Final Year Project 2015/2016 We l e a d

Final Year Project Title:

Deposition and Characterization of CdSe Nanoparticles Multilayer on
Conductive Substrate by Chemical Bath Deposition

Final Year Project Viva Presentation

Name: Sin Khai Wen

No. Matric: 116541

Supervisor: Dr. Khatijah Aisha Bt. Yaacob

 Introduction of CdSe We l e a d

• Important II-VI compound because of its size-dependent exceptional optoelectronic properties in the visible range

• It has a direct bulk band gap (1.74 eV) with high absorption coefficient near the band edge, high photosensitivity, tunable band
gap from around 450 to 700nm which cover the entire visible spectral range and quantum size effect, allow its use in thin film
devices, especially for application in solar hybrid system.

• Solar cell, light emitting diode, nano sensors, photo detectors

Figure 1: Left, absorption spectra of differently sized CdSe nanocrystals. Right, corresponding PL spectra representing deeper red, red, orange, yellow,
green and blue (from right to left) emitting CdSe cluster and nanocrystals under UV excitation at 380nm (Yuan & Krüger, 2012)

Yuan, Y. & Krüger, M., 2012. Polymer-Nanocrystal Hybrid Materials for Light Conversion Applications. Polymers, Volume 4, pp. 1-19.
,

Introduction of Chemical Bath Deposition We l e a d

• Chemical bath deposition (CBD) is the simplest deposition technique that do not require sophisticated and costly instruments.

• Extensively used for preparation of CdSe thin film because of its application as window layer material in solar cell fabrication

• Chemical Reaction:
Cadmium salt reacted with NTA to form complex Cd salt,

Cd2+ + NTA [Cd(NTA)]2+ (1)

Hydrolysis of potassium hydroxide in water gives OH- ions in solution according to the equation,

KOH(s) + H2O(l) K+ (aq) + OH- (aq) + H2O (l) (2)

Hence, from reaction of (1) and (2), it will give solid Cd(OH)2 formation.

Cd2+ + 2OH-  Cd(OH)2 (s) (3)

From the reaction of selenium and sodium sulfite, we will get equation (4), and when dissolving in [Cd(NTA)]2+ solution, the byproduct is (5)

Na2SO3 + Se Na2SeSO3 (4)

SeSO32- + OH- HSe- + SO42- (5)

The overall reaction can be described as follow

Cd(OH)2 (s) + HSe- CdSe + OH- + H2O (6)

 Introduction of QDSSC We l e a d

• The electrons will enter into the conduction band (CB) of the QD
and the hole remains in the valence band (VB).

• The excited QD injects the electron from its CB into the CB of the
wide band gap semiconductor (e.g. TiO2) and become oxidised.

• The injected electron from the QD percolates through the porous

TiO2, reaches the conducting glass, travels through the external

Figure 2: Operating principle of a typical QDSSC load, completes the circuit.

(Jun, et al., 2013)
• The oxidized QD is then restored (hole is filled with electron)
when it is reduced by S2- from the electrolyte and in turn it is
oxidized into S2- that diffuses to the counter electrode.
Jun, H., Careem, M. & Arof, A., 2013. Quantum dot-sensitized solar cells-perspective and recent developments: A review of Cd chalcogenide quantum dots as sensitizers. Renewable
and Sustainable Energy Reviews, Volume 22, pp. 148-167.
 Problem Statement We l e a d

• The deposition process in CBD uses a controlled chemical reaction which result in
the deposition of a nanocrystalline films by precipitation

• Small crystal size leads to quantum size effect and increase in the optical band gap

• The major problem of the CBD method is the difficulty to produce small CdSe
nanoparticle on the substrate

• Another problem is deposition of CdSe multilayer with different size of CdSe

nanoparticles on the substrate
 Research Objectives We l e a d

• To synthesis different CdSe nanoparticle size using chemical bath deposition

method by changing parameters such as complex agent concentration.

• To deposit two layer of CdSe nanoparticles with different particle size on fluorine
doped tin oxide(FTO) substrate.

• To determine and compare electrical properties of CdSe multilayer with CdSe

single layer solar cell.
 Methodology- Procedure We l e a d

FTO cleaning – 2-propanol Deposition of TiO2 mesoporous layer Deposition of CdSe on the
mesoporous TiO2 thin films by using
chemical bath deposition method

Parameters:
• NTA concentration
• Deposition time
Fabrication of Cu2S Synthesis of polysulfide electrolyte
• Deposition of multilayer CdSe
photocathode
thin film

Characterization:
• XRD
• SEM
• UV-Vis
• EDX
Solar cell assembly Characterization
• Photo-electrochemical
Measurement (I-V)
 Methodology We l e a d

Figure 3: Polysulfide electrolyte Figure 4: Brass counter electrode after immersed in

37% HCl at 70°C for 45 minutes

Figure 5: Cell assembly with polysulfide electrolyte

injected between the two electrodes
 Result and Discussion We l e a d

TiO2 Mesoporous Layer

Pore
Structure

(a) (b)

TiO2
nanoparticle

Figure 6: TiO2 thin films (a) before annealed and Figure 7: FESEM image of TiO2 mesoporous layer at magnification
(b) after annealed 30.00KX
 Result and Discussion We l e a d

2.5
40
35
2
30
Absorbance (a.u)

1.5 25

( hv)2
20
1 15
10
0.5 5
0
0 3.2 3.3 3.4 3.5 3.6
340 390 440 optical band gap(eV)
Wavelength(nm)

Figure 8: Absorbance spectra of TiO2 Figure 9: (αhν)2 versus optical band

mesoporous layer gap
Result and Discussion We l e a d

CdSe Solution

240mM 180mM 120mM

NTA NTA NTA

Figure 10: CdSe solution with 240, 180 and 120mM

NTA from left to right
 Result and Discussion We l e a d

XRD Analysis of CdSe Nanoparticles

selenium oxide

Figure 11: XRD pattern of CdSe at different NTA concentration Figure 12: XRD pattern of CdSe quantum dots
(Mahajan, et al., 2013)

S.Mahajan, Rani, M., Dubey, R. B. & Mahajan, J., 2013. Characteristics and Properties of CdSe Quantum Dots. International Journal of Latest Research in
Science and Technology, 2(1), pp. 457-459.
 Result and Discussion We l e a d

Table 1: Different parameters of different NTA concentration of CdSe

nanoparticles obtained from XRD

Sample Matching 2θ Spacing, d FWHM, β Crystallite

peaks (hkl) (degree) (Å) (°) size (nm)

120mM NTA 111 24.27 3.66 0.620 13.00

CdSe Scherrer’s Equation to

calculate crystallite
size,
180mM NTA 111 25.87 3.44 0.889 8.56 0.94λ
D=
β cosθ
CdSe

240 mM NTA 111 25.44 3.50 3.16 2.45

CdSe
 Result and Discussion We l e a d

FTIR Analysis of CdSe Nanoparticles

To determine the
existing of Cd(OH)2
Cd(OH)2 because hydroxide
C-O group, COO- stretching C-H bonding
NTA exist H bond crystal from Cd(OH)2
(-OH group)
in solution, act as
nuclei for formation of
CdSe (Corer & Hodes,
1994).

Figure 13: FTIR spectra of CdSe at different NTA concentration

Zhang, A. et al., 2012. Suppressed blinking behavior of CdSe/CdS QDs by polymer coating. Nanoscale, pp. 1-8.

Ingole, P. P. & Haram, S. K., 2010. Citrate-capped Quantum dots of CdSe for the Selective Photometric Detection of Silver Ions in Aqueous Solutions.

Liu, I.-S.et al., 2008. Enhancing photoluminescence quenching and photoelectric properties of CdSe quantum dots with hole accepting ligands. Journal of Materials Chemistry, Volume 18, pp. 675-682.

Corer, S. & Hodes, G., 1994. Quantum Size Effects in the Study of Chemical Solution Deposition Mechanisms of Semiconductor Films. J. Phys. Chem, Volume 98, pp. 5338-5346.
 Result and Discussion We l e a d

UV-Vis of CdSe nanoparticles with different concentration of NTA

120mM NTA CdSe
1.3 180mM NTA CdSe
1.2 1.2
1.1

Absorbance
1 1
Absorbance

0.9
0.8 0.8
0.7
0.6 0.6
0.5
0.4 0.4
400 500 600 700 400 500 600 700
Wavelength(nm) Wavelength(nm)
240mM NTA CdSe (b)
(a) 1.2

1
Absorbance

0.8

0.6

0.4
400 500 600 700
Wavelength(nm)
(c)

Figure 14: a) Absorption spectra of CdSe at NTA concentration of 120mM, b) Absorption spectra of CdSe at NTA
concentration of 180mM, c) Absorption spectra of CdSe at NTA concentration of 240mM
 Result and Discussion We l e a d

Average diameter, D= (1.6122x10-9)λ4-(2.6575x10-6) λ3+(1.6242x10-3) λ2-(0.4277)

λ+41.57 (Peng, et al., 2003)

Table 2: Wavelength, average diameter and band gap energy of CdSe

at different concentration

Sample 120mM NTA 180mM NTA 240mM NTA

CdSe CdSe CdSe

Wavelength 608.94 554.98 587.48

(nm)

Average 5.00 3.14 4.09

Diameter (nm)

Band gap 1.93 2.10 1.95

energy (eV)

Yu, W. W., Qu, L., Guo, W. & Peng, X., 2003. Experimental Determination of the Extinction Coefficient of CdTe, CdSe, and CdS Nanocrystals. Chemistry Material,
Volume 15, pp. 2854-2860.
 Result and Discussion
We l e a d

Deposition of CdSe on TiO2 Mesoporous Layer

120mM 180mM 240mM 8 hr 14 hr 20 hr 26 hr

NTA NTA NTA

Figure 15: Deposited CdSe for 26 hours Figure 16: Deposited CdSe with NTA
on FTO glass with different NTA concentration of 240mM at different time
concentration
 Result and Discussion We l e a d
Time deposition (hr) 10.0KX 30.0KX

14 Figure 17:
FESEM image
of CdSe from
concentration of
180mM at
20 different time
under
magnification
of 10.0KX and
30.0KX
26
 Result and Discussion We l e a d

NTA Time deposition Short Circuit Open Circuit Fill factor, FF Efficiency, η
Table 3: Summary of short
circuit current density, open concentration (hr) Current Voltage, VOC (%) (x 10-2)

circuit voltage and (mM) Density, Jsc (V)

efficiency at
(mA/cm2)
120mM,180mM and
240mM NTA concentration 8 0.055 0.145 0.323 2.6

120 14 0.095 0.085 0.366 3.0

20 0.465 0.091 0.283 12.0

26 0.905 0.182 0.286 47.1

8 0.212 0.184 0.388 15.1

180 14 0.350 0.217 0.281 21.3

20 0.127 0.160 0.336 6.8

26 0.105 0.123 0.283 3.7

8 0.967 0.227 0.316 69.4

14 0.509 0.195 0.326 32.4

240 20 0.550 0.131 0.244 17.6

26 0.448 0.131 0.331 19.4

 Result and Discussion We l e a d

Deposition of CdSe Nanoparticles Multilayer on TiO2 Mesoporous Layer

CdSe multilayer

FTO glass fracture

Figure 18: CdSe multilayer deposited with 1st

Figure 19: FESEM image of cross section
layer is from 120mM NTA concentration at 26
image of CdSe multilayer on FTO glass at
hours and 2nd layer is from 180mM NTA
magnification of 1KX
concentration at 14 hours
 Result and Discussion We l e a d

Table 4: Summary of short circuit current density, open circuit voltage and efficiency for deposited CdSe
multilayer at different NTA concentration and different time deposition
Short Open Fill Efficiency,
First Layer Second Layer Circuit Circuit factor, η (%)
Current Voltage, FF (x 10-2)
Density, Jsc VOC (V)
(mA/cm2)

NTA Time NTA Time

concentration deposition concentration deposition

(mM) (hr) (mM) (hr)

120 (b) 26 180 14 0.521 0.176 0.310 28.4

120 (b) 26 240 8 0.132 0.070 0.297 2.7

180 14 120 (b) 26 0.102 0.027 0.310 0.9

* (b) means bigger
average diameter 180 14 240 (b) 8 0.303 0.080 0.195 4.7
of particles
240 8 120 (b) 26 0.722 0.251 0.271 49.1

240 (b) 8 180 14 0.302 0.155 0.262 12.3

 Conclusion We l e a d

• By changing NTA complex agent concentration with 120mM, 180mM and 240mM, different CdSe
nanoparticle size 5.00nm, 3.14nm and 4.09nm with band gap energy 1.93eV, 2.10eV and 1.95eV
had been synthesized respectively.
• For NTA concentration of 120mM, as time deposition increased, the efficiency also increased.
However, for NTA concentration of 180mM and 240mM, overall efficiency decreased as the time
deposition increase.
• Two layer of CdSe nanoparticles with different particle size had been deposited on FTO substrate
by CBD method.
• However, 2nd layer deposition of CdSe did not enhance the overall cell efficiency
 Recommendation We l e a d

• Ostwald ripening process in the CdSe solution gives low conversion efficiency of the cells.
• The change in colour from yellow, orange and then finally red or dark red shown that CdSe
nanoparticles growing bigger.
• To avoid ostwald ripening, once the CdSe solution is synthesized, the substrate should be
deposited at once so that the CdSe nanoparticles can be deposited onto substrate and nucleation
takes place on the substrate before agglomeration occurs.
• Higher temperature deposition can be carried out too so that the CdSe nanoparticles gain energy
and will not agglomerate together.
• Besides that, when the CdSe solution is not used, the solution should always be stirred so that the
CdSe nanoparticles can be dispersed well and have a good particle distribution.
 We l e a d

Thank you!
Presented by
Sin Khai Wen 116541/ School of Materials & Mineral Resources
Engineering
 We l e a d

Back up Slides
 Result and Discussion We l e a d

(a) (b)

(c)
Figure 20: (αhν)2 versus optical band gap of (a) CdSe at NTA concentration of 120mM, (b) CdSe at NTA concentration
of 180mM, (c) CdSe at NTA concentration of 240mM
Result and Discussion We l e a d

Morphology of CdSe

Figure 21: EDX data of CdSe from 180mM NTA

concentration deposited at 26 hours
 Result and Discussion We l e a d
1

0.9

0.8

0.7
Current density, J (mA/cm2)

0.6

0.5
8h

0.4 14h

0.3 20h

0.2 26h

0.1

0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2
Voltage, V (v)

Figure 22: Graph of current density-voltage for deposited CdSe from NTA
concentration of 120mM
 Result and Discussion We l e a d
0.4

0.35

Current density, J (mA/cm2) 0.3

0.25

0.2

0.15 8h
14h
20h
0.1 26h

0.05

0
0 0.05 0.1 0.15 0.2 0.25
Voltage, V (v)

Figure 23: Graph of current density-voltage for deposited CdSe from NTA
concentration of 180mM
 Result and Discussion We l e a d

0.9

0.8

0.7
Current density, J (mA/cm2)

0.6

0.5

8h
0.4
14h
0.3
20h

0.2 26h

0.1

0
0 0.05 0.1 0.15 0.2 0.25
Voltage, V (v)
Figure 24: Graph of current density-voltage for deposited CdSe from NTA
concentration of 240mM
 Result and Discussion We l e a d

0.8

0.7

0.12mM 26h,0.18mM 14h

Current density, J (mA/cm2)

0.6

0.12mM 26h,0.24mM 8h
0.5

0.18mM 14h,0.12mM 26h

0.4

0.18mM 14h, 0.24mM 8h

0.3

0.24mM 8h,0.12mM 26h

0.2

0.24mM 8h,0.18mM 14h

0.1

0
0 0.05 0.1 0.15 0.2 0.25 0.3
Voltage, V (v)

Figure 25: Graph of current density-voltage for deposited CdSe multilayer

from different NTA concentration and different time deposition