The electrodeposition of tin coatings from deep eutectic solvents and their subsequent whisker growth

Tin electrodeposits produced from aqueous electrolytes are frequently used within the electronics industry due to their high solderability and corrosion protection. One limitation to using these deposits is their spontaneous formation of long conductive filament whiskers. These whiskers grow post-electrodeposition and increase the risk of unwanted electrical shorts within electronic devices. In this thesis, tin electrodeposits produced from a proprietary bright acid Tinmac electrolyte, currently used in industry, were studied. Electrodeposits were produced using a range of current densities with and without agitation and were characterised with respect to crystallographic orientation, topography and surface finish. Moreover, the intermetallic compound (IMC) growth produced at the copper substrate-tin coating interface was assessed over a period of time as its growth is considered to be a significant driving force behind whisker formation. In addition, a technique for the electrochemical anodic oxidation of tin electrodeposits on copper substrates was developed. This technique was used throughout this project for the study of IMC growth from tin electrodeposits as it was able to effectively remove the tin whilst leaving the IMCs and substrate unaffected. Ionic liquids exhibit promising electrochemical characteristics for electrodeposition but are still not widely utilised in industry. Their ability to deposit tin coatings has been studied in the present investigation. Trials concentrated on process optimisation to produce uniform electrodeposits by varying current density, SnCl2.2H2O concentration, and electrolyte composition. These deposits were then characterised and compared to tin coatings of similar thickness produced from Tinmac with respect to topography, surface finish, crystallographic orientation, IMC growth, and whisker propensity. Electrodeposits produced from the ionic liquid electrolyte exhibited a different crystallographic texture, topography, and IMC growth compared to those produced from Tinmac. Moreover, the deposit produced from the ionic liquid featured increased whisker growth compared to those produced from Tinmac, but in a wider context, far less growth than conventional tin electrodeposits in the literature. In addition, by exploiting other electrochemical characteristics of ionic liquids, such as their large potential window, future work may be able to produce novel tin or tin alloy electrodeposits which may further reduce the whisker propensity of deposits produced in this investigation

Evaluation of Environmental Tests for Tin Whisker Assessment

Tin whiskers are electrically conductive crystalline structures of tin that over time may grow outward from tin-rich surfaces and present a reliability hazard to electronic systems. While the problem has been known for decades, no satisfactory explanation of whisker growth mechanisms exists, leaving the industry to create whisker-assessment tests based on empirical data gathered under various environmental storage conditions controlled for temperature, humidity and temperature cycling. The long-term predictability of these environmental storage tests has not been addressed and the accuracy of these tests in foreseeing whisker growth is unclear. In this thesis, different tin finishes are assessed for whisker growth in accordance with existing environmental test standards and compared to growth seen in ambient storage conditions. The results indicate that environmental tests may over-predict, under-predict, or show little distinguishable growth as compared to ambient-stored tin finishes. In conclusion, environmental tests are not a reliable method of assessing future whisker growth

Study of Hillock and Zinc Whisker Evolution in Five Different Cable Tray Coatings

ABSTRACT: The main objective of this work is the study of the hillock and zinc whisker evolution of five different commercial zinc coatings applied on the same base steel wires of the patented EASYCONNECT system cable trays manufactured by VALDINOX Ltd.: white zinc alkaline electrolyte, yellow zinc trivalent electrolyte, acid zinc electrolyte, hot dip galvanized, and zinc nickel coating. The limited literature on the subject is summarized, and then the coating thickness, chemical composition, hardness and surface rugosity are characterized. The hillock and whisker density evolution are evaluated over a period of 12 months, considering the presence of compression bending stresses. It is concluded that the white alkaline and yellow trivalent coatings are the most affected, while the zinc-nickel shows the best behavior with no presence of whiskers; the acid zinc electrolyte also shows good results despite the delayed appearance of whiskers from the ninth month; the hot-dip galvanized coating does not show any presence of zinc whiskers or hillocks

Investigation of zinc whisker growth from electrodeposits produced using commercial electroplating baths

Electroplated zinc finishes have been widely used in the packaging of electronic products for many years as a result of their excellent corrosion resistance and relatively low cost. However, the spontaneous formation of whiskers on zinc electroplated components, which are capable of resulting in electrical shorting or other damaging effects, can be highly problematic for the reliability of long life electrical and electronic equipment. To date, most research has focused on tin whiskers and much less attention has been paid to zinc whisker research. A number of mechanisms to explain zinc whisker growth have been proposed, but none of them are widely accepted and some are in conflict with each other. This study has investigated the mechanism for whisker growth from three commercial zinc electroplated coatings on mild steel substrates. Firstly, whisker growth from an alkaline cyanide-free zinc electrodeposit was studied. A reduction in deposition current density (from 50 to 5 mA/cm2) and an increase in deposit thickness (from 2 to 15 μm) both contributed to reduced whisker growth. In terms of the mechanisms of whisker growth, it was observed that the presence of spherical raised surface features (nodules) with cavities beneath, promoted whisker growth by markedly shortening the incubation time from ~ 5 months to ~ 4 weeks. More importantly, the time dependent recrystallisation of the as-deposited columnar structure is closely associated with whisker growth from both nodules and planar regions of the deposit. The formation of Fe-Zn intermetallic compounds (IMCs) was not observed at either the Fe/Zn interface or within the electroplated coatings and does not appear to be associated with Zn whisker growth. Whisker growth from an acid chloride zinc electroplated coating and a Zn-Ni alloy electroplated coating were also investigated. These two coatings were immune to whisker growth after 18 months of storage at room temperature, regardless of deposition current density, deposit thickness and substrate surface modification. Finally, the effect of potential mitigation strategies on whisker growth was evaluated. Exposure to elevated temperatures (50 to 150°C) for 24 hours promoted whisker growth by reducing the incubation time for whiskers to first appear from less than 4 weeks to less than 10 days, whilst whisker growth was significantly retarded when samples were subjected to a short period of thermal treatment (50 to 150°C) for 0.5 hour. More importantly, for a short period of thermal treatment, whisker mitigation became increasingly effective as the treatment temperature was raised. In addition, the formation of a trivalent chromium passive coating on the alkaline cyanide-free zinc electrodeposits immediately after deposition was not an effective mitigation method to retard whisker growth

Electrochemical migration of Sn and Ag in NaCl environment

The impact of chloride ion concentration on electrochemical migration (ECM) of tin and silver was studied by using an in-situ optical and electrical inspection system. It was found, that in both cases, dendrites grow not only in an electrolyte solution at low chloride concentration but also in an electrolyte at medium and high or even saturated chloride concentrations as well. According to the results, the migration susceptibility has decreased at low and medium concentration levels in both cases. However, the ECM susceptibility of Ag has increased, while the migration susceptibility of Sn was decreased at the saturated concentrations

Fundamental Studies of Tin Whiskering in Microelectronics Finishes

Fundamental Studies of Tin Whiskering in Microelectronics Finishes Abstract Common electronics materials, such as tin, copper, steel, and brass, are ambient reactive under common use conditions, and as such are prone to corrosion. During the early 1940s, reports of failures due to electrical shorting of components caused by `whisker' (i.e., filamentary surface protrusion) growth on many surface types - including the aforementioned metals - began to emerge. Lead alloying of tin (3-10% by weight, typically in the eutectic proportion) eliminated whiskering risk for decades, until the July 2006 adoption of the Restriction of Hazardous Substances (RoHS) directive was issued by the European Union. This directive, which has since been adopted by California and parts of China, severely restricted the use of lead (<1000 ppm) in all electrical and electronics equipment being placed on the EU market, imposing the need for developing reliable new "lead-free" alternatives to SnPb. In spite of the abundance of modern-day anecdotes chronicling whisker-related failures in satellites, nuclear power stations, missiles, pacemakers, and spacecraft navigation equipment, pure tin finishes are still increasingly being employed today, and the root cause(s) of tin whiskering remains elusive. This work describes a series of structured experiments exploring the fundamental relationships between the incidence of tin whiskering (as dependent variable) and numerous independent variables. These variables included deposition method (electroplating, electroless plating, template-based electrochemical synthesis, and various physical vapor deposition techniques, including resistive evaporation, electron beam evaporation, and sputtering), the inclusion of microparticles and organic contamination, the effects of sample geometry, and nanostructuring. Key findings pertain to correlations between sample geometry and whisker propensity, and also to the stress evolution across a series of 4"-diameter silicon wafers of varying thicknesses with respect to the degree of post-metallization whiskering. Regarding sample geometry, it was found that smaller, thinner substrates displayed a more rapid onset of whiskering immediately following metallization. Changes in wafer-level stress were not found to correlate with whiskering morphology (number, density, length) after 6 weeks of aging. This result points either to the irrelevance of macrostress in the substrate/film composite, or to a difference in whiskering mechanism for rigid substrates (whose stress gradient over time is significant) when compared with thinner, flexible susbtrates (whose stress is less variable with time). Organic contamination was found to have no appreciable effect when explicitly introduced. Furthermore, electron-beam evaporated films whiskered more readily than films deposited via electroplating from baths containing organic "brighteners." Beyond such findings, novel in themselves, our work is also unique in that we emphasize the "clean" deposition of tin (with chromium adhesion layers and copper underlayers) by vacuum-based physical vapor deposition, to circumvent the question of contamination entirely. By employing silicon substrates exclusively, we have distinguished ourselves from other works (which, for example, use copper coupons fabricated from rolled shim stock) because we have better sample-to-sample consistency in terms of material properties, machinability, and orientation

Environmentally Sustainable Solvent-based Process Chemistry for Metals in Printed Circuit Boards

This chapter describes the development of several new processes relating to the fabrication, characterisation and recycling of printed circuit board (PCB) metal assemblies in alternative, sustainable solvent technologies based on an emergent class of liquids know as deep eutectic solvents (DES). It has been demonstrated that in many cases, the use of DES technologies can be disruptive to current process thinking and in principle can deliver benefits including increased efficiency,lower costs and better process control. These technologies offer the opportunity to incorporate new ideas into PCB fabrication and assembly that facilitate downstream, end-of-life recovery and separation consistent with a circular economy model. Current PCB manufacturing is carried out using many complex metal deposition processes involving aqueous solutions of toxic metal salts, strong inorganic acids, precious and expensive noble metals, and requires careful process control and monitoring. As a result, these processes are often costly to operate and inefficient. DES-based technologies can: (1) improve the economic and efficient use of essential metals; (2) reduce or eliminate use of precious and expensive metals; (3) reduce the use of complex and difficult to maintain process chemistry; (4) reduce reliance on toxic and noxious materials; and (5) improve recovery, recycling and reuse of PCB metals

The Art of Metal Whisker Appreciation: A Practical Guide for Electronics Professionals

No abstract availabl