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Prepararea si caracterizarea

filmelor subtire de
P3HT:CuInSe2:TiO2 applicatii in
celule solare hibride
Yang-Yen Yu, Wen-Chen Chien, Yu-Hsin Ko, Si-Han Chen

Student: VELNAZAROV Myrat

De ce panouri solare?

Ce facem?
Pentru ca se apropie Energie nucleara
sfarsitul la:[1]
Energie Solara

2066 Energie apei

Wind turbine
Energie geotermala
Calcule energetice[2]

Anul 2001:

Consum energetic total=430 EJ ( 430*1018J)

Energia Electrica furnizata de soare 0.0075 EJ/s=

430 EJ in 16ore

[2] Jeff Tsao, Nate LewisGeorge Crabtree, Solar FAQs, 2006

Cum functioneaza celula fotovoltaica?


[3] Prabakaran Kumaresan, Sureshraju Vegiraju, Yamuna Ezhumalai, Shueh Lin Yau, Choongik Kim, Wen-Hsi Lee, Ming-Chou Chen, Polymers, 2014, 6(10), 2645-2669
[5] [6]

a)Bilayer heterojunction Hybrid solar cells

b)Polymer–fullerene bulk heterojunction p-type conjugated polymers + n-type inorganic

PEDOT- poly(3,4-ethylenedioxythiophene) polystyrene sulfonate ITO- Indium tin oxide TCO- Transparent
Conductive Oxides
FTO- fluorine doped tin oxide

[5] Carsten Deibel, Vladimir Dyakonov, Rep. Prog. Phys., 73, 2010, 096401, 39
[6] Veluru Jagadeesh Babua, Sesha Vempatib, Subramanian Sundarrajan, Merum Sireesha, Seeram Ramakrishna, J.Sol.En, 106, 2014, 1-22
polymer s.c

Polymer-fullorene s.c

Hybrid s.c
Hybrid thin-film solar cell based on P3HT-
poly-hexylthiophene and CuInSe2

Low price

Front wall illumination

Schottky-berrier type-an interface CuInSe2/TiO2
between a metal and a
semiconductor provides the band PEDOT/PSS
bending necessary for charge

Why CuInSe2?
Large absortion coefficient

Suitably small band gap

Radiation stability
Metode de sinteza CuInSe2

1-Vacuum co-evaporation using multistage growth processes(large scale)

2-Deposition techniques( small scale)

De ce TiO2?

Stabilizeaza celula P3HT

Intensifica transfer de sarcini

Creste eficienta celulei solare

Partea experimentala

Synthesis of TOPO-capped
CuInSe2 nanoparticles
TEM- for det.particle size of TiO2
Was realized by hot injection method, CISe 04 SEM-fracture surface of hybrid thin film
particles were shielded by TOPO 01 AFM- surface morphology of coated film
X ray for crystalline struct., PL, UV-Vis,

Preparation of P3HT, colloidal Preparation of hybrid

TiO2 and PEDOT/PSS solar cell
03 A spin-coating process was used to
Was prepared by Gringard
fabricate solar cell devices
Synthesis of TOPO-capped CuInSe2

● After purification of TOPO by vacuum distillation, a mixture of Se powder TOP was

stirred at room temp. under inert gas for 24h to give a transparent solution of TOPSe.
● A solution of InCl3 and CuCl in TOP was added via syringe to TOPO in an oil bath at100
°C. After stirring the reaction mixture for 1 h, the temperature was increased to 330 °C
and then TOPSe solution was carefully injected into the reactionmixture.
● A color change from yellow to black occurred spontaneously. After 30 min, the reaction
mixture was cooled to 80 °C and an excess of methanol was added. A flocculate of
nanoparticles formed. The particles were separated by centrifugation and washing with
methanol three times to remove residual TOPO and other organic impurities. Finally, the
TOPO-capped CISe nanoparticles were suspended in toluene.
Preparation of P3HT, colloidal TiO2 and
● The P3HT prepared by Grignard metathesis has been reported in the literature . 2,5-Dibromo-3-
alkylthiophenes were prepared by bromination of 2-dibromo-3-alkylthiophene in acetic acid and methanol
solution (1:1 ratio). 2,5-Dibromo-3-hexylthiophene was dissolved in THF. The mixture was refluxed for 1 h and
then Ni (dppp)Cl2 was added. After a further 45 min at reflux, the reaction was poured over methanol. The
polymer was isolated via Soxhlet extraction using methanol, hexanes, and chloroform. The polymer was
recovered from the chloroform fraction by rotary evaporation of the solvent. The purple solid dried under
vacuum for 2 h to yield HT-coupled poly-3-hexylthiophene. To prepare TiO2 sol, 45.4 g aqueous hydrochloric
acid was diluted by 45.4 g 1-butanol, and then slowly dropped into a solution composed of 270 g TBOT
dissolved in 243.8 g 1-butanol. The sol–gel reaction was allowed to proceed for 3 h under stirring at room
temperature until no more TBOT could be detected by FTIR spectroscopy [32]. Highly conducting polymer
Preparation of hybrid solar cell

● A spin-coating process was used to fabricate the hybrid solar cell devices.
● Cleaning of ITO glass
● PEDOT/PSS was then mixed with DMSO solvent and spin-coated on the prepared ITO glass substrate
● The substrate was cured for 20 min at 120 °C under nitrogen to remove the solvent.
● Dichlorobenzene solutions composed of P3HT and CISe were then spin-coated over the PEDOT:PSS layer.
● Subsequently, the active layer was baked
● The cell was then heated.
● Calcium and aluminum were thermally deposited onto the device under vacuum
Results and discussions

XRD pattern

20.1 P3HT HRTEM images of CuInSe2(a,b) and TiO2(c,d)

26.6 CISe The CISe nanocrystal reveals a rod shape with a lattice fringe of 0.35 nm, and diameters
30.9 , 51.2 Cu2Se of approximately 15–20 nm are homogeneously dispersed in the film
60.9 In2O3 TiO2 solwith a spherical shape and a diameter of approximately 5 nm is well dispersed
in the n-butanol
• The long rodlike
P3HT (Fig. 3(a)) and particle-like TiO2
(Fig. 3(b)) can be seen in
the AFM images.

• Fig. 5(a) indicates that the long rod-like P3HT is homogeneously

blended with TiO2 particles to form hybrid aggregates, with an
approximate size of 30–50 nm in the PHCT10 film.
• The homogeneity between the P3HT and TiO2 particles increases
as the TiO2 content falls below 25 wt.%.
• As TiO2 content increases to 25 wt.%, the size of hybrid
aggregates grows to 100– 200 nm (Fig. 5(b)).
• However, significant TiO2 phase separation occurs when the TiO2
content increases to 30 wt.%.

• Hybrid solar cells with improved efficiency were fabricated

• The CISe and TiO2 nanocrystals with rod and spherical shapes and
sizes of 15– 20 nm and 5 nm, respectively, are prepared.
• The optimal TiO2 content for efficiency is 25 wt.%.
• The optimal results for the open circuit voltages (VOC), short-circuit
current density (JSC), fill factor (FF), and efficiency (η) of the hybrid
thin film solar cell are VOC=0.335 V, JSC=8.07 mA/cm2, FF=52.75, and
η=1.425, respectively.
Thank you!