in the carbon steel substrate (cathode) of Example 10 was carried out, and the forging titanium plate was again applied as an anode, and the potential difference was set to 3 〇 V. The liquid system is agitated using a top-mounted impeller disposed in the center. The current between the electrodes is monitored on a serially connected meter. 133195.doc •18· 1359880 After the current has flowed for several hours, the cathode is separated from the power source and taken out from the electricity. The plate was washed in water and propylene and then dried. Chemical analysis of the combined X-ray scattering by scanning electron microscopy (SEM/EDx) of the substrate confirmed that chromium was deposited on the carbon steel sheet. Extreme SFischer)., _ On-board measurement using a thickness measuring device (German® F1SCher) to measure the thickness of the deposited layer, such as _ ', to 7 in the substrate sample. The same thickness value was measured by the "knife metallographic analysis."

133I95.doc 19·

Claims (1)

1359880 : — • Patent Application No. 097129448 (Chinese Patent Application No. 119129), Japanese Correction Replacement j Patent Application Range: .-Selected from a group consisting of amorphous yttrium oxide, graphite powder and mixtures thereof The use of the additive for the process of electroplating or electropolishing a metal on a substrate using an ionic liquid as an electrolyte to increase the thickness of the metal layer. 2. The use of the additive of claim 1, wherein the ionic liquid system is selected from the group consisting of N+hl^HX·, n+Hhy•, and mixtures thereof, wherein any one of the scales to the ruler 8 independently represents hydrogen Or an alkyl group, a cycloalkyl group, an aryl group or an alkyl group, which may be selected from the group consisting of 〇H, Cl, Br, F, I, phenyl, NH2, CN, N02, CO〇R9, CHO, COR9 or OR9 The group replaces 'an anion wherein R9 is alkyl or cycloalkyl, wherein the oxime is compatible with the n+RiR2R3r4 bond cation' and wherein the γ-line has a ruthenium anion or an anthracene sulfonimide anion (_(:〇-Ν·-3〇2-) Functional cations 〇• 3. Use of the additive of claim 2 'At least one of the 丨 to 尺4 is a fatty alkane branched as appropriate Base chain. _ 4. Use of the additive of claim 2 'where & is (C2 to C6 alkyl)_N+R16R17r18 (wherein r16, :r17, R18 are the same as Ri, 1 <_4, respectively) Or (^ to (: 4 alkyl chain. 5. The use of the additive of claim 2) one or more of Yinxin to Rule 8 is (poly)oxyalkylene, wherein the alkylene group C〗 to C4 alkyl and oxygen extended base The total number of elements is from 1 to 50 oxygen alkyl units. 6. The use of the additive of claim 2 'where at least one of Ri to Re is a C! to C4 yard key. 7. Use of additives 'where X is an anion anion, 133195-1001228.doc 1359880 liHFu yakisaki correction replacement Μ - ' ·---1 carboxylate anion, sulfate (both organic and inorganic sulfate), sulfonate , a carbonate, a nitrate, a nitrite, a thiocyanate, a hydroxide, a saccharinate anion or a sulfonimide anion. The use of the additive according to any one of claims 1 to 7, wherein the electricity is passed through The metal that is electropolished on the substrate is derived from a metal source selected from the group consisting of chromium, aluminum, titanium, zinc, and copper salts, or one selected from the group consisting of complex, aluminum, titanium, The use of the additive of the group of zinc and copper anodes. The use of the additive of any one of claims 1 to 7, wherein the % ion of the ionic liquid is associated with the metal salt or the metal cation derived from the metal anode The molar ratio is between 1,000:1 and 3:1. 10. Addition to claim 9. The use thereof, wherein the cation of the ionic liquid and the metal salt or the metal cation derived from the metal anode have a molar ratio between 100:1 and 7:1. The use of the additive in an amount of between 1 wt% and 5 wt%, based on the total weight of the electrolyte. 12. Use of the additive according to any one of claims 1 to 7 The ionic liquid system is selected from the group consisting of choline saccharinate, choline acetyl sulphate, gasified hexadecyl trimethyl sulphate, octadecyl trimethyl ammonium chloride, chlorine Coconut trimethylammonium chloride, chlorinated tallow trimethylammonium, gasified hydrogenated tallow trimethylammonium, hydrogenated palmitoyltrimethylammonium chloride, chlorinated oleyl dimethyl chloride, chlorinated soybean trimethylammonium, Chlorinated coconut benzyl dimethyl record 'chlorinated C! 2' 6-alkyl benzyl dimethyl record, gasified hydrogenated tallow benzyl monomethyl s 'chlorinated octyl dimethyl record, chlorinated Dimercaptodimethylammonium, dicocodial dimethylammonium nitrite, diammonium dimethylammonium chloride 'chlorine 133J95-J00J228.doc K Year's Day Correction Replacement Page 2 (Hydrogen Tallow) dimethylammonium chloride, di(hydrogenated tallow) benzylmethyl chloride, chlorinated ditallow diterpene, chlorinated di-octadecyl dimethyl sulphate, gasified hydrogenated tallow (2-B Dihexyl)dimethylammonium, hydrogenated taurate (2-ethylhexyl)didecylammonium, tri-hexadecylmethylammonium chloride, vaporized octadecylmethyldi(2-hydroxyl Ethyl ammonium, coconut di(2-hydroxyethyl) methyl chlorinated, chlorinated coconut bis(2-hydroxyethyl)methylammonium, chlorinated coconut di(2-hydroxyethyl)benzylammonium, chlorinated Oleoyl bis(2-hydroxyethyl)methylammonium, chlorinated coconut [polyoxy-extended ethyl (15)]-methylammonium, methyl oxalic acid coconut [polyoxyethyl (15)] methyl Ammonium, gasified coconut [polyoxyethyl (17)] decyl ammonium, octadecyl chloride [polyoxyethyl (15)] methyl ammonium, gasified hydrogenated tallow [polyoxyethylene) 15)] mercapto ammonium, tris(2-hydroxyethyl) taurate acetate, di-gasified tallow-1,3-propane pentamethyl diammonium. 13. A method of electroplating or electropolishing a metal on a metal substrate, wherein an ionic liquid system is selected from the group consisting of N+HR^R^X·, N+r5r6R7R8Y-, and mixtures thereof, from the center to either Independently representing hydrogen, alkyl, cycloalkyl, aryl or aryl, which may be selected from the group consisting of 〇H, ci, Br, F, I, phenyl, NH2, CN, N02, COOR9, ch〇, COr9 Or a group substituted by OR9, wherein I is an alkyl group or a cycloalkyl group, wherein the oxime is an anion compatible with the N+RlR2R3R4 ammonium cation, and wherein the γ is a sulfonium imine anion or an N-mercaptosulfonate An anion of an imine anion (_c〇_N-_s〇2_); wherein a metal salt or a metal anode added to the ionic liquid is used as a metal source; and wherein the ionic liquid comprises, based on the total weight of the electrolyte At least 0.01 wt% of an additive selected from the group consisting of amorphous oxidized oxide, graphite powder, and mixtures thereof. 133195-1001228.doc 1359880 I. Bu Yue·^Revised replacement page I_______1 丨14. 15. 16 17 18 19. 20. 21. As in the method of claim 13, the center of the heart is at least Fat alkyl chain. The method of claim U, wherein Rz is (c2 to c6 alkyl)_N+R丨6R丨7R18 (wherein Ri6, Ri7, Ru are the same as Ri, R3, and I, respectively), or (^ to (:4) The method of claim 13, wherein one or more of the centers to the center are (poly)oxyalkylene groups, wherein the alkylene group is an alkyl group and an oxygen alkyl unit The total number is from 1 to 50 oxygen-extended base units. The method of claim 13, wherein at least one of & to & is a 〇1 to 〇4 alkyl bond. The method of claim 13, wherein X - a halide anion carboxylate anion, sulfate (both organic and inorganic sulfate), sulfonate, carbonate 'nitrate, nitrite, thiocyanate, hydroxide, saccharinate or an imine The method of any one of claims 13 to 18, wherein the metal which is electroplated or electropolished on the substrate is derived from a metal source selected from the group consisting of chromium, aluminum, titanium, zinc and copper salts. a metal salt of a group consisting of, or an anode selected from the group consisting of chrome, indium, ching, zinc, and copper anodes, as in any of claims 13 to 18. The method wherein the cation of the ionic liquid and the metal salt or the metal cation derived from the metal anode have a molar ratio between 1,000:1 and 3:1. The molar ratio of the cation of the ionic liquid to the metal salt or the metal cation derived from the metal anode is between 100:1 and 7:1. 133195-1001228.doc 丨 u u Μ 替换 替换 替换 22 The method of any one of claims 13 to 18, wherein the ionic liquid system is selected from the group consisting of choline saccharate, choline sulfonate, cetyltrimethyl chloride Ammonium, octadecyltrimethylammonium chloride, chlorinated coconut-methyl record, chlorinated tallow trimethyl chloride hydrogenated tallow trimethyl sulphate, chlorinated hydrogenated palmate triflate, chlorinated oil Trimethylammonium, chlorinated uranyl ammonium, gasified coconut benzyl dimethyl ammonium, chlorinated C! 2·! 6-alkylbenzyldimethylammonium, gasified hydrogenated tallow benzyl dimethyl Base ammonium, dioctyldimethylammonium chloride, dimercaptodimethylammonium chloride, dicocodimethylammonium nitrite, gasified two coconut Dimethylammonium, di(hydrogenated tallow) bis-f-ammonium chloride, gasified di(hydrogenated tallow) benzyl ammonium sulfonium chloride, ditallow dimethyl ammonium chloride, gasified di(octadecyl) dimethyl Alkyl ammonium, gasified hydrogenated calfium (2-ethylhexyl) dimethyl ammonium, methyl hydrogenated tallow (2·ethylhexyl) dimethyl ammonium, tri-hexadecylmethyl ammonium chloride, Octadecylmethyl bis(2-hydroxyethyl)ammonium chloride, coconut di(2-hydroxyethyl)methylammonium nitrate, gasified coconut bis(2-hydroxyethyl)methylammonium, chlorinated coconut II (2-hydroxyethyl)benzylammonium, oleyl bis(2-hydroxyethyl)methylammonium chloride, chlorinated coconut [polyoxy-extended ethyl (15)]-methylammonium, f-based sulfuric acid coconut [polyoxyethylidene]methylammonium, chlorinated coconut [polyoxyethyl (17)] methylammonium chloride, octadecyl chloride [polyoxyethyl (15)] methyl ammonium, gas Hydrogenated tallow [polyoxyethyl (15)] methyl ammonium, tris(2-hydroxyethyl) ammonium taurate, di-gasified tallow _ 1,3-propane pentamethyl diammonium β 133I95-1001228.doc