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.

Thanks every one!!!

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