N

NanotechnologyinChemicalEngineering
h l
i Ch i l E i
i
(CHN425)

LL4
4Synthesisofnanomaterials
Synthesis of nanomaterials
(Physical/Chemicalmethods)

byDr.T.Das
DepartmentofChemicalEngineering
p
g
g
IndianInstituteofTechnologyRoorkee,India

SynthesisofnanomaterialsII(Physical methods)

1.
2
2.
3.
4.

ChemicalVapordeposition(CVD)
Electric arc deposition
Electricarcdeposition
Ionbeamtechniques(IonImplantation)
MolecularbeamEpitaxy (MBE)

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
1.

FormationofSiO2onSi(byCVD)

SiO2
Si
2.FormationofGe onSi(byCVD)

GeAs
Ge
Si
RateofdepositionofGe orSiO2
R t l
Ratelaw,reactionmechanismandkinetics
ti
h i
d ki ti

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
1 ChemicalVapordeposition(CVD)(SWCNT/MWCNTsynthesis)
1.
Ch i l V
d
iti (CVD) (SWCNT/MWCNT
th i )

CH4forC(carbondeposition)
SiH4forSi(silicondeposition

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
1. ChemicalVapordeposition(CVD)
1
Ch i l V
d
iti (CVD)
(Produce high quality, high performance solid materials, used
semiconductor industry to produce thin film)
Nanocrystalline films/Single crystalline films are possible
A hybrid method using chemicals in vapour phase
Ease processing/simple instrumentation: used in industry
In this p
process,, the basic is transport
p
of reactant vapour
p
or reactant ggas towards
substrate
At high temperature reactants cracks into different products which diffuse on the
surface undergo chemical reaction at appropriate site,
surface,
site nucleate,
nucleate and grow to form the
desired material film
It is preferable that the reaction occurs at the substrate rather than gas phase
Vapours of desired material may be often pumped into reaction chamber using some
carrier gas

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
1 ChemicalVapordeposition(CVD)
1.
Ch i l V
d
iti (CVD)
Temperature:
p
~ 3001200 oC
Pressure: 100 Pa to 105 Pa are used
The growth rate and film quality depend upon the gas pressure and substrate
temperature
At low temperature growth takes place (it is limited by kinetics of surface reaction)
At intermediate temperature (It is limited by mass transport i.e supply of reacting gases
to the substrate)
At high temperature, growth rate reduces due to desorption of precursors from the
substrate

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example1:(applicationofCVD)
l 1 (
li ti
f CVD)
ManufacturingofSilayer
inMicroelectronicfabrication
Steps(sequences):
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11
11.

Wafer(startingmaterials)
FormationofSiO2onSi(byCVD)
Maskwithpolymerphotoresist
Developphotoresist
Etchandthenremovephotoresist
DopingbyPhosphorousdiffusion
SiO2 etching
SiO2etching
CVD(twofilmsformation)
Mask,etch,stripmask
CVD,mask,Etch,Stripmask
CVD f fi l l
CVDoffinallayer

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
M h i b hi h CVD
MechanismbywhichCVDoccurs:

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
MechanismbywhichCVDoccurs:
1. Mechanism:

(ratekineticsfollownonlinearequationandLangmuirHinshelWood kinetics)

Step-1: SiH4 (g)

SiH2 (g) + H2 (g)

-r"(SiH4) = kg [PSiH4 - PSiH2.PH2 / Kp ] .........(1)

Step-2: SiH2 (g)+ S

SiH2 (g).S

(2)
rAD = kA [PSiH2 . fv - fSiH2 / KSiH2 ] .........(2)

Step-3: SiH2 (g).S

Si + H2 (g)

rs = ks fSiH2 .........(3)

2. Rate limiting
li i i step (step-3):
(
)
rdep = rs = ks fSiH2

.........(4)

3. Expressing fSiH2 in terms of partial pressures:: (from equation-2) and put in equ...4
rAD / kA = 0 and fSiH2 = KSiH2 .PSiH2. fV
-r"SiH2 = rs = ks . fSiH2 = kS. KSiH2 . PSiH2.fV .........(5)
4. Site/surface area balance::
fSiH2 + fV = 1,
5. The rate equation:

KSiH2 .PSiH2. fV + fV = 1 , and fV =

(put fv from equ. 6 in equ.5)

PSiH2
-r"SiH2 = ks .KSiH2 .
1+ KSiH2 .PSiH2

1
1+ KSiH2 .PSiH2

.........(6)

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example2:(applicationofCVD)fabricationoftandemsolarcell
l 2 (
li ti
f CVD)f b i ti
ft d
l
ll
Growth of Germenium (Ge) epitaxial film as an interlayer
between a GaAs layer and a Silicon layer:
The growth of Germenium films can be accomplished by CVD
GeAs
Ge
Si

ElementsofChemicalReactionEngineeringH.S.Fogler,Ch10,701703

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example2:(applicationofCVD)fabricationoftandemsolarcell
l 2 (
li ti
f CVD)f b i ti
ft d
l
ll
Proposedmechanism(LangmuirHinshelwoodtypemechanism):
Gas phase dissociation:

GeCl2 (g) + Cl2 (g) ............(1)

GeCl4 (g)
kA

Adsorption: GeCl2 (g) + S

Adsorption: H2 (g) +2 S

kH

Surface reaction: GeCl2.S + 2H.S

GeCl2. S ............................(2)
2 H.S

..............................(3)

Ge (s) + 2 HCl (g) + 2 S .....(4)

Ratelawforratelimitingstep,assumingstep4asratedeterminingstep
l f
l
d
(5)

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example2:(applicationofCVD)fabricationoftandemsolarcell
l 2 (
li ti
f CVD)f b i ti
ft d
l
ll
Totalfractionalsurfaceareabalance(surfacesitesbalance):
.(6)

ThenetrateofGeCl2adsorptionusingequation(2)and

(7)

Atequilibrium:
WehavethefractionalsurfacecoverageofGeCl2
(8)

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example2:(applicationofCVD)fabricationoftandemsolarcell
l 2 (
li ti
f CVD)f b i ti
ft d
l
ll
ThedissociativeadsorptionofhydrogenonGe surface:
(9)
Atequilibrium:

(10)

(11)
PuttingfGeCl2 andfH insurfacesitebalanceequation(6)andrateofdesorption(6)
Weget,

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example2:(applicationofCVD)fabricationoftandemsolarcell
l 2 (
li ti
f CVD)f b i ti
ft d
l
ll
(12)
( )

TherateofdesorptionofGe (growthofGe films)expressedintermsof

(13)

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
EExample3:(applicationofCVD)SinglelayerormultilayerGraphene
l 3 (
li ti
f CVD) Si l l
ltil
G h
(Supercapacitor,compositematerials,gassensors/transparent
andflexibleelectrodestofabricatetouchscreendisplay)

Singlelayerhoneycomblatticeof
carbonatoms

Graphiteviewedasastackofgraphene
(Multiplelayer)

First Obtained in 2004 by Andre K. Geim and Konstantin S. Novoselov (awarded noble
prize in physics, 2010 for producing, isolating, identifying and characterizing graphene.
used a regular Scotch tape to extract thin layers of graphite from highly pyrolite graphite
(HOPG) and
then transferred these layers to a silicon substrate.
substrate

A. Kumar, Chee Huei Lee, Chap3, Synthesis and biomedical applications of graphene: present and future trends.

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example3:(applicationofCVD)SinglelayerormultilayerGraphene
l 3 (
li ti
f CVD) Si l l
ltil
G h
A.MethodofSynthesis:

Most promising, inexpensive, and feasible method for single layer graphene production
Graphene will grown on Cu, Ni, Pd, Ru, Ir (acts as substrate or as catalyst )
Flowing carbon source (CH4) for 510 min., and reactant gases at high temperature
(~1000 oC) for nucleation of graphene
Application: transparent electrode applications

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example3:(applicationofCVD)SinglelayerormultilayerGraphene
l 3 (
li ti
f CVD) Si l l
ltil
G h
Parameters:(affectssinglelayer/Multilayerofgraphene)
Temperature, gas composition, gas flow rate, deposition time and heating rate and
cooling rate.
CH4 is important to produce single and few layer graphene
Using concentrated methane will lead to multilayers of graphene (>5 layers)
Cooling rate affects the thickness and amount of defects of graphene
A fast coolingg p
process can suppress
pp
the amount of p
precipitated
p
C,, leadingg to single
g of
few layers graphene
A moderate cooling rate of 10oC/S is optimum for thin layer graphene.

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example3:(applicationofCVD)SinglelayerofGraphene
l 3 (
li ti
f CVD) Si l l
fG h
B.SynthesisofGraphene (Cuasacatalysts):
Cutogrowsinglelayergraphene andtransfergraphene ontoaninsulatingsubstratefor
devicefabricationandtesting
Cu foil with native oxide
Native Cu oxide is reduced while Cu
develops grains on the surface after
annealing at high temperature (1000oC/30
min) in H2 environment(to remove native
oxide layer)
The exposure of the Cu foil to CH4/H2
atmosphere
t
h
att 1000oC
1000 C (30 min)
i ) leading
l di to
t
the nucleation of graphene islands
g
of the ggraphene
p
flakes and
Enlargement
coalscene of graphene domains with
different lattice orientation

SynthesisofnanomaterialsII(Physical/Chemicalmethods)
E
Example3:(applicationofCVD)SinglelayerofGraphene
l 3 (
li ti
f CVD) Si l l
fG h
C.TransferofGraphene:
GrownonCufoil
Transferontodesiredinsulatingsubstrates,
suchaspolymericfoils(PET,glassandSiO2/Si.
Or
Or
onspincoatedathinpolymericlayerpoly
methylmethacrylate(PMMA)or
polydimethylsiloxane (PDMS).
CufoiliseachawaybyFeCl3solutionor
HCL/HNO3/Fe(NO3)3/CuCl2/(NH4)2SO8.
Dryingthepolymericfilm
Transferthegraphene todesiredtarget
substrate
DissolvingPMMAusingbyacetoneor
chloroform.

Thanks for your attention

Thanksforyourattention