Chakravorty, D

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17th University Glass Conference Glass Conferences and Workshops
Summer 6-26-2005
XII, Part 3: Novel properties of glass-metal
nanocomposites
D Chakravorty
Indian Association for the Cultivation of Science
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Chakravorty, D, "XII, Part 3: Novel properties of glass-metal nanocomposites" (2005). 17th University Glass Conference. 14.
https://preserve.lehigh.edu/imi-tll-conferences-17thuniversityglassconference/14
NOVEL PROPERTIES OF  GLASS-METAL 
NANOCOMPOSITES
D.CHAKRAVORTY
Unit on Nano Science and Technology
Indian Association for the Cultivation of Science
Kolkata 700032,India
A c k n o w l e d g m e n t :
S.Basu, P.K.Mukherjee, S.K.Saha, B.N.Pal, A.Dan,
S.Bhattacharya, Supriya Chakraborty
Department of Science and Technology,New Delhi
Indian National Science Academy, New Delhi
An IMI Video Reproduction of Invited Lectures 
from the 17th University Glass Conference
 Glass-Ceramics            Template for nano metal 
growth.
 Silver nanowires in gel derived silica glass          
Single electron tunneling
 Silver nanowires in fluorophlogopite mica glass-
ceramics                              Giant dielectric permittivity
 Metal core-metal oxide shell nanostructure in silica 
glass                                 Interfacial amorphous phase
 Glass-Ceramic- metal nanocomposites                   
Large Relative Humidity Sensitivity
 Silicate glass with nano metal arrays              
Diode- like behaviour
OUTLINE
Growth of Nanocrystalline Metal at
Glass-Crystal Interface
Glass 55SiO2 12ZnO 32.2 Li2O 0.8P2O5
Heat treated
5650C / 1 hr.+ 6300C/3 hr.
Glass- Crystal Composites
Zn2SiO4 + Li4P2O7 : Crystalline 
phase
Li+⇋Ag+(Silver Nitrate at 3100C/8 
hr.
Li+⇋Cu+ (CuCl,5100C/3 hr.)
3Li+⇋Fe3+(FeCl3,300
0C/50 hr)
Reducible ion enriched Glass-Crystal Composite Layer
Reduction in H2
Nanoparticles of Metal at Glass-Crystal Interface
Ion Exchange
Growth of Nanocrystalline Metal at 
Glass-Crystal Interface
Growth of Nanocrystalline Metal at 
Glass-Crystal Interface
Size distribution of Silver Particles 
Synthesized by ion exchange and 
reduction(873K for ½ hr) in a glass 
of Composition 
55SiO2 ,32.2 LiO2,12  ZnO,0.8P2O5
 x
x
x
n lnln/)ln(
2
1
exp
ln2
1
2

















 

Growth of Nanocrystalline Metal at 
Glass-Crystal Interface
50 100 150 200 250 300 350 400
-1
0
4
6
8
10
8.7 nm
6.7 nm
5.7 nm
4.5 nm
11.6 nm
7.8 nm
(o
h
m
 /
 s
q
u
a
re
)
lo
g
 
  
T (K)
Growth of Nanocrystalline Metal at 
Glass-Crystal Interface
Electron Tunnelling between Metal Islands
Neugebauer and Webb model:
:    Tunnelling exponent  (                   )
)/2exp( kTEs 

2/1
2
2








m
s     :  Inter-Grain distance
E    :  Energy to charge a grain
:  Effective barrier height








srr
e
E
11
2 0
2

(Tick and Fehlner 1972)
e    :   electronic charge
r    :   metal grain radius
ε :  dielectric constant of matrix
ε0 :  dielectric permittivity of free 
space

NANOWIRES IN SILICA GEL NANOPORES
GEL SAMPLES HEAT TREATED AT TEMPERATURES 523 TO 
823 K FOR 6 HRS
DIPPED INTO A SOLUTION OF AgNO3
SAMPLES COATED WITH SILVER PASTE ELECTRODES
ELECTRODEPOSITION AT 8 VOLTS
SILVER NANOWIRES IN SILICA GEL
TEM for silica gel heat at 723K/6h.soaked AgNO3 and 
Subjected to electrodiposition
SILVER NANOWIRES IN SILICA GEL
SILVER NANOWIRES WITH BREAK JUNCTION
IN SILICA GEL
BHATTACHARYYA et. al. Appl. Phys. Lett 77 3770 (2000)
GROWTH OF SILVER NANOWIRES IN NANO CHANNELS OF
FLUOROPHLOGOPITE MICA   ( KMg3AlSi3O10F2 )
GLASS COMPOSITION (TYPICAL) :
42 SiO2 15 B2O3 9Al2O3 8 MgO 20 K2O 6KF
HEAT TREATMENT AT 1168 K FOR 2 HRS
ION EXCHANGED IN AgNO3 AT 573 K FOR 24 HRS
ELECTRODEPOSITION WITH 10 VOLTS AT 370 K 
(SILVER PASTE ELECTRODES)
GROWTH OF SILVER NANOWIRES IN NANO 
CHANNELS OFFLUOROPHLOGOPITE MICA
Crystal Channels as Templates 
for Growing Nanowires
GLASS CERAMICS WITH FLUOROPHLOGOPITE MICA
SEM
NANOWIRES IN GLASS CERAMICS 
CONTAINING FLUOROPHLOGOPITE MICA
Experimental value
Specimen heat treated 
at 1163K for 2 hr.and ion 
exchanged at 573 K for 
24 hr.
(nm)
Standard X-ray  data 
for      K Mg 3Al Si 3
O10 F2
(nm)
1.0769 0.996 (001)
0.4666 0.459 (020)
0.375 0.365 (112)
0.304 0.313 (112)
0.250 0.249 (131)
Interplanar spacing  dhkl Specimen
heat treated at 1165 K / 2 hr +ion exchanged at 573 K / 24 hr
NANOWIRES IN GLASS CERAMICS 
CONTAINING FLUOROPHLOGOPITE MICA
GROWTH OF SILVER NANO PARTICLES 
IN GLASS CERAMICS CONTAINING 
FLUORPHLOGOPITE MICA
GLASS COMPOSITION
47 SiO2 15 B2O3 12Al2O3 10 MgO 10 K2O 6KF
SILVER NANOWIRES IN GLASS CERAMICS CONTAINING 
FLUOROPHLOGOPITE MICA
10 K2O
15 K2O
20 K2O
SILVER NANOWIRES IN GLASS CERAMICSCONTAINING 
FLUOROPHLOGOPITE MICA
COLE-
COLE 
DIAGRAM
SCHEMATIC OF BREAK JUNCTIONS
MUKHERJEE AND CHAKRAVORTY J. Mater. Res., 17 3127 (2002)
SILVER NANOWIRES IN MICA CHANNELS– ULTRA HIGH 
DIELECTRIC PERMITTIVITY
2
0)(2/1 lqS
SPACE CHARGE POLARIZATION MODEL FAILS TO EXPLAIN HIGH ε 
MECHANISM IS ELECTRONIC 
INTERRUPTED STRAND MODEL (RICE & BERNASCONI, 1972, PRL)
l0 : STRAND LENGTH  ; l0 = 1287 nm
qs : FERMI THOMAS SCREENING WAVE VECTOR OF CONDUCTION 
ELECTRONS
qs ~ a
-1 FOR METALLIC DENSITIES;  FOR ε ~ 107 AND a = 0.28 nm
IN AGREEMENT WITH MICA CRYSTALLITE DIMENSIONS
COPPER CORE COPPER OXIDE SHELL – INTERFACIAL 
AMORPHOUS PHASE
Preparation :
Terget gel composition 60 CuO. 40 SiO2 (mole%)
Precursors : CuCl2. 2H2O,  Si(OC2H5)4
Sol : 60 ml C2H5OH, 10 ml dist H2O, 1 ml HCL,125 ml Si (OC2H5)4
Reference
Sample
Hot Pressed GEL
REDCN  650oC / 30 Min
Nanosized 
Metal (Cu)
Hot PressedSample
(Metallic 
Conduction)
( =6.8 nm)
OXDN 450oC - 850oC / 30 Min
Cu2O (CuO) coated Cu
Hot PressedSample
CuCu
Cu2O
SPECIMEN REDUCED AT923K / 30MIN + OXIDIZED AT 823K / 
30MIN
COPPER CORE COPPER OXIDE SHELL – INTERFACIAL
AMORPHOUS PHASE
COPPER CORE COPPER OXIDE SHELL-INTERFACIAL 
AMORPHOUS PHASE
Variation of log resistivity as 
a function of inverse
temperature for different samples.
Das/Chakravorty Appl.Phys.Lett. 76 ,1273 (2000)
NORMALIZED PLOTS OF M` AND M``
SPECIMEN REDUCED AT 923K / 30 MIN + OXIDIZED 
AT 723K / 30 MIN
KWW FUNCTION : F(t) = exp[-( t/R)]
COPPER CORE COPPER OXIDE SHELL – INTERFACIAL 
AMORPHOUS PHASE
Macdonald  Basu  Chakravorty , J.Chem. Phys. 122, 241703,(2005)
COPPER CORE COPPER OXIDE SHELL – INTERFACIAL 
AMORPHOUS PHASE
Fe - Fe3O4 - SiO2 Gel  Nanocomposites
Target Composition :55 Fe2O3. 45 SiO2 (mol %)
Soln A :60 ml C2H5OH, 10ml H2O, 23.17 gm  FeCl3
Soln B :90 ml C2H5OH, 15ml H2O, 1 ml HCL
26.2 ml Si(OC2H5)4
Soln. A +    Soln. B
Ref. Sample
1123K / 2hr
Powder Hot Pressed
923K / 5 min
(Metallic Conduction)
2 weeks for gelation 
Redcn in H2 923 K  / ½ hr
Oxdn 573 K  / ½ hr
Powder Hot Pressed
Fe - Fe3O4 - SiO2 Gel  Nanocomposites
Heat treatment
Schedule for
gel powder before
hot pressing
Reduced at 923 K  /  ½ hr
Reduced at 923 K  /  ½ hr
Oxidized at 823 K  /  ½ hr
Reduced at 923 K  /  ½ hr
Oxidized at 1023 K  /  ½ hr
Reduced at 923 K  /  ½ hr
Oxidized at 1123 K  /  ½ hr
Reduced at 923 K  /  ½ hr
Oxidized at 1123 K  /  ½ hr
Reduced at 923 K  /  ½ hr
Oxidized at 1123 K  /  ½ hr
Median
Diameter
X
(nm)
5.3
4.9
4.6
4.4
4.2
4.1
Geometric
Standerd
Deviation
σ
1.4
1.4
1.4
1.4
1.4
1.4
X
Fe-Fe3O4/SiO2 Nanocomposites
Das et al J.Appl.Phys. 914573 (2002)
 4.9 nm
 4.6  nm
★ 4.4  nm
ʬ   4.2  nm
Fe - Fe3O4 - SiO2 Gel  Nanocomposites
speci
men
W
(cV)

(Ao-1)
R
(Ao)
C o
(s–1)

Ref 0.39 0.95 4.7 0.99 1.2x1013 4.9
2 0.08 0.89 4.7 0.99 1.3x1013 23.8
3 0.08 0.86 4.8 0.99 1.2x1013 23.3
4 0.07 0.87 4.9 0.99 1.1x1013 26.1
5 0.06 0.86 4.8 0.99 1.3x1013 31.1
Small polaron Hopping
R
eW
kT
WR
ccc
kTR
p
pp
o
3
1
)
6
(
2
1
4/
)exp()2exp(
)1(
2
2










SILVER / SILICATE GLASS CERAMIC 
NANOCOMPOSITES
COMPOSITION :
10 Na2O, 34 BaO, 34 TiO2,17 B2O3, 5 SiO2
Heat treatment at 843 K and 963 K
Powdered samples ION Exchanged at 583 K / 6 Hrs
Reduction at 573 K / 5 Min.s
SEM Micrograph 
of Glass Ceramic
X Ray Diffractogram 
of Glass Ceramic
Crystalline phases : Na2B4O7 ;  BaTiO3
SILVER / SILICATE GLASS CERAMIC NANOCOMPOSITES
a) TEM of ION Exchanged and reduced Glass Ceramic
b) Electron Diffraction of (a)
SILVER / SILICATE GLASS CERAMIC NANOCOMPOSITES
Histogram of Silver Particle Size
SILVER / SILICATE GLASS CERAMIC NANOCOMPOSITES
Reduction in Hydrogen at 573 K / 5 Min.s
SILVER / SILICATE GLASS CERAMIC NANOCOMPOSITES
3.4 nm
4.6 nm
10.1 nm
13.2 nm
Resistivity vs. Relative Humidity
Pal et al J.Appl.Phys. 93, 4201 (2003)
SILVER / SILICATE GLASS CERAMIC NANOCOMPOSITES
Surface Resistivity vs. T-1/4
Particle Diameter 3.4 nm
SILVER / SILICATE GLASS CERAMIC NANOCOMPOSITES
Current vs. Time
Silver Particle Diameter 10.1 nm
Relative Humidity 85 % 
SILVER / SILICATE GLASS CERAMIC NANOCOMPOSITES
IRON-IRON OXIDE NANO CORE-SHELL 
STRUCTURE
Optical micrograph of film with fractally grown Fe-
Fe3O4 core shell structure
IRON-IRON OXIDE NANO CORE-SHELL 
STRUCTURE
AFM micrograph
IRON-IRON OXIDE NANO CORE-SHELL 
STRUCTURE
TEM of the specimen
IRON-IRON OXIDE NANO CORE-SHELL 
STRUCTURE
TEM of core shell structure
IRON-IRON OXIDE NANO CORE-SHELL 
STRUCTURE
Electron diffraction pattern IRON-IRON OXIDE 
NANO CORE-SHELL STRUCTURE
IRON-IRON OXIDE NANO CORE-SHELL 
STRUCTURE
Surface resistivity as a 
function of temperature
 Reference 
Specimen
O 1 hour oxidation
 2 hour oxidation
 4 hour oxidation
2.2 2.4 2.6 2.8 3.0 3.2 3.4
6
7
8
9
10
11
12
L
o
g

 (
o
h
m
/s
q
u
a
re
)
1000/T
IRON-IRON OXIDE NANO CORE-SHELL 
STRUCTURE
Surface resistivity vs. 
relative humidity
 Reference Specimen
O 1 hour oxidation
 2 hour oxidation
 4 hour oxidation
30 40 50 60 70 80 90 100
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
L
o
g

(o
h
m
/s
q
u
a
re
)
Relative Humidity(%)
Pal et.al. J.Appl.Phys.97,034311(2005)
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
GLASS COMPOSITION : 30 Li2O 12 CaO 3 Al2O3 55 SiO2
ION EXCHANGED IN AgNO3 AT 573 K FOR 11 HRS
ELECTRODEPOSITION AT 600 K, 5 and 10 VOLTS 
FOR 10 HRS
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
TEM
OF SILVER NANO ARRAYS
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
TEM OF NANO ARRAYS 
OF SILVER IN 
SILICATE GLASS
NANO INTERFACES IN GLASS
METAL NANOCOMPOSITES
TEM OF SILICA GEL GLASS WITH COPPER NANO ARRAYS
COMPOSITION : 30Cu(NO3)2 70SiO2
ELETRODEPOSITION VOLTAGE : 5 VOLTS
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
191 K
161 K
138 K
GLASS COMPOSITION
30Li2O 12CaO 3Al2O3 55SiO2
ELECTRO DEPOSITION 
VOLTAGE : 5 VOLTS
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
SCHEMATIC REPRESENTATION OF 
METAL SEMICONDUCTOR 
NANO JUNCTION ARRAYS
DIODE LIKE BEHAVIOUR
SYMMETRICAL NON LINEAR V - I
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
125 K
167 K
208 K
30 LI2O 12CaO 3Al2O3 55SiO2
ELECTRODEPOSITION 
AT 10 VOLTS
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
213 K
238 K
275 K
30Cu(NO3)2 . 70SiO2 GEL
ELETRODEPOSITION 
AT 5 VOLTS
Dan et al J.Appl.Phys. 93,4794 (2003)
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
208 K
265 K
285 K
30Cu(NO3)2 . 70SiO2 GEL
ELETRODEPOSITION 
AT 10 VOLTS
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
DATA FITTED TO 











 1exp0
nkT
eV
II
COMPOSITION
ELECTRO
DEPOSITION
VOLTAGE
I0
(Amp)
n
1 5 0.5 X 10-3 30
1 10 0.2 X 10-3 60
2 5 0.7 X 10-7 42
2 10 0.07 X 10-7 55
NANO INTERFACES IN GLASS METAL NANOCOMPOSITES
TEM OF A NANO INTERFACE 
BETWEEN TWO COPPER PARTICLES
ELECTRODEPOSITION 
VOLTAGE 5 VOLTS
 Silicate glasses can be used as effective 
templates for nanostructure growth
 Glass nanocomposites show novel properties
 New functionalities can be generated by using 
a nanocomposite approach in glasses
CONCLUSIONS
THANK   YOU


XII, Part 3: Novel properties of glass-metal nanocomposites

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XII, Part 3: Novel properties of glass-metal nanocomposites

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