The resulting copper coated paper was then immersed in di water for 1 min and dried in flowing air at room temperature for. Electroless copper plating, however, offers advantages over electrolytic plating that make it the method of choice in certain cases. The deposition takes place only on the sensitized and activated surface. Electrolytic copper plating additives and contaminants. High throw electroless copper enabling new opportunities.
Us7297190b1 plating solutions for electroless deposition. Traditional electroless copper plating solutions often use formaldehyde as the reducing agent because of its low cost and the high quality of the deposit 38. The mechanism of electroless copper deposition with formaldehyde from alkaline ethylenediamine. Koc adepartment of chemical and environmental engineering, national university of singapore. Riddell, electroless plating involves the deposition of such metals as copper, nickel, silver, gold, or palladium on the surface of a variety of materials by means of a reducing chemic. Electroless deposition of copper nanostructures in aqueous. Figure 1 shows a generic electroless copper process, which typically consists of a desmear to remove excess resin after laser drill, a pretreatment step to clean and condition the copper, resin and glass reinforcement, followed by the activation and electroless copper deposition itself. Majid montazer, tina harifi, in nanofinishing of textile materials, 2018. Mallory the chemical deposition of a metal from an aqueous solution of a salt of said metal has an electrochemical mechanism, both oxidation and reduction redox, reactions involving the transfer of electrons between reacting chemical species. Oxidation and reduction could be investigated separately by use of a quartz microbalance in combination with fast solution exchange. Developments in electroless copper processes to improve. Know the impact of operational variables on the electroless nickel deposit. The deposition rate and deposited film properties critically depend on the reducing agent, complexing agent, and bath ph and temperature as well as bath additives. Copper layers were electrolessly deposited on the surface of carbon fiber without using the conventional palladium or silver catalyst to initiate redox reactions leading to metallization.
Electroless plating also coats the copper alloy with another metal material. However, the small size and large specific surface area intrinsically associated with acs pose challenges in the synthesis and stabilization of ptacs without agglomeration. Electroless deposition of cu thin films with cucl hno. The electroplated fibers benefit from electrical conductivity and electromagnetic interference emi shielding. Electrochemical control system for electroless copper deposition.
Electroless atomic layer deposition of copper article pdf available in electrochemistry communications 91 may 2018 with 253 reads how we measure reads. This process can obtain an electroless plating or deposition of a ductile, bright layer of copper on various surfaces such as insulating members, metal, ceramic, and other supporting surfaces. These should be removed prior to further processing to avoid plating nodulation at the burr site, tearing. Understand other electroless deposition processes, such as cobalt, copper, and gold. Parameters optimization of electroless deposition of. Electroless deposition of confined copper layers based on. Deposition rates of electroless copper from solutions with glyoxylic acid.
Us7306662b2 plating solution for electroless deposition of. Chapter the fundamental aspects of electroless nickel plating. Electroless copper plating is widely used for the fabrication of printed circuit boards and other electronic devices. Furthermore, 6 nm thin electroless copper films were integrated in a dual damascene process and electrically characterized. In an another investigation an electroless copper film was deposited on az31 magnesium alloy using organic coatings as interlayer fig. Vertical electroless copper metallization macdermid. In particular, electroless copper deposition, the most commonly used method of metallizing a nonconductive substrate, is susceptible to blistering or peeling due to the low adhesion of the copper film to the substrate. This paper describes metallization of pet surface by snfree electroless deposition eld of thin copper layer. Pdf recent progress in electroless plating of copper. These techniques have been known for hundreds of years for silvering mirrors. When gelatin is used as protective agent, only spherical cu nanoparticles with a mean diameter in the range of 37 to 44 nm are formed in the solution. The nonconductive part is treated with palladium catalyst and then made conductive by electroless copper plating.
Pdf in this study, the electroless deposition of copper and silver was investigated on epoxy and silicon dioxidebased substrates. Be aware of common problems with the electroless nickel plating process. Oxidationstable cu nanoparticles and nanowires were prepared in aqueous solution in the presence of protective agents. An electroless copper plating solution is disclosed herein. The resulting coppercoated paper was then immersed in di water for 1 min and dried in flowing air at room temperature for. Effect of ethanolamines on the electroless deposition of.
Pdf electroless deposition ed of copper coating on. With electroless copper, voidfree copper fill of 12. Electro nickel plating is a process that uses an electrical current to coat a conductive material, typically made of metal, with a thin. Inkjet catalyst printing and electroless copper deposition. The solution includes an aqueous copper salt component, an aqueous cobalt salt component, a triamine based complexing agent, and an acidic phmodifying substance in an amount sufficient to make the electroless copper plating solution acidic. Carbondefectdriven electroless deposition of pt atomic.
A precious metalfree electroless technique for the. Bottomup fill of copper in deep submicrometer holes by. Templated electroless nickel deposition for patterning applications. Electroless deposition of thin copper molybdenum layers is a method of producing highly reliable nanowires for interconnect applications to solve the problems in the use of copper interconnects. Spectroscopic studies on electroless deposition of copper on a hydrogenterminated si111surface in fluoride solutions shen ye,a taro ichihara, and kohei uosaki,z physical chemistry laboratory, division of chemistry, graduate school of science, hokkaido university. When formaldehyde is used as the reducing agent in the plating bath, the electroless copper deposition can be considered to consist of the following reaction. Electroless deposition an overview sciencedirect topics.
Electroless, or autocatalytic, metal plating is a non electrolytic method of deposition from solution. Formation of cu nanoparticles by electroless deposition of cu. Electroless deposition of copper modern electroplating. Electroless deposition is a process that has been used in practice for centuries. The metallic coating of ceramic particles is a useful technique in order to promote reinforcement bonding with the matrix alloy. Electrochemical mechanism of metal deposition from electroless bathes.
Milan paunovic and russ arndt concluded that guanine and adenine can accelerate electroless copper deposition. Riddell, electroless plating involves the deposition of such metals as copper, nickel, silver, gold, or palladium on the surface of a variety of materials by means of a reducing chemical bath. In electroless copper plating, there is always a tugofwar between the deposition rate and bath stability. Deposition of electroless copper for ic abrication. Electroless copper deposition on pet sheets scientific. D226 journal of the electrochemical society, 0046512009. Electroless copper can provide a seed layer on a dielectric material for subsequent acid copper electroplating. This reduces corrosion and prevents contamination of the silicon substrate. The deposition rate and deposit properties of electroless copper plating depend on the copper complexing agent, reducing agent and bath temperature and ph. In the manufacture of printed circuit boards, electroless plating is used to form the conductive part of plated through holes.
Although not recognized as such, electroless deposition of noble metals, e. In the present study, we report on cumn copper manganese fabricated by electroless deposition. First of all, ultrasonicator is used to clean the pc plastic with alsubstrate cohol. Mar 12, 2018 electroless deposition eld is widely used in industry to deposit metals because it is inexpensive and compatible with organic materials. The mechanism of electroless metal plating is thoroughly studied only for relatively deep stages of autocatalytic reduction when the deposition process proceeds on a metal substrate 1, 7. Properties of electroless cu films optimized for horizontal. However,many blisters were observed after electroless copper plating when a 612. For the past 20 years, this process has become the industry standard for void free coverage. The sample is prepared with the fixed size of 25mm x 40mm x 3mm. Electroless tin deposition on copper from thiourea type baths aneta arazna, tele and radio research institute abstract immersion tin coating can be deposited on the copper surface in two ways. Pdf electroless deposition of copper on organic and inorganic.
The fr4 board was prepared for electroless deposition by etching the copper from a copper clad board with nitric acid. The possibility of formation of a uniform electroless deposition ed of copper on micronsized sic particles was. A method for accelerating the deposition rate of electroless copper solutions is described which includes. Role of the reducing agent in the electroless deposition of. At the initial stage the electroless plating of copper and nickel lea ding to the formation and growth of solid particles in the bulk of a solution may be described by.
Surface modification with copper by electroless deposition technique. Pt atomic clusters ptacs display outstanding electrocatalytic performance because of their unique electronic structure with a large number of highly exposed surface atoms. The solution includes an aqueous copper salt component, an aqueous cobalt salt component, a polyaminebased complexing agent, a chemical brightener component, a halide component, and a phmodifying substance in an amount sufficient to make the electroless copper plating solution acidic. This new technique shows that nickel seeds can serve as excellent.
Zhu 7, schneider and their coresearchers8 investigated the electroless copper plating process using sulphur compounds as additives and found that the compounds enhanced the plating rate. Us7306662b2 plating solution for electroless deposition. Electroless deposition of copper on organic and inorganic. The electrochemical approach provides clarity of the mechanism by studying independently the partial anodic and cathodic reactions in electroless deposition of copper. The impurities generated from oil, ash or fingerprint could have complex and unexpected interaction with laser. The first example of galvanic displacement reaction of silver ag on cu was shown by abbott et al. Electroless plating of graphite with copper and nickel iopscience.
D226 journal of the electrochemical society, 004651. Pdf electroless deposition ed of copper coating on micron. By adding small amount of molybdenum the copper resistance to electromigration is increased. Another alternative is cu electroless plating, which, due to its conformal deposition pro. Instead, deposition occurs via an autocatalytic react that occurs between the workpiece and the liquid plating solution. Prior to introduction to eld process, the pet surface was plasmapretreated in argon atmosphere. A study on the interfacial composition of the electroless. Electroless deposition ed or chemical bath deposition cbd, in general, consists of a spontaneous deposition of films on a conducting or an insulating substrate by carrying out a redox reaction in solution.
An electrochemical investigation of electroless deposition. The electroless copper plating using sodium hypophosphite as the reductant and sodium citrate as the chelating agent was studied by gravimetric and. An indepth study of the electrooxidation of dimethylamine borane dmab was additionally carried out, due to its increasing relevance, not only in electroless. Electroless deposition of thin coppermolybdenum layers for. This paper reports a simple and low cost process for the synthesis of various cu nanostructures by electroless deposition. We have investigated the role of ethanolamine additives in the eld of copper using the. An electrochemical study of the copper electroless deposition process, using dimethylamine borane as a reducing agent, has been performed, in order to gain further understanding of the mechanism and kinetics of electroless deposition.
The surface of the organic interlayer must be sensitized and activated before electroless deposition. A study on the interfacial composition of the electroless copper plated bpdapda polyimide sheet w. The reducing and complexing agents play a vital role for the kinetics and. Chapter 12 fundamental aspects of electroless copper plating tau. Electroless plating, nonelectrical plating of metals and plastics to achieve uniform coatings by a process of controlled autocatalytic selfcontinuing reduction. The invention relates to a new and improved process for the electroless plating of copper, and to a novel and improved electroless copper plating bath.
This difference in the process sequence has an impact to the required electroless copper deposition thickness. Electroless deposition eld is widely used in industry to deposit metals because it is inexpensive and compatible with organic materials. Electroless cu plating microelectronics applications. So far as mechanism is concerned, it proceeds in an electrochemical pathway. Pdf in this article, the recent developments in electroless plating of copper, electroless bath formulation and effect of plating parameters have. Electroless deposition or plating of metals such as silver, aluminum, copper, nickel, and iron is a uniform coating of metallic layer on the surface of fibers through chemical reduction of metal ions in an aqueous solution and the subsequent deposition of metal without the use of. Electroless copper plates much more slowly, and is a much more expensive process, than electrolytic copper plating. This process of tin deposition on copper is widely used in. Eld is a multistep process involving silanization with tms, activation with pdcl2 and copper deposition.
The minimum necessary components of an electroless. Electroless deposition or plating of metals such as silver, aluminum, copper, nickel, and iron is a uniform coating of metallic layer on the surface of fibers through chemical reduction of metal ions in an aqueous solution and the subsequent deposition of metal without the use of electrical energy. Electroless copper has been the manufacturing standard for over 30 years, and we have been there since the beginning. Electroless deposition of ag is an important industrial process for printed circuit boards pcbs to prevent degradation of the copper surface and is usually done by plating silver on. Manganesedoped copper interconnects are known to provide superior electromigration resistance and thus are attractive for further downscaled interconnect metallization in future highperformance microprocessors. Firstly, the selection of electroless deposition solution could be extended. Electroless copper plates uniformly over all surfaces, regardless of size and shape. Surface modification with copper by electroless deposition. In general, electroless plating is characterized by the selective reduction of metal ions only at the surface of a catalytic substrate immersed into an aqueous solution of said metal ions, with continued deposition on the substrate through the catalytic action of the deposit itself. The all copper chiptosubstrate electroless process was able to correct for inplane and throughplane mismatches, similar to solder. This paper will introduce a formaldehydefree electroless copper bath for selective deposition at a high rate on polyimide patterned substrates. Study of coppersilicon junctions fabricated by selective.
This article introduces a new technique of electroless copper deposition on carbon fibers in the absence of precious metal as the catalyst. Spectroscopic studies on electroless deposition of copper. Electroless and electrochemical deposition of metallic. First of all, after drilling or punching, burrs of copper a will exist on the copper on the external copper layers of the sandwich. However, when electroless plating with copper is followed by nickel deposition the graphite becomes isolated from the exterior. However,we succeeded in the electroless deposition of copper without exfoliation by decreasing the concentration,as conventional electroless copper composition,as shown in table 2. Chapter electroless copper in printed wiring board fabrication. The purpose of this chapter is not to detail the fabrication of printed wiring boards, but rather to detail the important aspects of electroless copper deposition 8s they relate to pwb fabrication. Have a basic understanding of how electroless deposition is used in plating on plastics. Us7297190b1 plating solutions for electroless deposition of. Once the flow of reagent gas is terminated, addition of metal salts facilitates controlled, electroless deposition of an overlayer of subnanometer thickness. On the mechanism of electroless copper deposition wiese. However, this technique does not require an electrical current.
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