Electrodeposition

Objective: To understand and investigate the growth by electrodeposition of metal films on metal and glass/ITO substrates. To determine and explain aspects of electrodeposited films including crystallinity, microstructure, adhesion and optical properties.

Background: Theory Electroplating is often also called "electrodeposition", a short version of electrolytic deposition, and the two terms are used interchangeably. As a matter of fact, "electroplating" can be considered to occur by the process of electrodeposition. Its a process using electrical current to reduce cations of a desired material from a solution and coat that material as a thin film onto a conductive substrate surface. Figure 1 shows a simple electroplating system for the deposition of copper from copper sulphate solution.

Figure 1. Electrolytic cell for the deposition of copper from copper sulphate solution. The electrolytic solution contains positively charged copper ions (cations) and negatively charged sulphate ions (anions). Under the applied external electric field, the cations migrate to the cathode where they are discharged and deposited as metallic copper. Cu2+ + 2e Cu (metal) Copper from the anode dissolves into the solution to maintain the electrical neutrality. Cu Cu2+ + 2e The overall process is known as electrolysis. If some noble metal (such as platinum) is used as the anode, the overall reaction at the anode is the oxidation of water. 2H2O 4H+ + O2 + 4e The sulphate ions remain unchanged in quantity during the electrolysis. However, if noble metal is used as the anode, the concentration of Cu2+ ions will decrease and that of H+ ions will increase with time. Under this situation, extra copper sulphate must be added into the solution from time to time and the hydrogen ions must be removed by neutralization with an alkali or by using a buffering solution. In practical electrodeposition processes, the chemical reaction around the electrode area occurs in a more complicated way than that shown in Figure 1. Under the influence of an

applied potential, rearrangement of ions near the electrode surface results in an electrical double layer called the Helmholtz double layer, followed by the formation of a diffusion layer as shown in Figure 2. These two layers are referred as the Gouy-Chapman layer. The process is as follows: Migration: The hydrated metal ions in the solution migrate towards the cathode under the influence of impressed current as well as by diffusion and convection. Electron transfer: At the cathode surface, a hydrated metal ion enters the diffused double layer where the water molecules of the hydrated ion are aligned. Then the metal ion enters the Helmholtz double layer where it is deprived of its hydrate envelope. The dehydrated ion is neutralized and adsorbed on the cathode suface. The adsorbed atom then migrates or diffuses to the growth point on the cathode surface. Thickness of the electroplated layer on the substrate is determined by the time duration of the plating. In other words, the longer the time the object remains in the operating plating bath, the thicker the resulting electroplated layer will be. Typically, layer thicknesses may vary from 0.1 to 30 microns. An electroplated layer is usually composed of a single metallic element. Co-deposition of two or more metals is possible under suitable conditions of potential and polarization, such as a Cu-Zn alloy or a Au-Sn alloy.

Figure 2. Electrical double layer

Applications: Since its invention in 1805 by Italian chemist, Luigi Brugnatelli, electroplating has become an extensively used industry coating technology. Its applications are mainly in the following four groups: 1. Decoration: Coating a more expensive metal onto a base metal surface in order to improve the appearance. Applications are jewellery, furniture fittings, builders hardware and tableware. 2. Protection: Corrosion-resistant coatings such as chromium plating of automobile parts and domestic appliances, zinc and cadmium plating of nuts, screws and electrical components. Wear-resistant coatings such as nickel or chromium plating of bearing surfaces and worn shafts and journals. 3. Electroforming: Manufacture of sieves, screens, dry shaver heads, record stampers, moulds, and dies. 4. Enhancement: coatings with improved electrical and thermal conductivity, solderability, reflectivity etc.

Properties of deposited film: ADHESION: As one of the most important requirements, adhesion is mostly dependant upon the substrate. For proper adhesion, the substrate must be thoroughly cleaned and free of any surface films. It is desirable that the substrate and the deposited metal interdiffuse with interlocking grains to give a continuous interfacial region. Alloy formation by the interdiffusion of the substrate and the deposited metals provides good adhesion. However, an intermetallic compound is undesirable since it behaves like inorganic salts and results in poor adhesion. MECHANICAL PROPERTIES: Mechanical properties of the electrodeposited film depend to a considerable extent on the types and amounts of growth-inhibiting substance at the cathode surfaces. The purpose of using a growth-inhibiting substance is to obtain fine-grain structure of the deposited film, in which the grain boundaries act as the main obstacles to dislocation motion, leading to a higher yield strength and hard surface. Hardness of the deposited film can also be increased by introducing lattice strain through incorporating impurities into the film-growth process. Electroplating processes frequently result in the development of internal stresses. The reasons for internal stresses relate to coalescence of three-dimensional, epitaxial crystallites, dislocation configurations, hydrogen incorporated into the crystal lattice, or other factors. Tensile stress is more detrimental than compressive stresses since it easily causes cracks of the deposited film, reducing the fracture strength and ductility. Certain addition agents for some electroplating solutions have been developed to reduce tensile stress. BRIGHTNESS: Brightness of deposited film is critical for decoration applications. The brightness of thin deposited films depends on the surface finish of the substrate. Thick er bright deposited films are produced by additional agents in the plating solution which result in elimination of protrusions or crevices which deviate from the surface plane by about the wavelength of visible light. The addition agents are mostly organic compounds such as dextrose, saccharine, lactose, formaline, citrates, tartarates, etc. However, most good brighteners are sulphur compounds, especially thiourea and its derivatives and organic sulphonic acids. Brightening agents are foreign inclusions in the deposited film. Overdosage of these additives can cause brittleness and lead to cracks and peeling off of the deposited film from the substrate. Reference: http://electrochem.cwru.edu/ed/encycl/art-e01-electroplat.htm http://inventors.about.com/od/estartinventions/a/Electroplating.htm Lawrence J. Durney, Electroplating Engineering Handbook, 4th edition, Van Nostrand Reinhold Company, 1984, p364 Brian N. Chapman, J.C. Anderson, Science and Technology of Surface Coating, Academic Press Inc. (London), 1974, p69 Alloy Electroplating, http://www.flipchips.com/tutorial46.html

Lab Procedure: Samples: ITO coated corning 1737 glass, copper plates(need to be polished before use). 1. Cleaning samples before electroplating Clean sample with soap water followed by thorough deionized water rinse. Place a stainless steel strip in the Sparkleen 1 solution ( 5 wt%) that was heated to ~90oC. Connect it to the Anode of HP 6217A power supply. Place sample in the Sparkleen 1 solution too and connect it to the Cathode of HP 6217A power supply. Set the current density in the range of 20-50mA/cm2 until large amount of bubbles coming out along the sample surface. Run electrocleaning ~1-3 minutes Take out sample and rinse with deionized water for 1 minute. Water should wet the whole sample surface uniformly forming a liquid film. 2. Electroplating Place the Nickel plating solution (Easyplate Nickel plating solution #C-2, Dalmar Manufacturing Co.) onto a digital hot plate. Set the temperature to 90oC and the rotating speed of magnetic stir bar to 150 rpm Place the cleaned sample into plating solution and connect it to the Cathode of HP6217A power supply. Place the Nickel strip into plating solution and connect it to the Anode. Parameters that affect the electroplating process are: Voltage: 2-4 volts Temperature of plating solution: room temperature up to 80oC Convection/circulation of plating solution: rotating speed 0-300 rpm Electroplating time: 1-20 minutes. Electroplate at least 5 samples under different conditions to investigate the influence of some processing parameters on the film properties, such as plating time of 5, 10, 20 minutes, plating at room temperature or 80oC, etc. 3. Performance investigation Measure the thickness of the deposited nickel film using alpha-step profilometer. Using scotch tape to test the adhesion of deposited nickel film to the substrate X-ray diffraction on deposited nickel film to check the crystallinity Using SEM to evaluate the surface, cross-section, and microstructure of deposited nickel film. Lab Report: Based on the performance test, the lab report should include the following: Results of thickness measurements, adhesion test, X-ray analysis and SEM observation. Explain the influence of different processing parameter on the properties of the deposited nickel film.