Light Emitting Electrochemical Processes

This article serves as an introduction to the design and chemistry of organic light emitting diodes (OLED).

Light emission in the OLED arises from recombination (electron transfer ) reactions of cation and anion radical of conjugated aromatic molecules.

Several decades ago it was noted that poly(acenes) and related poly-aromatic hydrocarbons, in very dry nonaqueous (non-polar) solvents can be reduced by one electron (chemically or electrochemically) to produce an energetic radical anion state (D^-.). These same molecules can often be oxidized by one electron to produce a cation radical state (A^+.). Should A^+. and D^-. encounter each other in solution, a “recombination” electron transfer reaction can occur – the excess free energy in this reaction can be deposited in one of the molecular species, to form its lowest excited state (singlet), or in some cases, its lowest triplet excited state – states which are the same as those created by photoexcitation of the molecule. Emission from this state occurs with a lifetime of ca. nanoseconds, with quantum yields approaching 100% in some cases. These “electrogenerated chemiluminescence” (ECL) processes are direct analogues of the charge recombination processes which occur in the condensed phase in an OLED. They are also closely related to the chemiluminescence and bioluminescence processes which occur in living organisms, the most easily recognized example being the luminescence processes which occur in fireflys.

It was quickly released that in order to create the emissive state by injection charge the following processes took place: First the loss of an electron by this conjugated aromatic system to form a cation radical species.

Then the addition of electron to a similar species at the opposite electrode to give us an anion radical.

These two species react and do an electron transfer reaction from the donor species to an acceptor species. There is a lot of excess free energy that is given off in this process which is can be predicted by the formal potentials for the formation of these two species.

Finally one of the molecules harvests this energy in the form of an excited state in a singlet or triplet state or both. This is the species that is used to emit light.

We can write this from the point of view of a homogenous electrochemical process. At the same time this was being done in the condensed phase people were beginning to explore this processes in solution. Rudy Marcus used this as a central tenant in his development of electron transfer theory between small molecule systems.

The Jablonski diagram is used to describe the energy (wavelength) of absorbance and luminescence for aromatic molecules.

The Jablonksi diagram is our way of describing what is happening with small molecules and small conjugated aromatic systems.

First we have the absorption of a photon and the creation of excited singlets states with different vibronic excited levels. This shows the absorption spectra with its associated fine structure. This is the lowest energy of the absorption bands these are the vibronic levels associated with the population of the the ν=1 , ν =2 levels.

That is followed very fast non-radiative relaxation.

Finally there is fluorescent decay to give back the energy in form of an emissive state. The spectral response for this molecule which looks like a mirror image of the absorption spectrum. There is a small shift called the Stokes shift which very typical for planar aromatic compounds such as anthracene and related molecules. The lifetimes for fluorescence is on the order of nanoseconds typically.

A Jablonski diagram

Once the excited singlet state has been formed there is the possibility of doing intersystem crossing to a triplet state. This change in spin is a forbidden process and as a consequence triplet states tend to be much longer lived. Most molecules have lifetimes of the order of 1-100 microseconds. Those compounds that are most useful for organic light emitting diodes will have lifetimes closer to 1 microsecond. Most people are familiar with molecules that phosphorescence with much longer lifetime and these which are less useful. Vibronic excited states and a ground state. These tend to have emission events at much longer wavelengths.

This a summary taken from a Florida state website that gives all the different lifetime ranges associated with excitation, nonradiative relaxation an extremely fast process, with decay, fluoresces or via intersystem crossing and then phosphorescence back to the ground state.

The color of absorption and emission in simple molecular systems is controlled by the structure of the molecule and by the degree of conjugation in the aromatic system.

In general as the number of aromatic rings increases in these molecular systems the energy for both the absorption and emission events goes down, ie they shift to the red. The same can be said for the carotenoid like assemblies where just increasing the number of double bonds in the system changes both the energy of absorption and emission. To summarize for most polyacine- like systems which were among the first to be examined by this process. There is an absorption and emission event, a small Stokes shift, and a change of wavelength of these two depending on the degree of conjugation in the aromatic system.

The ratio of singlet state to triplet state formation helps to determine the OLED efficiency.

When see electrochemical excitation of these systems we tend to find that the number singlet state and triplet states partitions with 25% of energy deposited as singlet states and 75%of energy deposited in triplet states. This has a significant impact the optimization of organic light emitting diodes that either going to use fluorescent molecules to create the light to produce the light or phosphorescent dopants to create the light. The advent of the use of phosphorescent dopants has increased the efficiency to the near fluorescent lighting levels.

Singlet recombination

Triplet recombination

How does this happen? The spin statistics of recombination can be described in a number of ways. This is the simplest way but there are some short comings to this simplistic description. We start with a molecule in which an electron has been removed the spin of the remaining electron in the two level diagram can either be up or down. The electron in the donor molecular can either be spin up or spin down. During the process of electron transfer we create either an excited singlet state of the acceptor and the neutral donor or excited singlet state of the donor and the neutral acceptor.

The details of this are somewhat complicated. During this electron transfer event there forms a contact ion pair or solvent separated ion pair if it is in solution. It is single entity and by this means we can exchange electrons and create either a singlet of the donor or singlet of the acceptor. Typically it the molecule with the lowest emissive energy that winds up having the excess energy from this process. In this case you can’t really tell because they were both identical to begin with. In actual organic light emitting diode it is the lowest band gap molecule that ends up being the emissive species.

Finally, to form the triplet state you can have three types of triplets. Thus it is three times as likely to form a triplet as it is a singlet which accounts for the 3:1 triplet to singlet ratio in systems of this type. It is debated whether or not these ratios apply in the condensed phases. They apply in solutions and early indications are that it also applies in the condensed state. The consequence of this is that if you are going to optimize a light source you must harvest as much of energy of the triplet state as possible.

Small molecules are used in electrogenerated chemiluminescence (ECL) studies to help elucidate these light emitting processes in “condensed phases”

In the following discussions we will focus on polyacine derivatives. The diphenylanthracene (DPA) has been the fruitfly of the electro generated chemiluminescence community. It can be reduced by one electron to form the radical anion and can be oxidized to form the cation.

Rubrene is an elaboration of DPA. It is a yellow emitter. It has simple one electron oxidation and reduction events.

Di iosamyl quinacridone (DIQA) was introduced by the OLED community was the first category of dopants to produce green light. It has a very stable one electron oxidation and one electron reduction product. It undergoes solution electro generated chemiluminesence that tells us lot of about how light is formed in these devices.