Inert Gas Condensation

Submitted to: Dr.Muhammad Riaz

Submitted by: M.LUQMAN YOUSAF
Roll No : MP-1704

Department of Physics
University ofPunjab, Lahore
 Contents
Abstract………………………………………………………………………….1

History………………………………………………………….………………..2

Review of inert gas condensation process………………………………...…...2

Different Inert Gas Condensation Process……………………………………2

MagnetronSputtering…………………………..……………..................,.........3

Basic Steps in Condensation Process………………………..….…………..…4

Experimental setup of Inert Gas Condensation Magnetron Sputtering……4

Working……………………………………………………..………….……….4

Advantages of Magnetron Sputtering…………………………….….…..…....5

Conclusion…………………………………………..….……………………….6

References…………………………..………………….….………...……….….7
Abstract

Nanoparticles (NPs) are particles of any shape with dimensions in the 1 to 100 nm range . As
functional building blocks, NPs occupy a very important place in various areas of nano science
and biotechnology. NPs exhibit size-, shape-, composition- and structure dependent behavior
which is different from the corresponding bulk materials. By tuning these parameters, many
properties, such as melting temperature, band gap (electronic structure), catalytic, magnetic and
optical properties, can by controlled to meet the requirements of specific applications.

Among the wide range of existing synthesis methods, magnetron sputtering inert gas
condensation has been commonly used during recent years especially for the synthesis of
magnetic nanoparticles because of its superiority over other techniques (pulse laser ablation,
thermal evaporation, resistive heating. The method allows simultaneous control of composition,
magnetron power, inert gas pressure, NP drift velocity, and aggregation zone length. To achieve
a reliable control of the fabricated NPs, it is essential to change these experimental conditions. It
allows for flexible growth of complex, sophisticated NPs, owing to the fast kinetics and non-
equilibrium processes it entails. Nanoparticle synthesis is decomposed into four stages, i.e.
aggregation, shell-coating, mass-filtration, and deposition.

Inert Gas Condensation

History

The inert gas evaporation–condensation (IGC) technique, in which NPs are

formed via the evaporation of a metallic source in an inert gas, has been widely used in the
synthesis of ultrafine metal particles since the 1930s [1]. In this year the first experiment
recorded which form the basis for later developments of inert gas condensation methods was
carried out by Pfund [2] and later followed by Haris et al [3]. In this work, nucleation and growth
were found to occur in a nobel gas atmosphere and this technique reffered to as a inert gas
evaporation method. The inert-gas evaporation method was extensively used by the japan and
paper published by kubo in 1962 [4] in which e predicted that ultrafine metal particles should
exhibit physical properties that would be very different from bulk material. After few decades a
subsequent work by Burhman and Granqvist in 1974 [5] concentrated on the gas condensation
methods and defined different parameters such as type of gas used, as pressure, evaporation rate
etc. After that, inert as condensation methods were used by Glieter and is co-workers in 1989 [6]
and after that well defined techniques of inert gas condensation was developed.

Although the early work was mostly concerned with the synthesis and characterization of
nanoparticles of pure metals, some studies were also reported on the synthesis of compounds,
alloys, and mixtures of particles by inert gas condensation. In the early stages oxides were
investigated by the simplemethod of introducing oxygen into the vapor phase. Nitrides and
carbides of the metals could also be synthesized by filling the chamber with nitrogen or ammonia
gases or by maintaining a carbonaceous atmosphere. The types of nanostructured materials
prepared by the IGC method include metals (e.g., Cu, Fe, Ni, Pd, and W), ionic compounds (e.g.,
FeF2, CaF2, Fe2O3, and TiO2), and also covalent substances (e.g., Si)

Review of inert gas condensation process

Ward et al [7] presented their reported from experiments carried out using the inert gas
condensation method to produce manganese NPs which included both Mn3O4 and pure Mn
particles. The authors claimed that the use of moisture in untreated helium gas caused the
particles to oxidize, whereas when the helium was run through liquid nitrogen, it trapped and
removed the moisture thereby producing β-Mn particles in a meta stable state. The particle sizes
and the size distribution were determined to range from 2 nm to above 100 nm.

Wesley et al [8] also reported on the preparation conditions adopted to obtain different
morphologies of as deposited refractory metal-oxide (Y2O3) nanoparticles using inert-gas
condensation with CO2 laser heating. According to them, the micrometer-scale morphology of
the nanoparticles obtained depended on the specific metal oxide, the buffer gas composition and
pressure as well as the target-to-substrate distance. The above parameters actually controlled and
determined the extent to which a plume of non-agglomerated NPs reached the deposition
substrate.

Haberland et al. [9], rapid progress in NP synthesis using magnetron-sputtering has been
made; in-depth theoretical studies elucidated the main principles of particle formation and
numerous technologically advanced variations of NP fabrication systems, e.g. comprising
improved geometries, pulsed plasma or multiple-target usage, enabled high cluster yields, post-
deposition thermal treatment, oxidation control, etc.

Inert Gas Condensation

History

The inert gas evaporation–condensation (IGC) technique, in which NPs are

formed via the evaporation of a metallic source in an inert gas, has been widely used in the
synthesis of ultrafine metal particles since the 1930s [1]. In this year the first experiment
recorded which form the basis for later developments of inert gas condensation methods was
carried out by Pfund [2] and later followed by Haris et al [3]. In this work, nucleation and growth
were found to occur in a nobel gas atmosphere and this technique reffered to as a inert gas
evaporation method. The inert-gas evaporation method was extensively used by the japan and
paper published by kubo in 1962 [4] in which e predicted that ultrafine metal particles should
exhibit physical properties that would be very different from bulk material. After few decades a
subsequent work by Burhman and Granqvist in 1974 [5] concentrated on the gas condensation
methods and defined different parameters such as type of gas used, as pressure, evaporation rate
etc. After that, inert as condensation methods were used by Glieter and is co-workers in 1989 [6]
and after that well defined techniques of inert gas condensation was developed.

Although the early work was mostly concerned with the synthesis and characterization of
nanoparticles of pure metals, some studies were also reported on the synthesis of compounds,
alloys, and mixtures of particles by inert gas condensation. In the early stages oxides were
investigated by the simplemethod of introducing oxygen into the vapor phase. Nitrides and
carbides of the metals could also be synthesized by filling the chamber with nitrogen or ammonia
gases or by maintaining a carbonaceous atmosphere. The types of nanostructured materials
prepared by the IGC method include metals (e.g., Cu, Fe, Ni, Pd, and W), ionic compounds (e.g.,
FeF2, CaF2, Fe2O3, and TiO2), and also covalent substances (e.g., Si)

Review of inert gas condensation process

Ward et al [7] presented their reported from experiments carried out using the inert gas
condensation method to produce manganese NPs which included both Mn3O4 and pure Mn
particles. The authors claimed that the use of moisture in untreated helium gas caused the
particles to oxidize, whereas when the helium was run through liquid nitrogen, it trapped and
removed the moisture thereby producing β-Mn particles in a meta stable state. The particle sizes
and the size distribution were determined to range from 2 nm to above 100 nm.

Wesley et al [8] also reported on the preparation conditions adopted to obtain different
morphologies of as deposited refractory metal-oxide (Y2O3) nanoparticles using inert-gas
condensation with CO2 laser heating. According to them, the micrometer-scale morphology of
the nanoparticles obtained depended on the specific metal oxide, the buffer gas composition and
pressure as well as the target-to-substrate distance. The above parameters actually controlled and
determined the extent to which a plume of non-agglomerated NPs reached the deposition
substrate.

Haberland et al. [9], rapid progress in NP synthesis using magnetron-sputtering has been
made; in-depth theoretical studies elucidated the main principles of particle formation and
numerous technologically advanced variations of NP fabrication systems, e.g. comprising
improved geometries, pulsed plasma or multiple-target usage, enabled high cluster yields, post-
deposition thermal treatment, oxidation control, etc.

Different Inert Gas Condensation Process

Inert gas condensation involves evaporation of metal using any of the following which
includes

1. Resistive heating
2. Radiofrequency heating
3. Magnetron Sputtering,
4. Electron Beam Heating,
5. Laser/Plasma Heating,
6. Ion Sputtering
7. Chemical Vapor Deposition

In these methods inside a chamber that has been evacuated to a very high vacuum of
about 10-7 torr and then backfilled with a low pressure inert gas like helium. The evaporated
atoms collide with the gas atoms inside the chamber, lose their kinetic energy and condense in
the form of small, discrete crystals of loose powder [10]. Among different techniques describe
above magnetron sputtering is most appropriate one.

Basic Steps in Inert Gas Condensation

The basic steps involved in inert gas condensation for the formation of nanocrystalline
materials are.

1. The aggregation of evaporated atoms into clusters by appropriate heating of target

material.
2. Cooling of atoms by collision with cold inert gas atoms.
3. Growth of clusters by addition of atoms to individual clusters and by agglomeration of
clusters by collision between them [11].

Magnetron sputtering

Sputtering is a non-thermal physical vapor deposition process in which surface atoms are
physically ejected from the surface by momentum transfer from an energetic bombarding species
of atomic/molecular size. Typical sputtering uses a glow discharge or ion beam. Interaction
events which occur at and near the target surface during the sputtering process in magnetron
sputtering has advantage over diode and triode sputtering. In magnetron sputtering, most of the
plasma is confined to the near target region. Other alternate energy sources which have been
successfully used to produce clusters or ultra-fine particles are sputtering electron beam heating
and plasma methods. Sputtering has been used in low pressure environment to produce a variety
of clusters including Ag, Fe and Si [12].

Experimental setup of Inert Gas Condensation Magnetron Sputtering

A high-vacuum magnetron-sputter inert-gas-phase NP source, as shown schematically

in Figure 1.1, has been developed by Mantis Deposition ltd. The system has four
modules which are the cluster source and aggregation zone, shell coater, quadrupole mass-filter
(QMF), and main deposition chamber labeled A, B, C, and D, respectively.
 Fig1. Schematic representation of a magnetron-sputter inert-gas condensation NP deposition system.

Working

In module A, a water-cooled aggregation chamber with a 2-inch in diameter magnetron

sputtering target inside is used for vapor generation. The cluster source comprises a set of
permanent magnets, an inert gas source, a copper cathode and the target. Ar or Ar/He mixed gas
is heated up and ionized into the plasma. The Ar+ ions are accelerated by the electric bias
between the anode and the copper shield (the cathode), and bombard the target. The secondary
electrons are confined by the magnetic field and significantly enhance the ionization of the Ar
gas near the target surface. This way, more energetic Ar+ ions bombard the target, generating
supersaturated vapor for cluster nuclei formation.

The vapor is cooled by collisions with inert gas atoms and blackbody radiation. At the
initial stage, the temperature of nuclei are initially beyond their melting points due to the bond
forming energy, referred as "liquid growth" stage. Further growth occurs by more sputtered
atoms landing on the nascent NPs, and subsequently by collisions and coalescence of the NPs.
The temperature of NPs at this second stage is essential for the final properties of NPs, as it can
be either "liquid growth" or "solid-state growth". After the NPs passing the source aperture, the
growth finishes due to the long distance between each NPs. The optional further growth can
be done in shell coater chamber (module B). Depending on the power of the coating source
and residence time, the NPs grow into core-shell, core-satellite or Janus structure
After passing through a quadrupole mass filter (module C), the NPs a softly land on suitable
substrate in the deposition chamber (module D). Embedded NPs can be achieved by applying an
additional bias on the substrate. The final outcome of the NPs is a result of thermodynamics and
kinetics history during the aggregation, inoculation and deposition [13, 14].

Advantages of Magnetron Sputtering

The main advantage of the magnetron-sputtering method is its inherent flexibility. It

allows control over growth parameters such as magnetron power (and, therefore, sputtering
yield), inert-gas composition and pressure (affecting cooling and growth rates), NP drift velocity
(determining residence time, which affects NP size), and aggregation zone length (with potential
effect on NP sizes). The Advances in Physics: X 85 use of alloy targets or additional sputtering
sources allows for the design of multi-component NPs with tunable composition, structure, and
crystallinity, whereas control techniques employed after NP growth, such as in situ mass
filtration, and deposition-temperature and -energy control, offer practically endless possibilities
for the design and facile, one-step synthesis of tailored NPs.

Drawbacks of Inert Gas Condensation

(1) Agglomeration of particles is a problem in consolidated nanopowders. The van der Waals
forces caused by a temporally varying charge distribution in each individual nanopowder particle
can cause rapid agglomeration intobranched bodies. These entities are difficult to break up on
compaction and sintering, and thus lead to interagglomerate voids and residual porosity in the
sample.

(2) Cost becomes a factor because the entire process is carried out under UHV conditions. In
order for the substrate

substantial pumping of a large flow of an inert gas is necessary. The pumps make up most of the
cost and bulk of the apparatus.

(3) Maintaining a clean vacuum may not always be easy.

(4) Ensuring repeatability and stability of operating conditions can also be a problem, since
cluster generation is very sensitive to source conditions.

(5) IGC is not always suitable for synthesizing compound semiconductors such as GaAs and InP
because these easily decompose to the individual components.

(6) Neutral clusters produced require ionization, which is usually an inefficient process.

(7) It may be difficult to adjust conditions to obtain high fluxes for very small clusters of just a
few atoms.

(8) It has not been easy to scale-up the process. Consequently, the amount of powder produced
per batch is limited.

Conclusion
Gas-phase synthesis is a class of bottom-up methods for producing NPs. Especially
magnetron-sputter inert-gas condensation offers plentiful possibilities for facile design of NPs
with tailored properties and corresponding target applications; as such it is an attractive
alternative to other multi-step physical and chemical synthesis techniques. In parallel, it should
be emphasized that, due to its flexibility, gas-phase synthesis is one of the most widespread
methods for the production of multi-component NPs, such as multi-core/shell structures in which
the cores can present either “dumbbell-like” or “onion-like” structures [15,16]. Such NPs afford
the possibility of combining different classes of physical properties; an example of magneto-
plasmonic NPs [17,18] using three separated target materials (Fe, Ag, and Si) simultaneously
highlights the potential of a new generation of optimized NPs for future nanotechnologies and
bio-applications. With applications ranging from semiconductor devices to capacitor dielectrics,
from optical and anti-corrosion coatings to photo-catalysts and solar cells, and from bio-
implantable devices to chemical reactors and catalysts, it is safe to assume that the industrial
interest in NP technologies via gas-phase synthesis is only going to increase in the years to come.

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