Martin P.M. Handbook of Deposition Technologies for Films and Coatings, Third Edition: Science, Applications and Technology

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Glancing Angle Deposition 671

An increase in α will lead to larger variations in the longitudinal direction, but have minimal

effect in the transverse direction. Since there is no substrate motion, no averaging of ﬁlm ﬂux

can take place; slanted posts represent a worst case. For different structures, such as vertical

posts or helices, a signiﬁcant reduction in variation is observed.

13.6 Summary

GLAD is a highly ﬂexible nanofabrication technique combining oblique angle deposition and

precise manipulation of substrate position during deposition. By depositing at oblique angles,

columnar structures arise owing to a combination of ballistic shadowing and limited surface

diffusion. The resulting columns are tilted toward the incident ﬂux direction, and can be

sculpted into various morphologies: slanted and vertical posts, helices, chevrons, square

spirals, and combinations thereof. GLAD can partially decouple the different length scales

involved in thin ﬁlm production, yielding novel materials with interesting properties. GLAD is

compatible with a large number of materials, further increasing the combinatorial power of the

GLAD technique.

Advanced GLAD techniques may offer additional control or modiﬁcation of the canonical

GLAD structures. Such techniques include forced nucleation through seeding and advanced

substrate motion control to combat ﬁlm broadening. GLAD ﬁlms are robust, such that several

postdeposition techniques such as annealing, etching, and oxidization can be used to further

modify the structures. Many of these techniques may be applied in parallel, producing

high-quality structures that may be tuned to match application needs.

GLAD can produce single-crystal columns without catalysts or postdeposition annealing.

GLAD ﬁlms have extremely large surface areas, and values as high as 10

−3

have been

observed. Stress in GLAD ﬁlms is extremely low, because the porous structure is free to move.

The refractive index of GLAD ﬁlms can be tuned from a material’s bulk value down to ≈ 1.

The ﬂexibility of the GLAD process has produced a variety of interesting properties, and rapid

progress in the near future is expected.

While GLAD has been used for many applications, the dominant use to date is in optics.

GLAD offers the unique ability to produce an engineered index gradient with a single material

in a one-step deposition process, and has been used to produce high-quality optical ﬁlters.

Control over 3D structure on the same length scale as optical band wavelengths has led to

photonic crystal applications. Developing applications include sensors and energy

applications, which depend on the large surface area of GLAD ﬁlms. However, such

applications are not as well developed, limited in part by insufﬁcient understanding of the

nanoscale physics accessible by GLAD thin ﬁlms.

Although GLAD has seen impressive developments over the past 15 years, empirical studies

are far ahead of theoretical ones. The factors controlling the ﬁne details of column growth are

672 Chapter 13

not yet well understood. However, it is clear from the literature that GLAD has access to an

extremely large parameter space, and with further work the full power of GLAD will become

available. As physical understanding and experimental techniques improve, exciting new

applications for GLAD are expected.

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CHAPTER 14

Nanocomposite Coatings for Severe

Applications

Ali Erdemir

and Andrey A. Voevodin

Argonne National Laboratory, Energy Systems Division, Argonne, IL 60439, USA

Air Force Research Laboratory, Materials and Manufacturing Directorate,

Wright-Patterson Air Force Base, OH 45433-7750, USA

14.1 Introduction 679

14.2 Advances in Deposition Processes for Nanocomposite Coatings 682

14.2.1 Hybrid Deposition Processes for Nanocomposite Coatings 682

14.2.2 Modern Coating Practices for the Synthesis of Nanocomposite Coatings 685

14.3 Mechanical and Tribological Properties of Nanocomposite Coatings 689

14.4 Nanostructured and Composite Coatings for Tribological Applications 693

14.4.1 Self-Lubricating Nanocomposite Coatings 696

14.4.2 Superhard Nanocomposite Films 699

14.4.3 High-Temperature Adaptive Nanocomposite Coatings 700

14.4.4 Nanostructured Diamond and Diamond-Like Carbon Films 704

14.5 Summary 708

14.1 Introduction

Bulk nanomaterials and thick nanocomposite coatings (i.e. thicker than 50 ␮m) have been

available for a long time and are currently used in the fabrication of some critical components

in microelectronics, tooling, biomaterials, catalysis, and a wide range of energy-related ﬁelds

(fuel cells, batteries, etc.) [1–3]. However, during the last two decades, multifunctional

nanostructured and nanocomposite coatings have become increasingly more popular, mainly

because of their impressive property and performance characteristics as well as lower cost.

∗

The submitted manuscript has been created by the University of Chicago as Operator of Argonne National

Laboratory (‘Argonne’) under Contract No. DE-AC02-06CH11357 with the US Department of Energy. The US

Government retains for itself, and others acting on its behalf, a paid-up, nonexclusive, irrevocable worldwide

license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly

and display publicly, by or on behalf of the Government.

679

680 Chapter 14

Figure 14.1: Schematic representation of various design architectures for nanostructured

and composite coatings [4].

Figure 14.1 schematically illustrates some of the design architectures that are typically used

for nanostructured and composite ﬁlms at the moment [4]. These coatings certainly represent a

new class within the very broad ﬁeld of surface engineering and are the result of breakthrough

developments in physical and chemical vapor deposition (PVD and CVD) technologies in

recent years. Regardless of the coating type and architecture, they are able to reduce friction

and wear; improve thermal and electrical properties; and increase resistance to corrosion,

erosion, and fatigue-related degradations even under very harsh operating conditions. Most of

the mechanical tools and components that used to be coated with conventional or

single-component coatings (like TiN) are nowadays coated with a nanostructured or

nanocomposite ﬁlm, mainly because of its longer durability and much better performance

characteristics. Some of the key advantages of nanostructured and composite coatings over

traditional coatings are their superior mechanical hardness, resilience, and toughness; high

resistance to wear, scufﬁng, fatigue, oxidation, and corrosion; lower friction; and ability to

produce low shear triboﬁlms on dry or marginally lubricated sliding surfaces with

self-adaptive behavior in variable environments and temperatures [4–15].

Nanostructured and composite coatings are primarily produced by advanced PVD and CVD

techniques. Among others, deposition systems based on ion plating, multicathode arc-PVD,

and magnetron sputtering have dominated the coating industry in recent years. Most of these

techniques rely on the generation of energetic plasma streams and control of the energy,

density, and chemistry of highly ionized deposited atomic and molecular ﬂuxes to generate

complex compositions, nanostructures, and architectures optimized for a coating application.

As an additional beneﬁt, highly energetic deposition ﬂuxes permit production of desired

coating structures at low processing temperatures, broadening the application to

temperature-sensitive substrates. The use of multiple targets or evaporation sources and, most

recently, a combination of different types of plasma sources in these methods provides the

ﬂexibility and convenience that are needed for achieving a truly nanocomposite structure.

Compared to bulk nanocomposites, these coatings are much cheaper to produce and more

ﬂexible to apply on all kinds of substrate materials. It takes little material to produce such

coatings on substrates at a desired thickness; hence, the cost due to raw materials is minimal.

The bonding between the latest generation nanocomposite coatings and their substrates is very

strong, thanks to the recent advances in interface engineering and novel technologies like