ELECTROLUMINESCENCE

IN
NANOCRYSTALS
AND
NANOCOMPOSITS
Meera Ramrakhiani
Department of Post-Graduate Studies and Research
in Physics and Electronics
Rani Durgavati University , Jabalpur
1

Introduction

Nanometer sized semiconductor clusters are
representative of a state of matter intermediate
between molecules and bulk matter.

This new class of material shows a number of
striking effects such as surface effect, size
quantization, lattice contraction, unusual
fluorescence and enhanced oscillator strength,
which are potentially useful for technological
applications.
2


Semiconductor nanocrystals exhibit many

unique properties, which are promising for the
improvement of electroluminescence devices.

1st: the color of emission can be tuned by varying

the size of the particle, while their chemical
properties remain nearly the same.
2nd: high fluorescence quantum yield and
photochemical stability can be achieved by careful
modification of nanocrystal surface and this may
improve the efficiency of the device.
3rd: oscillator strength is enhanced in nanocrystals
due to modified density of states.
3


The hybridization of organic and inorganic

semiconductors is expected not only to permit
wide range selection of emitter and carrier
transport materials, but also provide a new
approach to construct high performance EL
devices
taking
advantage
of
high
photoluminescence efficiency of organic
materials and high carrier density and low
resistivity of inorganic semiconductors.

The incorporation of nanocrystals in polymer is
expected to increase the life of the device and
enhance the brightness of emission.
4


The study electroluminescence of nanocrystals

as well as their nanocomposites with polymers
is described here.

Undoped and doped II-VI semiconductor
nanocrystals and their nanocomposites in
polymers have been prepared by chemical
route.

The samples have been characterized by SEM,
TEM, AFM, XRD and/or optical absorption
and
photoluminescence
and
their
electroluminescence has been investigated.
5

Preparation of samples

In our laboratory, following methods has
been used for preparation of nanocrystals:
a. Chemical precipitation with capping
agent
b. Organometallic precursor (at low
temperature)
c. Chemical capping method
6

Chemical Precipitation With Capping Agent

Nanocrystals of CdS and ZnS doped with Mn, Ag or
Cu are synthesized by chemical precipitation method
using mercaptoethenol as capping agent.

In 0.01M solutions of CdCl2 or ZnCl2 and Na2S was
added in presence of different concentrations of
metrcaptoethenol.

CuCl, MnCl2 or AgCl was mixed in starting solution
for doping.

Chemical reaction gave CdS or ZnS with proper
doping.

The resulting precipitate was washed, centrifuged and
then air dried to obtain nanocrystalline powder.
7

0.01M (aq) ZnCl2

Add 0.01M (aq) C2H5OSH dropwise

Add 0.01M (aq) Na2S dropwise

Kept for 24 hours

.
Washed 3 times

Centrifuged 30 min at 3500 rpm.

Spread on the glass substrate.

Powder ZnS nanoparticles

8

0.01 M Sol
0.01 M Sol

0.01 M Sol

Organometallic Precursor (at Low Temperature)

The CdS nanocrystals of various sizes were prepared by single
source organometallic precursor.

Solution A was prepared by dissolving 36 mg cadmium chloride
(CdCl2) and 12 mg thiourea into a 30 ml ethanol in a flask under
magnetic stirring at 60C in an oil bath.

Solution B was prepared by dissolving 10 mg Sodium Hydroxide
(NaOH) in 10 ml ethanol.

Solution A and B were mixed and stirred at 60C.

In the beginning a white solution was obtained which gradually
become transparent and the colour changed from white to greenyellow.

Nanocrystalline CdS samples were extracted from the flask at
different reaction times of 20 - 90 minutes.

These samples were then centrifuged and washed with acetone and
dried to obtain nanocrystalline CdS powder.
10

Chemical Capping Method

CdSe nanocrystals have been prepared by this method.

Aqueous solutions of cadmium acetate and
mercaptoacitic acid were prepared with adjusting proper
pH as 10.

The solutions were deaeraced with N2 bubbling for 30
minutes and then sodium selenosulfite solution was
mixed.

2 propanol was added drop-wise while stirring the
mixture till it becomes turbid.

The precipitate was separated by centrifuge and dried
to get powder.

Different concentration of mercaptoacitic acid gave
nanoparticles of various sizes.
11

Nanocrystal-polymer composites of ZnS-PVK, CdSPVK, ZnS/PVA and CdS-PVA have been prepared
with different loading of nanocrystals.

The polymer granules of PVK or PVA were
dissolved in dimethyl farmamide (DMF). Then
proper amount of zinc or cadmium acetate was added
to it and stirred for 30 minutes and concentrated to
reduce the solution volume to half of the initial
volume.

To this clear solution, H2S was passed for a few
seconds and then degassed with nitrogen.

Then the dense liquid was transferred to glass slides
and allowed to dry for 24 hours. This gave optically
12
clear films of nanocomposites.


CdSe-PVA polymer nanocomposite films were

prepared by reacting cadmium chloride with sodium
selenosulfite (Na2SeSO3) in polyvinyl alcohol (PVA)
solution at proper pH.

CdCl2 was dissolved in distilled water to obtained 0.10
M solution.

20 ml PVA solution was taken and 1.05 ml of cadmium
chloride solution was added with constant stirring.

Ammonia solution was used to adjust pH value to
about 10 and then 1ml of diluted sodium selenosulfite
(0.1M) was introduced.

The mixture was stirred for 3 hours to obtain a red
solution.

The solution was cast on a glass substrate; upon solvent
evaporation, nanocomposite films were obtained.

Various samples were prepared by changing Cd:Se
13
ratio.

Characterization

The samples were characterized by Scanning
Electron Microscope (SEM), Atomic Force
Microscope (AFM), transmission electron
microscope (TEM) and x-ray diffraction (XRD).

UV-VIS absorption spectra of the samples have
been recorded by Perkin Elmer Lembda-12
spectrometer.

PL Studies have been carried out by exciting
with monochromatic light from a UV lamp or
mercury lamp and also using a filter. PL spectra
were obtained by using a monochromator.
14


The change in colour of samples has been observed

by changing the nanoparticle size by varying
preparation conditions.

Small particles

Largerer particles

Large particles

CdSe nanoparticles prepared at different pH

15

a) Morphological studies

The morphology of the sample is seen by
SEM, TEM and AFM images.

AFM of ZnS nanoparticles

prepared by chemical
precipitation method

In nanocrystalline powder

specimens, agglomeration of
16
particles is observed.

SEM of ZnS Nanoparticles

(By chemical bath deposition - particle size: 23nm)

17

SEM image of clusters of CdS nanoparticles onto

plastic substrate (particle size: 26 nm)
18

TEM image of nanocrystalline ZnS

19

Percentage( %)

45
40
35
30
25
20
15
10
5
0
8

10

11

12

14

Particle size (nm)

TEM micrograph of
CdSe/PVA nanocomposite

Particle size distribution

It is difficult to determine individual particle size

since the particles are clustered together.

The average particle sizes were in the range of 10-12
20
nm.

b) X-ray diffraction studies

The
XRD
studies
indicate
that
the
nanocrystalline powder
specimens of ZnS are
cubic in nature having
zinc-blende structure.

For all the samples
three
peaks
are
observed
corresponding
to
diffraction from (111),
(220) and (311) planes.

XRD of ZnS nanoparticles prepared by

21
chemical precipitation method with different
capping agent concentrations


The broadening of peaks is indicative of

small particle size. The sizes have been
computed by using Dubey-Scherrer
formula D=k/Cos .
where k is instrumental constant, is
wavelength of x-rays, is width of the
peak and is Bragg angle.

The sizes have been obtained in the
range of 2 to 10 nm.
22

XRD for Mn doped and undoped nanocrystals

Mn doping causes broadening of the XRD

peaks; but other methods do not show smaller
23
particle size.


The XRD pattern of CdS can

be consistently indexed on the
basis of the hexagonal, wurtzite
structure with lattice constant a
= 4.121, c = 6.682, in which the
six prominent peaks at 2 values
of 24.4, 26.7, 28.4, 44, 47.8
and 51.9 angles corresponds to
the reflections at (100), (002),
(101), (220) (103) and (112)
planes.

The weak peak due to (102)
plane was also observed.

In case of CdS nanoparticles,
size increases with increasing
reaction time.

XRD of CdS nanocrystals prepared by

organometallic precursor method with
diff. reaction time 24

10 mmol
9 mmol
8 mmol
7 mmol
20

25

30

35

40

45

50

55

60
6 mmol

2 Theta

XRD of CdSe nanocrystals prepared by different capping agent

concentrationsn (XRD indicate hexagonal phase)

25


It is observed that in case of powder

specimens, smaller particles are
obtained by increasing capping agent
concentration.

In case of samples prepared by
organometallic precursor technique,
the crystal size increases with
increasing reaction time period.

26


In nanocrystal /polymer composites, XRD

shows halo due to amorphous polymer and
peaks superimposed on it due to the
nanocrystallites.

CdSe as well as its polymer composite and
CdS/PVA composite have found to contain
hexagonal crystals.

The lattice constants have been found in
close agreement with the standard ones.
27

PVA
111

200
220

Intensity (arb. unit)

311

PVA
CdS 5 %
CdS 20 %
CdS 40%

10

20

30

40

50

60

Two Theta (in degree)

XRD Pattern of CdS/PVA

28

Structural parameters of CdS/PVA

Sample

2 theta hkl
(degre
e)

Standard d
(JCPDS80-0019)

Lattice
Average a
constant (in )
a (in )

Diameter
D (in
nm)

CdS 5%

29.26
44.08
52.6

200
220
311

3.0489
2.051
1.738

2.90
2.05
1.75

6.0978
5.80
5.76

5.78

11.2 nm

CdS 20%

26.54
44.06
52.34

111
220
311

3.355
2.052
1.745

3.35
2.05
1.75

5.811
5.80
5.79

5.79

6.4 nm

CdS 40%

26.54
43.9
52.1

111
220
311

3.35
2.05
1.75

3.35
2.05
1.75

5.80
5.79
5.80

5.80

3.8 nm

29

XRD pattern of ZnS/ PVA nanocomposite film

(A- 2 % ZnS, B- 5%, D- 20 % & F- 40 %)

30

Analysis of X-Ray diffraction pattern of ZnS/PVA

nanocomposite film

Sample Loadin
name
g of
ZnS

2
hkl
(degree)

28.3

002 3.14

3.12

39.7

102 2.26

28.5

D
F

5%
20 %
40 %

Inter
Stand Lattice
planner ardd constant
spacing
a ()
d

Lattice
consta
nt c
()

Crystal
size D
(nm)

3.85

6.29

5.8 nm

2.27

3.82

6.24

002 3.12

3.12

3.82

6.24

47.7

110 1.90

1.91

3.81

6.22

28.9

002 3.08

3.12

3.78

6.16

39.9

102 2.25

2.27

3.80

6.21

4.7 nm
3.2 nm

31

CdSe 2:1

PVA

CdSe 3:1

100

CdSe 4:1

102

002
INTENSITY (arb. Unit)

PVA

10

202

20

30

40

50

60

TWO THETA (in degree)

XRD patterns of CdSe/PVA Nanocomposite film

indicating hexagonal structure

32

c) Absorption studies

Absorption spectra of powder and film
specimens have shown blue shift in
absorption edge or first absorption peak
as compared to their bulk counterpart
indicating increased band gap energy
due to quantum confinement effect.

No effect of doping has been observed
on the absorption spectra.
33

ZnS-I
ZnS-II
ZnS-III
ZnS-IV
ZnS-V

ABS (in arb. units)

Fig. shows the UV/VIS

optical absorption spectra
for ZnSI, ZnSII, ZnS
III, ZnSIV and ZnSV
samples in the range 400
nm-200 nm prepared with
capping
agent
concentration
of
0M.
0.005M, 0.01M, 0.015M
and 0.02M respectively.

Absorption edge shifts
towards
lower
wave
lengths
by
increasing
capping
agent
concentration.

200

250

300

350

400

Wavelength (in nm)

34


The effective band gap energy has been

determined from the absorption spectra and
particle size is computed from the effective
mass approximation (EMA) model using
the formulaEg = Eg +

22
2r2

1
m*e

1
m*
h

The particle sizes obtained by this method

are in agreement with those from XRD.
35

The particle size obtained for various

concentration of capping agent
Sample

ZnS-I
ZnS-II
ZnS-III
ZnS-IV
ZnS-V

Capping
agent
concentration
0.000M
0.005M
0.01M
0.015M
0.02M

Absorption
Edge
Wavelength
260 nm
250 nm
240 nm
230 nm
220 nm

Band
gap
(in eV)
4.76
4.96
5.16
5.39
5.63

Size by
EMA
(in nm)
2.4
2.2
2.08
1.9
1.78
36

ABSORBANCE (arb. unit )

In
case
of
CdS
nanoparticles,
the
absorption edge for all
CdS
the samples is blue
V
shifted as compared to
CdS
that of bulk CdS.
III
CdS II

For CdS V sample, the
absorption edge is nearly
CdS I
equal to that of the bulk
CdS.
400
450
500
550
600

The blue-shift in the
WAVELENGT (in nm)
absorption edge indicates
Optical absorption spectra of
increase in effective band CdS nanoparticles.
37
of the samples.

Size of CdS nanoparticles by various techniques

(Prepared by organometallic technique)

S.
Reaction
No.
time
(in min )

Size by
TEM
(in nm )

Size by Absorpti Size by

XRD on Edge abs. Edge
(in nm ) ( in nm)
(in nm)

20

470

5.7

II

30

480

6.6

III

60

490

IV

80

90

12

500

11
38


Absorption spectra of CdSe nanocrystals prepared by

different capping agent concentrations show a small
absorption peak and then sudden increase in absorption.
1 .9

Absorption (in Arb. Unit)

1 .7

1 .5
5mMo l

1 .3

6mMo l
7mMo l
8mMo l

1 .1

9mMo l

0 .9

0 .7

0 .5
300

350

400

450
W a v e le n g t h ( in n m )

500

550

600

39

CdSe nanocrystal size for various capping

agent concentration
Sample Concentration Absorption Band gap Diameter
Eg
by EMA
peak
(in mmol)
(in nm)

(in eV)

(in nm)

C1

350

3.54

2.86

C2

345

3.60

2.82

C3

340

3.64

2.79

C4

330

3.75

2.71

C5

10

310

2.53
40

Particle size of CdSe Nanocrystals

Capping agent Particle size by
Concentration absorption using
EMA (in nm)
6 mmol
2.86
7 mmol
2.82
8 mmol
2.79
9 mmol
2.71
10 mmol
2.53

Particle size
by XRD
(in nm)
2.97
2.94
2.77
2.76
2.58

41


In case of nanocomposites, pure polymer is

found to be transparent in visible region and
absorption is obtained in ultraviolet region.

When nanocrystals are incorporated in it,
their absorption is superimposed.

In case of CdS, absorption edge is obtained
in visible region and shift towards lower
wavelengths by increasing nanocrystalline
loading from 0 to 40% .

This indicates that crystal size decreases
with increasing nanocrystalline loading.
42

Absorption spectra of CdS/PVA nanocomposite film

(CdS loading in polymer is 2, 5, 10, 20, 30 and 40 %
by weight for a, b, c, d, and f samples )
a
b
c

Absorbance (a.u.)

400

e
f

500

600
Wavelength (nm)

700

800
43

Size of CdS/PVA composite films

Sample Loading
name of
CdS
a
2%
b
5%
c
10 %
d
20 %
e
30 %
f
40 %

Absorption
wavelength
(nm)
500
490
470
450
440
430

Estimated size
by absorption
edge (nm)
12.2
9
6.4
5.1
4.75
4.3

Particle size decreases with increasing CdS loading

44

Absorption Spectra of ZnS/PVA Composite

Film

It is noticed that the

absorption edge is blue
shifted with increasing the
loading of ZnS.

The energy band gap is
increased with higher loading
of ZnS in PVA matrix due to
formation
of
smaller
crystallite,
which
is
confirmed by the XRD
studies.

The absorbance is also
increased with increasing the
loading of ZnS in PVA
matrix, because of the
transparency of the film is
reduced with higher loading
of ZnS.

Absorption spectra of ZnS/PVA

nanocomposite films (A- ZnS 2%, B- 5%,
45
C- 10%, D- 20 %, E- 30%, and F- 40%)


The particle size is estimated by the effective mass

approximation model.

By increasing ZnS loading (% at wt), the particle size is
decreased.
Estimated particle size from absorption edge of ZnS/PVA
nanocomposite film
Sample
name

% (at
wt)ZnS

Absorption Energy
edge
band gap
wavelength Eg (eV)
(nm)

Radius of
crystal
r (nm)

Crystal
size
D (nm

2%

327

3.79

4.9

9.8

5%

316

3.92

3.3

6.7

10%

310

4.0

2.91

5.8

20%

305

4.06

2.6

5.3

30%

300

4.13

2.4

4.8

40%

290

4.27

2.1

4.2

46

Absorption Spectra Of CdSe/PVA Composite

Films
0.95
0.85
ABSORBANCE (arb. unit)

It is seen that the band edge

is
shifted
to
shorter
wavelengths compared to the
bulk CdSe.

This may be attributed to
the quantum confinement
effect on the electron band
structure of CdSe samples.

The shoulder present in the
spectra is assigned to the
optical transition of the first
excitonic state.

0.75

III

0.65

IV
0.55

II
0.45

I
0.35
400

500

600

700

WAVELENGTH (in nm)

Optical absorption spectra of

CdSe/PVA composite film47

800


The crystal size of CdSe in CdSe/PVA composite film is

estimated by the change in the absorption edge using EMA
model.
Sample
name
CdSe I
CdSe II
CdSe III
CdSe IV

Precurs Absorption
or ratio
edge
Cd:Se
1:1
660 nm
2:1
590 nm
3:1
620 nm
4:1
670 nm

Energy
band gap
Eg
1.87 eV
2.06eV
1.93 eV
1.85 eV

Size by
EMA
10.6 nm
6.39 nm
7.6 nm
11.5 nm
48

d) Photoluminescence studies
250

200

0.000M

PL Intensity (in arb. units)

0.005M
0.01M
0.015M

150

0.02M

100

50

0
300

400

500

600

700

800

Wavelength (in nm)

PL spectra for ZnS nanoparticles at various concentration of capping

agent (excited by 250nm UV light).

PL intensity increases and the peak shifts towards lower

wavelength for smaller particles.

49

PL for ZnS nanoparticles at various concentration of

capping agent
Samples

Concentration

PL emission peak
Relative
Wavelength Energy
Intensity

ZnS I

0.000M

460nm

2.69 eV

119

ZnS II

0.005M

440nm

2.82 eV

135

ZnS III

0.01M

430nm

2.88 eV

144

ZnS IV

0.015M

420nm

2.95 eV

195

ZnS V

0.02M

390nm

3.35 eV

21950

140

0%
0.10%
0.50%

120

1%
5%

PL Intensity (in arb. units)

100

80

60

40

20

0
300

400

500

600

700

800

Wavelength (in nm)

PL intensity Of ZnS:Mn at various Mn concentration

PL intensity increases by increasing Mn%

51

1mmol
2mm
3mm
4.8mm
6mm
7mm
8mm
9mm
10mm

200
180
Intensity ( in a.m.u.)

160
140
120
100
80
60
40
20
0
300

400

500

600

700

Wavelength ( in nm)

PL Spectra of CdSe Nanoparticles

52


It is seen that as the particle size is

reduced,
the
intensity
of
luminescence increases and the peak
becomes wider and shifts towards
shorter wavelength.

This indicates that surface states are
better passivated by increasing
capping agent.
53

Photoluminescence of CdS nanoparticles of different sizes

prepared by orgenometallic precursor

PL INTENSITY ( arb. unit)

15
12

CdS II
CdS III

CdS V

6
3
0
500

520

540

560

580

600

WAVELENGTH (in nm)

In the PL spectra of CdS nanocrystals, band edge luminescence was

not detected. One PL peaks has been observed, at 528 nm. The peak
54
intensity increases by decreasing particle size. No shift is observed.

Photoluminescence spectra of CdS/PVA

nanocomposite films excited by 450nm light
(a -2%, b 5%, d -20% and e -30%)

A broad peak at 535
nm and a long tail
towards higher wave
lengths.

Peak due to
recombination of
electrons in sulphur
vacancy with hole in
valence band

Intensity increases
with CdS loading,
i.e.
55
for smaller particles.

PL spectra of ZnS/PVA composite film excitation by 325 nm

( B- 5% ZnS, D- 20 % ZnS and F- 40 % ZnS)

PL spectra of ZnS/PVA
composite film show a
broad emission due to
broad particle size
distribution.

Peaks are obtained at
400 nm, 416nm and 446
nm.

This emission could be
attributed to recombination
from surface traps.

PL intensity is found to
56
increase with ZnS loading


In
case
of
CdSe/PVA
nanocomposite films, PL was
excited by 475 nm light and PL
spectrum shows two peaks.

First peak at 525 nm do not shift,
but the second peak at 575-585 nm
shifts to shorter wave length for
smaller particles.
57

CdSe IV
4

CdSe I
CdSe II

3.5
PL Intensity (arb. unit)

CdSe III
3
2.5
2
1.5
1
0.5
0
450

500

550

600

650

700

Wavelength (in nm )

PL Spectra of CdSe/PVA Nanocomposite

58

Peak Position of Photoluminescence

Sample

Absorption Absorptio I

st

PL II

nd

Edge

n Maxima Peak

peak

(nm)

(nm)

(nm)

(nm)

CdSe I

660

590

525.5

590

CdSe II

590

530

525

576

CdSe III 620

540

525

580

CdSe IV 670

580

525.5

586

PL

59


This excitonic emission peak is

Stoke shifted with respect to
band edge emission.

Nanocrystalline CdSe powder
show intense PL as compared to
nanocomposite.

60

Electroluminescence Studies

For EL investigations, the emission material layer is
placed between two electrodes.

The transparent electrode has been prepared by
depositing a layer of SnO2 on heated glass substrate
by chemical vapor deposition technique. ITO coated
glass is better for this purpose.

For study of electroluminescence in nanocrystalline
powder samples, a piece of mica sheet having a
window of 2x2 mm is placed over the conducting
glass and the sample powder is placed within this
window and fixed with adhesive.
61


In case of nanocrystal/polymer composites mica

sheet with window was placed over the composite
layer on the conducting glass plate.

An aluminum strip is fixed over the sample along
with conducting gel in order to obtain good contact.

Voltage is applied at the conducting glass and the
aluminum strip, and light emitted from the sample is
viewed through the conducting glass side.

The EL brightness is measured with the help of
photomultiplier tube. The EL was studied at different
voltages and frequencies.

EL spectra was recorded with the help of HM 104
62
monochromator.

Setup for Electroluminescence

63


The EL studies on nanocrystalline powder

samples and nanocrystal/polymer composites
have shown that the light emission starts at
certain threshold voltage, different for
different specimens, and then usually
increases rapidly with increasing voltage.

It is found that for smaller nanocrystals,
threshold voltage is lower and EL brightness
(B) increases rapidly with voltage.
64

EL of CdS nanoparticles prepared by organometallic

precursor method (30, 60 & 90 minutes)

65

Higher brightness is obtained for smaller nanocrystals


EL starts at a threshold voltage (200 V)

and then increases with increasing
voltage.

As voltage is increased, more electrons
and holes are injected into the emission
layer.

Due to high field, bending of bands
takes place and release the electrons from
traps. Their subsequent recombination
with holes give rise to the light emission.
66

I-V Characteristics of CdS nanoparticles prepared by

organometallic precursor method

67


The linear relation between current

and voltage indicates the ohmic
nature.

The slope of the lines increases
with increasing particle size,
indicating decrease in impedance of
the cell.

68


EL intensity increases exponentially with increasing voltage.

Higher intensity is obtained for higher Mn doping. 69


The EL brightness of CdS nanocrystals increases by

increasing Mn concentration.
70

But above 1.0% Mn, there is reduction in EL brightness.

Electroluminescence Spectra of CdS nanoparticles

INTENSITY (arb. unit)

12
11
10
9
8

PL

7
6

EL

5
4
3
2
450

500

550

600

WAVELENGTH (in nm )

EL and PL Spectra of CdS 30 minute sample

71


The room temperature EL Spectrum is nearly

identical to the PL with same peak position.

The EL peak is broader than the PL peak.

This is probably due to local joule heating
from the large current flux and poor thermal
conductivity. The correspondence between EL
and PL spectra indicates that EL and PL
originate from the same states.

In the PL and EL
spectra of CdS
nanocrystal, band edge luminescence was
not detected.

One PL peaks has been observed, at 528
72
nm.

EL of ZnS Nanocrystals
BRIGHTNESS (arb. unit)

30
25
20

1 Khz
900 hz
800 hz

15
10
5
0
550

600

650

VOLTAGE (in volts)

The threshold voltage is quite high.

EL brightness increases with frequency

73


In case of ZnS:Mn also the EL brightness increases with voltage.

Frq.1Khz

BRIGHTNESS (arb. unit)

frq800Hz
140

frq600hz

120
100
80
60
40
20
0
250

300

350

400

450

500

VOLTAGE (in volts)

EL starts at lower voltage for higher frequencies.74

Current (in mA)

frq 1Khz

0.1

900hz

0.09

800hz

0.08

700hz

0.07

600hz

0.06

500hz

0.05
0.04
0.03
0.02
0.01
0
0

100

200

300

400

500

600

700

Voltage (in Votls)

I-V Characteristics of ZnS:Cu nanocrystals

It is seen that impedance decreases with frequency.

75

EL Brightness (arb. unit)

0

0.02
0.04
0.06
0.08
C u Dopent C oncentration (in %

0.1

Dependence of EL brightness on dopent concentration

For ZnS:Cu maximum brightness is obtained at

0.01%.

At higher concentration intensity decreases due to
concentration quenching.
76

Intensity (in a.u.)

400
300
200

5mM
6mM
7mM
8mM
9mM

100
0
280

330 380 430 480

Voltage (in volts)

Electroluminescence Brightness for CdSe nanocrystals

77

EL Intensity (in a.u.)

400
5 mMol

300

6 mMol

200

7 mMol
8 mMol

100

9 mMol

0
500

600

700

800

900 1000

Frequency (in Hz)

Frequency dependence of EL intensity of CdSe nanocrystals

EL brightness increases with frequency of applied voltage.

The figure reveals higher EL brightness for smaller CdSe
78
nanocrystals.


Similar results are obtained for nanocrystal/polymer

composites

Electroluminescence Brightness for CdS/PVK Composites

By increasing nanocrystalline loading, EL starts at

lower threshold voltage and higher intensity is obtained.
79

EL Brightness of CdS/PVK Nanocomposites

EL Bright (in a.u.)

250

375 V

200

325 V
280 V

150

265 V

100

250 V

50
0
0

10

15

20

25

CdS Concentration (in %)

EL Brightness vs Nanocrystal Concentration
Characteristics of CdS/PVK Nanocomposites
80


Initially EL brightness increases with

increasing nanocrystalline content in the
polymer but beyond 5% of nanocrystal
concentration, saturation is observed in the EL
intensity.

At higher voltages saturation of EL intensity
occurs
for
lower
concentrations
of
nanocrystalline loading.

This shows that such composites can be easily
used for EL devices with advantage of better
flexibility and good quality films.
81


Electroluminescence spectra of CdS/PVA nanocomposite

films show single peak from recombination at defect states.

82
Electroluminescence spectra of CdS/PVA nanocomposite films.


The emission peak is observed at 530 nm for

30% loading. For the same sample
photoluminescence peak has been obtained
at 535 nm.

It has been speculated that the luminescent is
due to recombination emission from electron
trapped in the shallow defects and hole
trapped in the deep defects, and shallowly
trapped electron still posses small effective
masses and therefore exhibit the quantum
size effect.
83


The EL peak shifts towards lower

wavelengths
by
increasing
nanocrystalline loading.

This suggests a multimodal particle size
distribution with higher loading of CdS
in polymer, which indicate smaller
particle size with wider size distribution
and could be full of defects.
84


Similar results are obtained for ZnS/PVA.

Voltage Brightness Characteristics of ZnS/PVA (A - 2% ZnS, B

85
- 5 %, D 20 %& F 40 %) at freq. 1 Khz

Voltage Current Characteristics of ZnS/PVA at diff. Freq,

The impedance decreases with increasing frequency.

86

12
F

Brightness (a.u.)

10

0
350

400

450

500

550

600

Wavelength (nm )

Electroluminescence spectra of ZnS/ PVA composite film

87
(voltage 312V ; D 20 %& F 40 %))


From the spectra two peaks at about 425

nm and other at about 480 nm were
observed.

The peak becomes sharper with higher
loading of ZnS.

It is speculated that the emission is from
the some deep trap luminescence.

88

300

CdSe II
CdSe III

250

Brightness (a.u.)

CdSe IV
CdSe I

200
150
100
50
0
200

400

600

800

Voltage ( volts)

Brightness- Voltage curve of CdSe/PVA nanocomposite film

89
with different precursor ratio of Cd/Se

12

EL Intensity (arb. unit)

10
8
6
4
2
0
470

520

570

620

670

Wavelength (in nm)

EL Spectra of CdSe/PVA II sample (Cd:Se 2:1) at 1 Khz

90


There is only one emission peak in

electroluminescence of CdSe/PVA
nanocomposite film at 580 nm.

Electroluminescence peak position is
same as photoluminescence second
peak position.

This indicates that charge carries
injected from the metal electrodes
recombine solely at the CdSe
nanoparticles and not in PVA.
91

Electroluminescence spectra of all the Three

nanocomposites
12

EL Intenstity (a. u.)

10
8
ZnS

CdS
4

CdSe

2
0
350 400 450 500 550 600 650 700
Wavelength (nm)
92


It can be seen from the EL spectra of

CdS/PVA, ZnS/PVA and CdSe/PVA that

CdS/PVA gives emission peak at 520 nm in

green region,
ZnS/PVA gives two peaks at 425 and 480 nm
with violet-blue color and
CdSe/PVA gives only one peak at 580 nm in
orange region.

93


For powder as well as nanocomposites, Log B

vs. 1/V is a straight line with negative slope.

This indicates that EL is produced by
acceleration-collision mechanism.

The polymer luminescence is absent in EL of
nanocomposites.

The smaller nanoparticles show enhanced
electroluminescence at lesser turn-on voltages
and higher brightness due to increased
oscillator strength, which improves the electron
hole recombination and enhance the
electroluminescence.
94


In case of doped samples, optimum

EL is obtained for a particular dopant
concentration.

Usually Low energy states are also
populated by electrical excitation that
can not be populated by optical
process. Therefore EL emission is
obtained at photon energies much less
than the band gap of the material.
95


The luminescence intensity increased in all

the
samples
with
increasing
nanocrystalline loading in the composite.

This indicate that the donor states involved
in the light emission is mostly related to
the surface states of the particle, which
increase as size of particle is reduced since
the surface to volume ratio is increased.

The surface states need to be passivated in
order to get efficient luminescence.
96

CONCLUSION
The investigations have revealed that

The EL efficiency can be increased by reducing
the size of semiconductor crystals to nanometer
range.

Nanocrystallites show better photoluminescence
but for electroluminescence, nanocomposites are
beneficial.

Different materials or various sizes of same
material may be used for different color light
emission in polymer matrix.
97


The EL properties of composite film consisting

of polymer (PVA) and semiconductor
nanocrystals (CdS, ZnS, CdSe) are reported to
be interesting and promising, even though
these studies are still in the early stage, and
demand improvements in terms of luminescent
power efficiency and device life time.

The presented material system of II-VI
semiconductor nanocrystals embedded in a
polymer could be promising for luminescence
devices.
98

Acknowledgement

The work has been carried out with the help of:

Ms Rubi Tamrakar
Ms Vikas Nogriya
Ms Preeti Gupta
Mr. Piyush Vishwakarma
Ms Amrita Diwedi
Ms Sakshi Sahare
Ms Mamta Tiwari
Ms Reena Teckchandani

The financial support by M.P.Council of Science

and Technology is gratefully acknowledged.
99

100