UC LEADS symposium 2015

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Stability of PbTe Quantum Dots

Lead (II) Telluride Quantum Dots

Stability of PbTe QDs in Solution

PbTe QDs in Solar Technology

Glen Junor1, Juliette A. Micone2, Jason Tolentino2, Sam Keene3, Matt Law1,2

5.5 nm Diameter

PbTe vs PbSe in Air

Air Stable PbTe Films

Behaviors:

• Blue shifting

• Decreased Absorbance

• Loss of first exciton definition

Behaviors correspond to

uneven oxidation of QDs

Trends:

• PbTe blue shifts faster for all sizes

• PbTe peaks become

indistinguishable

What is Multiple Exciton Generation (MEG)?

Reference 2.

1. Photon is absorbed hv = n(Eg)

• Promotes “hot” Electron

2. Hot carrier undergoes MEG

• MEG is in competition with

cooling (emission of phonons)

Department of Chemistry1, Department of Chemical Engineering and Materials Science2,

Department of Physics3 at University of California, Irvine

References

Acknowledgements

Three Sizes

After Air-Exposure

Quantum Dot (QD) Solar Cells

Benefits:

• Solution Based Processing

• High absorption coefficient

• Increased theoretical solar

cell efficiency with MEG1

• 33% to 44%

• 152 nm Exciton Bohr Radius3

• Best Multiple Exciton Generation

(MEG) efficiencies2

• Labile and oxidizes easily

Electrochemical Analogues:4

• ½ O2 + 2H+ +2e- H2O 1.23 V

• S + 2H+ +2e- H2S 0.17 V

• Se + 2H+ +2e- H2Se -0.37 V

• Te + 2H+ +2e- H2Te -0.72 V • .

Making PbTe Quantum Dots

Synthesis of all QDs was carried out using standard air-free

techniques.

3.1 nm Diameter QDs

• PbO: 0.7009 g

• Oleic Acid: 1.7 g

• 1-Octadecene:

15.78 g

Heated and Degased 1

hour

• TOPTe: 12 mL of

0.75 M

Injected into round

bottom at 140 ̊ C

React for 3 minutes

Conclusions

PbTe QD films can be made air stable by ligand exchange

with 1,2-ethanedithiol followed by infilling and over-coating

with Al2O3 by atomic layer deposition (ALD). Since the general

stability of all sizes of PbTe QDs are very similar in solution,

Al2O3 ALD will most likely work for all sizes.

Future Work

Studies on PbTe must investigate electronic characteristics of

these air stable films to predict the ideal configuration of the

final solar cell.

1. Nozik, A. Spectroscopy and Hot Electron Relaxation Dynamics in Semiconductor

Quantum Wells and Quantum Dots. Annual Review of Physical Chemistry 2001

52,193-231.

2. Stewart, J.; Padilha, L.; Bae, W.; Koh, W.; Pietryga, J.; Klimov, V. Carrier Multiplication

in Quantum Dots within the Framework of Two Competing Energy Relaxation

Mechanisms. J. Phys. Chem. Lett. 2013, 4, 2061-2068.

3. Murphy, J.;Beard, M.; Norman, A.; Ahrenkiel, P.; Johnson, J.; Yu, P.; Micic, O.; Ellingson,

R.; Nozik, A. PbTe Colloidal Nanocrystals: Synthesis, Characterization, and Multiple

Exciton Generation. J. Am. Chem. Soc. 2006, 128. 3241-3247.

4. Standard Reduction Potentials. http://www.av8n.com/physics/redpot.htm (Accessed Mar

19, 2015

5. Ihly, R.; Tolentino, J.; Liu, Y.; Gibbs, M.; Law, M. Photothermal Stability of PbS Quantum

Dot Solids. ACS Nano. 2011, 5 , 8175-8186.

6. Urban, J.; Talapin, D.; Shevchenko, E.; Murray, C. Self-assembly of PbTe quantum dots

into nanocrystal superlattices and glassy films. J. Am. Chem. Soc. 2006 128, 3248-

3255.

• University of California Leadership Excellence through Advanced Degrees

(UC LEADS)

• Daniel Fabrega

• Jason Tolentino

• Dr. Markelle Gibbs

• Dr. Matt Law

PbTe QDs in

tetrachloroethylene

PbTe QD Thin Film

3.1 nm Diameter 7.1 nm Diameter

5.5 nm 3.1 nm

7.1 nm

Overall:

• PbTe is less stable in

air than PbSe

Film conditions:

• 1494 nm 1st exciton

• Spin Coat 125 nm thick

• Soak in 1,2-ethanedithiol

• Al2O3 ALD

• Infill + 20 nm overcoat

Behaviors:

• Red shift + Broadening

• No visible changes even

after 3.5 months in air!

7.1 nm Diameter QDs

• PbO: 1.5 g

• Oleic Acid: 5 g

• 1-Octadecene: 10 g

Heated and Degased 1

hour

• TOPTe: 10 mL of

1.5 M

Injected into round

bottom at 140 ̊ C

React for 3 minutes

5.5 nm Diameter QDs

• PbO: 1.5 g

• Oleic Acid: 5 g

• 1-Octadecene: 10 g

Heated and Degased 1

hour

• TOPTe: 10 mL of

1.5 M

Injected into round

bottom at 180 ̊ C

React for 30 seconds