![Page 1: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/1.jpg)
Chemistry with bigger atoms
Anshu PandeySolid State and Structural Chemistry Unit
Indian Institute of Science
H Cd Hg U ?
![Page 2: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/2.jpg)
Quantum Dots: A Coarse-grained view
• Quantum Dot Electronic Structure can be approximated remarkably well as a Spherical Particle in a Box Problem
V=0V=
V=-4 eV
V=0 eV
![Page 3: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/3.jpg)
Quantum Dots: Artificial AtomsElectrons and holes in a spherical box
• Electronic Wavefunctions: 1Se, 1Pe, 1De…..2Se, 2Pe etc.• Hole Wavefunctions: 1Sh, 1Ph, 1Dh…..2Sh, 2Ph etc.
Looks like hydrogenic orbitals: 1s, 2s, 2p etc.The term “Artificial Atom” was coined to reflect this similarity.
![Page 4: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/4.jpg)
QDs vs Atoms
Spatial Extent 10 nm 0.1 nm
10 eV
0.3 eVEnergy Separation between levels
![Page 5: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/5.jpg)
Bringing Chemistry to QDs
• Introduce a redox active dopant into a redox inert QD
Rekha M. et. al. JPC C, 118, 30101 (2014)
![Page 6: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/6.jpg)
Bringing Chemistry to QDs
• Put this QD near a redox-active QD
Rekha M. et. al. JPC C, 118, 30101 (2014)
![Page 7: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/7.jpg)
Charge transfer
• Charge is transferred between the QDs
• The transferred charge resides in a quantum confined state
Rekha M. et. al. JPC C, 118, 30101 (2014)
![Page 8: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/8.jpg)
Charge transfer: Signatures
• The spectator hole can quench PL emission via an Auger mechanism
• Both QDs are individually very bright. Together, neither emits.
![Page 9: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/9.jpg)
Bleaching• The formation of a free
carrier bleaches absorption
• Absorptions of the two materials are non additive.
![Page 10: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/10.jpg)
Intraband Absorption
• The most emphatic confirmation for this process comes from the appearance of an intraband absorption in the infrared
(eV)
![Page 11: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/11.jpg)
Coulomb binding
• Following charge transfer, the two QDs attract each other via coulomb interactions
• Conceptually, this is no different from the ionic bonds that hold together compounds such as NaCl.
![Page 12: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/12.jpg)
Coulomb binding
• Formation of a QD solid held together by coulomb interactions
Rekha M. et. al. JPC C, 118, 30101 (2014)
![Page 13: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/13.jpg)
Disordered glassy solids• The behavior of these materials is
typical of a disordered, granular material that evolves in response to each perturbation, but does not reach its energetic minimum.
• Not NaCl, but quite like Sodium Calcium Silicate (soda-lime glass).
![Page 14: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/14.jpg)
This is a chemical transformation
The concept of stoichiometry still holds!!!
Rekha M. et. al. JPC C, 118, 30101 (2014)
![Page 15: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/15.jpg)
Why are QD-QD solids Stoichiometric
• Adjacent QD levels are <0.1 eV apart.
• In contrast, atomic oxidation states are separated by ~1 eV
• Creation of a Stoichiometric defect is 1012 times easier.
× Packing Effects × (Impossible in disordered solids)
× Shell Filling× (Insufficient level separation)
![Page 16: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/16.jpg)
Validating the origins of Stoichiometry
Pull
Na1Cl1 Na1Cl1Thought Experiment: continuously increasing the lattice parameter of NaCl 1
6
![Page 17: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/17.jpg)
Conclusions
• QDs react the same way as atoms
• This “Chemistry” allows synthesis of stoichiometric compounds
• QDs however lack valence and do not obey the rules of conventional chemistry
• This chemistry though rudimentary, is promising – We have observed analogs for:
• Na + Cl Na+ + Cl-
![Page 18: Cd Hg U - ias.ac.in · • Ananth Kamath • Vishikh Athavale • Funding: – DST – IISc Acknowledgements C QD? Thank You! Prof. D. D. Sarma. Title: Chemistry with bigger, better](https://reader034.vdocuments.site/reader034/viewer/2022052011/6026ed5b5660f352e87a16f3/html5/thumbnails/18.jpg)
• Rekha M.• Biswajit Bhattacharyya• Veena Iyer• Arpita Mukherjee• Dev Kumar Thapa• S. Anumol• Nitin Tomer• Dr. Triloki Pandit• Gurupratheep• Ashutosh Gupta• Aniruddha Y. R. • Ananth Kamath• Vishikh Athavale
• Funding: – DST – IISc
Acknowledgements
C
QD
?
Thank You!
Prof. D. D. Sarma