Abstract

Thin films, ubiquitous in today's world, have a documented history of more than 5000 years. However, thin-film growth by sputter deposition, which required the development of vacuum pumps and electrical power in the 1600s and the 1700s, is a much more recent phenomenon. First reported in the early 1800s, sputter deposition already dominated the optical-coating market by 1880. Preferential sputtering of alloys, sputtering of liquids, multitarget sputtering, and optical spectroscopy for process characterization were all described in the 1800s. Measurements of threshold energies and yields were carried out in the late 1800s, and yields in reasonable agreement with modern data were reported in the 1930s. Roll-to-roll sputter coating on flexible substrates was introduced in the mid-1930s, and the initial demonstration of sustained self-sputtering (i.e., sputtering without gas) was performed in 1970. The term magnetron dates to 1921, and the results of the first magnetron sputtering experiments were published in the late 1930s. The earliest descriptions of a parallel-plate magnetron were provided in a patent filed in 1962, rotatable magnetrons appeared in the early 1980s, and tunable “unbalanced” magnetron sputtering was developed in 1992. Two additional forms of magnetron sputtering evolved during the 1990s, both with the goal of efficiently ionizing sputter-ejected metal atoms: ionized-magnetron sputtering and high-power impulse magnetron sputtering, with the latter now being available in several variants. Radio frequency (rf) glow discharges were reported in 1891, with the initial results from rf deposition and etching experiments published in the 1930s. Modern capacitively-coupled rf sputtering systems were developed and modeled in the early 1960s, and a patent was filed in 1975 that led to pulsed-dc and mid-frequency-ac sputtering. The purposeful synthesis of metal-oxide films goes back to at least 1907, leading to early metal-oxide and nitride sputtering experiments in 1933, although the term “reactive sputtering” was not used in the literature until 1953. The effect of target oxidation on secondary-electron yields and sputtering rates was reported in 1940. The first kinetic models of reactive sputtering appeared in the 1960s; high-rate reactive sputtering, based on partial-pressure control, was developed in the early 1980s. While abundant experimental and theoretical evidence already existed in the late 1800s to the early 1900s demonstrating that sputtering is due to momentum transfer via ion-bombardment-induced near-surface collision cascades, the concept of sputtering resulting from local “impact evaporation” continued in the literature into the 1960s. Modern sputtering theory is based upon a linear-transport model published in 1969. No less than eight Nobel Laureates in Physics and Chemistry played major roles in the evolution of modern sputter deposition.

Highlights

  • The use of thin films to enhance the physical and chemical properties of materials is ubiquitous in today’s world

  • The first thin films grown from the vapor phase, as discussed in Ref. 1, were likely metal layers deposited accidently on the ceramic pots and rocks surrounding hot charcoal fires used to reduce metal ores, a process which can be traced back more than 7000 years

  • In a little more than 160 years, sputter deposition has metamorphosed from a scientific curiosity to a platform for investigating solid-state physics via atomic-scale billiards combined with quantum mechanics to a tool for massproducing industrial thin-film products

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Summary

INTRODUCTION

The use of thin films to enhance the physical and chemical properties of materials is ubiquitous in today’s world. Examples are shown in Fig. 1: copper metallization layers for electronic communication among billions of transistors in a silicon integrated-circuit; coated architectural glass in office buildings for which the thin films are designed to enhance energy efficiency and comfort by, depending on the time of year and latitude, reflecting ultraviolet and infrared sunlight, while transmitting visible light, to minimize air conditioning usage, or reflecting infrared radiation from within offices to minimize heating; and coated cutting tools developed to reduce friction and wear during use and, increase tool lifetimes. With thicknesses

HISTORY OF THIN-FILM DEPOSITION FROM THE VAPOR PHASE
Evolution of early vacuum technology
Pulsed to dc power
Glow-discharge sputtering
Mechanism of sputtering
Early sputter-yield measurements
Ion-bombardment-induced secondary-electron emission
Use of ion guns to measure sputtering yields
Cylindrical-post and inverted hollow-cathode magnetrons
Planar magnetrons
S-gun magnetron
Rotatable magnetrons
Magnetically-unbalanced magnetrons
More on mechanisms of sputtering
Bias-sputtering for composition control
Seminal events in the development of reactive sputtering
High-rate reactive sputtering
Pulsed-dc and midfrequency ac reactive sputtering
Modeling reactive sputtering
RECENT DEVELOPMENTS AND CONCLUSIONS
Ionized-metal magnetron sputter deposition
High-power impulse magnetron sputter deposition
MPP magnetron sputtering
Findings
Conclusions

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