BATANGAS STATE UNIVERSITY

College of Engineering, Architecture and Fine Arts

Gov. Pablo Borbon Campus II,
Alangilan, Batangas City, Philippines 4200
www.batstate-u.edu.ph Telefax: (043) 300-4044 locs. 106-108

CHEMICAL AND FOOD ENGINEERING DEPARTMENT

ChEE 401
ChE ELECTIVE 1 - NANOTECHNOLOGY

GAS PHASE CLUSTERS

Bonifacio, Nestor Jr.

Fusi, Genina Joy
Llaga, Roed Alejandro
Panaligan, Kerby
Saballero, Jessica

ChE 4201

Dr. Sicily B. Tiu

GAS PHASE CLUSTERS
Clusters
Belong to a new class of systems and are studied to understand several aspects related to
the science of nanomaterials
At cluster stage, nanoparticles are nucleated and it is important to understand these
systems in the naked state using mass spectrometry in order to know the origin of
molecular and electronic structure in bulk systems.
In size, they fall between bulk materials and their atomic or molecular constituents
Depending on the kind of constituent units: atomic or molecular clusters
Molecular Clusters
o Implies clusters which behave like super molecules
Include species existing only in the gas phase or in the condensed phase or vice versa
Classifications: net charge (Ionic clusters) or no charge (Neutral clusters)
Differ from bulk materials in terms of the presence of a magic number of atoms or
molecules they contain
Nuclearity of Clusters
- The finite aggregates of atoms of molecules constituting clusters are ond by forces which
may be metallic, covalent, ionic, hydrogen bonded or van der waals in character and can
contain up to a few thousand atoms
As shown in the figure, Clusters can be depicted as a state between isolated atoms or bulk solid.

Reasons of investigating clusters:

1. As clusters bridge the gap between molecules and materials, the evolution in properties of
molecules as they become materials can be understood by investigating clusters.
2. Properties such as chemical reactivity and catalysis depend strongly on specific geometry,
electronic structure, etc., clusters help to understand such fundamental phenomena.
Difference between atom, molecule, clusters, and bulk materials
Property Atom/Molecule Cluster Bulk Material
Size of constituting Few Angstroms Angstrom to Microns to higher
entries nanometer
Number of 1 for atom, many for 2 to several Infinite
constituents (n) molecule thousands
Electronic structure Confined (quantized) Confined (quantized) Continuous
Geometric structure Well-defined and Well-defined and Crystal structure
predictable predictable decides
Example Na/NaCl/C6H6 C60 (NaCl)n Bulk gold, silver
History of Cluster Science
Robert Boyle
An Irish-born chemist
His book, The Sceptical Chymist published in 1661 was first to propose the
importance of clusters
In the book, it was critical of Aristotles four elements theory of matter and proposed
that it exists in the form of corpuscles
For him, Clusters were not collections of atoms or molecules as both were unknown
then
Buckminsterfullerence (C60)
After it was discovered, the field of cluster science witnessed an enormous growth
Applications
1. Photography (AgBr clusters in films)
2. Glass works (staining)
Rayleigh
Recognized that colors of stained glasses are due to the scattering of light by small
metal particles, clusters of atoms embedded in the glass
Cluster Formation

F=4 /n1 /3

Formula used for spherical clusters where n is the total number of atoms
Gas phase clusters are generated in cluster sources
Cluster Sources:
o Laser vaporization-flow condensation source
o Pulsed arc cluster ion source
o Laser ablation cluster source
o Supersonic (free jet) nozzle source
o Knudsen cell (effusive source)
o Ion sputtering source
o Magnetron sputtering source
o Gas aggregation/ Smoke source
o Liquid metal ion source
Laser Vaporization
- A pulsed cluster source which is used to produce small- and medium-sized clusters
- Combines laser ablation and supersonic jet expansion
- Vapor is generated by pulse laser ablation of a rod of the starting material (UV laser is
used)
- Each 10 ns pulse vaporizes 1014 1015 atoms per mm2 of the target
- Advantages of Pulsing:
1. Get an intense light capable of evaporation of materials directly breaking their
bonds in the lattice
2. Produces a pulse of clusters suitable for time of flight analysis
3. Pulsed laser firing and subsequent expansion of the evaporated plasma into
vacuum is generally done in presence of carrier gas, which is also pulsed,
reducing the pumping requirements
Pulsed arc cluster ion source (PACIS)
- Instead of laser, the cluster precursor is vaporized by an intense electrical discharge.
- More intense compared to laser vaporization
- Nearly 10 percent of the clusters formed by using this technique are charged.
- Post ionization is not necessary for mass analysis
Supersonic (Free Jet) Nozzle sources
- Types: unseeded and seeded
1. Unseeded
Clusters of inert gases, molecules and low boiling metals are like Hg are formed.
2. Seeded
The metal is vaporized (with a vapor pressure of 10-100mbar) In an oven and the
vapor is mixed with (seeded) an inert carrier gas at a pressure of several
atmospheres (105-106 pa) at a temperate of 77-1500 K. the metal/carrier gas
mixture is then expanded through a nozzle (with diameter of 0.03-0.1 mm) into
high vacuum (10-1 10-3 Pa), which creates a supersonic beam.
Produces large clusters while in the absence of a carrier gas
Gas-Aggregation or Smoke Sources
- The vapor generated by one of the several means are introduced into a cold inert gas at a
high pressure of the order of 1 torr.
- The species at a high temperature are thermalized.
- Produce continuous beams of clusters of low-to-medium boiling (<2000 K) metals
Knudsen Cell
- Produces a continuous, low flux beam of clusters
- Velocity of species is low (subsonic).
- In design, this is similar to a smoke source.
- In these sources, as the aperture is small, the solid-gas mixture is nearly at equilibrium
b / N
- Formula used: I ( N )=a e where a and b are parameters

Liquid Metal Ion Source

- Primarily used to produce clusters of multiple charges, low-melting metals
- A needle is held above the melting point of the metal to be studied. The tip is wetted with
the metal and it is held at a potential. Very high electric fields at the tip of the needle
cause the emission of a spray of tiny droplets from it.
- Used in which a high-energy ion beam is used to sputter atoms, ions and clusters from a
surface
Cluster Growth
- 2 stages:
1. Nucleation
o Can be homogenous or heterogenous
o Heterogenous- implies the nucleation occurs on foreign objects, dust
particles
o Collision between like or unlike atoms occurs such that the thermal energy
is lower than the binding energy of the species formed.
o Dimer formation- occurs when the body involved in the collision removes
the excess internal energy as kinetic energy; dimer acts as a seed for
further condensation and additional growth occurs.
2. Growth
o Occurs by the aggregation of atoms or molecules one at a time
o Coalescence of clusters results in the formation of larger clusters
Detection and Analysis of Gas Phase Clusters
- Clusters can exist as neutrals or ions (both positively and negatively charged)
- Mass spectrometers are used to detect the ionic clusters.
- Clusters (solid or liquid) can be analyzed by spectroscopic, microscopic or diffraction
techniques
- Mass spectrometric techniques for clusters:
1. Wien Filter
2. Time of flight (TOF)
3. Quadrupole mass filter (QMF)
4. Ion cyclotron resonance (ICR)
Wien Filter
- A low resolution (m/m 10-2), low mass range (less than m/z 1500) instrument
- Mass separation is accomplished using crossed homogenous electric (E) and magnetic
(B) fields, perpendicular to the ionized clusters beam, which travels along the axis of the
filter.
- Formulas:
E=Bv
M/Q = 2V/ (E/B)2
 Where Q is charge, V is voltage M is mass, v is velocity
- Depends on the velocity spread of cluster ions, the strength of the fields, and the slit
width

Quadrupole Mass Filter (QMF)

- Most widely used type of mass pectrometers today because of its ease of use,
compactness and low cost
- Based on the achievement of a stable trajectory for specific ions in a hyperbolic
electrostatic field
- An idealized QMF consists of four parallel hyperbolic rods.
o=U +Vcost

U is dc voltage
Vcost is the time-dependent rf voltage in which V is rf amplitude and rf frequency

Mathieu equations
Mathieu parameters au and qu:
2 2
au =a x =a y =4 zU /m r o

qu =q x =q y =2 zV /m 2 r 2o

m/z is the mass-to-charge ratio of the ion

ro is the half distance between two opposite rods
- Resolving power of QMF depends on the number of cycles experienced by an ion within
the rf field
- Advantages of QMF:
1. Good transmission
2. High scan speed
3. Wide acceptance angle to facilitate high sensitivity
Time of Flight (TOF) Mass Filter
- Efficient mass analyzer, no mass limit
- Used to study the dissociation of metastable clusters
 - A reflectron can also be used to investigate dissociation in the field-free region (Post
Source Dissociation) so that slower process exhibited by the ion may be observed.
- Post Source Dissociation- ions are accelerated in an appropriate electric filed of the orer
of kilovolts

6.5.4 Ion Cyclotron Resonance

Is a unique technique wherein we can, in principle, perform all the mass spectrometric
studies in a single cell. They include, mass analysis, ion selection, ion interaction and product ion
mass analysis.

The equations of interest are,

F = zv x B (x referes to a cross product)

t = zB/2m,

m/z = B/2

where: F = Lorentz Force

v = incident velocity

= induced cyclotron frequency

m = mass of the ion

z = charge

Fig. 1 A schematic of FT-ICR- MS showing the iron trapping detection and signal generation.

6.6 Types of Clusters

Table 1.0 Various cluster types and their properties

Type Examples Nature of binding Binding

energy/mole
Ionic clusters ( NaCl)n , Ionic Bonds ~50-100 kcal
(Strong binding)
(CsI )n
Covalent clusters C60 , Si n , Covalent bonding ~20-100 kcal
(Strong binding)

Metal clusters Au n , Na n , Agn , Metallic Bond ~ 10-50 kcal

(Moderate to strong
binding)

Molecular clusters H Molecular < 10 kcal

( 2 O)n
interactions,

hydrogen bonding,
van der Waals, etc.

van der Waals clusters Ar n , Xen , Polarization effects < 5 kcal

(Weak binding)

6.6.1. Metal Clusters

Formed from alkali metals, alkaline earth metals and transition metals.
They may be formed from a single metallic element or from more than one metal, giving
rise to intermetallic or nanoaaloy clusters

Neutral sodium clusters

Produced in a gas aggregation source.

Heated in an oven to a temperature of about 400C.
Fig. 2 (a) Mass Spectrum of Sodium Clusters, N= 4-75. Inset shows N = 75-100 region. (b)
MALDI spectrum of silver clusters produced from silver trifluoroacetate.

6.6.2 Semiconductors Clusters

Generated from elements which are semiconductors in nature such as silicon, catbon, and
germanium.

Carbon Clusters

C60 (Fullerene) , Carbon cluster, stimulated researchers to explore the possibility of a

number of semiconductor clusters.

Has a tendency to form a greater variety of clusters as compared to other elements.
The bonding in these cluster is covalent in nature.

Silicon Clusters

The first reported silicon clusters were generated by laser flash evaporation, quenched in
a carrier gas and then cooled by superionic expansion.

Apart from bare metal clusters, metal oxides (e.g. Mo O3 , WO3 , V 2 O5 , FeO, LiO,

MgO,, PuO), metal chalcogenides (e.g. MoS, W S 2 , TeS, FeS, ZnS, MoTe, N b2 S2 ,

VS4 ) and metal halides (e.g. Ni Cl2 , NaCl), are also known to prodice clusters.

6.6.3 Metcars

Close-cage clusters made of metals and carbon.

Such as Mo-C, Ti-C, Hf-C, V-C, Cr-C, etc. are known.
Were discovered by castleman, et. al by laser vaporization of titanium metal in the
presence of methane gas.
Also called as matallocarbohedrenes or met-cars
 Chemical reactivity was found to be very high towards polar molecules like H 2O, NH3,
CH3, OH,etc.

Fig 3. (1) Laser desorption ionization (LDI) mass spectrum of MoS 2, in the negative
mode showing magic closed cage clusters. Inset: Experimental spectrum (a) shows the expected
isotope distribution for Mo13S25 (b) Atomic structure of the Mo13S25 cluster.

Fig. 4 Optimized tetrahedral structure of the Ti8C12 metcar.

6.6.4 Rare Gas or Noble Gas Clusters and Magic Numbers

Earliest clusters detected in molecular beam experiments.

Fig. 5 Mass Spectra of positively charged Ar. Kr, Xe clusters.

6.6.5 Ionic Clusters

Signifies those clusters derived from ionic solids having large differences in
electronegativity, such asNaCl, CsCl, etc.
May exist in positive or negative charge.
Canbe generated by methods like heating or laser vaporation of ionic compounds in a
stream of cold inert gas.

6.7 Properties of Clusters

All properties varies with size, as all of them are dependent on energy.
The energy of the system is affected by fractional surface atoms and that makes
properties change.
The properties of clusters explain the transition from single atoms to the solid state.

MERCURY CLUSTERS
Clusters generated by molecular cluster beam source.
Monochromatized radiation used to photoionize the neutral cluster beam
PIE curve recorded between the ionization corresponding to the ejection of one s
or d electrron
OPTICAL PROPERTIES
Photodetachment Spectroscopy technique which electron removal of negatively
charged species is investigated
- Can obtain information of optical properties
- Separation of energy levels of the neutral cluster results to optical absorption
properties

IONIZATION POTENTIAL
Ionization potential shell structure and stability of clusters were confirmed
- Origin of metallicity in clusters
- Electrical affinity is similar to the bulk

BONDING IN CLUSTERS
Metallic Clusters delocalized electron exists
Noble Gas Clusters have closed valence electron shell resulting to van der Waals
forces
Kinds of theoretical models

Jellium Model
- Explains the structures and stability of atomic nuclei
- Electronic structure of the atom
- Metal cluster is uniform, positively charged sphere filled with electron gas
- Empirical
- Gives electronic shell structure for clusters
Liquid Drop Model
- Electrostatic model
- Metal cluster is uniform conducting sphere
SEMICONDUCTOR QUANTUM DOTS
What are Quantum Dots?

Semiconductor dots also referred as semiconductor nanocrystals

Quantum dots semiconductor particles
Nanocrystal inorganic entity in which there is a crystalline arrangement of
constituent atoms/ions.
Energy levels of semiconductor crystal forms bands which is separated by
energy gab.
o Valence Band filled
o Conduction Band empty
Electron-hole pair created due to thermal excitation with electron in
conduction band and hole in valence.
Exciton delocalized bound pair throughout the crystal
de Broglie wavelength range of nanometers where strong confinement are
manifested on particle dimension
The electronic structure of materials is strongly related to the nature of the
material.
Quantum well notation the electron feel a potential as they trapped in the
film
Sphere model simplest model of quantum dot
Electrons of quantum dots are confined to a point in space. N
2D confinement electron is confined within two dimensional area
1D confinement confinement along one dimension resulting to quantum
wire
In quantum dot, there is no freedom along any direction

SYNTHESIS OF QUANTUM DOTS

Properties of nanocrystals

Monodispersity
Possibility of further chemical derivation
High degree of crystallinity and specificity
Chemical integrity
Lack of defects

Two kinds of general approach in synthetic protocol

Top-Down Approach
- Bulk material is brought into smaller dimension by various tools
- Semiconductor electronics
- Creating powder from bulk material
Bottom-Up Approach
- Clasified as two:
o Gas Phase tha material to be synthesized is mixed in the atomic
state in the gas phase itself.
o Liquid State

7.2.2 SYNTHESIS IN CONFINED MEDIA

In this approach, nanoparticles are synthesized in a space that is already
available. The chemical reaction occurs inside a reactor, which is prepared by one of
the following ways.

Reverse micelles
Langmuir-Blodget films
Zeolites
 Porous membranes
Clays

In confined cages, maximum dimension of the particle formed is fixed.

7.2.3 MOLECULAR PRECURSORS

In the precursor route, nanocrystal seeds are prepared in a medium which
can control the growth of the particles by coordinating with it. The solvent
universally chosen for this approach is trioctylphosphineoxide (TOPO). *Fig. 7.2

7.2.4 CHEMICAL SYNTHESIS USING CLUSTERS

This atomic building approach has many advantages, one of which is the
removal of all possible defects while the other is the possibility to have truly
monodisperse materials. A good example of this approach is using
[(NMe4)4Cd10S4(SC6H5)16] to form Cd32S14(SC6H5)34.4DMF

7.2.5 MODIFICATION OF THE SURFACE OF NANOCRYSTALS

1. It removes surface states, thus making near band gap emission possible. Due
to the removal of defects, the emission becomes narrow.
2. It adds chemical versatility to the system allowing it to become part of the
larger structure. It is also important in making the system biocompatible.
3. Surface passivation and suitable functionalization make the system
chemically inert and thermally stable.
The most common approach used is that of functionalizing the surface of the
nanocrystal with various molecules, which can be thiols, amines, alkyl or silyl
groups, etc. In all these cases, the chemical functionality of the molecule interacts
with the metal atom at the surface of the nanocrystal.

7.2.6 InP NANOPARTICLES

It is called a group III-V semiconductors as In belongs to group III and

phosphorus to group V.
The indium precursor used is indium oxalate, indium chloride or indium
fluoride.
Trimethylsilyphosphine is used as the phosphorus precursor.

7.3 ELECTRONIC STRUCTURE OF NANOCRYSTALS

A material will behave differently when the size regime is smaller than that
required for bulk properties. While dealing with nanocrystals, one has to distinguish
between three different kinds of size regimes. The size regimes depend on the
nanocrystal radius, r and the bulk exciton, a.

For strong confinement regime, r << a, the Coulombic interaction between

the electron and the hole is much smaller than the confinement range
energies.
A weak confinement regime, r << a occurs when the electron and hole
motions are strongly correlated.
In the intermediate regime, r~a, the electronic structure depends strongly on
both quantum confinement and Coulombic interaction.
The simplest model used to represent the energy states of a nanocrystal is a
spherical quantum well, with an infinite potential barrier.
7.4 HOW DO WE STUDY QUANTUM DOTS?
One needs to characterize its physical, structural, electronic and other
properties to qualify it as a nanomaterial.
7.4.1 ABSORPTION AND EMISSION SPECTROSCOPY
Absorption and emission spectroscopy are performed to understand the
quantum confinement of the system. The spectra are measured in absorption and
fluorescence spectrometers for absorption and emission, respectively.

Life Time and Dynamics of the Excited States

Excited States - decays eventually wherein non-radiative processes dominate in nanocrystals
Excited State Dynamics - deals with stability and rate of decay of the excited states
Surface defects - reduce the quantum efficiency of radiative decay
- occur in the form of unsatisfied valencies which provide an easy sink for the
charge carriers

X-ray Diffraction
- principal method used to identify the phases present in a solid state material
- producing smaller dimension crystallites of an already known phase
- crystal dimension decreases; diffraction peaks broaden
- may be compared with the data from other techniques
Scherer formula - used to find size of the particles

Transmission Electron Microscopy

- the most important characterization tool for a nanomaterial
- observes shape of the object and reveal microscopic structure and atomic composition
- uses energy dispersive X-ray analysis
- area of the order of 1 nm in diameter
- studies large cross section of the sample instead of one particle
- a histogram of particle size distribution is plotted which is more representative of the material
synthesized
- higher magnification provides image of the lattice structure of individual nanoparticles

Ancillary Techniques
- Other techniques used for nanomaterial characterization:

Thermogravimetry measures the thermal loss/gain of the material when it is subjected

to heating at a constant rate
- gives kinetics of thermal events (decomposition, reaction, etc.)
- estimates the extent of surface coverage in nanomaterials

Differential Scanning Calorimetry evaluate phase changes in the material

 X-ray Photoelectron Spectroscopy provides direct information on the electronic
structure
- useful in understanding the valence state of the
elements present in the sample

Raman Spectroscopy useful in finding the vibrations in the sample (characteristic of

the molecular and crystal structures)
Infrared Spectroscopy

Chemical Properties
Photocatalysis can lead to reduction using the electron in the conduction band
- TiO2 is the most used photocatalyst
Organic Synthesis utilized the power of semiconductor particles
- aromatic ketones and olefins have been converted into alcohols and
corresponding saturated compounds

Single Electron Devices

- cannot be used for properties like rectification or memory because these can only be
attained by the use of single electron transistors and single electron traps
- it is capable to charge or discharge nanosized regions selectively
Quantum dots used in single electron devices
Electroneutral dot number of electrons that it has is the same as the number of holes
Tunneling most common means of putting a charge into single electron device because the
device most often has an insulating barrier around it
- Q (charge) = -e produces an electric field E which repels any incoming negative
charge
- fundamental charge = 1.6 x 10-19
- electric field around the dot = 140 kV on a 10 nm diameter particle
Electronic energy states at smaller dimensions the materials are quantized
- at larger regimes up to 100 nm the addition energy is dominated
by the charging energy and the energy required for addition is of
the order of eV
Single electron transition manifested dramatically in current-voltage measurements of
nanocrystals
Coulomb staircase a device structure where a single nanoparticle is trapped between an
electron source and an electrode and the said electrode is separated at a
large distance for tunneling to cease to occur which applies a potential U.
This corresponds to external charge Q which produces a step-like function Qe
= CU in which Q is the function of U
- when thermal energy becomes comparable to the charging energy, the
thermal fluctuations smear out the staircase
- implies that electrons can be transferred one at a time