TW591124B - Plating bath and method for depositing a metal layer on a substrate - Google Patents

Abstract

A metal plating bath and method for plating a metal on a substrate. The metal plating bath contains hydroxylamines that inhibit the consumption of additive bath components to improve the efficiency of metal plating processes. The additive bath components are added to metal plating baths to improve brightness of plated metal as well as the micro-throwing and macro-throwing power of the bath. In addition to brighteners, the additive bath components may include levelers, suppressors, hardeners, and the like. The hydroxylamines that inhibit additive consumption may be employed in metal plating baths for plating copper, gold, silver, platinum, palladium, cobalt, cadmium, nickel, bismuth, indium, tin, rhodium, iridium, ruthenium and alloys thereof.

Description

591124 A7

Connect the ball to the power supply using a suitable fixing method. During the deposition of such an anode, the copper is decomposed at about the same rate as the copper deposited by the deposition bath, and a certain copper content Q is maintained in the deposition solution, so no additional copper is needed. Another form of anode is an insoluble anode. The external dimensions of the insoluble anode do not change during metal deposition. Such anodes consist of inert materials, such as titanium or lead, which are covered with a catalytic metal such as platinum to avoid high anode overvoltages. In printed circuit and circuit board manufacturing, insoluble anodes are better than soluble anodes. In addition, the electroplating process using insoluble anodes is more suitable than their use of consumable anodes. Insoluble anodes can allow higher plating speeds, require smaller equipment sizes, easy maintenance, improved solution flow and mixing, and can be discharged. Near the cathode. Particularly advantageous is the fact that the insoluble anode does not change size (i.e. the geometry of the tank remains unchanged). As a result, a more uniform plated product is obtained. In addition, the copper salt used to provide the copper source is usually obtained from the products of the remaining steps associated with the manufacture of steel-plated components. For example, in the manufacture of a circuit board, a steel layer is placed on the entire surface of the insulating substrate and a portion of the steel is etched away to produce a desired circuit board. Plated metals (such as copper plating) on substrates are widely used in various manufacturing processes. Copper plating is used to prevent corrosion on various surfaces (such as iron surfaces), as a bonding layer with an additional metal layer, to increase electrical or thermal conductivity and to provide a conductive pathway in many electrical applications. Copper plating is used in the manufacture of electrical devices such as circuit boards, integrated circuits, and electrical contact surfaces. Plating metal is a complex process covering multiple components in a plating bath. In addition to providing metal source metal salts, pH adjusters and surfactants or humectants ---- * 1 «, · (Please read the precautions on the back before filling this page) Order ---- r ---- -Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economics This paper is printed to the Chinese National Standard (CNS) A4 (21 × 297 mm) 2 91983 591124 A7 V. Invention Description (3 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economics Manufacturing I? Re-employment order 1 (please read the precautions on the back before filling out this page), many plating baths, such as plating baths, contain chemical compounds that improve various aspects of the plating process. Such chemical compounds or additives It is a supplementary component of the plating bath, used to improve the gloss of the metal coating, the physical properties of the metal, especially the ductility, and the micro-electric and mineral power of the electroplating bath. The main consideration of additives is on the surface The metal deposition layer has the effects of glossy surface treatment, flatness and uniformity. Keeping the concentration of the plating bath of such additives within a small allowable range is important for obtaining high-quality metal laminates. It is important. Such additives will decompose during metal plating. Decomposition of additives is caused by anodic oxidation, cathodic reduction and chemical degradation. When additives decompose during plating, the decomposition products may cause the deposition of metal layers It is difficult to meet the requirements of industrial standards. The general method of adding additives used in the industry is to try and maintain the optimal concentration of additives according to the rules of thumb established by the operator. However, the additives are used in small amounts in the plating bath. The concentration exists, that is, one millionth of the solution, so it is still extremely difficult to monitor the concentration of additives that can improve the metal coating. Moreover, during the plating process, the mixture of additives and degradation products formed by the additives make the replenishment process Complicated. Furthermore, the consumption of specific additives does not always change over time or the use of the plating bath. Therefore, it is impossible to know the concentration of the specific additive and the final reduction or increase of the additive in the plating bath beyond the allowable range .If the content of additives exceeds the allowable range too much, it will damage the gold It is a laminate quality and the laminate may lose its appearance and / or be brittle or powdery in structure. Other results include low plating ability and / or plating f0Ms with poor flatness. In the manufacture of multilayer printed circuit boards, the inner wires of the plated through-holes are required to be highly plated. This paper is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297). 591124 A7 V. Description of the invention (4 Examples of quality. ( Jing first read the precautions on the back before filling out this page) The stability and life of the ore bath are extremely important. The added stability of the additives that improve the metal bond layer results in a longer life of the plating bath. Overcoating is extremely economically important. As mentioned above, frequent replacement of baths and treatment of plating baths containing degrading additives can interrupt metal plating operations. This interruption reduces productivity. Therefore, a stable plating bath system that can prevent or reduce the decomposition of additives is highly expected. Printed by the Consumer Affairs Agency of the Intellectual Property Agency of the Ministry of Economic Affairs, US Patent No. 4,469,564 reveals the copper plating process that claims to increase the life of the plating bath. The patent states that the process can use soluble or insoluble anodes. A cation-permeable membrane surrounds the anode to prevent organic additives from contacting the anode and being oxidized by the anode. The disadvantage of this process is that prolonged exposure of the cationic permeable membrane to residual chemicals may cause the membrane to decompose. For example, the pH range of the plating bath may be lower than 丨 0 to as high as u 〇 and more so when the components of the field plating bath are consumed or decomposed, the ρΉ range of the mineral coating bath may fluctuate during this time. Therefore, the operator of this technique must have the ability to select a film that will not decompose due to fluctuations in the plating process in accordance with the chemical composition. In addition, as discussed above, the plating bath contains various ingredients. Components such as organic additives or their decomposition products may block the pores in the cation-permeable membrane and prevent cations from passing through the plating bath. Therefore, the operator must stop the electroplating process and replace the sheet. Blocking the holes and stopping the process can lead to inefficient plating processes. Japanese patent application 63014886 A2 discloses an acid copper plating bath having chloride ions and containing transition metal ions at a content of 0.001 to 100 g / l. The electric mineral bath claims to not suffer from the consumption of organic additives. This kind of organic paper ruler-degree applies to the Chinese National Standard (CNS) A4 specification ⑵G x 297 public love) 4 919 & 3 591124 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 '—__________ B7 ___ 5. Description of the invention (5) Additives include gloss agents, levelling agents, hardeners, ductile and ductile modifiers, and deposition modifiers. EP 0402 896 discloses a method for stabilizing organic additives such as gloss agents in acid copper plating solutions. This method uses soluble anodes of copper filings in a titanium basket. The transition metal salts of manganese, iron 'chromium and titanium are added to the power ore solution at a concentration not exceeding 5 g / 1. The transition metal can exist in at least two positive oxidation states, but exists substantially in solution in its lowest common positive oxidation state. The presence of the positive oxidation state of the transition metal ion in the solution claims to stabilize the organic additive. U.S. Patent No. 6,099,711 discloses a plating method using an insoluble anode. The method uses a metal ion generator in a plating bath to replenish metal ions, such as copper ions, in a reversible redox system. Since an insoluble anode is used instead of a soluble anode, metal ions are not supplemented in this plating bath by anode dissolution. Therefore, this reversible redox system is used to supplement metal ions. Iron (II) and iron (111) compounds were used as the electrochemical reversible redox system. Other redox systems disclosed in the patent include titanium metal, trim, starvation, ferrous and chromium. Such metals can be iron sulfate (η) heptahydrate, iron (II) sulfate nonahydrate, titanyl sulfuric acid, titanium (IV) sulfate, sodium metaquinone, sodium sulfate, or Sodium chromate was added to the copper deposition solution. The patent states that the redox systems can be combined with each other. ^ 1 ^ 1 1 ϋ · ϊ * ϋ y er a ^ i I 1_1 I "(Please read the precautions on the back before filling out this page) In addition to supplementing metal ions in the plating bath, the patent states that the method can Significantly prevent the degradation of organic additives. Due to the anode potential, a large amount of organic additives will be degraded by electrolysis at the anode in the plating bath.

591124 A7 V. Description of the invention (6) The operator of this technology believes that the redox reaction of iron (11) to iron (m) (approximately 0.530v relative to SCE) will provide the anode with a sufficiently low potential to prevent gloss The agent is oxidized at the anode. Therefore, the consumption of the gloss agent can be reduced. Such organic additives include gloss agents, levelling agents, and wetting agents. The gloss agents used include water-soluble sulfur compounds and oxygen-containing high molecular weight compounds. Other additive compounds include nitrogen-containing sulfur compounds, polymeric nitrogen compounds, and / or polymeric phenazine nitrogen gun compounds. Filling out Although the patent claims to replenish metal ions and reduce the consumption of gloss agents, the method disclosed in the 711 patent still has disadvantages. In the reversible oxidation reduction reaction, iron (III) can be reduced back to iron (11), while copper is oxidized to copper (π). In addition, after some time, iron may accumulate in the system, requiring problems such as downtime and cleaning operations. This operation reduces the efficiency of the method and increases the method. Another disadvantage of the method is that the compound concentration in the redox system must be such that the metal ion in the deposition solution can be maintained at a fixed concentration. Therefore, there is a small or non-existent margin of operation error in the redox compound concentration in the deposition solution of this method. Thus, a small change in the oxidation compound concentration may hinder the operation of the method. ”, Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Japanese Patent Application No. 96199385, discloses a plating method and a solution containing a fluoride-based surfactant and an additive such as a glossing agent. & Adding the fluoride-based surfactant claimed to stop the consumption of I-zeolite. Nine Although there are methods to prevent the degradation of additives in metal plating baths, there is still a need to prevent the degradation of plating bath additives. Requirements for other methods of interpretation The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 91983 6 591124 Printed by A7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) [Overview of the invention The present invention relates to a plating bath containing hydroxylamine, which can suppress the degradation of additives in a mineral coating bath, and a method for plating a metal on a substrate using the plating bath. Such hydroxylamines include compounds having the formula: (R'-NHR ^ OH) ^ where R1 and R2 are each independently hydrogen, or (^ to alkyl, 11 is ι 戋 2, and when η is 1, X It is HS04-, H2P04-, N03-, F-, cr, or _ or industrial. When n is 2, X is so42_. The above hydroxylamine can be used to plate steel, gold, silver, palladium, platinum, Inscriptions, braces, chromium, nickel, bismuth, indium, tin, rhodium, lead, iridium, ruthenium or their alloys in metal plating baths. The addition of amines to the baths is helpful to prevent or reduce the metal ore bath additives. Degradation. Therefore, amines are provided for plating baths with long service life and efficient metal ore coating methods. Furthermore, since the amines of the present invention prevent the degradation of the additives, the plating baths of the present invention can be used in The substrate provides a uniform, high-gloss metal layer with good physical and mechanical properties. The metal plating bath of the present invention can be used to plate a metal layer on any substrate that can be plated with metal. The metal plating method of the present invention includes Passing current between two electrodes immersed in a plating bath containing dissolved plating metal, plating bath additives And one or more compounds for inhibiting the consumption of additives of the present invention. The amines and methods of the present invention can be used in any industry using metal plating. For example, the metal plating bath can be used in electrical devices such as printed circuits and circuit boards, product Body circuits, electrical contact surfaces and connectors, electrolytic wafers, silicon wafers for microchip applications, semiconductors and semiconductor packages, lead frames, optical_standards (CNS) A4 specifications (G χ 297 public love_)? ------ --Order --------- | (Please read the notes on the back before filling this page) 591124 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Components and optoelectronic component packaging, and for example, the manufacture of solder bumps on wafers. And the metal plating bath can be used to metal plate jewelry, furniture accessories, automotive parts, sanitary equipment, etc. In addition, the hydroxylamine also It can be used in waste treatment methods. The invention also includes a metal plating bath consisting of a power source, an anode and a cathode, and a compound containing a compound that suppresses the consumption of additives. The cathode of the device is a metal plating. The device may be Straight or horizontal metal plating device. The main object of the present invention is to provide hydroxylamine in the metal plating bath to prevent or reduce the degradation of additives. Another object of the present invention is to provide a metal ore coating bath with a long operating life. The object is to provide an effective method for plating metal on a substrate. A further object of the present invention is to provide a method for plating a uniform, high-gloss metal layer with good physical and mechanical properties on a substrate. Yet another object of the present invention is to provide hydroxylamine-containing Device for metal plating bath. Those skilled in the art can understand other objects and advantages after reading the detailed description of the present invention and the scope of the attached patent application. [Simplified illustration of the figure] Figure 1 shows the processing of working parts by the vertical method according to the present invention. Device schematic diagram. Fig. 2 is a schematic diagram of an apparatus for processing a working part using a horizontal method according to the present invention. M's Zhang scale 剌 Chinese National Standard (CNS) A4 specification ⑵ G χ 297 public compound y ---------- " 1 «·· -------- Order ------ --- j (Please read the notes on the back before filling this page) 591124 A7

[Description of Symbols] 10 Device 12 Container 14 Metal plating bath 16 Working parts 18 Anode 20 Power supply 22 Storage tank 24 Spray chamber 26 Slot 28 Flat plate 30 Center roller 32 Roller brush 34 Anode 36 Power supply device 38 Nozzle 40 Metal plating Bath 42 Tank --------- ί · (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Detailed description of the invention] tmetal M cover of the present invention The bath contains hydroxylamine that prevents or reduces consumption of additives added to the metal ore overlay bath to improve metal deposition on the substrate. The metal plating bath can be used in any suitable process for plating metal on a substrate. Two kinds of amines have the following formula: (R'-NHR ^ OH) ^ wherein R1 and R2 are each independently hydrogen, or (^ to (^ alkyl, 11 is when η is 1, X is Hs), H2P04-, NO ,, F-,, or. When n is 2, X is SO. The (^ to alkyl group includes methyl, ethyl, propyl, isopropyl, butyl , Isobutyl, second butyl, second tamibutene, pentyl, isopentyl, neopentyl, third pentyl, hexyl, λ-d group, 3-methylpentyl, 2,2-di Methylbutyl, or 2,3-dimethylbutyl. Preferred hydroxylamines R1 and R2 are hydrogenated hydroxylamines, such as ▲ 1J such as hydroxylamine sulfate, hydroxylamine nitrate and gasified hydroxylamine. More preferred are hydroxylamine sulfate and nitrate. Monthly hydroxylamine. The above-mentioned order: --------- · This paper size is applicable to China National Standard (CNS) A4 (210x 297 mm) 9 91983 591124 A7

591124 Α7 B7 5. In the description of the invention (11), R11 is 〇1 to C6 alkyl or aryl); or H03S_Ar_S-S-Ar-S03H (where Ar is phenyl or aryl). The alkyl and aryl substituents may be, for example, alkyl, halogen, or alkoxy. Examples of such gloss agents are 3-M-propylsulfonic acid (sodium salt), 2-M-methyl-ethanesulfonic acid (sodium salt), propyl disulfide bissulfonate (BSDS). Such compounds are disclosed in U.S. Patent Nos. 3,770,598, 4,374,709, 4,376,685, 4,555,315, and 4,673,469, all of which are incorporated herein by reference. Such polysulfides can also be used to increase the ductility of the deposited metal. Especially for copper plating baths, examples of other suitable glossing agents include N, N-dimethylthiocarbamate (3-contanoic acid propyl) ester, sodium salt (DPS), (〇_ethyl di Thiocarbonate) -S- (3-phenoxypropyl) -ester 0, potassium salt (ορχ), 3-[(amino-iminomethyl) _ thio] -1 -propionic acid ( UPS), 3 · (2-benzothiazolylthio) _ι_propionic acid, sodium salt (ZPS), and dithiodisulfonic acid propyl mercaptan (mps). Examples of levelling agents that can be used in the ore-covered bath include, but are not limited to, calcined polyimide, organic horizontal acid-based continuous acid salts. Examples of such compounds include 1- (2-hydroxyethyl) -2-ethylenethiourea (HIT), 4-mercaptopyridine, 2-fluorenylthiazoline, thiourea, thiourea, and thiourea Polyimide. Such compounds are disclosed in U.S. Patent Nos. 4,376,685, 4,555,315, and 3,770,5 98, the disclosures of which are all incorporated herein by reference. Within the scope of the present invention, examples of other additives that can be used as a glossing agent in a plating bath include, but are not limited to, for example, 3- (benzothiazolyl_2_thio) _propylacetic acid sodium salt, 3. mercaptopropane -1—Sodium salt of sulfonic acid 'sodium salt of ethylene dithiodipropyl diacetate, bis- (p-_contanoic acid phenyl) _disodium disulfide, bis_ (ω_acetic acid butyl) _ Di sodium salt monosulfide, bis (ω_ji acid via propyl) _ disodium disulfide salt, ί «_ · (Please read the precautions on the back before filling this page) Order -------- -? Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 11 91983 591124 A7 B7 V. Description of the invention (12) Double- (ω-sulfonic acid Propyl)-disodium disulfide, bis _ (. Sulfopropyl) _ disodium sulfide, methyl- (ω-sulfopropyl) sodium disulfide, methyl- (ω_propionic acid propyl) Group)-disodium trisulfide, 0_ethyl-dithiocarbonate sulfonate) ester, potassium thioglycolate, thiophosphoric acid · 〇_ethyl-bis_ (ω · propanesulfonic acid) Ester sodium disodium salt, phosphorothio-tris (ω-sulfopropyl) -ester trisodium salt, etc. Examples of oxygen-containing high molecular weight compounds that can be used as inhibitors include, but are not limited to, carboxymethyl cellulose, nonylphenol polyethylene glycol ether, octanediol bis- (polyalkylene glycol ether), octane Alcohol polyethylene glycol ether, polyethylene glycol oleate, polyethylene propylene glycol, polyethylene glycol, polyethylene glycol dimethyl ether, polypropylene oxide glycol, polypropylene glycol, polyvinyl alcohol, polyethylene glycol stearate Alcohol esters, stearyl alcohol polyethylene glycol ether, polyethylene oxide, etc. Phenotype dyes (saffron type) and phenoxazo dyes (Janus green type B) can be used as leveling agents. Polyethers are used. In order to increase the thickness and uniformity of the metal ore layer, the glossing agent and the leveling agent are added to the plating bath in an amount of one billionth to about 1.0 g / L of the plating bath. The glossing agent and the leveling agent are in millions The range of 10 parts per million to 500 parts per million is better. The range of the composition of the plating bath can be printed by a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -------------- I --- Write the item again (please read the notes on the back before filling this page) The composition of the mineral coating bath is changed to the next composition. Therefore the weight of the above additives This is a general range. Examples of suitable wetting agents or surfactants that can be used in the plating baths of the present invention include non-ionic surfactants, such as alkylphenoxy polyethoxyethanol. Other polyoxyethylene groups can also be used Suitable humectants. Such humectants include compounds of polyoxyethylene polymers with 20 to 150 repeating units. Such compounds also act as inhibitors. The polymers also include polyethylene oxide— Block copolymer with polypropylene oxide. Added in the conventional amount. The paper size is applicable to Chinese National Standard (CNS) A4 specification (X 297 public copy) --- '~~ _____ 11 919S3. 591124 A7

13 Surfactants and wetting agents. In addition to the additive, the remaining components of the plating bath include, for example, a metal ion source, a pH adjusting agent (for example, an inorganic acid), and a thallium ion source. Generally, the plating bath is an aqueous solution. The pH of the plating bath may range from 0 to about W, preferably from 0 to 8. Wetting agents for plating baths and the amounts used in such plating cooling are well known in the art. The inorganic acids used include, but are not limited to, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and the like. Sulfuric acid is preferred. # 素 ionic is used as needed. The halide ions used in the plating bath include chlorides, fluorides and bromides. This dentate is added to the plating bath as a water-soluble salt. Preferably, a gaseous substance is introduced into the plating bath with sodium gasified, preferably HC1. The metal water-soluble salt supplies the source of the metal to be plated on the substrate. Such water-soluble salts include metal salts of steel, nickel, chromium, gold, silver, braided platinum, Ming, Syria, tin, money, iridium, ruthenium, metal and indium. The plating bath can also be used to plate solder. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Copper is a preferred metal to be plated using the plating bath of the present invention. Electroplated steel is preferred. Suitable steels can be in the form of any solution-soluble steel compound. Suitable steel compounds include, but are not limited to, copper compounds, steel sulfates, copper alkanesulfonates, copper alkoxides, and the like. When steel dentate is used, chloride is the preferred dentate. The preferred steel compound is copper sulfate, alkanesulfonic steel, or a mixture thereof. More preferred is copper sulfate, copper methanesulfonate or a mixture thereof. Steel compounds suitable for use in the present invention are generally commercially available or can be prepared by methods known in the literature. When copper is plated on a substrate, the pH of the plating bath can range from 0 to about 14. The plating bath preferably has a pH ranging from 0 to about 80. 91983 Bu Family Standard (CNsi_A4 Specification⑵Q χ 297 Public Love) 591124 A7 B7 V. Description of the Invention (14) The concentration distribution of metal ions in the plating bath ranges from 001 g / L to about 200 g / L 'Preferably ranges from 0.5 g / L to about 100 g / L. When steel is used, the 'steel content may be in the range of about 0.01 to about 100 g / L. The amount of steel used in the plating bath is preferably in the range of about 0.10 g / L to about 50 g / L. When the plating bath of the present invention is used in a non-high-speed mineral coating process, the copper content in the plating bath is preferably in the range of about 0.02 g / L to about 25 g / L. When the plating bath of the present invention is used in a high-speed plating process, the copper content in the plating bath is in the range of about 1.0 g / L to about 100 g / L, and in the range of about 20 g / L to about 50 g / L. Is better. • — — — — I1IIL »— (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, especially for copper plating baths, the halide concentration is 0mg / L In the range of about 1 g / L, preferably about 10 nig / L to about 150 mg / L, adding acid to the plating bath results in a pH range of about 0 to about 80, with less than 1.0 to about 2.0 optimal. Therefore, the amount of acid added is about 10 g / L to about 600 g / L, and preferably about 15 g / L to about 500 g / L. An example of an acidic copper plating bath embodying the present invention has the following composition: · Copper ions (such as sulfuric acid steel) 0 · 01 to 50 g / L · Agrosulfuric acid 15 to 500 g / L Gas ions (such as sodium gasification) lppm to 150ppm Additives such as Add the required amount of hydroxylamine sulfate 0.1 to 10g / L water to 1 liter and the carboxamide compound can be used to prevent the degradation of the additives in the plating bath of any suitable metal-plated substrate. The hydroxylamine compound of the protective additive is used for electroplating A bath is preferred. Such electroplating baths are used in the manufacture of electrodeposited metals on substrates such as printed wiring boards and silicon wafers for microchip applications, and other components of electrical devices. The electroplating process covers the size of the paper. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 meals). 14

9198S — Order -----------? V. Description of the invention (15) The current passing through the electrode, plating solution and cathode to the desired thick time makes the substrate metal ore coated as a soluble anode (when plating occurs) The metal that can dissolve and replenish the electroplating bath will be a soluble anode (consisting of an inert material such as 4 steel). Alternatively, the invention can be used in the process of ore coating, such as surface and platinum plating. Using thunder ㈣ = qi, etc.). Use of plating rate and additive consumption (through anodes are preferred. Insoluble anodes that use the cold% anode process are examples of suitable insoluble anodes with oxides on the surface: electrode. This anode has about 20 to Approximately 90 mole percent of silver and the rest of the group. Preferred is about 6G to approximately 9 (mole percent of the silver μ remaining group). By coating the conductive substrate (such as a substrate) with silver and Other suitable anodes include at least about 10 mol percent of the νΐΗ group metal, at least about 10 mol percent of valve metal (valvetai), and up to about 5 mol percent of bonded metal (bin (jer metai ) Composed of anodes. Group VIII metals include cobalt, nickel, ruthenium, germanium, palladium, iridium and platinum. Tube metals include titanium, zirconium, hafnium, vanadium, niobium and buttons. Combined metals include beryllium, employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer cooperatives print scandium, pin, barium, scandium, yttrium, lanthanum and rare earth elements with atomic numbers 58 to 71. With a barium with a percentage of about 5 to about 20 moles, and a ratio of iridium to the group of about 1 / Oxides between 4 and about 4 The composition is particularly suitable. Such a composition is about 5 mole percent of barium, about 30 to about 40 mole percent of iridium and the rest of tantalum. In addition, insoluble anodes can also use rhenium, silver and gold or their oxides. As mentioned above, the plating bath of the present invention can be used on any suitable substrate | This paper size is applicable to the Chinese National Standard (CNS) A4 (210x 297 mm) 15 91983 591124 A7 B7

V. Description of the invention (16) Metal plating process printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Examples of such plating processes include, but are not limited to, direct current (DC) plating and pulse plating. The plating bath of the present invention is particularly suitable for the use of mineral-coated substrates in the manufacture of electronic devices in the printed circuit board industry and in the manufacture of silicon semiconductor wafers. In the plating process, a substrate to be plated is used as a cathode. As the second electrode, a soluble anode or preferably an insoluble anode as described above is used. Instead, pulse plating, DC (direct current) plating, or a combination of both is used. These plating methods are all known in the art. The current density and electrode surface potential can be changed according to the specific substrate to be plated. Generally, anode and sac current densities range from about 1 to 1000 amps / ft2 (ASF). The plating bath is maintained in a temperature range of about 20 ° C to about 110 ° C. The specific range varies depending on the metal being plated. These temperature ranges are well known in the art. Electroplating is continued for a time sufficient to form a deposited layer of the desired thickness. Generally, the plating time of the circuit board is about 45 minutes to about 8 hours. For circuit board manufacturing, the desired thickness may be in the range of about 0.05 to about 3.0 mils. More common layer thicknesses range from about 10 to about 1.5 mils. Both vertical and horizontal mining processes can be used. In a vertical process, a substrate (such as a printed circuit or a circuit board) is vertically sunk into a container containing a plating bath solution of the present invention. The substrate serving as the cathode is vertically opposite to at least one anode (preferably an insoluble anode). Connect the substrate and anode to a power source. Instead of adjusting the current density of the power supply, the voltage between the substrate and the anode can also be adjusted to have a voltage arrangement. The transfer bath (such as a pump) is used to continuously introduce the plating bath through the container. -IJ --------- Voice, (Please read the note on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 meals) 16 91983 591124 A7

V. Description of the invention (17) Printing of clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Figure 1 shows an example of a configuration suitable for processing substrates or working parts using vertical methods and devices. The device 10 is composed of a container 12 and an amine-containing metal plating bath 14 containing an additive-resistant material. This metal plating bath 14 can be used for steel plating, for example, and contains the aforementioned components and additives. A working part 16 (cathode) (for example, a circuit board) and an anode 18 (for example, an insoluble titanium anode covering a surface of a dioxide dioxide) are immersed in a metal plating bath 14. The working member 16 and the anode 18 are electrically connected to a power source 20. Instead of adjusting the power supply current, a voltage distribution (not shown) can be used to adjust the voltage between the working member 16 and the anode 18. The metal plating bath 14 is continuously introduced into the second container or tank 22 using a conveying device (not shown) such as a pump. The metal plating bath 14 flows through the storage tank 22, and supplements the metal plating bath components and additives of the metal plating bath 14, such as steel salts, gloss agents, levelling agents, hydroxylamine (additive consumption inhibitor), and the like. In the horizontal plating process, the substrate is moved in a horizontal direction in a horizontal state, and is conveyed by a unit converted by an automatic conveying device. The splash nozzles or flood pipes are used to continuously inject the plating bath from below and / or above the substrate. The anode is arranged at an interval from the substrate, and the anode is brought into contact with the plating bath by a suitable device. Use rollers or pallets to transport substrates. Fig. 2 illustrates an example of a horizontal method and a device for implementing the present invention. The spraying chamber 24 with the slits 26 forming means 46 at both ends enables the flat plate 28 (such as a metal-clad circuit board) to be continuously transported into and out of the spraying chamber 24. Wherever a circuit board is used as an illustration ', however, any suitable surface that can be covered with a horizontal device is within the scope of the present invention. Flat plate 28 with intermediate rollers (idler 1. Aw order ---- 1 ----- (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297) 17 91983 591124 A7 B7 V. Description of the invention (18) roller) The 3G support moves in the direction of the arrow. The rows of roller brushes 32 are located in contact with the upper and lower surfaces of the flat plate, and the rows of anodes 34 are located at the end of the intermediate roller 30 away from the plate 28 and in contact with the roller brushes 32. The anode 34 is formed of any suitable metal, such as arsenic coated with iridium dioxide. Although any suitable anode can be used, an insoluble anode such as titanium coated with iridium monoxide is preferred. The anode 34 is located at a position where the anode contacts the roller brushes 32 in the upper row from above and a position where the roller brushes 32 in the lower row are contacted from below. All anodes 34 are electrically connected in parallel to the positive electrodes of the power supply device 36. The negative electrode of the power supply device 36 is connected to the plate 28 (cathode) to be plated. A nozzle 38 is arranged to spray the metal plating bath 40 downward to the anode 34 and the roller brush 32 and the flat plate 28 between the roller brush 32. The nozzle 38 is connected to the metal plating bath button through a line 44 The storage tank 42. The arrow indicates the path of the metal plating bath through the line 44. The metal plating bath is withdrawn from the storage tank 42 by means of a drawing device (not shown) mechanically connected to the storage tank 42. The conveying mechanism (not shown) of the plate 28 is a conveyor-type mechanism that can provide the plate 28 to move through the spray chamber 24 in succession while maintaining the electrical connection between the negative electrode of the power supply device 36 and the plate 28. Eliminate

I By preventing or reducing the amount of decomposition of the additive, the hydroxylamine compound provides increased gloss and improved physical and mechanical properties by the mineral metal. The metal layer plated with the ore bath of the present invention is not structurally brittle or powdered. Furthermore, the metal layer plated with the ore bath of the present invention has a good electric ore capacity and no visible ore cover. The properties of this metal layer are particularly satisfactory for through-holes in printed circuits and wiring boards. At the same time, since the compounds selected during the metal cladding process can prevent or substantially reduce the drop of additives ^ China National Standard (CNS) A4 specification ⑵0 x 297 issued by the public) 18 591124 Staff Consumption of the Ministry of Economic Affairs Cooperative printed A7 V. Description of invention (19) Solution 1 Therefore, supplementary additives are rarely needed. In addition, preventing the decomposition of the additives allows the metal plating operation to be continued for a longer period of time without the need for replacement of the plating bath. Furthermore, since the hydroxylamine compound inhibits the degradation of the additive, an expensive semi-permeable film can be omitted from the device during the plating process. A plating bath containing hydroxylamine compounds provides a more effective and economical method of metal plating than a plating bath containing no hydroxylamine compounds. Therefore, the metal plating bath of the present invention provides an improved metal plating process. Although the description of the present invention emphasizes the plating process in the printed circuit board industry, the present invention can be applied to any suitable plating process. The hydroxylamine compound can be used in electronic devices such as printed circuits and circuit boards, integrated circuits, electrical contact surfaces and connectors, electrolytic wafers, silicon wafers for microchip applications, semiconductors and semiconductor packages, lead frames, optoelectronic components and optoelectronic components Metal plating baths for packaging and manufacturing of solder bumps on wafers, for example. In addition, the metal plating bath can be used for metal plating of jewelry decorations, furniture accessories, automobile parts, sanitary equipment, and the like. In addition, the compound that suppresses the consumption of additives can be used in waste disposal methods. The following examples are provided to better illustrate the invention, but are not intended to limit the scope of the invention. [Example] Example 1 In a plating bath, a Hull cell was used to measure the gloss agent consumption. Each of the Hor batteries used is a hydrodynamically controlled Hor battery (HCHC). The plating bath contains copper ore covering bath of the following composition: 91983 1 I -------- Order ---------. (Please read the precautions on the back before filling this page) 591124 A7 V. Description of Invention (20)

The first Hor battery test had a soluble steel anode and a copper-coated glass epoxy resin plate as the cathode. The second and third Hall batteries used have insoluble iridium dioxide anodes instead of soluble steel anodes. In addition to the plating bath composition described above, the third Hor battery contains approximately 1 乩 羟 of hydroxylamine sulfate. Copper was plated on the copper-clad glass epoxy cathode. Consumption of the gloss agent was measured as the percentage of matt steel surface. A matte surface within the meaning of the present invention means that the steel bonded to the cathode has a matte or non-reflective surface appearance. Each horror battery test is operated for about 2 minutes at about 3 amp, and then for about 10 minutes. After about 2 minutes and about 10 minutes, the percentage of matt on the copper-plated surface was measured. Therefore, using a soluble copper anode for electron microscopy 'consumes very little polishing agent between about 2 minutes and about 10 minutes. In a second test, using an insoluble anode of iridium dioxide, after about 2 minutes, about 30% of the copper metal lost its luster. After about 10 minutes, almost all of the copper metal was tarnished. Therefore, after plating for about 10 minutes using an insoluble iridium dioxide anode, almost all of the gloss agent is consumed. In a third experiment, approximately 1.0 mg / L of hydroxylamine sulfate was added to a copper plating bath as a gloss agent consumption inhibitor. After about 2 minutes and about 10 minutes' copper on the cathode, the matte surface is about the photo paper size Applicable to Chinese National Standard (CNS) A4 specification (G X 297 public love) 20 ^ ---- ---------- 丨 · # (Please read the phonetic on the back? Matters before filling out this page} --Order --------- 00 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591124 A7 B7 21 1. Description of the invention (same percentage. Therefore, it usually consumes a little brightener between about 2 minutes and about 10 minutes. Compared with soluble copper anodes, the consumption when using insoluble anodes will cause especially Question. However, when hydroxylamine is added to the copper plating bath, the consumption of sulfur-based gloss agents can be suppressed by the incompatible anode. -------- i (Please read the Please fill in this page again for attention) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 (210 X

Claims (1)

H3 No. 90129377 Patent Application Amendment to the Patent Scope (July 14, 1992) 1. A metal ore bath, including a compound that suppresses the consumption of additives, which includes 0.001§ of the ore bath to i. 〇g / L, and has the formula (R ^ NHR ^ oh) ^ where and R2 are each independently hydrogen, Ci to q alkyl, n is ι or h when n is! Χ is HS (V, H2p (v, n ..., f, C1 ·, Br, or Ι ·, when n is 2, χ is so, and copper, gold, silver, palladium, platinum, cobalt, Metal salts of cadmium, chromium, nickel, bismuth, indium, tin, rhodium, lead, ruthenium, iridium or their alloys. 2. The metal plating bath of item 1 in the patent application scope, wherein the J, 6 alkyl group includes Fluorenyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isopentyl, neopentyl, third pentyl, hexyl, isohexyl , 3-fluorenylpentyl, dimethylbutyl, or 2,3-dimethylbutyl. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs. Wherein, the compounds that suppress the consumption of additives include hydroxylamine sulfate, hydroxylamine nitrate, vaporized hydroxylamine, or mixtures thereof. 4. For example, the metal plating bath of the scope of patent application, wherein the compounds that suppress the consumption of additives include the plating bath. 01 g / L to 20.0g / L〇5. For example, the metal plating bath in the scope of patent application No. 1 includes: containing pre-sizing agent, levelling agent, hardener, wetting agent, Natural modifiers, ductility | This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1 91983 Modifiers, deposition changes _ 'Mell or inhibitor additives. 6 · If you apply The scope of patent is 5 metal plating baths of Shenggudi, in which the glossing agent u and the compound having the formula: H〇3-S-Rn-SH; H〇3S-Rn-SS〇3H (where R11 is 1 to [6 alkyl or aryl); or Η〇γ S Ar SC ^ H (where & is phenyl or naphthyl, the alkyl and aryl may be unsubstituted or alkyl, halogen or alkoxy (Substitute).-7 · = Shenqiao's patent No. 6 metal bell bath, in which the gloss agent i includes 3-^-propyl sulfonic acid sodium salt, 2_yl-sulfonic acid sodium salt Salt, mono- & bis-stilbene propyl, dimethyl dithiocarbamic acid (3-sulfomethylpropylsulfonium salt, (0_ethyldithiocarbonate) -S- (3 -Propylsulfonic acid> ester potassium salt, 3 _ [(amino_iminofluorenyl) -thio] -1-propanesulfonic acid '3- (2-benzothiasialylthio) propanesulfonic acid sodium Salt or mixture thereof.% 8. The plating bath of claim 5 in which the leveling agent includes a calcined base. Polyimide, organic sulfonic acid salts, phenoxine dyes, phenoxazo dyes or mixtures thereof. Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs. Bath-covering, wherein the glossing agent includes 3- (benzothiazolyl-2-thio) -propyl lutein sodium salt, 3-cyanopropane-1-sulfonic acid sodium salt, and ethylenedithiodi Propylsulfonic acid sodium salt, bis- (p-sulfonic acid phenyl) -disodium disulfide salt, bis_ (ω-contanoic acid butyl) -dissociated disodium salt, bis- (ω-ceramic acid Propyl) -di-nano-sulfide, bis- (ω-succinic acid propyl) -disodium disulfide, bis- (ω-sulfopropyl) -disodium sulfide, fluorenyl- (ω-sulfo Acid propyl) sodium salt, fluorenyl- (ω-sulfopropyl) -disodium trisulfide, 0-ethyl-dithiocarbonate-S- (o-sulfopropyl) _ester, thio Potassium glycolate, phosphorothioate-0-ethyl · · bis- (ω-sulfopropyl) -diacetate This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) H3 Ministry of Economy Central Standards Bureau Staff Welfare Committee printed salt, thio-acid-tris (ω-contanoic acid propyl) -ester trisodium Or mixtures thereof. 10. The plating bath according to item 5 of the patent application scope, wherein the inhibitor includes carboxymethyl cellulose, nonylphenol polyethylene glycol ether, octanediol bis (polyalkylene glycol ether), octanol polymer Burning glycol ethers, polyethylene glycol oleate, polypropylene glycol, polyethylene glycol, polyethylene glycol dimethyl ether, polypropylene oxide glycol, polypropylene glycol, polyvinyl alcohol, polyethylene oxide, Polyethylene glycol stearates, polyethylene glycol ethers of stearyl alcohol, or mixtures thereof. 11. The metal mirror covering bath according to item 1 of the patent application scope, wherein the mineral covering bath has a pH value from 0 to 14.0. 1 2. The metal plating bath according to item 11 of the patent application scope, wherein the plating bath has a pH value from 0 to 8.0. 1 ·· A copper metal electroplating bath including a copper salt and a compound for suppressing consumption of additives, the compound including 0.0000 lg / L to 100 g / L of the plating bath, and having a formula: (R ' -NHR'-OH) ^ where R] and R2 are each independently hydrogen, q to C6 alkyl, η is 1 or 2, and when η is 1, X is hs〇4-, Η2Ρ〇 /, NO3 · , F, Cl ·, Br or Γ, when η is 2, X is S042 ·. 14. The copper metal plating bath as claimed in claim 13, wherein the Ci to C6 alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third Butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, isohexyl, 3.methylpentyl, 2,2-diamidylbutyl, or 2,3-dimethylbutyl base. 15. For the application of copper metal electroplating baths in the scope of item 1 to item 13 of the scope, where the paper size is applicable to the China One Country (CNS) A4 specification (210 X 297 mm) " H3 additive consumption compounds include broken hydroxylamine or Its mixture. : Amine, Hydroxylamine's Gasification 16 · As in the patent application scope No. 13 of the steel Ba Si additive consumption 榀 榀 θ, mainly belongs to the electroplating bath, wherein the compound that inhibits Qi consumption includes the 2.0%. g /] L. It is in the range of 0.01g / L to 17. If you apply for copper, gold, copper, copper, copper, etc. in the scope of the patent application No. 13, ^ Electric money bath, including the right side of the first 4, leveling agent, hardener, wetting Temporary 1 & Ϊ Development 丨 additives for biodegradation, extension of 18 I quality, deposition of modifiers or inhibitors. 8 · As for the nth item in the scope of patent application, since; te n,. Metal plating bath, where the gloss = includes compounds having the following structural formula: called s_r "other; '3S'R11-S ^ group); or H 〇3S_Ar_S_S_Ar_SQ3H (where ^ is a phenyl group or a Czeki group, and the alkynyl group and the aryl group may be unsubstituted or substituted by an alkynyl group, a halogen group, or an alkoxy group). % 19. The copper metal electroplating bath according to item 17 of the application, wherein the leveling agent includes alkylated polyimide, organic sulfonate, phenocyanine dye, phenorphine azo dye or Its mixture. The Bureau of Staff Welfare of the Central Bureau of Standards of the Ministry of Economic Affairs printed a 20 'copper metal plating bath such as the 17th in the scope of patent application, where the copper metal salt includes copper compounds, copper sulfates, copper alkanesulfonate, copper alkoxide, Or a mixture thereof. 2 1 · The copper metal plating bath according to item 13 of the patent application scope, wherein the plating bath has a pH value from 0 to 8.0. 22. —A method of plating metal on a substrate, including: making the substrate in contact with a metal bell bath; and applying a current density of 1ASF to I000ASF This paper is sized to Chinese National Standard (CNS) A4 (210 X 297) 591124 to the plating bath to deposit metal on the substrate; the plating bath includes gold, silver, palladium, platinum, cobalt, cadmium, chromium, nickel, bismuth, indium, tin, iridium, ruthenium, lead or its The metal salt of the alloy, and the inhibitor additive compound, the compound includes the metal oxide of the plating bath and has the formula: § / LJ (R1-NHR2 ^ OH) nX. Where R and R2 are each independently hydrogen, (^ to Ce alkyl, η is 1 or 2, when η is i, χ is HS (V 'Η2ρ (ν, ν; Cl, Br- or r, when η When it is 2, χ is so42-. 23. The method according to item 22 of the application, wherein the ^ to C include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. : —Butyl, third butyl, pentyl, isopentyl, neopentyl, third pentyl, hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutane 2,3 -Difluorenyl butyl. 3% 24. The method according to item 22 of the patent application, wherein the compound that suppresses the consumption of additives includes hydroxylamine sulfate, hydroxylamine nitrate, and a mixture of hydroxylamine chlorides. 印 Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs Preparation 25. The method according to item 22 of the scope of patent application, which includes a gloss agent, a leveling agent, a hardener, a wetting agent, a ductile modifier, a ductile modifier, a product modifier, an inhibitor, or a mixture thereof. J 26. The method of claim 22, wherein the glossing agent includes a compound having the formula: H〇3S-R] i-SH; H〇3S-Rn-SS-RH-s 3h (where r) i is Ci to q alkyl or aryl group; or h〇3_a "s · S_Ar-S03H (where Ar is benzyl or naphthyl group, the alkyl group and aryl group can be used for this paper standard China) National Standard (CNS) A4 specification (21 × X 297 issued 1 ---'- ^^ 1124 unsubstituted or substituted with alkyl, halogen or alkoxy). Method, wherein the substrate includes printed circuit boards and integrated circuits, electrical contact surfaces, connectors, electrolytic wafers, silicon wafers, semiconductors, lead frames, optoelectronic components, solder bumps on wafers, decorations, sanitary equipment Etc. 8. A method for electroplating copper metal on a substrate, comprising: bringing the substrate into contact with a metal plating bath; and applying an electrical power of 10,000 ASF to 4,000 ASF to 4 Å after plating A metal is deposited on the substrate; the copper metal bath includes a copper salt and a compound that suppresses consumption of additives, the compound includes 0.001 g / L to 100 g / L of the plating bath, and has the formula: (R'-NHR ^ oh) ^ where R1 and R2 are each independently hydrogen, or d to qalkyl, n is 1 or 2, when η is!, χ is HS (V, h2P04, N ( V, F, Cl, Br_, or I. At that time, χ is so.% 29. The method of claim 28 in the patent scope, wherein the q to C6 alkyl group includes methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, first butyl, second butyl, pentyl, isopentyl, neopentyl, tertiary pentamyl, etc. , 3 -fluorenylpentyl, 2,2-dimethylbutyl, or 2,3-dimethylbutyl. 30. The method of claim 28, wherein the compound that inhibits the consumption of the additive includes hydroxylamine sulfate, hydroxylamine nitrate, vaporized hydroxylamine, or a mixture thereof. The size of this paper is suitable-using China National Materials (CNS) A4 Regulation (21Gx 297 & t) · 3 1. The method of item 28 of the patent scope, including gloss agent, leveling agent, hardener, wetting agent , Malleable modifier, ductile modifier, Shen 91983 H3 product modifier, inhibitor or mixture thereof. For example, the method of claim 31 in the patent scope, wherein the gloss agent includes a compound having the formula: H03s-Rn-SH; HC ^ S-RH-SS-R1, s〇3H (where rii is ^ to q alkane Or aryl or η〇3 · Αγ · ι S: Al " S〇3H (where Ar is phenyl or naphthyl, the CJ C6 alkyl and square groups may be unsubstituted or via alkyl, halogen or alkane Oxygen substitution) 33. The method of claim 28, wherein the substrate includes a printed circuit board, an integrated circuit, an electrical contact surface, a connector, an electrolytic thin semiconductor, a lead frame, and a photovoltaic element , Solder bumps on the wafer, decorations, sanitary equipment, etc. 34-A device for a metal plating bath 'includes a power source electrically connected to the anode and the cathode so that a current can pass through the anode and the cathode. The cathode system is in contact with the metal plating bath, so that when Λ 〇 is used for power supply, the metal is plated on the cathode by plating> the metal is platinum, cobalt, cadmium , Chrome, nickel, bismuth, copper, gold, silver, m ...: again covered with indium and tin containing metals. Member of the Central Standards Bureau of the Ministry of Economic Affairs The Welfare Committee prints π rhodium, lead, ruthenium, iridium, or alloy salts thereof, and compounds, which include 001 ... two ^ 岣 of the plating bath and have the formula: to 2.0 g / L (R'-nhr ^ oh) ^ is where R1 and R2 are each independently hydrogen, or ^ to c-1 or 2; when 11 is 1, X is HS (V, H 6 alkyl, n F · 2ru4 ', Κη. CT, Br ·, or Γ, when η is 2, χ is s35. · As for the device in the scope of the patent application No. 34, its φ #, τ. 豕 metal yarn includes gloss, leveling agent, hardening Agent, humectant, and cold-coated duplicate paper size applicable to Chinese national standard (CNi) .A4 specification (21 ^ x 297 public love) ~ ~ quality agent, DV11Z4 3 6 Γί = product modifier, inhibitor or its Mixtures: devices or soluble anodes surrounding item 34. qpieces / King I. 37. For example, the insoluble anodes covered by item 36 of the patent application scope include metal, metal, nails, ruthenium, rhodium, palladium Iridium type 38. If the device in the 37th scope of the patent application is applied, “'^ includes metals”, #L, # 4 " The insoluble anode is re-leaded, hungry, sharp, or new. 39. If applied The insoluble anodes include the beryllium, titanium, aluminum, barium, sharp, etc. The insoluble anode compound 4. For example, the second device or the rare earth element of the 36th scope of the patent application: ... includes a button with an outer layer of iridium dioxide. ", 3, Indestructible anode package 41. For example, board 34, integrated circuit, electrical contact of the scope of patent application. The cathode includes line electricity & contact surface, connector silicon wafer, semiconductor, and wire. ' Special film. Jewelry: sanitary equipment and other electricity_, solder bumps, printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs