NANO MATERIALS AND NANO

TECHNOLOGY- SYNTHETIC METHODS

1. HYDROTHERMAL
2. SOLVOTHERMAL
3. CVD TYPES
M KIRUTHIKA
4. LOW PRESSURE CVD MSc CHEMISTRY
NANO SEMINAR
2023-2025
METHODS OF CHEMICAL SYNTHESIS IN THE SYNTHESIS OF NANOMATERIAL:
• In general, chemical synthesis involves the process by which a product precipitates from a liquid
(or solution) phase containing a precursor.
• Chemical synthesis are opposed to mechanical methods of nanomaterial production (top-down
approach)
• It also referred to as wet synthesis methods or solution-phase synthesis. During this process,
soluble species become insoluble or insoluble and precipitate.
• Since chemical methods of nanomaterial synthesis have a bottom–up approach, so with the help
of this method, nanostructured engineering, as well as surface modification, can be done easily.
ADVANTAGE: Chemical methods do not require complex and expensive equipment compared to
physical methods.
BOTTOM UP APPROACH METHOD:

SOLUTION GROWTH TECHNIQUE:

Hydrothermal method:
• Hydrolysis reactions at high temperatures of the various compounds directly in steel pressure vessels (called
autoclaves with or without Teflon liners).
• This method involves heating the reactants in water/steam at high pressures and temperatures. The water has two
functions, as a pressure-transmitting medium and as a solvent, in which the solubility of the reactants is P,T
dependent.
• This method is quite simple; reactants and water are placed inside a Teflon-lined cylinder or bomb which is
either sealed or connected to an external pressure control. The bomb is then placed in the oven, usually at a
temperature in the range of 100-500°C.
• By P/T Phase diagram, the curve AB is the saturated steam curve and separates water (above) from the steam
(below); at temperatures above 374°C, point B, the water is in the supercritical condition and there is no
distinction between liquid and vapor states.
MECHANISM OF CRYSTAL GROWTH BY HYDROTHERMAL METHOD:
Crystallization process.
2 step process
• Crystal nucleation
• Subsequent growth

Solute precipitates into clusters of crystals which can further grow into macroscopic size.
APPLICATION:
• For zeolite synthesis, the final stage is to heat aluminosilicate gels hydrothermally to crystallize the zeolites.
• Single crystals of quartz, SiO2,
The solubility of SiO2 in NaOH solution increases with temperature therefore, SiO2 dissolves at the hot end, is
transported to the cooler end by convention and crystallizes on the suspended seeds.
NaOH acts as a mineralizer, SiO2 is only sparingly soluble in H2O, but solubility increases greatly when NaOH
is dissolved in H2O. if NaOH solution is used instead of pure H2O greatly speeds up the growth of quartz crystals
by hydrothermal treatment.
SOLVOTHERMAL METHOD
• It is identical to the hydrothermal method, solvent - nonaqueous.
• Temperature (usually 100-1000°C)
• pressure (1-10,000 atm)
• The process typically carried out close or above the boiling point of the reaction medium in a sealed vessel(e.g.
Autoclave)
• The solvothermal method normally has better control than hydrothermal methods of the size and shape
distributions and the crystallinity of nanoparticles.
• It is employed to synthesize metals, semiconductors, ceramics and polymers. The process can be used to prepare
many geometries including thin films, bulk powders, single crystals, and nanocrystals.
• In addition morphology (sphere (3D), rod(2D), or wire (1D)) of crystals formed is controlled by manipulating the
solvent supersaturation, chemical of interest, concentration and kinetic control.
Examples:
CdSe QDs are prepared by dissolving
Cadmium source:
CdO in trioctylphosphine oxide(TOPO) – solvent (cation source material that is soluble in the chosen solvent)
Selenium source:
Elemental Selenium in tributylphosphine (TBP)
Temperature: 300ºC
Trioctyl phosphine (TOP) - surfactant (that caps or stabilizes the quantum dot, arresting its growth)
.The reaction is the quenched and nanocrystals are observed.
Additionally, a shell of one composition (e.g., ZnS) can be synthesized over a core of another nanocrystal (e.g.,
CdS). The core can also be used as a seed to grow larger particles by adjusting the concentration after the initial
growth.

Uses:
• Nanocircuits
• Nano-optical circuits to nanomagnetic and biotech.
A typical TEM image of the TiO2 nanoparticles prepared with the
solvothermal method.
 1. Transport of reactants by forced convection
to the deposition region.
2. Transport of reactants by diffusion from the
main gas stream through the boundary layer to the wafer
surface.
3.
Adsorption of reactants on the wafer surface.
4. Surface processes, including chemical
decomposition or reaction , surface migration to
attachment sites (such as atomic level ledges and kinks),
site incorporation and other surface reactions.
5. Desorption of by-products from
the surface.
6. Transport of by-products by diffusion
through the boundary layer and back to the main gas
stream.
Advantages of CVD
The reasons for the success of CVD are simple:
• CVD is a flexible technology which can accommodate many variations.
• With CVD, it is possible to coat almost any shape of almost any size.
• Unlike other thin film techniques such as sputtering, CVD can also be used to produce fibers, monoliths,
foams and powders.
• CVD is economically competitive.

CVD-DISADVANTAGES,
1. It is most versatile at temperatures of 600°C and above; many substrates are not thermally stable at these
temperatures, the development of plasma-CVD and metalloorganic CVD partially offsets this problem.
2. The requirement of having chemical precursors (the starter materials) with high vapor pressure which are
often hazardous and at times extremely toxic.
3. The by-products of the CVD reactions are also toxic and corrosive and must be neutralized, which may be a
costly operation.
Chemical vapor deposition (CVD):
Applications of this fabrication process are now key elements in many industrial products
• semiconductors
• Optoelectronics
• optics
• cutting tools
• refractory fibers
• filters and so..
TYPES OF CVD PROCESSES:
1. Atmospheric Pressure Chemical Vapour Deposition (APCVD)
2. Low Pressure Chemical Vapour Deposition (LPCVD)
3. Metal-Organic Chemical Vapour Deposition (MOCVD)
4. Plasma Assisted Chemical Vapour Deposition (PACVD) Or Plasma Enhanced
Chemical Vapour Deposition (PECVD)
5. Laser Chemical Vapour Deposition (LCVD)
6. Photochemical Vapour Deposition (PCVD)
7. Chemical Vapour Infiltration (CVI)
8. Chemical Beam Epitaxy (CBE)
TYPE OF CLASSIFICATION TEMPERATURE AND ADVANTAGES DISADVANTAGES
CVD PRESSURE
APCVD ------- 10 – 100 kPa Simple reactor, fast Poor step coverage
350 – 1200ºC Deposition and low temperature

PYROLYTIC LCVD Laser usage Due to the thermal effect is suited Correct choice of
write small features rather than lasers should taken
large-area deposition into account
LCVD PHOTOLYTIC Laser usage Additional flexibility and Correct choice of
LCVD selectivity lasers should taken
into account

PECVD ------- 200 – 600 Pa Low temperature Rise of particle and

300 - 400 ºc(low Fast deposition, good step chemical
temperature) coverage, good gap fill contamination
LPCVD ------- 100Pa Excellent cleanness, conformity High temperature, low
425– 900 ºC(can be and uniformity deposition rate
higher)
MOCVD ------- 10mtorr – 100 torr(usually High purity, most flexible, large Expensive sources,
performed at room sale production , selective in in- most parameters to
pressure or low pressure) situ process control accurately
350 – 370 ºC hazardous precursors
 CBE ------- 500 - 700ºC Easy implementation More pumping
(HYBRID OF <10-4 torr of in-situ diagnostic required compared
MOCVD AND instrument, absence to MOCVD
MBE) of oval effect, easier
multiwalled scaleup
CVI ------- 900-1200ºC High flexibility, Production rate is
Pressure (depends on large number of low and high capital
the type of the preforms are there, and production costs
product) usually fibre damage is less
ranges from 1-
100kPa
PCVD ------- Photon energy – Compound thin film Slow rate of
3.4eV (XeF laser) to is easily formed, deposition
6.4eV (ArF lkaser) electrical and
Room temperature mechanical
properties are good
Low Pressure Chemical Vapour Deposition (LPCVD)
1. Heat is used to initiate the reaction.
2. Quartz tube is used here. Low pressures ranges from 10m torr- 1 torr.
3. When the tube is under vacuum it is heated up to the required deposition of the precursors.
4. Temperature – 425-900°C depending upon the reactive gases and process
5. The gas then diffuses in the tube and reacts with the surface of the substrate which leads to formation of the solid
phase material.
APPLICATIONS:
6. Doped and high doped high temperature oxide
7. Silicon nitride
8. Polysilicon
Advantages:
Excellent purity, Comfortable step coverage
Large wafer capacity.
Disadvantages:
High temperature
Low deposition rate
Example: PREPARATION OF Si NANOPARTICLE:
1. CHEMISTRY : Pure Silane (SiH4)
2. TECHNOLOGY : IC Technology compatible Low Pressure Chemical Vapour Deposition
technique.
3. TEMPERATURE : 550-600°C
4. RESISTIVITY : 20 Wcm
5. DIAMETER : 2 inches
6. DURATION : 30-90s
7. REQUIREMENTS :
Synthesis of SiO2 layers and SiNO3 layers using silicon wafers.
 Ultrathin SiO2 (8-10 nm) thermally grow at low temperature on some Si wafers.
 Rest of the wafers contains thin silicon nitride (approx. 2000 angstrom layer)
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