C H A P T E R

15
Vapor-Deposition Techniques

Raúl J. Martín-Palmaa and Akhlesh Lakhtakiab

a
Department of Materials Science and Engineering, Pennsylvania
State University, University Park, PA 16802, USA
b
Department of Engineering Science and Mechanics, Pennsylvania
State University, University Park, PA 16802, USA

Prospectus specific functionalities. As such, for either repro-

The term vapor deposition encompasses a large ducing specific geometric features of biological
palette of techniques essential for both the repro-
­ structures or replicating biological structures,
duction of certain structural features of a biotem-
fabrication techniques have to be suitable for the
plate and the replication of a biotemplate. Physical
vapor ­deposition, chemical vapor deposition, atomic accurate replication of features at very ­different
layer deposition, and molecular beam epitaxy are length scales. A variety of vapor-deposition
­succinctly described in this chapter in the context of techniques is available for both biomimetics and
engineered biomimicry. bioreplication.
In this chapter, the most commonly used vapor-
deposition techniques are reviewed. These tech-
Keywords niques include physical vapor ­deposition (thermal
Atomic layer deposition (ALD), Chemical vapor depo- and electron-beam e­ vaporation, s­puttering, laser
sition (CVD), Electron-beam evaporation, Ion-beam- ablation, ion-beam-assisted d ­ eposition, oblique-
assisted deposition (IBAD), Laser ablation, Molecular
beam epitaxy (MBE), Oblique angle deposition (OAD),
angle deposition, and conformal-evaporated-film-
Physical vapor deposition (PVD), Pulsed laser deposi- by-rotation technique), chemical vapor deposition
tion (PLD), Sputtering, Thermal evaporation (CVD), atomic layer deposition (ALD), and
molecular beam epitaxy (MBE). Given its
importance for engineered ­ biomimicry, ALD is
also treated in Chapter 16 by Zhang and Knez.
15.1 INTRODUCTION Although not discussed in this chapter, it is worth
noting that the combined use of a focused ion
Biological species are endowed with multiscale beam (FIB) and a scanning ­electron microscope
structures, ranging from the nano- to micro- (SEM) could develop into a ­ bioreplication
to macroscale, which provide them with very ­technique in the near future [1].

Engineered Biomimicry 383 © 2013 Elsevier Inc. All rights reserved.

http://dx.doi.org/10.1016/B978-0-12-415995-2.00015-5
384 15.  VAPOR-DEPOSITION TECHNIQUES

15.2  PHYSICAL VAPOR by a heater filament. Figure 15.1 presents a sche-

DEPOSITION matic representation of an evaporation system.
Alternatively, during electron-beam (e-beam)
Physical vapor deposition (PVD) involves the evaporation, a beam of electrons bombards the
generation of a vapor flux and its subsequent bulk material in the crucible to generate the
condensation in the form of a thin film on a vapor flux. The crucible and its contents are
substrate in a vacuum chamber. The term PVD placed in a vacuum chamber, with pressure typ-
encompasses several techniques, including ther- ically below 10–4 Torr. The vapor flux condenses
mal and electron-beam evaporation, sputter- on a substrate. Although the use of an electron
ing, and laser ablation. The major differences beam to vaporize metals in vacuum is usually
between all of these PVD techniques are in the credited to Rühle [6], the basic process had been
way that the vapor flux is generated from a tar- discovered serendipitously by von Pirani [7]
get made of a specific material. More than one slightly more than a century ago.
target may be used, and vapor fluxes from more In a typical thermal evaporation process, the
than one material may be generated. At the same target material is heated by Joule effect to an
time, one or more gases may also be introduced appropriate temperature at which there is an
to chemically modify either the vapor species or appreciable vapor pressure. For most materials
the growing thin film. that vaporize below a temperature around
PVD techniques are used to fabricate a wide 1,500 °C, ­evaporation can be achieved simply by
variety of thin films ranging from decorative putting the source material in ­contact with a hot
optical coatings to high-temperature supercon- surface that is r­esistively heated by passing a
ducting films. The thickness of the deposits can current through it. Typical resistive heating
vary from a few angstroms to several millimeters, elements are carbon, molybdenum, tantalum,
and very high deposition rates (up to 50 μm s–1) tungsten/wolfram, and BN/TiB2 composite
can be achieved [2]. A very large number of inor- ceramics [8]. The heated surface may have one
ganic materials (metals, alloys, compounds, and of many configurations––including basket, boat,
mixtures) as well as some organic materials can crucible, and wire––for rapid heating and to
be deposited using PVD techniques [3]. realize a uniform ­distribution of the vapor flux.
Thus, the term PVD comprises several versa- Among the major advantages of thermal evapo-
tile methods for the fabrication of thin films of ration, high d­ eposition rates, relative simplicity,
a wide variety of materials. PVD provides quite and low cost of the equipment must be men-
good structural control at the micrometer and/ tioned. ­However, thermal evaporation is not
or nanometer length scales by carefully monitor- very s­uitable for fabricating multicomponent
ing the processing parameters [4]. thin films, since some bulk materials evaporate
before others due to differences in their melting
points and vapor pressures.
Electron-beam evaporation uses high-energy
15.2.1 Thermal/Electron-Beam
electron beams, typically accelerated with volt-
Evaporation ages from about 5 to 20 kV, to bombard the target
Thermal evaporation was devised by Faraday dur- material or materials that are placed in a crucible.
ing the 1850s [5]. During this process, atoms and Crucibles of copper have been widely used for
clusters of atoms or molecules are removed in the many years, although crucibles of boron nitride,
form of a vapor flux from a metal crucible, con- graphite, nickel, and tungsten are also used,
taining some bulk material (target) by heater the depending on the target material(s) [8]. This
crucible, either by passing a current through it or evaporation technique can vaporize most pure
 15.2  PHYSICAL VAPOR DEPOSITION 385

FIGURE 15.1  Schematic of a typical thermal or electron-beam evaporation system. The source material is heated by an
electrical current in thermal evaporation or by bombardment by an electron beam in electron-beam evaporation.

metals, including those with high melting points. Morpho wings can thus be reproduced using
E-beam evaporation is particularly suitable for widely available technologies at a relatively low
the deposition of thin films of refractory materi- cost.
als, including most ceramics (oxides and nitrides),
glasses, carbon, and refractory metals. Among all
PVD techniques, e-beam evaporation provides
15.2.2 Sputtering
probably the highest deposition rates. By the use In the basic sputtering process, a cathode made
of high-power e-beam sources, deposition rates of the target material is bombarded by ­energetic
as high as 50 μm  s–1 have been achieved. Moreo- ions generated in a glow-discharge plasma
ver, with adequate adjustment of the waist of the situated in front of the target, as shown in
electron beam, uniform films of high purity can Figure 15.2. The target can be an element, alloy,
be obtained. compound, or their mixture. The bombard-
A biomimetic technique based on e-beam ment process causes the removal, i.e., sputter-
deposition was used to reproduce the blue color ing, of target atoms by momentum transfer
of the wings of butterflies of the genus Morpho. from the bombarding energetic gas ions (such
Multilayers composed of alternating thin films as argon ions) accelerated in an electric field.
of TiO2 and SiO2 were evaporated onto a sub- The sputtered atoms form a vapor flux, which
strate that had been nanopatterned using may then condense on a substrate as a thin film
e-beam lithography and etching [9, 10]. The [11]. This process can be performed in a vac-
optical characteristics of the structurally colored uum chamber using either low-pressure plasma
386 15.  VAPOR-DEPOSITION TECHNIQUES

FIGURE 15.2  Schematic of a typical sputtering system in either the DC or the RF configuration.

(<5 × 10−3 Torr) or high-pressure plasma (5 × 10−3 such as oxides and polymers. When a RF
– 30 × 10−3 Torr) [8]. Secondary electrons are also potential is capacitatively coupled to a target
emitted from the target surface as a result of ion (cathode), an alternating positive/negative
bombardment. These electrons play an impor- potential appears on its surface. In one half
tant role in maintaining the plasma. cycle, positively charged ions are accelerated
Three widely used configurations to generate toward the surface of the target with enough
the plasma for sputtering deposition are the energy to cause sputtering. In the next half
direct-current (DC) configuration, the radio- cycle, electrons reach the surface of the target to
frequency (RF) configuration, and the magnetron- prevent the build-up of charge. Frequencies
assisted configuration. The simplest of the three used for sputtering deposition are typically in
is the DC configuration, comprising a cathode the range of 0.5–30 MHz, with 13.56 MHz [8]
(target), an anode (on which the substrate is being the most widely used. RF sputtering is
placed), and a DC power source. The cathode used at a low pressure (<10−3 Torr).
and the anode are placed in a vacuum chamber Finally, in the magnetron-assisted configura-
[8]. Argon is widely used to establish a dis­ tion, a magnetic field is imposed to increase the
charge. Because the plasma can be established plasma density as well as the current density at
uniformly over a large area, a solid target with the cathode (target), thereby effectively increas-
a large area can be used. The surface of the target ing the sputtering rate. The magnetic field is
does not need to be planar, so targets with tangential to the cathode surface. The electrons
different shapes can be used to be conformal to ejected from the cathode are deflected to stay
the surface of a given substrate, resulting in close to the target surface. If the magnets behind
improved thickness homogeneity. the target are arranged properly, the electrons
The RF configuration is generally used for the can circulate on a closed path on the target sur-
deposition of electrically insulating materials face. This electron-trapping effect effectively
 15.2  PHYSICAL VAPOR DEPOSITION 387
increases the collision probability between elec- 15.2.3  Laser Ablation
trons and the gas molecules, thereby creating a
high-density plasma. This configuration enables In laser ablation, also called pulsed laser depo-
sputtering at low pressure with a high deposi- sition (PLD), an intense, pulsed laser beam
tion rate. irradiates the target. When the laser pulse is
The basic sputtering process was devised absorbed by the target, its energy is used first
about a century and a half ago by Grove [12], for electronic excitation and then converted
who used the term cathode disintegration, but into thermal, chemical, and mechanical forms
later researchers began to use both spluttering of energy, resulting in evaporation, ablation,
and sputtering. Thin films of many materials plasma ­ formation, and even exfoliation. The
have been successfully deposited using this ejected material expands into the surrounding
technique. In particular, sputtering is capable vacuum in the form of a plume containing many
of depositing high-melting-point materials energetic species, including atoms, molecules,
such as refractory metals and ceramics. electrons, ions, clusters, particles, and molten
Moreover, since the sputtered atoms usually
­ globules. These diverse species finally condense
carry more energy than the evaporated atoms, onto a substrate as a thin film.
the sputter-grown films generally have higher Laser ablation is often carried out in a high or
mass density, superior adhesion to the sub­ ultra-high vacuum chamber. Reactive gaseous
strate, and good crystalline structures. How­ species, such as oxygen, can be introduced for
ever, sputtering is limited by low ionization the reactive deposition of oxides or other com-
efficiencies in the plasma as well as by the pound materials.
heating of the substrate that often necessitates Generally speaking, laser ablation provides
the use of cooling equipment. Significantly, the better control by simultaneous evaporation of
typical deposition rate of sputtering is multicomponent materials in a very short period
considerably lower than that of thermal or of time. Because the ablation rate is related to
electron-beam evaporation. the total mass ablated from the target per laser
Reactive sputtering is the sputtering of pulse [14], the development of lasers with high
elemental targets in the presence of chemically repetition rate and short pulse durations makes
reactive gases that react with both the vapor laser ablation––in combination with the conden-
flux ejected from the target and the target sation of an inert gas on the substrate––very
surface. It is a widely used technique for the attractive for the mass production of well-
deposition of a very wide range of thin films of defined thin films with complex stoichiometry.
compounds, including oxides, nitrides, carbides, There are three possible growth modes in
fluorides, arsenides, and their alloys [13]. laser ablation [8]: First, the step-flow growth is
Although reactive sputtering is conceptually often observed during deposition, either on
simple, it is in fact a complex and nonlinear a substrate with steps present on its surface (i.e.,
process that involves many interdependent a highly miscut substrate) or at elevated tem-
parameters. peratures. Upon arrival at the substrate surface,
Given its versatility, sputtering has become a atoms diffuse to atomic step edges and form into
process widely used for the deposition of a surface islands. The growing surface is viewed
broad range of industrially important coatings. as steps travelling across the surface. Second, in
Examples include hard, wear-resistant coatings, the layer-by-layer growth mode, islands c­ ontinue
low-friction coatings, corrosion-resistant coat- to nucleate on the surface until a critical island
ings, decorative coatings, and coatings with spe- density is reached. As more material is added,
cific optical or electrical properties [11]. the islands continue to grow until neighboring
388 15.  VAPOR-DEPOSITION TECHNIQUES

islands begin to coalesce, resulting in a high den- the fabrication of thin films with columnar
sity of pits on the surface. The addition of more morphology [16]. Thermal and electron-beam
atoms to the surface results in their diffusion into evaporation techniques are commonly used
these pits to complete the layer. This process is to generate the vapor flux. The substrate is so
repeated for each subsequent layer. Finally, the positioned as to receive the vapor flux at an
three-dimensional growth mode is similar to the angle χv greater than 0° and as high as 90° with
layer-by-layer growth mode except that once an respect to the substrate plane. The columnar thin
island is formed, an additional island will nucle- film (CTF) thus formed comprises parallel, tilted
ate on top of the previous island. Continuing nanocolumns whose assemblage is optically
growth in one layer will not persist, leading to a equivalent to a biaxial crystal in the infrared
roughened surface. and visible regimes. The CTFs are highly dense,
with the vapor flux normally incident on the
15.2.4 Ion-Beam-Assisted Deposition substrate, but the density trails off as the vapor
flux angle χv is reduced toward 0°.
Ion-beam-assisted deposition (IBAD) is not a depo- Rocking the substrate about a tangential axis
sition technique per se. Instead, it is a technique during deposition imparts the nanocolumns
wherein ion implantation is combined with with a two-dimensional shape, whereas rotating
another PVD technique. The evaporated spe- the substrate about a central normal axis makes
cies produced by the chosen PVD technique are the nanocolumns acquire a three-dimensional
simultaneously impinged by an independently shape. Rocking and rotation can be made to
generated flux of ions [15]. Thus, while the indi- ­happen concurrently or sequentially. The thin
vidual atoms or molecules condense on the sub- films this forms are called sculptured thin films
strate to form a thin film, highly energetic ions (STFs). The nanocolumns are made of 1–3 nm
(typically from 100 to 2,000 eV) are produced clusters, which accounts for the ease with which
and directed at the growing thin film. columnar shapes can be sculptured during
IBAD is particularly advantageous in that it deposition.
has many independent processing parameters. STFs are useful as polarization transformers
The concurrent ion bombardment significantly and polarization filters, optical sensors, and
improves adhesion and permits control over vehicles for launching multiple surface-
the morphology, density, internal stresses, crys- plasmon-polariton waves. Their intrinsic high
tallinity, and chemical composition of the thin porosity, in combination with optical ani­ so­
film. Ion bombardment can also blend together tropy and possible two-dimensional electron
coating and substrate atoms. The energy and confinement, make STFs potential candidates
flux of bombarding ions can be exploited to for electroluminescent devices, high-speed and
modify the size and crystallographic orienta- high-efficiency electrochromic films; optically
tion of grains. Columnar morphology often transparent conducting films sculptured from
observed in conventional, low-temperature pure metals; and multistate electronic switches
PVD is negated by IBAD to create very dense based on filamentary conduction.
thin films [15]. For example, Figure 15.3 shows a cross-
sectional view of a distributed Bragg reflector
grown using the OAD technique. The structure
comprises CTFs of two different types grown
15.2.5  Oblique-Angle Deposition alternatingly, one with χv = 90° and the other
Oblique-angle deposition (OAD) is a PVD method with χv = 15°. The CTFs grown with a nor­­mal
wherein the vapor flux is collimated to enable vapor flux (χv = 90°) are very dense and
 15.2  PHYSICAL VAPOR DEPOSITION 389

FIGURE 15.3  Cross-sectional SEM of a distributed Bragg reflector [17], consisting of alternate layers of very different
CTFs, which have different porosities and different effective permittivity tensors.

comprise upright nanocolumns, whereas the

CTFs grown with a highly oblique vapor flux
are highly porous and comprise tilted
nanocolumns. As a result, their effective
permittivity tensors are very different, and the
periodic stacking of the two types of CTFs leads
to the exhibition of the Bragg phenomenon.

15.2.6 Conformal-Evaporated-Film-by-
Rotation Technique
The conformal-evaporated-film-by-rotation (CEFR)
technique allows fabrication of high-fidelity rep-
licas of biotemplates with micro- and nanoscale
features distributed over planar and curved
surfaces [18, 19]. In the CEFR technique, the
template is mounted on a substrate holder that
is rotated rapidly about its central normal axis
while the OAD technique is being implemented
to coat the exposed surface of the template with
a thin film. The vapor flux angle χv is fixed in the
neighborhood of 5°, as shown schematically in
Figure 15.4. After the coating of thickness about FIGURE 15.4  Schematic of the CEFR technique.
390 15.  VAPOR-DEPOSITION TECHNIQUES

400 nm is separated from template, the coating The modified CEFR technique is one of the two
becomes a high-fidelity replica. main steps of the Nano4Bio technique devised to
To date, this technique has been applied for fabricate multiple high-fidelity replicas of a single
replicating the compound eyes of tephritid flies biotemplate [22]. As depicted schematically in
[18], as shown in Figure 15.5, and the wings of Figure 15.7, in the first step of this technique, the
butterflies [19,  20], as shown in Figure 15.6, modified CEFR technique is used to deposit a
without compromising their optical characteris- ∼250-nm-thick conformal coating of nickel on the
tics that are due to nanoscale (<100 nm) struc- biotemplate. In the second step, a roughly
tural features. The CEFR technique is particularly 60-μm-thick structural layer of nickel is electro-
well suited for bioreplication because the tem- formed onto the thin layer to give it the structural
peratures involved during deposition are suffi- integrity needed for casting or stamping. The
ciently low and the replication process occurs in biotemplate is then plucked off and plasma ash-
a non-corrosive environment, thereby avoiding ing is carried out to completely remove all organic
damage to the underlying biotemplate. material in the third step. What is left behind is a
The CEFR technique has been modified to master negative made of nickel. This can be used
improve the uniform thickness of the replica by in the fourth step as either a die for stamping or
introducing a second degree of freedom to the a mold for casting multiple replicas. Casting pro-
biotemplate motion during deposition [21]. The duces high fidelity at the 2-μm length scale [22],
first degree, as in the original CEFR technique, but stamping will improve the reproduction
is the rotation of the biotemplate about a central fidelity at lower length scales [1, 23]. Because the
normal axis. The second degree is the rocking of Nano4Bio technique can simultaneously produce
the biotemplate so as to continuously vary χv multiple replicas of multiple biotemplates, it is
during deposition. suitable for industrial bioreplication.

FIGURE 15.5  SEM of the eye of a tephritid fly (common fruit fly) coated with GeSbSe chalcogenide glass using the CEFR
technique [18].
 15.2  PHYSICAL VAPOR DEPOSITION 391

FIGURE 15.6  High-resolution SEM of a wing of the butterfly Battus philenor coated with GeSbSe chalcogenide glass
using the CEFR technique [19]. Features at the nanoscale are evident.

FIGURE 15.7  Schematic of the Nano4Bio technique.

392 15.  VAPOR-DEPOSITION TECHNIQUES

15.3  CHEMICAL VAPOR products and transport of reaction products

DEPOSITION away from the surface. The main CVD process
parameters––such as temperature, pressure,
Chemical vapor deposition (CVD) involves either the reactant gas concentration, and total gas flow––
dissociation of a gaseous chemical and/or chemi- require accurate control and monitoring. The
cal reactions between gaseous reactants when chemical reactions include pyrolysis, oxidation,
heated, irradiated by photons, or subjected to a reduction, hydrolysis, or a combination of these
plasma [24]. As a product, a thin film is deposited and may be catalyzed by the substrate. The
on a surface. This technique is used to produce actual chemical reactions determine the operating
very pure high-performance solid materials. temperature range.
Depending on the activation sources for the CVD is a well-established technique for the
chemical reactions, the deposition process can deposition of metallic, ceramic, and semicon-
be categorized into thermally activated, laser- ducting thin films because it offers the advan-
assisted, or plasma-assisted CVD. The CVD pro- tages of a relatively simple apparatus, excellent
cess occurs in a vacuum chamber, with pressures uniformity, high density, high deposition rate,
ranging from the atmospheric pressure (atmos- and amenability to large-scale production. CVD
pheric-pressure CVD) to below 10−8 Torr (ultra- is a more complex method of forming thin films
high-vacuum CVD). Figure 15.8 represents a and coatings than PVD. CVD exhibits several
typical plasma-assisted CVD system. distinct advantages, such as the capability of pro-
The main steps that occur in a typical CVD ducing highly pure and dense films or fine par-
process can be summarized as follows [14]: ticles at reasonably high deposition rates and the
(1) transport of reacting gaseous species to the capability of coating surfaces of complex shapes.
surface of a substrate, (2) adsorption of the Many forms of CVD are in wide use and are
species on that surface, (3) heterogeneous surface frequently referenced in the literature. These
reaction catalyzed by the surface of the substrate, processes differ in the means by which chemical
(4) surface diffusion of the species to growth reactions are initiated (e.g., activation process)
sites, (5) nucleation and growth of the film on the and process conditions [4]. As such, atmos­
substrate, and (6) desorption of gaseous reaction pheric-pressure CVD, low-pressure CVD, and

FIGURE 15.8  Schematic of a plasma-assisted chemical vapor-deposition system.

 15.3  CHEMICAL VAPOR DEPOSITION 393
ultrahigh-vacuum CVD are named after the generated from CO2, Nd:YAG, or excimer lasers.
typical chamber pressure at which the reactions Laser-assisted CVD differs from conventional
take place. Depending on the characteristics of CVD in that the area of growth can be limited to
the plasma, the following forms can be found: that of where the laser beam passes. Neverthe-
microwave plasma-assisted CVD, plasma- less, laser-assisted CVD can be used for a large
enhanced CVD, magneto-microwave plasma variety of target materials and substrates [25].
CVD, and remote plasma-enhanced CVD. If the Although CVD is a complex chemical process,
characteristics of the vapor used are considered, it has several advantages [24]. Highly dense,
the following two forms are commonly found: very pure, uniform thin films are produced with
aerosol-assisted CVD and direct liquid-injection good reproducibility and adhesion at reasonably
CVD. Metal-organic CVD uses metal-organic high deposition rates. Control of crystal struc-
precursors, whereas in rapid thermal CVD the ture, surface morphology, and orientation of the
­substrate is heated. Catalytic CVD is based on CVD products is easily possible by c­ ontrolling
the catalytic decomposition of precursors using the CVD process parameters. The deposition
a resistively heated filament. This technique is rate can be adjusted readily. Low deposition
also known as hot-wire CVD or hot-filament rates are preferred for the growth of epitaxial
CVD. In laser-assisted CVD, a laser heats a thin films for microelectronic applications. How-
­localized spot and no other heating source is ever, for the deposition of thick protective coat-
present [25]. ings, a high deposition rate is preferred, and it
In conventional thermally activated CVD, can be greater than tens of mm per hour. High
resistive heating of the hot-wall reactor provides deposition rates lower the production costs.
sufficiently high temperatures for dissociation CVD also exhibits the flexibility of using a
of the various gaseous species. This leads to the wide range of chemical reagents such as halides,
entire heating of the substrate to a high tempera- hydrides, and organometallics that enable the
ture before the desired reaction is achieved. It deposition of a large spectrum of materials,
precludes the use of substrates having melting including metals, carbides, nitrides, oxides,
points much lower than the reaction tempera- sulfides, III–V materials, and II–VI materials.
ture. Alternately, one could heat the reacting Relatively low deposition temperatures are
gases in the vicinity of the substrate by placing employed in CVD, and the desired materials can
a hot filament of tungsten inside the chamber. be deposited in situ at low energies through
Plasma-enhanced CVD is known to exhibit a vapor phase reactions, followed by nucleation
distinct advantage over thermally activated CVD and growth on the substrate. This enables the
owing to its lower deposition temperature. Vari- deposition of refractory materials at a small frac-
ous types of energy resources––e.g., DC, RF, tion of their melting points. For example, refrac-
microwave, and electron-cyclotron-resonance tory materials such as SiC (melting point:
microwave (ECR-MW)––are used for plasma 2,700 °C) can be deposited at 1,000 °C. Finally,
generation in CVD. In a DC-activated process, the CVD can be used to uniformly and conformally
reacting gases are ionized and dissociated by an coat substrates with complex surfaces.
electrical discharge, thereby generating a plasma Like any deposition technique, CVD has
consisting of electrons and ions. Microwave several drawbacks as well [24]. Foremost are the
plasma is an attractive option because the micro- chemical and safety hazards caused by the use
wave frequency (2.45 GHz) can oscillate electrons; of toxic, corrosive, flammable, and/or explosive
thus, high ionization fractions are generated as reagent gases. However, these drawbacks have
electrons collide with gas atoms and molecules. been minimized using variants of CVD, such as
Laser-assisted CVD is associated with the electrostatic spray-assisted CVD and combus-
deposition of chemical vapors using a laser beam tion CVD, that use environmentally friendly
394 15.  VAPOR-DEPOSITION TECHNIQUES

reagents. Furthermore, it is difficult to deposit self-limiting growth mechanism that imparts

multicomponent materials with well-controlled to it several attractive characteristics: accurate
stoichiometry using multiple reagents because and easy control of film thickness, production
different reagents have different vaporization of sharp interfaces, uniformity over large areas,
rates. excellent conformality with the substrate, good
Finally, the use of sophisticated CVD reproducibility, multilayer processing capabil-
variants––such as low-pressure or ultrahigh-
­ ity, and desirable qualities in thin films made at
vacuum CVD, plasma-assisted CVD, and photo- relatively low temperatures [31]. For nanotech-
assisted CVD––tends to increase the cost of nologists, the two most important characteris-
fabrication. If production costs need to be tics of ALD are excellent conformality and the
reduced, however, simpler variants of CVD, possibility of subnanometer-level control of film
such as aerosol-assisted CVD and flame-assisted thickness.
CVD, may be employed. ALD relies on alternate pulsing of the
Low-temperature CVD has been used for bio­ ­precursor gases and vapors onto the substrate
replication. Controlled vapor-phase ­oxidation of ­surface––in a vacuum chamber––and subsequent
silanes on the surface of biological struc­tures chemisorption or surface reaction of the
produces exact, inorganic oxide replicas of precursors. The vacuum chamber is purged with
several biological structures, including a wing an inert gas between the precursor pulses. The
of a butterfly, a wing of a housefly, and a leaf of ALD process is schematically depicted in
Colocasia esculenta (a self-cleaning plant) [26]. Figure 16.1. With a proper adjustment of the
Thus, CVD was used to replicate intricate and experimental conditions, the process proceeds
hierarchical structures on several length scales. via saturative steps, i.e., the precursors exposed
Likewise, multifunctional zinc oxide interfaces on the surface chemisorb on it (or react with the
were fabricated by the use of metal-organic surface groups), saturatively forming a tightly
CVD, with the compound eyes of b ­utterflies bound monolayer on the surface. The subsequent
serving as biotemplates [27]. purging step removes all the excess molecules
Moreover, a combination of the FIB from the vacuum chamber. When the next
technique [28] and CVD has been used to precursor is sent in to the chamber, it encounters
fabricate artificial structures inspired by the only the surface monolayer with which it reacts,
scales of the ­Morpho wings [29]. The original producing the desired solid product and g ­ aseous
and artificial scales show comparable optical byproducts. Under such conditions, the growth
characteristics, as discussed by Dushkina and of the thin film is self-limiting, since the amount
Lakhtakia in Chapter 11. The overall reflectance of solid deposited during one cycle is dictated
spectrums of both structures for various by the amount of precursor molecules present in
incidence angles of light are quite similar and the saturatively formed surface monolayer.
contain reflectance peaks at around 440-nm Therefore, the growth is stable and the thickness
wavelength. increase is constant in each deposition cycle. The
self-limiting growth mechanism facilitates the
growth of conformal thin films with accurate
15.4  ATOMIC LAYER DEPOSITION thickness on large areas. This technique also
allows the growth of multilayer structures.
Atomic layer deposition (ALD) is a surface- However, a major limitation of ALD is its very
controlled and self-limiting method for deposi­ low deposition rate.
ting thin films from gaseous precursors [30]. The distinctive sequencing feature in ALD
Although ALD can be considered a modifica- makes it an attractive method for the precise
tion of CVD, ALD’s distinctive feature is the growth of crystalline compound layers, complex
 15.5  MOLECULAR BEAM EPITAXY 395
layered structures, superlattices, and layered 15.5  MOLECULAR BEAM EPITAXY
alloys with precise interfaces [24]. ALD can
be used to produce thin films with good confor- Molecular beam epitaxy (MBE) is a technique
mal coverage, and it has the ability to control used to produce ultrathin films as high-quality
film thickness accurately at the subnanometer epitaxial layers with very sharp interfaces and
level. Such distinctive advantages have made it good control of thickness, doping, and composi-
a potentially valuable tool for nanotechnology. tion [37]. Deposition usually takes place under
The same advantages make it useful for high or ultrahigh vacuum conditions (typically
bioreplication. Indeed, ALD has been used to below 10−10 Torr). Because of the high degree of
fabricate alumina replicas of the corneal layer of control possible with MBE and the possibility of
the compound eyes of flies [32] and butterfly growing compound semiconductors, it is a valu-
wings [33]. For example, ALD was used to pro- able tool in the development of sophisticated
duce a 100-nm-thick alumina coating on a fly electronic and optoelectronic devices.
eye, and then the biotemplate was removed by The MBE process can be considered a refined
pyrolysis. The resulting replica captured the form of evaporation. Ultrapure target materials
200-nm nipple-like features patterning the com- are placed in effusion cells (also called Knudsen
pound eye [32]. ALD has also been used to cells) and heated to their sublimation points [8].
replicate the spines of the sea mouse [34], to infil- Molecular beams thereby produced are then
trate spider silk in order to toughen it [35], and directed toward a single-crystal substrate, in the
to prepare photocatalytic replicas of the inner vicinity of which they may react chemically with
membranes of avian eggshells [36]. Chapter 16 each other or other gaseous species introduced
provides a detailed treatment of ALD for into the vacuum chamber and then condense as
biomimicry. a layer on the substrate. Figure 15.9 shows the

FIGURE 15.9  Schematic of a typical system for molecular beam epitaxy (MBE). Solid target materials are heated in effusion
cells to produce molecular beams. The substrate is heated to the necessary temperature and, when needed, continuously rotated
to improve the growth homogeneity. A reflection high-energy-electron diffraction (RHEED) gun is used for in situ monitoring.
396 15.  VAPOR-DEPOSITION TECHNIQUES

schematic of a typical MBE apparatus. Each fab-   [3] P. Ehrhart, Film deposition methods, in Nanoelectronics
ricated layer has a definite c­ rystallographic rela- and information technology: advanced electronic materials
and novel devices (R. Waser, ed.), Wiley-VCH, Wein-
tionship with the substrate. The substrate is heim, Germany (2005).
usually heated and often rotated continuously   [4] R.J. Martín-Palma and A. Lakhtakia, Nanotechnology: a
to improve uniformity of deposition. crash course, SPIE Press, Bellingham, WA, USA (2010).
The molecular beams are typically obtained   [5] M. Faraday, Experimental relations of gold (and other
from thermally evaporated elemental target metals) to light, Phil Trans R Soc Lond 147 (1857),
145–181.
materials. However, metal–organic group-III   [6] R. Rühle, Verfahren zur Bedampfung im Vakuum,
compounds, gaseous group-V hydrides, organic Deutsche Reich Patent 764927 (1939).
compounds, or some combination may also be   [7] M. von Pirani, Production of homogeneous bodies
used as target materials. To obtain high-purity from tantalum or other metals, US Patent 848600
epitaxial layers, it is critical that the target materials (26 March 1907).
  [8] W. Gao, Z. Li, and N. Sammes, An introduction to elec-
be extremely pure and that the entire process be tronic materials for engineers, 2nd ed., World Scientific,
carried out in an ultrahigh-vacuum environment. River Edge, NJ, USA (2011).
Growth rates are typically on the order of a few   [9] A. Saito, Y. Miyamura, M. Nakajima, Y. Ishikawa,
Å s–1 and the molecular beams can be shuttered in K. Sogo, Y. Kuwahara, and Y. Hirai, Reproduction of
a fraction of a second, enabling precise control of the Morpho blue by nanocasting lithography, J Vac Sci
Technol B 24 (2006), 3248–3251.
the composition, doping, microstructure, and  [10] A. Saito, Y. Miyamura, Y. Ishikawa, J. Murase,
thickness of the growing layer at the molecular M. Akai-Kasaya, and Y. Kuwahara, Reproduction,
level. Given the ultrahigh-vacuum environment mass-production, and control of the Morpho-butter-
of the system, analytical techniques such as fly’s blue, Proc. SPIE 7205 (2009), 720506.
reflection high-energy-electron diffraction  [11] P.J. Kelly and R.D. Arnell, Magnetron sputtering: a
review of recent developments and applications,
(RHEED) and mass spectrometry are often used Vacuum 56 (2000), 159–172.
for in situ monitoring of the growing thin film.   [12] W.R. Grove, On the electro-chemical polarity of gases,
Phil Trans R Soc Lond 142 (1852), 87–101.
  [13] I. Safi, Recent aspects concerning DC reactive magne-
tron sputtering of thin films: a review, Surf Coat
15.6  CONCLUDING REMARKS Technol 127 (2000), 203–218.
 [14] S.C. Tjong and H. Chan, Nanocrystalline materials
In many cases, a specific functionality of a bio- and coatings, Mater Sci Eng R 45 (2004), 1–88.
logical specimen emerges from its particular  [15] J.R. Davis, Handbook of materials for medical devices,
structure at the nano-, micro-, and/or mac- ASM International, Materials Park, OH, USA (2003).
 [16] A. Lakhtakia and R. Messier, Sculptured thin films:
roscale. This diversity of length scales makes it nanoengineered morphology and optics, SPIE Press, Bell-
crucial to identify the most adequate bioreplica- ingham, WA, USA (2005).
tion technique, depending on the characteristics   [17] R.J. Martín-Palma, V. Torres-Costa, and C.G. Pantano,
of the chosen biotemplate. Vapor-deposition Distributed Bragg reflectors based on chalcogenide
techniques are attractive for both biomimetics glasses for chemical optical sensing, J Phys D: Appl
Phys 42 (2009), 055109.
and bioreplication.   [18] R.J. Martín-Palma, C.G. Pantano, and A. Lakhtakia, Rep-
lication of fly eyes by the conformal-evaporated-film-
by-rotation technique, Nanotechnology 19 (2008), 355704.
References  [19] R.J. Martín-Palma, C.G. Pantano, and A. Lakhtakia,
 [1] D.P. Pulsifer and A. Lakhtakia, Background and Biomimetization of butterfly wings by the conformal-
survey of bioreplication techniques, Bioinsp Biomim 6 evaporated-film-by-rotation technique for photonics,
(2011), 031001. Appl Phys Lett 93 (2008), 083901.
  [2] K.L. Chopra, Thin film phenomena, McGraw-Hill, New  [20] A. Lakhtakia, R.J. Martín-Palma, M.A. Motyka, and
York, NY, USA (1969). C.G. Pantano, Fabrication of free-standing replicas of
 REFERENCES 397
fragile, laminar, chitinous biotemplates, Bioinsp  [29] K. Watanabe, T. Hoshino, K. Kanda, Y. Haruyama,
Biomim 4 (2009), 034001. and S. Matsui, Brilliant blue observation from a
 [21] D.P. Pulsifer, A. Lakhtakia, and R.J. Martín-Palma, Morpho-butterfly-scale quasi-structure, Jpn J Appl
Improved conformal coatings by oblique angle deposi- Phys 44 (2005), L48–L50.
tion for bioreplication, Appl Phys Lett 95 (2009), 193701.  [30] M. Ritala and M. Leskelä, Atomic layer epitaxy—a
 [22] D.P. Pulsifer, A. Lakhtakia, R.J. Martín-Palma, and valuable tool for nanotechnology? Nanotechnology 10
C.G. Pantano, Mass fabrication technique for (1999), 19–24.
­polymeric replicas of arrays of insect corneas, Bioinsp  [31] M. Leskelä and M. Ritala, Atomic layer deposition
Biomim 5 (2010), 036001. (ALD): from precursors to thin film structures, Thin
 [23] D.P. Pulsifer, A. Lakhtakia, M.S. Narkhede, M.J. Solid Films 409 (2002), 138–146.
Domingue, B.G. Post, J. Kumar, R.J. Martín-Palma,   [32] J. Huang, X. Wang, and Z.L. Wang, Bio-inspired fabri-
and T.C. Baker, Fabrication of polymeric visual decoys cation of antireflection nanostructures by replicating
for the male emerald ash borer (Agrilus planipennis), fly eyes, Nanotechnology 19 (2008), 025602.
J Bionic Eng 10 (2013), 129–138.   [33] J. Huang, X. Wang, and Z.L. Wang, Controlled replica-
 [24] K.L. Choy, Chemical vapour deposition of coatings, tion of butterfly wings for achieving tunable photonic
Prog Mater Sci 48 (2003), 57–170. properties, Nano Lett 6 (2006), 2325–2332.
  [25] S.N. Bondi, W.J. Lackey, R.W. Johnson, X. Wang, and   [34] F. Mumm, M. Kemell, M. Leskelä, and P. Sikorski, A
Z.L. Wang, Laser assisted chemical vapor deposition bio-originated porous template for the fabrication of
synthesis of carbon nanotubes and their characteriza- very long, inorganic nanotubes and nanowires, Bioinsp
tion, Carbon 44 (2006), 1393–1403. Biomim 5 (2010), 026005.
 [26] G. Cook, P.L. Timms, and C. Göltner-Spickermann,   [35] S.-M. Lee, E. Pippel, U. Gösele, C. Dresbach, Y. Qin,
Exact replication of biological structures by chemical C.V. Chandran, T. Bräuniger, G. Hause, and M. Knez,
vapor deposition of silica, Angew Chem Int Ed 42 Greatly increased toughness of infiltrated spider silk,
(2003), 557–559. Science 324 (2009), 488–492.
  [36] S.-M. Lee, G. Grass, G.-M. Kim, C. Dresbach, L. Zhang,
 [27] S. Liu, Y. Yang, Y. Jin, J. Huang, B. Zhao, and Z. Ye,
U. Gösele, and M. Knez, Low-temperature ZnO atomic
Multifunctional ZnO interfaces with hierarchical micro
layer deposition on biotemplates: flexible photocata-
and nanostructures: bio-inspiration from the compound
lytic ZnO structures from eggshell membranes, Phys
eyes of butterflies, Appl Phys A 100 (2010), 57–61.
Chem Chem Phys 11 (2009), 3608–3614.
 [28] R.M. Langford, P.M. Nellen, J. Gierak, and Y. Fu,
 [37] A.Y. Cho and J.R. Arthur, Molecular beam epitaxy,
Focused ion beam micro- and nanoengineering, MRS
Prog Solid State Chem 10 (1975), 157–191.
Bull 32 (2007), 417–423.
398 15.  VAPOR-DEPOSITION TECHNIQUES

ABOUT THE AUTHORS

Raúl J. Martín-Palma is Professor of Physics at Akhlesh Lakhtakia received degrees from the
the Department of Applied Physics of the Uni- Banaras Hindu University, India (BTech and
versidad Autónoma de Madrid (Spain) and DSc), and the University of Utah, USA (MS and
adjunct professor at the Pennsylvania State Uni- PhD), in electronics engineering and electrical
versity’s Department of Materials Science and engineering, respectively. He is the Charles God-
Engineering (University Park, PA, USA). He frey Binder (Endowed) Professor of Engineering
received his MS Degree in applied physics in Science and Mechanics at the Pennsylvania State
1995 and his PhD in physics in 2000, both from University and currently serves as the editor-in-
the Universidad Autónoma de Madrid. He has chief of the Journal of Nanophotonics. His current
been Post-Doctoral Fellow at the New Jersey research interests include nanotechnology,
Institute of Technology (Newark, NJ, USA) and bioreplication, surface multiplasmonics, complex
Visiting Professor at the Pennsylvania State Uni- materials, metamaterials, and sculptured thin
versity. He has received several awards for films. He is a Fellow of SPIE, the Optical Society
young scientists for his research on nanostruc- of America, American Physical Society, Institute
tured materials from the Materials Research of Physics (UK), and American Association for
Society (USA), European Materials Research the Advancement of Science.
Society, and Spanish Society of Materials. He
serves as an associate editor of the Journal of
Nanophotonics and is a Fellow of SPIE.