Che Elective 1 - Nanotechnology
Che Elective 1 - Nanotechnology
Che Elective 1 - Nanotechnology
ChEE 401
ChE ELECTIVE 1 - NANOTECHNOLOGY
ChE 4201
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
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
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.
t = zB/2m,
m/z = B/2
v = incident velocity
z = charge
Fig. 1 A schematic of FT-ICR- MS showing the iron trapping detection and signal generation.
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
Generated from elements which are semiconductors in nature such as silicon, catbon, and
germanium.
Carbon Clusters
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
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.
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.
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?
Monodispersity
Possibility of further chemical derivation
High degree of crystallinity and specificity
Chemical integrity
Lack of defects
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
Reverse micelles
Langmuir-Blodget films
Zeolites
Porous membranes
Clays
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
Ancillary Techniques
- Other techniques used for nanomaterial characterization:
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