• Dr Monika Szumilo
  • Worked on graphene!!

Main devices to be covered: Diodes Photovoltaics Transistors Thermoelectrics

Organic Semiconductors:

What are organic semiconductors?

  • Carbon based
  • Typically polymers, such as plastics, rubbers, etc
  • Aka Plastic Electronics

Helps overcome problems with traditional semiconductors, such as silicon. Silicon is high-quality and easy to obtain, but:

  • very energy-intensive and expensive to refine
  • Doesn’t work well for large area applications.
  • Very heavy.

OSC’s are cheap to make, flexible, biocompatible, and can be made in large sizes, but:

  • slower then silicon
  • sensitive to water, UV, o2

OSC’s fall into two classes, polymer and molecular.

How do OSC’s work?

Carbon has 6 electrons, stored in 3 orbitals.

These electrons can be stored in a “hybridized” orbital, between the S and P orbitals.

We are most interested in the sp2 hybridization, because with this the remaining electron in the p_z orbital has interesting properties.

Carbon Atom bonding:

Sigma bonds:

  • Strong
  • Single direction
  • can rotate
  • Responsible for carbon chaining

bonds:

  • Weaker
  • Prevents rotation
  • Most importantly: Allows de-localisation of orbitals, which allows carbon to conduct electricity.

Adjustable band gaps:

  • The presence of pi bonds allows for adjustable band gaps. HOMO: Highest Occupied Molecular Orbital LUMO: Lowest unoccupied molecular orbital

In summary: Size of bandgap in molecule depends on two major things:

  • Molecule composition
    • This is length of
  • Planarity

Key question:

Q: How does the concept of hybridization contribute to the understanding of organic semiconductors?

  • It explains the formation of delocalized electron clouds.
  • It predicts the geometry of the molecules.
  • It helps to understand the energy levels of molecular orbitals.

Polarons:

Peierl’s transition, aka dimerization:

  • When carbon atoms come in pairs?

Key Question:

Q: What is the main driving force for Peierl’s transition in conjugated polymers? A: To achieve a lower energy state.

Q: How does the presence of polarons affect the optical properties of an organic semiconductor? A: It leads to the formation of new absorption bands.

Excitons:

  • Quasi-particle
  • Comes in Wannier and Frenkel flavours

Wannier Excitons:

  • Weak
  • 10 milli- eV
  • Large distance
  • Found in inorg. semiconductors Frenkel Excitons:
  • Strong
  • Binding energy 0.2-1 eV
  • Small distance
  • Typically in OSC’s
  • Easily recombines

Singlet-triplet splitting:

  • Ground state is typically a singlet
  • The exchange energy is the difference between first excited singlet state and first excited triplet state
  • Triplet states are useless, and cant be converted to singlet states.
    • Active area of research due to being source of inefficiency
  • What does “manifold” mean in this context

Spectroscopy

An exciton is a bound state of an electron and a hole