Soft chemical routes for synthesis of

nanomaterials

A. K. Tyagi

Chemistry Division
Bhabha Atomic Research Centre
Mumbai, 400 085, India

Email: aktyagi@barc.gov.in
 Plan of the talk

• General introduction

• Common soft chemical routes

• Size and shape control

• Some specific examples of chemical sensors

• Conclusions
Why some compounds do not exist in nature or are difficult to
synthesize in laboratory ?

Thermodynamic
Barriers Crystallographic
Kinetic

There are some chemical bonding constraints.

There are ways to over come these barriers

Soft-chemical methods are the low energy chemical
processes for synthesis of materials.

Soft-chemical methods and solution methods -

(Are they one and the same ?)

All the solution methods are soft-chemical methods but all the
soft-chemical methods are not solution method.

Solution methods is a sub-group of soft-chemical methods.

Nature makes most of the materials at ambient or slightly above

ambient conditions.
 Electro-ceramics

Multi-ferroic materials

Spintronics materials

Nanomaterials

Optical material

For societal

applications
Preparation of Nanocrystalline materials
A physicist’s approach: Top down
Laser ablation
Vacuum evaporation
High energy ball milling
Inert gas condensation
Sputtering
A chemist’s approach: Bottom up
Combustion
Solid state metathesis
Hydrothermal
Solid state pyrolytic reaction
Self-organization, Template method
Sonochemical process
Micelle assisted synthesis

Biological route: Fungus, Bacteria

 Combustion reaction

Oxidants:
Metal nitrates, metal oxynitrates
Reductants or Fuels:
Hydrazine : N2H4
Urea : NH2CONH2
Glycine : NH2CH2COOH
Citric acid : C6H7O8
HMTA : (CH2)6N4
Ascorbic acid : C6H8O6
Malonic acid : C3H4O4
DABCO : C6H12N2
• Low ignition temperature & good complexing agent

Disadvantage: Poor or no shape control

 Combustion synthesis of nano-ceramics
Oxidant (metal nitrate) and a Fuel (Glycine, Citric acid etc.)

Step I : Formation of viscous liquid/gel Step II : Combustion/Auto-ignition

precursor of the precursor

RT 200-250oC
 Shape control of nanomaterials
1. Solution-Based Synthesis
• Solvothermal Chemical Synthesis
• Template-Based Synthesis (Hard or Soft)
• Template free synthesis
• Shape directing agents

2. Gas-Phase Synthesis
• Vapor-Liquid-Solid (VLS) Method
• Laser ablation
• PVD and CVD (LPCVD, MOCVD)
• Vapor-Solid (VS) Method
• Flux - Assisted Growth
We have synthesised ZnO and TiO2 based nanorods by:
1.Solvothermal Chemical Synthesis
2.PVD method and
3.Ag nanorod@ZnO film by Template method
Nano-crystalline ceria by citrate-nitrate combustion: Size control

TG/DTA

TEM

X-ray line broadening

Flame temperature
(a). Fuel-deficient increases as amount
(b). Stoichiometric of fuel increases
(c). Fuel-rich
(a) Fuel-deficient : 4-12 nm
Surface area : 127 m2/g
Mater. Res. Bull. 36 (2001) 2711
(b). Stoichiometric: 6-28 nm J. Nanosci. Nanotech. 6 (2006) 209
Ce0.55Y0.45O1.775 with superior powder properties by citrate-nitrate
combustion
Crystallite size: 6 nm, Surface area 140 m2/g, Soft-agglomerates (~ 1 μm)
Small angle X –ray scattering studies TEM

SEM image of Ce0.55Y0.45O1.775

sintered at 1400oC / 2h

* Density : 99% of Th.D.

* Avg. grain size  1.0 m
* A step towards Nano-ionics
J. Mater. Res. 19 (2004) 474
Porosity creation : LSM- a case study

20 % Graphite as a pore former

(Sintered at 1300 oC)

20 % Starch as a pore former

(Sintered at 1300 oC)

Four Probe DC Conductivity

Dense: 128 Scm-1
Porous: 58 Scm-1
 Synthesis of YCrO3 and YCrO4 by glycine-nitrate combustion

CrO6 CrO4

YO8

YCrO3 (Perovskite) YCrO4 (Zircon)

1:1.66 (stoichiometric) 1:0.5 (fuel-deficient)

a = 5.5248(1) Å
a = 7.1030(2) Å
b = 7.5408(2) Å
c = 6.2440 (2) Å
c = 5.2425(1) Å
 Intensity (a.u.)

(1 0 1)

20
(0 1 1)
(1 0 1)
(0 2 0)

(2 0 0) (1 1 1)

30
(2 0 0)
(1 1 2) (0 0 2) (1 2 1)
(2 2 0) (2 1 0)

(2 0 2) (0 3 1)
(1 1 2)

40
(3 0 1) (2 2 0)
(0 2 2)
(1 3 1)

(1 0 3)
(2 0 2)
(3 2 1) (0 4 0)
(3 1 2) (2 3 0)

50
(2 1 2)
(4 0 0)

2(degrees)
(3 1 1)
(1 1 3)
(4 2 0)
(3 2 1)
(3 0 3) (2 4 0)

60
(0 4 2)
(3 3 2) (1 2 3)

(2 0 4) (3 3 1)
(5 0 1)
YCrO4
YCrO3

(4 3 1) (4 1 0)
70

(2 4 2)
(4 1 3)
(0 0 4)
(5 1 2)
Glycine-Nitrate Combustion for YCrO3 and YCrO4

ratio

ratio
1675oC
(1:1.66)

(1:0.50)
No Flame
Flame temp.
Stoichiometric

Fuel-deficient
 YCrO3 (Multi-functional material): Difficult to synthesize

Glycine-nitrate method: Facile route

YCrO3 combustion route 100Hz
1kHz
5 10000 100Hz
1.2x10 1kHz 10kHz
10kHz
8000 50kHz
100kHz
50kHz
1MHz
100kHz
5 6000
1.0x10 1MHz

'
4000

4
8.0x10 2000

0
300 400 500 600
T
4
6.0x10

'
4
4.0x10

4
2.0x10

0.0
300 400 500 600

T (K)

HRTEM : onion-like rings SEM

0.80 Dielectric data
1.4
0.67 10K
ZFC
130K
FC 0.53
1.2
0.40

1.0 0.27 (Crystallite Size: 36 nm;

M (emu/g)

0.13
M (emu/g)

0.8 0.00 Surface area: 17 m2/g)

-0.13
0.6
-0.27

-0.40
0.4
-0.53

0.2 -0.67
0 50 100 150 200 250 300
-10000 -5000 0 5000 10000
T (K)
H (Oe)
Nanotechnology
Antiferromagnetic (TN=141 K) 18 (2007) 155706
with weak ferromagnetism
 Nano-crystalline HoCrO4: Challenging synthesis
Glycine in Fuel –deficient ratio 1:0.5

60 FC 500 Oe
FC 1000 Oe
ZFC 500 Oe
50 ZFC 1000 Oe
12

40
M (emu/g)

10
 (Oe mol emu )
-1

8
30
6

20
-1

2
10
60 80 100 120 140
T (K)

0
0 20 40 60 80 100
T (K)
Nano-crystalline HoCrO4 is relatively soft magnet (Tc ~ 18 K)
as compared to the bulk
J. Nanosci Nanotech 9 (2009) 501
 Novel synthesis of Ce3+ based oxides

Challenge: To develop a facile route for Ce(III) stabilization

Two steps synthesis:

(i) Combustion method, followed by
(ii) Vacuum heating in reducing atmosphere
 CeCrO3 : A multi-functional material

Band Gap : 3.04eV, Crystallite size: 42 nm 10kHz

20kHz
800
50kHz
100kHz
200kHz
700 1MHz

600

'
500

400

300

300 350 400 450 500 550 600

T (K)
TEM

•Relaxor ferroelectricity
•Antiferromagnetism
•Potential visible light driven
photocatalyst

J. Phys. Chem. C 113 (2009) 12663

 La1-xCexCrO3 (0.0 ≤ x ≤ 1.0) : A new series of solid solutions
with tunable magnetic and optical properties

3
234 Vol (Å )
cell vol (Å )

Ideal solid solution formation

3

233

232
(a)

3.25 10 20 30 40 50 60 70 80 90 100
Tunable band gap from
Band gap (eV)

3.20 Band Gap (eV)

3.15 3.21eV to 3.04 eV
3.10
3.05
(b)
3.00
285 10 20 30 40 50 60 70 80 90 100
Neel temp TN(K)

280 TN (K)
275 Linear trend of TN from
270
265
282 K to 257 K
260 (c)
255
10 20 30 40 50 60 70 80 90 100
3+
Ce (mol %)
Inorganic Chemistry 48 (2009) 11691
 Agglomeration: How to avoid it ?
(Doped ceria - A case study)

Ce(NO3)3 + RE(NO3)3 Ce(NO3)3 + RE(NO3)3

H2O2 Solution Solution

NaOH NaOH

Precipitate Precipitate

Calcined Calcined
SDC
SDCN
GDC
GDCN
 XRD patterns of doped ceria

Single phasic product

11nm GDC

Peak broadening
Intensity (a.u)

GDCN
17nm
SDC>SDCN
GDC>GDCN
SDC
10nm

16nm SDCN Crystallite Size

20 30 40 50 60 70
SDC < SDCN
2 
GDC < GDCN

J. Mater. Res. 24 (2009) 2845 H2O2 has effect on crystallite size

 Comparison of particle sizes . . .

HRTEM

Histogram

SDCN (median ≈15nm) SDC (median ≈7nm)

 Raman Spectra uncovers the fact...
Before calcination After calcination

Breakdown of –O-O- linkage

Presence of -O-O- linkage
 Sol-gel method

M Si(OR)4 + n B(OR)3 + p Al(OR)3 + q Ti(OR)4 + r NaOR

Complexation Hydrolysis

Sintering Condensation

(SimBnAlpTiqNar)Ox
 Solid State Metathesis
AX + BY AB + XY
LiCoO2 + LaOCl LaCoO3 +LiCl
Li2TiO3 + PbCl2 PbTiO3 + 2LiCl
Li2MnO3 + ACl2 AMnO3 + 2LiCl
(A = Ca, Sr, Ba)
Li4MWO6 + 2 SrCl2 Sr2MWO6+ 4LiCl
(M = Mn, Fe, Ni)

Synthon approach, Double exchange reactions.

Driving force is the stability of alkali-metal chlorides.

 Hydrothermal Method

Advantages of this method

1. Defect free materials

2. Highly crystalline
3. Can be used for making nanoparticles
4. Nano-tube, Nano-wire, Nanorod

You need some soluble salts

 HYDROTHERMAL SYNTHESIS
What is Hydrothermal
Synthesis?
Synthesis at Moderate
Temperature and Pressure

Procedure
-Combining reactants
(Salts of Zn, Mn and Fe etc. Teflon
And NaOH, KOH, NH4OH)
- Transfer to Teflon lined
autoclave
-Heat at 100-200°C ~ 1, 2 days
Stainless steel
-Centrifgue and Wash materials
(Synthesis of Room Temperature Ferromagnetic
Mn or Fe doped ZnO)

ZnO (2 at. %Mn):ZnO Fe 5%:ZnO

Characterization:
1. Power X-ray diffraction
2. HRTEM, SAED
3. VSM
 1-D titanate nanorods / Tubes
2.2
A100

Hydrothermal method 2.0

1.8
R300
R200
R100
used for preparation of 1.6 A300
A200

Intensity (a.u)
nanorods of titanates 1.4

1.2
Anatase Bulk

using anatase and rutile 1.0

TiO2 in the presence of 0.8

0.6

NaOH. 0.4

0.2

0.0
200 300 400 500 600
Wavelength (nm)
 Solid state pyrolitic reaction
Zn0.94Mn0.03Li0.01O Nano-particles (30-35 nm)

 Acetates of Zn, Mn, and Li and NaHCO3 heated at

160oC for 2 h
 The particles have wurtzite structure.
 The obtained precursor powders were further
Zn0.96Mn0.03Li0.01O treated with AOT at 400oC for 1h

0.16
0.006
Zn0.97Mn0.03O+AOT
0.12 ZFC, H = 50 Oe
Zn0.96Mn0.03Li0.01O+AOT RT
0.08 ZnO+AOT FC, H = 50 Oe
0.005

M (emu/g)
0.04
M(emu/g)

0.00
0.004
-0.04 Zn0.96Mn0.03Li0.01O + AOT
Zn0.96Mn0.03Li0.01O + AOT -0.08
0.003
-0.12

-0.16 100 150 200 250 300

-9000 -6000 -3000 0 3000 6000 9000

H(Oe)
Temperature (K)

J. Cryst. Growth 307 (2007) 315

 Templated Synthesis nanomaterials
Soft Templates
 Soft template method is based on process of self assembly.
Common soft templates: Surfactants, colloidal particles, shape-directing
molecules, oligomers, ‘‘soap bubbles”, and colloids.
 The templates provide wide range of manipulation of shapes.
 Removal of soft template requires
less vigorous process. Micelle as Template

Silver nanoparticles
synthesized using block
copolymer template
 Templated Synthesis of nanomaterials
Hard Templates
 Nano pores / channels of a porous solid (hard template) are used as nano-
reactors (such as MCM, ZSM, KIT, PS, PAA).
 Growth of the product is restricted by the walls of the template pores.
 After synthesis of material, template framework is selectively removed.
 Removal of template involves rigorous process and at times
destroys/modifies the product.

•Template formed by anodization of Al

using Pt as cathode and oxalic acid as
Bi2Te3 electrolyte.
nanowir
e
• Pore filling via various physical and
Unfille
Anodized d pore chemical deposition methods such as
alumina alumina electrodeposition, high pressure
templat
template e injection.
( 90% filling achieved)
 Template Assisted Synthesis
(Mn doped ZnO based spintronics nanomaterials)
SEM TEM Polystyrene beads (630nm) act as the
unique template.
 Dried polystyrene beads are soaked in aqueous
solution of Zn2+ and Mn2+.
 The templates are then removed by heating @ 900C.

• Single phasic Mn doped ZnO (25-30nm)

• Wurtzite structures
• Flower-like morphology.
1.6 Zn0.95Mn0.05O-PS-900-5m RT 0.65

1.2 ZnO-PS-900-5m
0.60
0.8

0.4
0.55
ZFC
Crystal Growth &
M(emu/g)

M(emu/g)

FC
0.0 0.50
-0.4

-0.8
0.45 Design
-1.2 0.40 9 (2009) 1944
-1.6
0.35
-8000 -4000 0 4000 8000 0 50 100 150 200 250 300
H(Oe) Temperature (K)
CNT as Hard Template for TiO2 nanorods
Synthesis of TiO2 Core - CNT Shell
Objective: Use of CNT template for the synthesis of
TiO2@CNT core shell structure.

Results: (a) Core shell structure is formed initially.

The core comes out with ageing as is evident from
color change and the successive SEM images.
(b) Phase pure anatase TiO2 rods are formed as
evidenced from XRD and Raman.

Mechanism:

Ti(OR)4+ 2(CH2OH)2 (solvent)  Ti(OH)4 +

2(CH2OR)2 {R= (CH3)2CH.}
 CNT as Hard Template
Synthesis of β -In2S3 nanorods by ultrasonication of
(In(S2COMe)3) and CNT

(a) High thermal stability of the encapsulated phase.

(b) Nanorods ranging between 14-17nm in diameter

(c) Due to their stability at higher temperature, it was possible to

get rid of optically active defects undesirable for PV
applications.

PL spectrum of (1) encapsulated In2S3

nanorods and (2) In2S3 nanoparticles

TEM image of encapsulated In2S3 nanorods.

Inset: corresponding SAED pattern exhibiting
diffused concentric rings.
Pristine ZnO Zn0.97Co0.03O Zn0.95Co0.05O

1D morphology
Stabilization after
Li substitution
in ZnO (template free)

Zn acetate, Co acetate,
Li acetate heated
in try-octylamine
at 320 oC. Zn0.90Co0.05Li0.10O
Zn0.90Li0.10O
Crystal Growth & Design 9 (2009) 4450
First principle theoretical modeling (DFT) Magnetization data at RT
(Clas Persson, RIT, Stockholm)
ZnO
(a) Zn0.97Co0.03O (b) Zn0.91Co0.03Li0.06O Zn0.90Li0.10O
Zn0.97Co0.03O
Demonstrating strong relaxation Zn0.95Co0.05O
effects due to presence of Li substitutional Zn0.85Co0.05Li0.10O
Dopants
 Preparation of dispersible nano-materials: Solvo-thermal
method (A case study of ZnGa2O4:Ln3+)

Zn2+ Zn2+ Ga3+

Ga3+ HOH2C-CH2OH D = 2.9 Å

Zn2+
Zn Zn2+
Ga3+ Ga3+
3+
Ga3+
NH2CONH2 / H2O, 120 C
Zn2+ Ga
2+ 2+
Zn2+ Zn Zn

50 nm

Kilocounts persecond
30

20

10
0 2500 5000 7500
Time (seconds)

Emission spectrum of 5% Eu3+-ZnGa2O4 coated with oleic acid and dispersed in

Chloroform (λex = 320 nm). Adjoining Fig shows intensity of scattered light Vs. Time

J. Nanosci. & Nanotech 8 (2008) 5776

 CePO4:Ln (Tb3+ and Dy3+) nano-leaves dispersible
in methanol and water

3+
Ce3+ Ce3+ Ce NH4H2PO4 HOCH2-CH2OH
3+
Ce3+ Ce3+ Ce
Ce3+ Ce3+ Tb
3+ 120 C

CePO4:Tb nanoparticles capped

with ethylene glycol
Ener gy
Ener gy t r ansf er 5
H6
t r ansf er 5
5
D0
L7
5
5D L9
3/2 5
G5
TEM 5

5
G6

D3
4
F9/2 5
D4
Energy

6
H11/2 0
1
2
20 nm 6
H13/2
2F
3
4 7F
J
7/2 5
6
H15/2 2F 6
5/2

Dy3+ Ce3+ Tb3+

nm
Crystal Growth & Design 920 (2009) 2541 Energy Transfer Scheme
CdSe nanocrystals

Peng, X. Adv. Mater. 15 (2003) 15

 Sonochemical synthesis of nanocrystalline In2O3

In(OH)3 TEM
In(OEt)3 + CTAB
pH =10

2In(OH)3 In2O3 + 3H2O

TEM
Average Size In(OH)3 nanocubes
~ 9 nm 30-35 nm

J. Phys. Chem. C
112 (2008) 6781
In2O3
Niobates and Tantalates in Nanoform: Very scantily reported
(MNbO3 where M = Na, K, Li – A case study)
Aqs.soln MNO3 Aq. Soln of Nb-
Nb2O5 in HNO3 tartarate complex

>7 mol HF 48-50

h in water bath

[NbF7]-2 /[NbOF5]-2
White ppt.
1) Add > 4M (NH4)2C2O4
2) Dilute ammonia
Conc.HNO3
White Precipitate
Clear solution
Filtered and washed
with 5% ammonia
Evaporated at ~2000 C
to dryness
Nb2O5·nH2O
Precursor
1) 2M aqueous
tartaric acid(20%)
2) H2O2 (2-5M%) Calcined at 7000C/2 h

Nb-taratarate
Perovskite MNbO3
complex solution
 Preparation of metal nanoparticles
(A case study of nanocrystalline – Pb)

Nano-crystalline Pb was synthesized by a polyol method.

Lead acetate + Glycol heated at 160oC.
Glycol served as a solvent as well as reducing agent.

Particle size of Pb (40 nm) was smaller than its penetration

depth (83 nm).
Tc of Nano-lead was 7.2 K
(No change compared to value of bulk sample).
Hc of Nano-lead was found to be 2000 Oe
(800 Oe for bulk sample).

Physica C 468 (2008) 944

 Thin Films of nanomaterials
ink jet printed highly (002) axis oriented ZnO film on Si

1 pass 1time dried at 180 heated at 500 15 min.

1 pass 2 times dried at 180 heated at 500 15 min. after each pass

1 pass 3 times dried at 180 heated at 500 15 min. after each pass

1 pass 3 times dried at 180 heated at 500 15 min. only once finally
Intensity (a.u)

30 35 40 45 50 55 60

Best oriented
2

0.00004
Film of Co2%:ZnO

RT
Polyimide
0.00002
M(emu)

0.00000

-0.00002
Silicon
-0.00004

-10000 -5000 0 5000 10000

H(Oe)
Different patterns printed
M vs. H at RT shows
on different substrates
ferromagnetism
Preparation of fluoride based nanomaterials: Under reported

Doped GdF3 nanoparticles: Potential bio-sensor materials

(210)
Synthetic Procedure

(112)
(111)

(131)
(020)

(321)
(400)
(121)
(d)

Intesity (a.u.)
(c)

(b)

(a)

20 40 60

2(degrees)

XRD pattern of (a) GdF3, (b) GdF3: Eu3+,

(c) GdF3: Tb3+, (d) GdF3: Eu3+,Tb3+

HRTEM image of GdF3: Tb3+ nanoparticles

Collaborator: Radiation Biology Division, BARC

Uptake studies on GdF3 nanoparticles for breast cancer detection

First reading
100 second reading Fluorescence intensity of MCF-7 cells labeled
with nanoparticles coated with EG (Sample
80
A), Oleic acid (Sample B) and silica (Sample
Fluorescence intensity (a.u.)

60
C).
40

20
Magnitude of fluorescence intensity
dependent on modifying agent
0
SampleA SampleB SampleC

stock Nanoparicles solutios

a. EG b. Oleic acid c. Silica

Confocal microscopy of human breast cancer (MCF-7) cells after uptake

of nanoparticles modified with (a) Ethylene Glycol (b) Oleic acid (c)
Silica ; Scale: 10 µm
ACS Nano (Submitted)
 Silver nanoparticle based sensor for Pb2+ ions
AgNO3 in Stir, 140 oC, 1 h; Cool, centrifuge + R6G
ethylene wash with ethanol and acetone
glycol &
polyvinylpyr
olidone
Ag(NP) - R6G
(111)

(200)

Ag (NP)

(220)

30 35 40 45 50 55 60 65 70
2

XRD TEM Luminescence

Pb2+(aq) Linear
Fluorescence
in solution Proportion
to Pb2+ conc

Lowest level detected = 50 ng / mL of Pb2+ ions

Tolerance to Na+, K+, Mg2+, Ca2+, Sr2+, Cu2+, Co2+, Ni2+, Zn2+, Al3+

Interference from Fe2+ Reduced significantly using a suitable masking agent

 Isolation of metastable phases: Role of synthesis

A schematic representation 1 Conventional solid-state method

2 Combustion method
3 Oxidation of Ce2 Zr2O7

CeO2 + ZrO2 Ce2Zr2O8 -K

Ce2Zr2O7 Ce2Zr2O7.5 Ceria rich &
Zirconia rich
phases
Energy (a.u.)

1 Reaction parameters

Chemistry of Materials, 29 (2009) 5848

 Conclusions

A wide variety of methods for materials synthesis are available.

The selection depends on the requirement.
Soft-chemical routes are going to play important role.
Metastable phases are the materials of the future.
Scaling up of the synthesis is a challenge.

Nano-materials synthesis is a big scientific-art

• Patience
• Some imagination
• Never give up attitude
• Some aggressiveness
There is no compound, which can't be synthesized
 Thanks to the organizers

Thanks for your kind attention!