Electroless plating of graphite with copper and nickel iopscience. Electroless plating, nonelectrical plating of metals and plastics to achieve uniform coatings by a process of controlled autocatalytic selfcontinuing reduction. Electroless atomic layer deposition of copper article pdf available in electrochemistry communications 91 may 2018 with 253 reads how we measure reads. Koc adepartment of chemical and environmental engineering, national university of singapore. However,many blisters were observed after electroless copper plating when a 612. 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. Us7297190b1 plating solutions for electroless deposition of. Electroless copper can provide a seed layer on a dielectric material for subsequent acid copper electroplating. Know the impact of operational variables on the electroless nickel deposit. Electroless copper plating an overview sciencedirect topics. Bottomup fill of copper in deep submicrometer holes by.
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. Us7306662b2 plating solution for electroless deposition of. Understand other electroless deposition processes, such as cobalt, copper, and gold. One sample was seeded for electroless plating directly after stripping the copper, and a second sample was spincoated with poss on the roughened epoxy surface, which will be discussed in later in this section. Electroless deposition of copper nanostructures in aqueous. Formation of cu nanoparticles by electroless deposition of cu. First of all, after drilling or punching, burrs of copper a will exist on the copper on the external copper layers of the sandwich. Us7306662b2 plating solution for electroless deposition. Electroless deposition of thin coppermolybdenum layers for. Have a basic understanding of how electroless deposition is used in plating on plastics. Be aware of common problems with the electroless nickel plating process. On the mechanism of electroless copper deposition wiese. The minimum necessary components of an electroless.
This new technique shows that nickel seeds can serve as excellent. However, the small size and large specific surface area intrinsically associated with acs pose challenges in the synthesis and stabilization of ptacs without agglomeration. The possibility of formation of a uniform electroless deposition ed of copper on micronsized sic particles was. Electrochemical mechanism of metal deposition from electroless bathes. The surface of the organic interlayer must be sensitized and activated before electroless deposition. These techniques have been known for hundreds of years for silvering mirrors.
The electrochemical approach provides clarity of the mechanism by studying independently the partial anodic and cathodic reactions in electroless deposition of copper. Electroless copper plating, however, offers advantages over electrolytic plating that make it the method of choice in certain cases. 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. Electro nickel plating is a process that uses an electrical current to coat a conductive material, typically made of metal, with a thin. 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. Electroless deposition of confined copper layers based on. Early innovations led to the development of the msystemsm85, our highly successful heavy deposition electroless copper process. Eld is a multistep process involving silanization with tms, activation with pdcl2 and copper deposition. A high reliability, stressfree copper deposit for fpc. This process of tin deposition on copper is widely used in.
However, when electroless plating with copper is followed by nickel deposition the graphite becomes isolated from the exterior. Electroless copper plates uniformly over all surfaces, regardless of size and shape. 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. 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. An electrochemical investigation of electroless deposition. Pdf electroless deposition ed of copper coating on. Role of the reducing agent in the electroless deposition of. 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. Electro nickel plating also known as nickel electro deposition, is becoming an increasingly popular process for a variety of different manufacturing applications. The all copper chiptosubstrate electroless process was able to correct for inplane and throughplane mismatches, similar to solder. Mar 12, 2018 electroless deposition eld is widely used in industry to deposit metals because it is inexpensive and compatible with organic materials. 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. 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. 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. Instead, deposition occurs via an autocatalytic react that occurs between the workpiece and the liquid plating solution. 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. Oxidationstable cu nanoparticles and nanowires were prepared in aqueous solution in the presence of protective agents. This difference in the process sequence has an impact to the required electroless copper deposition thickness. Pdf in this study, the electroless deposition of copper and silver was investigated on epoxy and silicon dioxidebased substrates. 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. 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. Chapter electroless copper in printed wiring board fabrication. 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. An electroless copper plating solution is disclosed herein. A method for accelerating the deposition rate of electroless copper solutions is described which includes. An indepth study of the electrooxidation of dimethylamine borane dmab was additionally carried out, due to its increasing relevance, not only in electroless.
Pdf in this article, the recent developments in electroless plating of copper, electroless bath formulation and effect of plating parameters have. Electroless copper deposition on pet sheets scientific. With electroless copper, voidfree copper fill of 12. Although not recognized as such, electroless deposition of noble metals, e. Electroless copper plates much more slowly, and is a much more expensive process, than electrolytic copper plating. Us7297190b1 plating solutions for electroless deposition. Electrolytic copper plating additives and contaminants. 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 article introduces a new technique of electroless copper deposition on carbon fibers in the absence of precious metal as the catalyst.
For the past 20 years, this process has become the industry standard for void free coverage. 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. Deposition rates of electroless copper from solutions with glyoxylic acid. 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. Effect of ethanolamines on the electroless deposition of copper on functionalized organic surfaces. The deposition takes place only on the sensitized and activated surface.
Surface modification with copper by electroless 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. Chapter the fundamental aspects of electroless nickel plating. In the manufacture of printed circuit boards, electroless plating is used to form the conductive part of plated through holes. Furthermore, 6 nm thin electroless copper films were integrated in a dual damascene process and electrically characterized. The resulting copper coated paper was then immersed in di water for 1 min and dried in flowing air at room temperature for.
This paper describes metallization of pet surface by snfree electroless deposition eld of thin copper layer. 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. 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. Pdf recent progress in electroless plating of copper. Inkjet catalyst printing and electroless copper deposition. The mechanism of electroless copper deposition with formaldehyde from alkaline ethylenediamine.
Majid montazer, tina harifi, in nanofinishing of textile materials, 2018. Parameters optimization of electroless deposition of. In the present study, we report on cumn copper manganese fabricated by electroless deposition. D226 journal of the electrochemical society, 0046512009. Electroless deposition is a process that has been used in practice for centuries. Vertical electroless copper metallization macdermid. Another alternative is cu electroless plating, which, due to its conformal deposition pro. We have investigated the role of ethanolamine additives in the eld of copper using the. The reducing and complexing agents play a vital role for the kinetics and. Electroless deposition eld is widely used in industry to deposit metals because it is inexpensive and compatible with organic materials. Deposition of electroless copper for ic abrication.
Spectroscopic studies on electroless deposition of copper. High throw electroless copper enabling new opportunities. Pdf electroless deposition ed of copper coating on micron. Carbondefectdriven electroless deposition of pt atomic. The electroplated fibers benefit from electrical conductivity and electromagnetic interference emi shielding. Electroless plating also coats the copper alloy with another metal material. Properties and barrier material interactions of electroless. The sample is prepared with the fixed size of 25mm x 40mm x 3mm. Electroless copper has been the manufacturing standard for over 30 years, and we have been there since the beginning. The electroless copper plating using sodium hypophosphite as the reductant and sodium citrate as the chelating agent was studied by gravimetric and. This paper reports a simple and low cost process for the synthesis of various cu nanostructures by electroless deposition. First of all, ultrasonicator is used to clean the pc plastic with alsubstrate cohol.
So far as mechanism is concerned, it proceeds in an electrochemical pathway. 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. Pt atomic clusters ptacs display outstanding electrocatalytic performance because of their unique electronic structure with a large number of highly exposed surface atoms. Electroless copper plating is widely used for the fabrication of printed circuit boards and other electronic devices.
Chapter 12 fundamental aspects of electroless copper plating tau. Electrochemical control system for electroless copper deposition. 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. Electroless, or autocatalytic, metal plating is a non electrolytic method of deposition from solution. 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. Milan paunovic and russ arndt concluded that guanine and adenine can accelerate electroless copper deposition. This reduces corrosion and prevents contamination of the silicon substrate. The first example of galvanic displacement reaction of silver ag on cu was shown by abbott et al. Study of coppersilicon junctions fabricated by selective. Electroless deposition of copper on organic and inorganic. 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. In electroless copper plating, there is always a tugofwar between the deposition rate and bath stability. Electroless and electrochemical deposition of metallic.
A study on the interfacial composition of the electroless copper plated bpdapda polyimide sheet w. In an another investigation an electroless copper film was deposited on az31 magnesium alloy using organic coatings as interlayer fig. 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. These should be removed prior to further processing to avoid plating nodulation at the burr site, tearing. Once the flow of reagent gas is terminated, addition of metal salts facilitates controlled, electroless deposition of an overlayer of subnanometer thickness. A precious metalfree electroless technique for the. The nonconductive part is treated with palladium catalyst and then made conductive by electroless copper plating. 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. Electroless cu plating microelectronics applications. The deposition rate and deposit properties of electroless copper plating depend on the copper complexing agent, reducing agent and bath temperature and ph. 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 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.
Prior to introduction to eld process, the pet surface was plasmapretreated in argon atmosphere. The resulting coppercoated paper was then immersed in di water for 1 min and dried in flowing air at room temperature for. Electroless deposition an overview sciencedirect topics. Effect of ethanolamines on the electroless deposition of. The impurities generated from oil, ash or fingerprint could have complex and unexpected interaction with laser. This paper will introduce a formaldehydefree electroless copper bath for selective deposition at a high rate on polyimide patterned substrates. By adding small amount of molybdenum the copper resistance to electromigration is increased. Properties of electroless cu films optimized for horizontal. However, this technique does not require an electrical current. Surface modification with copper by electroless deposition technique. Firstly, the selection of electroless deposition solution could be extended.
D226 journal of the electrochemical society, 004651. The metallic coating of ceramic particles is a useful technique in order to promote reinforcement bonding with the matrix alloy. Pdf electroless deposition of copper on organic and inorganic. Electroless deposition of cu thin films with cucl hno. Electroless deposition of copper modern electroplating.
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