A photovoltaic cell is a specialized semiconductor diode that converts light into direct current (DC) electricity. Depending on the band gap of the light-absorbing material, photovoltaic cells can also convert low-energy, infrared (IR) or high-energy, ultraviolet (UV) photons into DC electricity . A common characteristic of both the small molecules and polymers (Fig 1) used as the light-absorbing material in photovoltaics is that they all have large conjugated systems. A conjugated system is formed where carbon atoms covalently bond with alternating single and double bonds. These hydrocarbons’ electrons pz orbitals delocalize and form a delocalized bonding π orbital with a π* antibonding orbital. The delocalized π orbital is the highest occupied molecular orbital (HOMO), and the π* orbital is the lowest unoccupied molecular orbital (LUMO). In organic semiconductor physics, the HOMO takes the role of the valence band while the LUMO serves as the conduction band. The energy separation between the HOMO and LUMO energy levels is considered the band gap of organic electronic materials and is typically in the range of 1–4 eV.

All light with energy greater than the band gap of the material can be absorbed, though there is a trade-off to reducing the band gap as photons absorbed with energies higher than the band gap will thermally give off its excess energy, resulting in lower voltages and power conversion efficiencies. When these materials absorb a photon, an excited state is created and confined to a molecule or a region of a polymer chain. The excited state can be regarded as an exciton, or an electron-hole pair bound together by electrostatic interactions. In photovoltaic cells, excitons are broken up into free electron-hole pairs by effective fields. The effective fields are set up by creating a heterojunction between two dissimilar materials. In organic photovoltaics, effective fields break up excitons by causing the electron to fall from the conduction band of the absorber to the conduction band of the acceptor molecule. It is necessary that the acceptor material has a conduction band edge that is lower than that of the absorber material.

Polymer solar cells usually consist of an electron- or hole-blocking layer on top of an indium tin oxide (ITO) conductive glass followed by electron donor and an electron acceptor (in the case of bulk heterojunction solar cells), a hole or electron blocking layer, and metal electrode on top. The nature and order of the blocking layers – as well as the nature of the metal electrode – depends on whether the cell follows a regular or an inverted device architecture. In an inverted cell, the electric charges exit the device in the opposite direction as in a normal device because the positive and negative electrodes are reversed. Inverted cells can utilize cathodes out of a more suitable material; inverted OPVs enjoy longer lifetimes than regularly structured OPVs, but they typically don’t reach efficiencies as high as regular OPVs.

In bulk heterojunction polymer solar cells, light generates excitons. Subsequent charge separation in the interface between an electron donor and acceptor blend within the device’s active layer. These charges then transport to the device’s electrodes where the charges flow outside the cell, perform work and then re-enter the device on the opposite side. The cell’s efficiency is limited by several factors, especially non-geminate recombination. Hole mobility leads to faster conduction across the active layer.

Organic photovoltaics are made of electron donor and electron acceptor materials rather than semiconductor p-n junctions. The molecules forming the electron donor region of organic PV cells, where exciton electron-hole pairs are generated, are generally conjugated polymers possessing delocalized π electrons that result from carbon p orbital hybridization. These π electrons can be excited by light in or near the visible part of the spectrum from the molecule’s highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital(LUMO), denoted by a π -π* transition. The energy bandgap between these orbitals determines which wavelength(s) of light can be absorbed.

Unlike in an inorganic crystalline PV cell material, with its band structure and delocalized electrons, excitons in organic photovoltaics are strongly bound with an energy between 0.1 and 1.4 eV. This strong binding occurs because electronic wave functions in organic molecules are more localized, and electrostatic attraction can thus keep the electron and hole together as an exciton. The electron and hole can be dissociated by providing an interface across which the chemical potential of electrons decreases. The material that absorbs the photon is the donor, and the material acquiring the electron is called the acceptor. In Fig. 2, the polymer chain is the donor and the fullerene is the acceptor. Even after dissociation, the electron and hole may still be joined as a “geminate pair”, and an electric field is then required to separate them. The electron and hole must be collected at contacts. If charge carrier mobility is insufficient, the carriers will not reach the contacts, and instead recombine at trap sites or remain in the device as undesirable space charges that oppose the flow of new carriers. The latter problem can occur if electron and hole mobilities are not matched. In that case, space-charge limited photocurrent (SCLP) hampers device performance.

Organic photovoltaics can be fabricated with an active polymer and a fullerene-based electron acceptor. Illumination of this system by visible light leads to electron transfer from the polymer to a fullerene molecule. As a result, the formation of a photoinduced quasiparticle, or polaron (P+), occurs on the polymer chain and the fullerene becomes a radical anion (C
60). Polarons are highly mobile and can diffuse away.