Synthesis of CuInxGa1-xSe2 nanoparticlesusing ODE-Se injection method
Meng Cao
05/14/2017
Shanghai University
I BackgroudII Synthesis of CuInSe2
III Synthesis of CuInxGa1-xSe2
IV Conclusion
Selenourea1g --61.9 $
Cu3Se2 nanocrystals synthesized with ODE-Se method under the effects of Al3+
0.5 mmol CuCl + 5 mmol HDA + 0.1 mmol
Al(NO3)3. 9H2O+ 10 mL Octadecence (ODE)
------------180 C + 4 mL (3 mM) ODE-Se,
------------ 180 C 5 min
Wenhua Li, Andreu Cabot, et al J.Am.Chem.Soc. 2013, 135, 4664-4667
CuAlSe2
CuInSe2
No
?
I BackgroudII Synthesis of CuInSe2
III Synthesis of CuInxGa1-xSe2
IV Conclusion
1 mmol CuCl + 1 mmol InCl3 + 10~15 mmol hexadecylamine
(HDA) + 0.3~0.6 mmol Al(NO3)3. 9H2O + 20 mL ODE
------------110 C degased 30 mins
------------160 C + 3 mL (2.4 mmol/L) ODE-Se,
------------240 C 30 mins
Typical synthesis condition
Effects of the amount of Al(NO3)3. 9H2O
1 mmol CuCl + 1 mmol InCl3 + 10 mmol HDA + 20 mL ODE + 0.3~0.9
mmol Al(NO3)3. 9H2O
------------160 C + ODE-Se,
------------240 C 30 min
CuxSe y or chalcopyrite CISe or wurtzite CISe?
Effects of the amount of Al(NO3)3. 9H2O
J. AM. CHEM. SOC. 2010, 132, 12218–12221Wang JJ, Wan LJ, et al
No Al(NO3)3. 9H2O 0.3 mmol Al(NO3)3. 9H2O
CISe-DPP Se
chalcopyrite CISe
wurtzite CISe
Element Weight% Atomic%
Cu K 46.18 51.98
Se L 51.21 46.39
In L 2.61 1.63
Element Weight% Atomic%
Cu K 13.85 18.64
Se L 51.00 55.21
In L 35.14 26.12
No Al(NO3)3. 9H2O 0.3 mmol Al(NO3)3. 9H2O
Element Weight% Atomic%
Cu K 24.55 31.45
Se L 46.72 48.17
In L 28.72 20.36
Element Weight% Atomic%
Cu K 24.78 31.95
Se L 44.36 46.03
In L 30.85 22.02
0.6 mmol Al(NO3)3. 9H2O 0.9 mmol Al(NO3)3. 9H2O
Effects of the amount of Al(NO3)3. 9H2O
Effects of Reaction times
1 mmol CuCl + 1 mmol InCl3 + 10 mmol HDA + 20 mL ODE + 0.3 mmol
Al(NO3)3. 9H2O
-------160 C + ODE-Se,
------- increasing to 240 C , the time was calculated after ODE-Se was injected
Effects of Reaction times
0.3 mmol Al(NO3)3. 9H2O
Effects of the amount of HDA
1 mmol CuCl + 1 mmol InCl3 + 0~20 mmol HDA + 20 mL ODE + 0.3 mmol
Al(NO3)3. 9H2O
-------160 C + ODE-Se,
------- 240 C , 30 min
Wurtzite CISe
Element Weight% Atomic%
Cu K 22.75 29.84
Se L 42.66 45.03
In L 34.59 25.12
0 mmol HDA
Element Weight% Atomic%
Cu K 25.52 32.82
Se L 43.88 45.41
In L 30.58 21.77
20 mmol HDA
Effects of the amount of HDA
Effects of injection temperature
1 mmol CuCl + 1 mmol InCl3 + 0~20 mmol HDA + 20 mL ODE + 0.3 mmol
Al(NO3)3. 9H2O
-------110~240 C + ODE-Se,
------- 240 C , 30 min
Effects of injection temperature
Effects of reaction temperature
1 mmol CuCl + 1 mmol InCl3 + 0~20 mmol HDA + 20 mL ODE + 0.3 mmol
Al(NO3)3. 9H2O
-------160 C + ODE-Se,
------- 220~260 C , 30 min
Effects of reaction temperature
I BackgroudII Synthesis of CuInSe2
III Synthesis of CuInxGa1-xSe2
IV Conclusion
CuCl 1 mmol + InCl30.5mmol +GaCl3 0.5 mmol+ HDA 10 mmol + Al(NO3)3.9H2O 0.3 mmol + 20 mL ODE------160 C + 2 mol ODE-Se-----240 C 30 min
Wurtzite CISe
Element Weight% Atomic%
Cu K 23.21 30.45
Se L 40.61 42.90
In L 35.38 25.69
Ga L 0.78 0.94
CuCl 1 mmol + InCl3 0.1 mmol +GaCl3 1mmol+ HDA 10 mmol + 20 mL ODE+2 mol OLA
------------240 C + 2 mol ODE-Se,
------------240 C, 9 ~25 min
CuCl 1 mmol + InCl3 0.5 (1 ) mmol +GaCl3 1mmol+ HDA 10 mmol + 20 mL ODE+2 mol OLA
------------240 C + 2 mol ODE-Se,
------------240 C, 9 min
InCl3 0.5 mmol
InCl3 1 mmol
InCl3 0.5 mmol
InCl3 1 mmol
InCl3 1 mmol
InCl3 0.5 mmol
2.25%
We & Korgel group
Conclusion
1 The amounts of Al3+, reaction temperature and injection temperature affect the
structure of CISe and also contribute to form CISe with triangular shape.
HDA is important to form well dispersed and small particles.
2 the molar ratio of InCl3 and GaCl3 has a effect on the formation of CuInxGa1-
xSe2.
3 Annealing process may enhance the PEC of CISe thin film solar cells.
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