Topic 2.

SYNTHESIS, PROCESSINGAND FABRICATION METHODS OF SOLID STATE

MATERIALS
Introduction
Solid State Chemistry,isa subdiscipline of Inorganic Chemistry primarily concerned with the study of
extended solids.Most substances, helium being a notable exception, if cooled sufficiently form asolid
phase; the vast majority form one or more crystalline phases, where the atoms,molecules or ions
pack together to form a regular repeating array. Solid State Chemistryis concernedmostly with the
structures of metals, ionic solids and extended covalent structures; structures that do not contain
discrete molecules as such, but that compriseextended arrays of atoms or ions. We look at the
structure of, and bonding in, thesesolids, how the properties of a solid depend on its structure, and
how the propertiescan be modified by changes to the structure.
Interest in the properties of solids and in the development of new materials has givenrise to the
development of a huge variety of methods for preparing them. The methodchosen for any solid will
depend not only on the composition of the solid but alsoon the form it is required in for its proposed
use. For example, silica glass for fibreoptics needs to be much freer of impurities than silica glass
used for manufacturinglaboratory equipment. Some methods may be particularly useful for producing
solidsin forms that are not stable under normal conditions, for example, the synthesis ofdiamond
employs high pressures. Other methods may be chosen because they favourthe formation of unusual
oxidation states, for example, the preparation of chromiumdioxide by the hydrothermal method, or
because they promote the production offine powders or, by contrast, large single crystals. For
industrial use, a method thatdoes not employ high temperatures could be favoured because of the
ensuing energysavings.
In the preparation of solids, usually, care has to be taken to use stoichiometricquantities, pure starting
materials and to ensure that the reaction hasbeen completed, because it is usually not possible to
purify a solid once it hasformed.

As we navigate through the various methods of solid state synthesis below, we will discover that
there are essentially two steps, one called synthesisand the other is crystal formation or crystal
Growth.

-In the synthesis part, you synthesize the crystal units and this is typically accomplished
in one of two ways, either through a solid state synthesis or some sort of wet chemical
synthesis. So, here what is done is that you synthesize the units of the crystals which could be atoms,

1
molecules or ions. So if it has molecules like an oxide, then you have to synthesize the oxide. The
second step is called crystal formation and here the synthesized molecules or atoms are arranged into
high quality crystals. Sometimes this crystal formation takes place simultaneously together with
synthesis i.e. starting materials or reactants called precursors and you accomplish both the synthesis
and the crystal formation simultaneously. But in many other cases, you often do the solid state
synthesis and then you recrystallize your sample.

Because there are so many different kinds of solid state materials there is a whole array of strategies
for each of these two steps of synthesis and crystallization. For solid state synthesis (i.e the
precursors are all solids), the basic idea is you take the constituent reactants in the solid form
(nitrates, carbonates, acetates, citrat(using ball milling, grinding etc), powder them and introduce into
reaction chamber and heat to high temperatures(e.g. between 700 oC to 1200 oC depending on the
material that you want to synthesize). The materials disintegrate as reaction occurs and usually
release gases which escape leaving the solid product behind. For the alternative synthetic method of
soft chemical synthesis it does not require such high temperatures as we make use of the chemistry of
the precursors , to make sure that the reaction takes place at much lower temperature, and the basic
idea is that we use good precursor materials. For example, if we want to make an oxide, we can just
use alkoxides as precursors of whichever metals you have and heat at low temperatures to get the
metal oxides.

Another procedure of soft chemical synthesis used quite often is called a sol-gel process. One of the
characteristics of the soft chemical synthesis is that we use solutions, and when the initial mixing of
your materials is done in a solution form, then that leads to much better mixing. So, here a solution is
made and essentially evaporate it slowly to form a colloid called sol, then keep evaporating it until it
forms a gel. So, starting from a solution, and by slowly heating it you get a gel, andwhen this gel is
heated at high temperature we get a product. There is another variant of this called a hydrothermal
method, where you use water at very high pressures, to achieve reactions at very low temperatures.

So this is the overall strategy of solid state synthesis and again I emphasizethat, there are several
techniques that fall withinthe class of solid state synthesis and every material requires unique
strategies, becauseevery material to be synthesized presents different set of challenges.

2
2.1 HIGH-TEMPERATURE CERAMIC METHODS
 Direct Heating of Solids:
I) Ceramic method: Consists of heating two non-volatile solids which react to form the
required product.
The solid-state method can be used to prepare a whole range of materials including mixed
metal oxides, sulfides, nitrides, aluminosilicates, etc.
ZrO2 (s) + SiO2(s)→ ZrSiO4 (s) heat to 1300°C
The method can be used to prepare an extremely large number of compounds.
Disadvantages
•High temperatures are generally required (500-2000°C), because it takes asignificant amount of
energy to overcome the lattice energy so a cation or anioncan diffuse into a different site.
•The desired compound may decompose at high temperatures.
•The reaction may proceed very slowly, but increasing the temperature speeds upthe reaction since it
increases the diffusion rate.
•Generally, solids are not raised to their melting point, so reactions take place inthe solid state
(subsolidus).
Solid State Reactions
Diffusion controlled: Fick’s 1st Law: J=-D (dc/dx)

• Small particle sizes that are well mixed are needed to maximize the surface contact area.
• Tamman’s Rule suggests a temperature of about two-thirds of the melting point (K) of the lower
melting reactant is needed to have reaction to occur in a reasonable time.
•Thorough grinding is necessary to achieve a homogenous mixture of reactants.
•The number of crystallites in contact may be increased by pelletizing the powdersusing a hydraulic
press.

3
•The reaction mixture is typically removed and reground to bring fresh surfaces into contact, which
speeds up the reaction.
•Reaction times are sometimes hours, but may range into several days or weeks for acomplete
reaction, with intermediate grinding.
•Sample purity is typically examined using powder X-ray diffraction.

•Furnaces use resistance heating with metal, SiC, or MoSi2 heating elements.
•Conversion of electrical energy into heat (to 2300 K). An electrical arc directed at thesample may
achieve 3300 K. A CO2 laser can give temperatures up to 4300 K.
•Containers for the reaction (crucibles) must be able to withstand high temperaturesand be
sufficiently inert to the reactants. Common crucibles are silica (to 1430 K),alumina (to 2200 K),
zirconia (to 2300 K), or magnesia (2700 K). Platinum (m.p. 2045K) and silver (m.p. 1235 K) are also
used for some reactions.

FIGURE 2.1 The basic apparatus for the ceramic method: (a) pestles and mortars for fine grinding; (b) a selection of porcelain,
alumina and platinum crucibles; and (c) a furnace.

4
 a)Sealed Tubes Method
If reactants are volatile or air sensitive, then heating in an open atmosphere is inappropriate.
Evacuated tubes are used when the products or reactants are sensitive to air or water, or are volatile.
Sm (s) + 1/8 S8 (s) → SmS
Sulfur has a low boiling point (717 K), so the reaction mixture is placed in an evacuated tube to
prevent it from boiling off and being lost.

The tube is often made of Pyrex or silica, since these are fairly inert and can be flame sealed with a
Pyrex vacuumsystem. Usable to about 1000-1100 K.
The sample might be ground, then heated in a tantalum tube for high temperature reactions (to 2300
K).
The Ta tube must be sealed by welding the tube. An electric current is passed through the tube,
generating high pressures and temperatures. Safety precautions must be taken in case of tube rupture.
b) Special atmospheres: Synthesis of some compounds must be carried out under a
specialatmosphere.
•annoble gas, argon, may be used to prevent oxidation to higher oxidation state.
•an oxidizing gas, oxygen, might be used to form a high oxidation state.
•a reducing gas, hydrogen, might be used to form a low oxidation state.
Reactions usually take place in a small boat crucible placed in a tube in ahorizontal tube furnace.
•Gas is passed for a period of time to expel all air from the apparatus, then continues to flow during
the heating and cooling cycle. A bubbler isused to ensure positive pressure is maintained.

FIGURE 2.2 Reacting solids under a special gas atmosphere.

5
2.2 LOWERING THE TEMPERATUREOR CHIMIE DOUCE METHODS(or Soft Chemistry
methods)
Polycrystalline samples might have particle sizes from 1-10 μm.
-with significant grinding, particles sizes of near 0.1 μm may be obtained
-diffusion is taking place over between 100 and 10,000 unit cells.
Many methods, both physical and chemical, have been developed toimprove mixing and particle size
to reduce the diffusion path length at the atomic level.
Spray-Drying:
Reactants are dissolved in a suitable solvent and sprayed as fine dropletsinto a hot chamber. The
solvent evaporates and leaves a mixture of thesolids as a fine powder which can be heated to give the
product.
Freeze-Drying:
Reactants are dissolved in a suitable solvent and frozen to liquid nitrogentemperatures (77 K). The
solvent is removed by pumping to leave a finepowder.
2.2.1 Co-precipitation and precursor methods:
Precursors such as nitrates and carbonates can be used as startingmaterials instead of oxides.
Co-precipitation involves taking a stoichiometric mixture of solubleoxalates, or formates. The
mixture is filtered, dried, and then heatedto give the final product.
Precursor method involves atomic level mixing by forming a solidcompound (precursor) in which the
metals of the desired compoundare present in the proper stoichiometry. For example, a mixed salt
ofan oxyacid (e.g. acetate) containing M and M’ in the ratio of 1:2 isformed in the case of formation
of MM’2O4.
•the precursor is heated to decompose it to the desired product.
•homogeneous products are formed at relatively low temperatures.
•it is not always possible to find a suitable precursor
Precursor method example:
Ti(OBu)4(aq) + 4H2O(l) →Ti(OH)4(s) + 4BuOH(aq):Excess oxalic acid re-dissolves the precipitate.
Ti(OH)4(s) + (COO)22-(aq)→TiO(COO)2(aq) +2OH-(aq) + H2O(l)

Ba2+(aq) + (COO)22-(aq) + TiO(COO)2(aq)→Ba[TiO((COO)2)2](s)

Decomposition by heating (920 K) gives the desired oxide phase.

Ba[TiO((COO)2)2](s)→BaTiO3(s) + 2CO2(g) + 2CO(g)

6
2.2.2 Alkoxide Sol–Gel Methods
•The procedure is first prepare a homogeneous solution containing all the cationic ingredients in the
desired ratio.
•Then, solution is gradually dried and, depending on the species present, should transform to a
viscous sol containing particles of colloidal dimensions and finally to a transparent, homogeneous,
amorphous solid known as a gel, without precipitation of any crystalline phases.
•The gel is then fired at high temperatures to remove volatile components trapped in the pores of the
gel or chemically bonded hydroxyl and organic side-groups and to crystallize the final product.
There are two main types of sol–gel methods, materials and applications.
•First, organometallic precursors, particularly alkoxides, often containing several different cations are
widely used.
The reagents for alkoxide-based sol–gel syntheses are metal–organic compounds, such as:
 tetraethyl orthosilicate (TEOS), Si(OCH2CH3)4, as a source of SiO2,
 titanium isopropoxide, Ti(OiPr)4,as a source of TiO2, and
 aluminiumbutoxide, Al(OBu)3, as a source of Al2O3.
•These covalent liquids are mixed in the appropriate ratios, often with an alcohol to promote
miscibility of the alkoxide and H2O. Water is a key reagent since it hydrolyses the alkoxides, usually
in the presence of either acid or base as a catalyst to speed up reaction.
Hydrolysis occurs in two steps:
(i) Replacement of –OR groups by –OH, e.g.
Si(OCH2CH3)4→ Si(OCH2CH3)3OH + Si(OCH2CH3)2(OH)2+ etc.
(ii) Condensationpolymerization with elimination of H2O, e.g.
(RO)3Si–OH + HO–Si(OR)3→ (RO)3Si–O–Si(OR)3
General Sol-Gel Method can be summarized as follows:
•A concentrated solution or colloidal solution of the reactants, the’sol’, is prepared and then further
concentrated to form the gel.
•The gel is heat-treated to form the product.

Fig.2.2.1 Steps in the sol-gel synthesis route.

7
•A sol is a colloidal suspension of particles in a liquid (~1-100 nm diameter)
•A gel is a semi-rigid solid in which the solvent is contained in a frameworkof material that is either
colloidal or polymeric.
•A dispersal stage may involve oxides or hydroxides in water with a specificpH so the solid particles
remain in suspension rather than precipitate.
•A hydrolysis may involve addition of metal alkoxides to water, which arehydrolyzed to give the
oxide as a colloidal product.
•The sol forms a gel by dehydrating or polymerizing.
•The gel forms the product by heating to decompose the alkoxidesorcarbonates to give the oxide.
Time and temperature is reduced compared totheconventionalCeramicmethods
Illustrative Examples of Sol-gel method
i)Sol-Gel Preparation of LiNbO3:
Preparation by solid-state method may lead to secondary phases at the higher temperatures needed for
reaction.
LiNbO3 may be prepared by the sol-gel method by starting with lithium ethoxide (LiOC2H5) and
niobium ethoxide [Nb2(OC2H5)10].
•Each ethoxide may be dissolved in absolute EtOH and mixed.
•Addition of water leads to partial hydrolysis giving hydroxyalkoxides.
Nb2(OC2H5)10 + 2H2O →2Nb(OEt)4(OH) + 2EtOH
•Hydroxy-alkoxides condense to form a polymeric gel with metaloxygen-metal links.
•LiNbO3 is formed when the gel is heated – the remaining ethanol and water is evaporated and any
remaining ethyl groups are pryolysed (forming CO2 and H2O).

ii)Sol-Gel Preparation of doped SnO2

Conductivity of SnO2 may be increased by the addition of dopants suchas Sb3+, forming an oxygen
deficient n-type semiconductor,
•Sol-gels are suitable for the preparation of materials with a largesurface area with a controlled
distribution of dopants.
•Titanium doped SnO2 may be prepared by adding titanium butoxide,Ti(OC4H9)4, to a solution of
SnCl2▪2H2O in absolute EtOH.
•The tin(II) salt is easily hydrolyzed to give hydroxyl complexes andcan be oxidized to tin(IV) by
oxygen in air.
•Leaving the sol in an open container, a gel will be formed in about fivedays.
8
•Heating (333 K) at reduced pressure for two hours dries the gel.
•Heating (600 K) for 10 minutes produces a layer of SnO2 doped withTi4+.
iii)Silica for Optical Fibers
Optical fibers need to be free from metallic impurities.
•use of volatile compounds of silica, liquid silicon alkoxide
[Si(OR)4] are more easily purified than solid silica (SiO2).
Si(OR)4+ 4H2O →Si(OH)4+ 4ROH

Fibers can be pulled as gelation occurs, then heated 1300 K to increase density.

iii) Sol-gel: Biosensor

A sol-gel may be used to create a biosensor.
•A biosensor, often an enzyme, is often very specific.
•One limitation includes denaturing, if the enzyme is removed from theaqueous environment or the
pH is altered.
•An approach to minimize this problem is to trap the enzyme with itsmicroenvironment in a silica gel.
•A sol of silica may prepared by acid hydrolysis of Si(OMe)4.
•The sol is buffered at a suitable pH for the enzyme and the enzyme is added.
•As the sol forms a gel by condensing, the enzyme is trapped in the cavities inthe gel and is
surrounded by an aqueous medium of the correct pH.

9
 http://biomaterials.kaist.ac.kr/research/research.htm

2.2.3 Citrate Gel and Pechini Processes

Figure 2.2.3 Reagents and esterification mechanism in the Pechini process.

• Figure 2.2.3 illustrates another family of sol–gel processes, often with a combustion step to
decompose the gel product, utilizes carboxylic acids such as citric acid and polyhydroxy alcohols
such as ethylene glycol.
•Citric acid is a chelating agent in which the carboxylate groups act as ligands to form complexes
with metal cations. Citric acid is a very useful complexing agent, with three carboxylic ligands on
each acid molecule.
The carboxylic acid groups can also take part in esterification reactions, by condensation with
hydroxyl groups on ethylene glycol.

This reaction could be of much varying scope where other organic acids such as tartaric acid and
poly(acrylic acid) can be used; also, other polyhydroxy alcohols ranging from small molecules such
as glycerol to larger polymers such as poly(vinyl alcohol) and poly(ethylene glycol) can be used.
10
To facilitate decomposition of the polymeric gel products, combustion synthesis aids such as urea and
nitric acid may be added to the reaction mixture.
The combustion synthesis step can give highly porous foam products which may be beneficial either
for subsequent ceramic processing associated with the high surface area of crushed foam powders or
for applications requiring high surface area materials.
The nitric acid also acts to control the pH during reaction and in particular to avoid precipitation of
insoluble citrates, which can lead to loss of homogeneity during the intermediate stages of reaction or
in the finalproduct.
The Pechini process is chemically complex and involves both acids and alcohols together with
esterification,whereas in the citrate gel method, the alcohols are not utilized and, instead, citric acid is
simply added to metal nitrate aqueous solutions. The citrate gel method has lower organic content in
the gel product with less weight loss and shrinkage during firing and is often preferred for film
fabrication.
Many materials have been made by Pechini and citrate gel processes with much scope to modify the
natureof the final product by attention to the composition of the reaction mixtures. Examples include
synthesis ofYBa2Cu3O7 superconductor, Sr(Co,Fe)O3–δ for use as solid oxide fuel cell cathode and
LiMn2O4 lithiumbattery cathode.

2.3. Microwave Synthesis.In a liquid or solid, the molecules of ions are not free to rotate.
The alternating electric field of the radiation:
•If charged particles are present, these move under the influence of thefield and produce an oscillating
electric current. Resistance to the movementcauses energy to be transferred to the surroundings as
heat, known asconduction heating.
•If no particles are present that can move freely, but molecules or units withdipole moments are
present, then the electric field acts to align the dipolemoments. This is dielectric heating. This is the
type of heating that acts onwater molecules in food.
The electric field of the microwave radiation is oscillating at the frequency ofthe radiation, but the
electric dipoles in solids do not change their alignmentinstantaneously, but with a characteristic time,
t.
The oscillating electric field changes its direction rapidly so that the timebetween changes is much
smaller than t, then the dipoles cannot respondfast enough and do not realign (lags behind).
The solid absorbs some of the microwave radiation and the energy isconverted to heat.
11
Depends on the dielectric constant and the dielectric loss.
To use microwave heating, at least one component of the reaction mixturemust absorb microwave
radiation.

Fig.2.3.1 Microwave irradiation raises the temperature of the whole volume simultaneously (i.e. bulk heating).

Example:
2.3.1The High Temperature Superconductor YBa2Cu3O7−x

Conventional ceramic method takes about 24 hours to complete, whereas it takesapproximately 2

hours using microwave synthesis.
•A stoichiometric mixture of CuO, Ba(NO3)2, Y2O3 are placed in a modifiedmicrowave oven that
allows the safe removal of nitrogen oxides formed duringthe reaction.
•The reaction mixture is treated with 500 watts of microwave radiation for fiveminutes, then reground
and exposed to microwave radiation between 130-500watts for 15 minutes. The reaction mixture is
ground again and exposed tomicrowave radiation for 25 minutes.
•The microwaves couple to the CuO.
•A 5 to 6 g sample of CuO exposed to 500 W of microwave radiation for 30seconds attained a
temperature of 1074 K.
•Other oxides that strongly absorb microwave radiation include ZnO, V2O5,MnO2, PbO2, Co2O3,
Fe3O4, NiO, and WO3. Carbon, SnCl2, and ZnCl2 are alsostrong absorbers.
•A 5 to 6 g sample of CaO exposed to 500 W of microwave radiation for 30minutes attained a
temperature of 356 K.
•Microwave synthesis does not solve the problem of chemical inhomogeneity.
•The reaction temperatures are high, and relatively difficult to precisely control.
12
•One advantage is less problems with cracking, since heating is from inside.

2.4Combustion Synthesis
Combustion synthesis is a self-propagating high temperature syntheticmethod that has been
developed as an alternative to the standard method.
•Combustion synthesis uses highly exothermic (ΔH ~ -170 kJ/mol) andeven explosive reactions to
maintain a self-propagating high reactiontemperature.
•The method has been used to prepare many refractory materials includingborides, nitrides, oxides,
silicides, intermetallics, and ceramics.
•Reactants are mixed to together, formed into a pellet, and ignited (laser,electric arc, heating coil) at
high temperature.
•Once ignited, the reaction propagates as a synthesis wave, the reactionmust lose less heat than it
generates, or it will quench.
•Temperatures up to 3000 K are maintained during the fast reaction.
•Self ignition can sometimes be achieved by ball milling.
•In some cases, the presence of a magnetic field will make the reactionproceed faster and with a
higher temperature wave.

Combustion synthesis production of BaFe12O19 from Fe, Fe2O3 and BaO2.The solid flame propagates from left to right in a
silica tube with a constant flow of oxygen.

13
 Combustion Synthesis Of Powder Mixtures in Ti-C-Al System

http://umfacts.um.edu.my/gallery/index.php?menu=research_details&cid=98

Compounds prepared using self-propagating high temperature synthesis:

•Hydrides for hydrogen storage (e.g. MgH2)

•Borides for abrasives and cutting tools (e.g. TiB2)

•Carbides for abrasives and cutting tools(e.g. SiC and TiC)

•Nitrides for high strength, heat resistant ceramics (e.g Si3N4)

•Oxides for high temperaturesuperconductors (e.g. cuprates)

•Silicides for high temperature heatingelements (e.g. MoSi2)

14
•Composites have been used to coat theinside of steel pipes with an inner layer ofFe and a surface
layer of Al2O3.
3Fe3O4 + 8 Al →4 Al2O3+ 9Fe

2.5HIGH PRESSURE METHODS

High pressures are employed directly and indirectly in various synthetic methods:
• High solvent pressures in an autoclave—the hydrothermal method
• Using a high pressure of a reactive gas
• Directly applied hydrostatic pressure on solids
• Detonation
• Ultrasound.
2.5.1.Hydrothermal Methods:The hydrothermal method increases homogeneity and lowers the
operating temperaturesand is also used to grow single crystals, which are needed in some solid-
stateapplications.
•The hydrothermal method involves heating the reactants in a closed vessel (anautoclave).
•an autoclave is constructed from thick stainless steel and fitted with safetyvalves.
•typically lined with a non-reactive material such as teflon.
•the autoclave is heated to above its normal boiling point, the pressure isincreased and is called ‘super
heated water’.
•these hydrothermal conditions also exist in nature and many minerals areformed in this process (e.g.
zeolites, emeralds, etc.)
•low temperatures are one advantage of the method.
•unusual oxidation states may be stabilized.
•Superheated water may dissolve some metal oxides that are insoluble underambient conditions.

15
 Figure. 2.5.1 An Autoclave

Hydrothermal synthesis of quartz

Uses a temperature gradient to dissolve the reactant at higher temperature, which is transported up the
reaction tube by convection, then crystallizesout at a lower temperature.

Hydrothermal synthesis of CrO2

Cr2O3 is the stable oxide of chromium at normal conditions.
Cr2O3 + CrO3→3CrO2
CrO3→CrO2 + ½ O2
3 CrO3 + Cr2O3→ 5 CrO2 + O2

16
Hydrothermal synthesis of zeolite A, Na12[(AlO2)12(SiO2)12]▪27H2O.
•Hydrated alumina, Al2O3▪3H2O is dissolved in concentrated NaOH.
•The cooled solution is mixed with sodium metasilicate, Na2SiO3▪9H2O and a thick white gel forms.
•The gel is placed in a closed teflon bottle and heated to 363 K over 6hours.
•Changes in the form of alumina, pH of the solution, type of base used,and proportions of alkali,
aluminum compound, and silica lead to theproduction of different zeolites.

Microporous and Mesoporous Solids Largecations, e.g. tetramethylammonium (NMe4+) and

tetrapropylammonium (N(C3H7)4+), may be used as a templatearound which the aluminosilicate
framework crystallizes with largecavities to accommodate the ion.
•upon later heating the cation is pyrolyzed, but the structureretains the cavities.
•these structures are known as microporous, with a pore size ofbetween 200 and 2000 pm.
Zeolites with pore sizes of 2000-10000 pm are known as mesoporous solids. Liquid crystal
templating is a technique to prepare mesoporous solids.

17
 The formation of mesoporous MCM-41 by liquid crystal templating.
Yttrium Aluminum Garne
Starting materials have very different solubilities.
•Y2O3 is placed in a cooler section of the autoclave and Al2O3(sapphire) in the hotter section to
increase the solubility.
•Y3Al5O12 forms where the two zones meet.
3Y2O3+ 5Al2O3→2Y3Al5O12

2.5.2 Using Ultrasound

When very high intensity sound waves—ultrasound—travel through a liquid, aphenomenon known as
cavitation occurs. The travelling sound wave causes highpressure areas (compression) of the liquid,
which is followed by low pressure andsudden expansion (rarefaction) and the formation of tiny
bubbles, which expand toan unsustainable size and then collapse. The expansion and collapse of the
bubblescreateverylocalized hot spots, which reach instantaneous pressures of more than
100 MPa (1000 atm) and temperatures of up to 5000°C. The consequent collisionsand fast cooling
can cause chemical reactions and decomposition to occur. Forinstance, when Fe(CO)5 dissolved in
decane under argon is subjected to ultrasound,decomposition to amorphous iron occurs, but in

18
pentane, Fe3(CO)12 is formed. Whena suspension of graphite in an organic solvent (at room
temperature and atmosphericpressure) is subjected to ultrasound, micron-sized (0.001 mm) diamonds
result inabout 10% yield.

2.6CHEMICAL VAPOUR DEPOSITION (CVD)

In CVD, powders and microcrystalline products are prepared fromreactants in the vapor phase, then
can be deposited on a substrate toform single crystal films for devices.
•Volatile starting materials are heated to form vapors, then mixed at asuitable temperature and
transported to the substrate by carrier gas.
•Typical starting materials include hydrides, halides, and organometalliccompounds, since these tend
to be volatile.
•When an organometallic precursor is used, it is called MOCVD (MetalOrganic Chemical Vapor
Deposition).

2,7.1 Semiconductors by Chemical Vapor Deposition

AsCl3 + Ga + 3/2H2→ GaAs + 3HCl
SiCl4+ 2H2→ Si + 4HCl
SiH4→ Si + 2H2

Read also the formation of the following:

 Diamond Films
 Optical Fibres
 LitiumNiobate

19
2.7 PREPARING SINGLE CRYSTALS
2.8.1 Epitaxy methods:
Vapor Phase Epitaxy– possible to prepare high purity thin films.The epitaxial growth, a precursor is
decomposed in the gas phaseand a single crystal is built up layer by layer.
Gallium Arsenide (GaAs)
2Ga(g)+ 2AsCl3(g) →2GaAs(s) + 3Cl2(g)
or
Ga(CH3)3(g) + AsH3(g) →GaAs + 3CH4(g)
Mercury Telluride (HgTe)
(C2H5)2Te(g)+ Hg(g) ----H2, UV light→ gTe(s)
Substrate temperature = 470 K, about 200 °C lowerthan thermal decomposition temperature
2.7.1 Melt methods
Melt methods depend on both the compound being stable in the liquid phase and theavailability of a
high-temperature, inert, containing vessel.
The silicon required by the electronics industry for semiconductor devices hasto have levels of key
impurities, such as phosphorus and boron, of less than 1 atomin 1010 Si. Silicon is first converted to
the highly volatile trichlorosilane (SiHCl3), which is then distilled and decomposed on rods of high-
purity silicon at 1000°C togive high-purity polycrystalline silicon. This is made into large single
crystals by the Czochralski process. The silicon is melted in an atmosphere of argon, and then
a single-crystal rod is used as a seed that is dipped into the melt and then slowlywithdrawn, pulling
with it an ever-lengthening single crystal in the same orientationas the original seed (Figure below).

Fig 2.7.1 The Czochralski process for producing a very pure single crystal of silicon.

20
In addition to silicon, this method is also used for preparing other semiconductor materials such as Ge
and GaAs and for ceramicssuch as perovskites and garnets. Dopant impurity atoms can be added to
the moltensilicon to make n-type or p-type semiconductors.
2.7.2 Solution Methods
Crystallisation from solution takes place either by cooling a saturated hot solution orby allowing
evaporation to take place. Many crystalline substances have traditionally been grown from saturated
solutions in a solvent; hot solutions are prepared andthen cooled and crystals precipitate from the
supersaturated solution.
Various other techniques can be used to induce crystallization and these include: evaporating the
solvent by heating; leaving in the atmosphere; placing in a desiccators or using reduced pressure;
freezing the solvent; and addition of other components (solvent or salt) to reduce solubility.
For solids such as oxides that are very insoluble in water, it may be possible todissolve them in melts
of borates, fluorides or even metals, in which case the solventis generally known as a flux because it
brings down the melting temperature of thesolute. The melt is cooled slowly until the crystals form,
and then the flux is pouredoff or dissolved away. This method has been successfully used for
preparing crystalline silicates, quartz, and alumina, among many others.

2.8 SYNTHESIS OF NANOMATERIALS

The methods of synthesis of nanoparticles (diameter range 1to 20nm and play significant role in
developing technology) are often divided into top-downand bottom-up syntheses. The meaning of
these terms is becoming increasinglyblurred, but the original meaning of ‘top-down’ referred to
making products in bulkand then manipulating them into the form required, for example, casting,
recrystallising and etching. ‘Bottom-up’ was coined to refer to the building up of a structure,atom by

21
atom, in a controlled fashion, so that each atom is placed in its specific place
and the structure is built with no defects.
2.8.1Top-Down Methods
That is breaking down bulk materials already synthesized into nano-sized particles; for instance, the
electronics industry routinely uses lithography and etching methods(read these methods from text) to
form nanoscale patterns on circuits. A few other examples include:
I) Mechanical grindingsuch as high-energymilling can be used to formnanoparticles from bulk
solids.
There arevarious kinds of mills in use, but the principlebehind the technique is the samein that
mechanical attrition can be used toproduce uniformly sized particles.
• In micronizing milling, cylindricalgrinding media is arranged in acontainer and shaken.
• In ball milling, the solid is rotated in acylindrical container with a grindingmedium such as ceramic
or metal balls.
Care must be taken to avoid contamination of the product from the grinding medium.
• Reduces grinding time compared toconventional grinding by hand.
ii)Mechanochemical synthesis of nanoparticles
•This uses a milling process to induce achemical reaction between the components, such that the
reaction produces nanoparticles embedded in a matrix that can be subsequently washed away.
Advantages: a) Particles are kept well apart from one another, so one of the big problems of
synthesizing nanoparticles is avoided—that of agglomeration.
•The reactions occur at the interfaces of the particles generated in the milling and are constantly
renewed.
•Reactions take place at much lower temperatures than would otherwise be required, but must not be
allowed to go too fast or to combust.
•With highly exothermic reactions, diluents such as NaCl are added to reduce the contact between the
components and slow the reactions down.
This technique has been successfully used to produce:
• Fine metal powders, such as Fe, Co, Ni, Cu and Ag, for example,
NiCl2+ 2Na = Ni + 2NaCl, produces 5 nm Ni particles embedded in NaCl.
A top-down milling approach gives particles that are several thousand
times larger.
• Oxides, such as Al2O3, ZrO2, Cr2O3, SnO2 and ZnO, for example,
ZrCl4 + 2CaO = ZrO2+ 2CaCl2.
22
• Sulfides, such as ZnS and CdS, for example, CdCl2+ Na2S = CdS+ NaCl,
produces 4 nm particles of the CdS II–VI semiconductor.

Read Synthesis of nanoparticles by a)Microemulsions method b)Fullerenes

2.8.2 Bottom-Up Methods: Manipulating Atoms and Molecules

The term bottom-up is often used to mean structures that are built from constituent atoms, ions or
molecules or that self-assemble. Many of the techniques covered earlier seen above, i.e. sol–gel,
hydrothermal, combustion, detonation, CVD, ultrasound cavitation etc. have been used to prepare
nano-sized particles.

2.8.3 Synthesis Using Templates

Template methods can used to make nanoparticles and nanowires. There are broadly three main ways
of doing this and these are summarized in a scheme for the formation of one-dimensional structures
in Figure 3.23 below:
• Porous solids and membranes
• Organic and biological templates
• Using a preexisting nanostructure

23
Schematic illustrations showing three different template processes for the synthesis of one-
dimensional inorganic nanostructures: (a) cylindrical micelle, (b) porous membrane and (c)
preexisting nanostructure templates.

In the first method, porous solids that possess nano-sized cavities or channels areimpregnated with a
solution of the reactants so that the cavities are filled. Sufficientheat is then applied for the reaction to
take place within the cavities, thus restrictingthe size of the product. The final step removes the
original template scaffold bydissolving (silica-based scaffolds) or reaction (oxidation of carbon-based
scaffolds).
If the pores of the template scaffold interconnect, then an inverse replica structureof the template will
be formed. If the cavities are discrete, as in some zeolites, forinstance, then nanoparticles result (see
Figure below).

24
 A schematic showing the use of a silica xerogel to form either nanoparticles or a nanostructure of Fe 2O3.

- Porous solids such as silica gels, mesoporous silica and zeolites can be used for the templates.
Mesoporous silica has a long-range order with specificpore sizes and geometry and has been used to
form nanostructures or nanoparticlesof such diverse solids as mesoporous carbon, metal oxides,
sulfides, nitrides, spinels and phosphates. Mesoporous carbon, made by this method, can then itself be
used asa template to form metal oxides.

Read :Choosing a Method at end of chapter

Exercise (1)Answer questions from page 178

Exercise (2) Answer the questions below

25
2.1 Discuss the use of ‘chimie douce’ methods for the synthesis of inorganic solids. What are the
advantages and disadvantages compared with traditional ‘shake ‘n bake’ methods?
2.2 How could ‘chimie douce’ methods be used to prepare the following: LiTiS2, Li0.5CoO2,
BaTiO3,CoFe2O4?
2.3 Solid state reactions of inorganic materials generally require long periods of heating at high
temperatures. Explain the reasons for this and the steps that may be taken to speed up reactions.
2.4 Synthesis of crystalline materials is greatly facilitated if the reaction mixture is homogeneous on
anatomic scale.
(a) Describe some (at least three) of the routes that could be used to synthesis a sample of BaTiO3
powder and compare the advantages/disadvantages of each.
(b) Describe the strategies that can be adopted to synthesis thin films of semiconductor materials
such as CdS or GaAs.
2.5 Synthesis of diamonds traditionally requires very high temperatures and pressures, yet it is now
possible
to synthesis diamonds from the gas phase at sub-ambient pressures. Account for these observations
and discuss the thermodynamic/kinetic factors involved in diamond synthesis.
2.6 Compare the response of crystalline and amorphous silicon to doping with (a) a trivalent and (b) a
pentavalent element.
2.7 Explain why, and how, TiS2 could, in principle, be used as a cathode in lithium cells. Could NiS
be used in a similar way?
2.8 What methods could be used to prepare a film of BaTiO3 on a glass substrate?
2.9 What is the role of the template in zeolite synthesis?

26