Trimolecular Recombination … really?

10. October 2008

As you might already have guessed, I am interested in loss mechanisms in organic photovoltaics. Despite considering the impact of recombination on the solar cell performance, also the physical origins are challenging… and many open questions remain.

Just a view days ago, there was another publication about recombination of free polarons (free carriers) – also called nongeminate recombination *1 – more specifically, trimolecular recombination. Abendstimmung im Vogelschutzgebiet GarstadtYou might remember that, a while ago, I already mentioned third order recombination, including a reference to private communications with Prof. Juska and another recent paper by the Durrant group [Shuttle 2008]) as well as a potential candidate for its origin. The new paper [Juska 2008] uses three different experimental methods, including photo-CELIV, to measure the temperature dependence of the trimolecular recombination rate in polymer:fullerene solar cell. The authors mention very briefly a possible mechanism responsible for the third order recombination, Auger processes. Shuttle et al. argue in their paper that a bimolecular recombination with a carrier concentration dependent prefactor could be the origin, in particular as they observe a decay law proportional to n2.5-n3.5, depending on the sample. We are also in the game, an accepted APL awaiting its publication (preprint here) Update 20.10.2008: now published online [Deibel 2008b]. We rather tend to believe the explanation by Shuttle, but that’s just an assumption at the present stage: the generally low recombination rate could also be due to a rather improbable process.

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Short Note: OPV Lifetime

13. August 2008

Another brief note from the SPIE conference. Right now, the results of an organic photovoltaics lifetime workshop are being presented. Information and roadmap are summarised on a free wiki page.

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Brief Headline: Organic Bulk Heterojunction Solar Cell Efficiency

13. August 2008

Continuing my recent history of only brief notes (sorry, busy…) here a short headline from the SPIE Optics and Photonics Conference in San Diego.

Today I heard a talk by Darin Laird, Plextronics. Green Lizards in the Loire valleyUsing an undisclosed organic donor material (well, they call their product Plexcore OS 2000 [Update below], as opposed to their P3HT OS 1000 or so) blended with the usual suspect PCBM, they managed to process an NREL certified lab scale (0.1cm2) solar cell with 5.94% power conversion efficiency! Fill factor was almost 72%, I believe, with the major improvement as compared to the reference material P3HT coming from an increased open-circuit voltage.

The corresponding solar cell module, 15×15 cm2 large, has an efficiency of 1.1% (or 2.3% active area efficiency, if you consider that only 46% of the module are active area). These numbers are brand new, but generally, uptodate solar cell efficiencies can be found in the efficiency tables (V32) by Martin Green.

So, who’s next to boost the organic solar cell efficiencies? ;-)  

P.S. As there sadly was a history of overestimated efficiencies published, followed by letters to the editors by watchful scientists and statements, a solar cell characterised by a certified institute is important to regain the trust.

P.P.S. Of course, not every university group can afford to spend 1000 bucks on a certified solar cell measurement. Still, at least some effort can be put into doing the current-voltage characterisations carefully. In January, Jan Kroon gave an interesting talk about measuring organic solar cells properly; find the video here.

Update (5.9.2008): The donor Plexcore OS 2100 available at Sigma Aldrich is not the one with which the 5.9% efficiency where achieved. The undisclosed donor material used is not yet available commercially, it seems.

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Picture Story – How Do Organic Solar Cells Function?

5. June 2008

After the introductory posts about organic solar cells – split in parts zero, one and two, – I would like to present a somewhat more intuitive picture today… well, picture indeed says it all;-)

Step 1: Light Absorption => Exciton Generation

osc bhj morphology scheme - 1.jpg absorption bands polymer vs cis.jpg
  • light is absorbed in the donor material, e.g., a conjugated polymer
  • excitons are thus created, strongly bound electron-hole pairs on the polymer chain
  • very high absorption coefficient, device thickness on ~100nm scale, as compared to the inorganic polycrystalline semiconductor CuInSe2 (~1 micron) and crystalline Silicon (~100 micron)
  • but: only narrow absorption bands, as shown for two conjugated polymers P3HT and PCPDTBT in comparison to CuInSe2. This drawback could be circumvented by synthesis of novel materials, or multijunction concepts (tandem solar cells).

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Organic Photovoltaics Publications

20. May 2008

Today I came across a graph I prepared two years ago: the number of papers published per year in scientific journals within the field of organic photovoltaics. OPV in WOS (Number of Publications per Year) - 2007.pngI just updated it using Web Of Science, up to year 2007.

In case you want to reproduce the graph, I used the topic

“organic photovoltaic cell” or “organic photovoltaics” or “organic solar cell*”

for organic photovoltaics and related phrases, and

“bulk heterojunction solar cell*” or “bulk-heterojunction solar cell*” or “polymer photovoltaic” or “polymer fullerene photovoltaic” or “polymer solar cell*” or “polymer fullerene solar cell*” or “polymer-fullerene solar cell*” or “polymer-fullerene solar cell*”

Web of Science can also combine search sets in the history, so that publications matching both sets are not counted twice; the result is shown as the curve “both” in the graph. Probably, by a more appropriate choice of search terms, even some more papers can be found. For instance, I should have included small molecules.

The result is not strictly growing exponentially, but the interest still is increasing continuously. Let’s hope that the commercial interest will have similar growth rates soon;-)

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A potential candidate for trimolecular recombination?

16. May 2008

Lately, we have talked about recombination, also discussing instances where trimolecular recombination has been observed experimentally. From the different excited states observed in organic solar cells, it is not obvious which combination could be participating in a trimolecular loss process. By the way, chemists seem to know the occurance of termolecular recombination, though in different circumstances.

One candidate for an excitation involving three species it the so called trion. Turkish Coast in November SunComing from inorganic semiconductor physics, and meaning charged exciton, it has been described for organic matter already more than 20 years ago [Pope 1984] as

bound exciton plus hole (excitonic ion)

In this review (including the references therein, in particular [Agranovich 1979]), an attractive interaction between exciton and charge is described.
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Polaron, Polaron Pair, Exciton, Exciplex, …

15. April 2008

I’ve talked a lot about polaron pairs and excitons lately, and will continue to do so, Venus Transitthat this time I’ll give short explanations of what I am actually talking about. Call it definitions… ;-)

A polaron is a charge, i.e., an electron or a hole, plus a distortion of the charge’s surroundings. In a crystalline inorganic material, setting a charge onto a site does not change the surroundings, as the crystal lattice is rigid. Not so in many disordered organic materials. Putting a charge onto a certain molecular site can deform the whole molecule. Moving the charge from this to another molecule means that first the energy for the deformation – the polaron binding energy or reorganisation energy – has to be mustered. The implication is that charge transport becomes more difficult, the charge carrier mobility becomes lower, … This process is also described as self-trapping. As a side note, it is often difficult to distinguish between the influence of polaronic self-trapping and of gaussian disorder, as both have a similar impact on the charge transport properties. This similarity is also reflected in the corresponding hopping rates used to calculate charge transport: Marcus theory is a function of the reorganisation energy, where as the Miller Abrahams rate [Miller 1960] is related to the energetic disorder of the density of states. The polaronic deformation can be quantified in terms of a (lattice) polarisation, or a phonon cloud, or just as the above-mentioned polaron binding energy. Mostly, however, when hearing polaron, think charge;-) See also what wikipedia has to say about polarons.

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For starters: Recombination

24. March 2008

In disordered organic semiconductors, there is no band transport, as there are no delocalised, just localised charges. Consequently, there is no simple band-band recombination of free carriers, and no Shockley-Read-Hall recombination! Of course, there is still recombination going on, a lot of it;-) Church inside
Here I’ll just quote some definitions concerning different types of recombination, and get back with details later.

For a general classification we take a look at Kwan-Chi Kao’s book “Dielectric Phenomena in Solids“.
Looking for monomolecular recombination, we find

The recombination that involves one free carrier at a time, such as indirect revombination through a recombination center (e.g., an electron captures by a recombination center and then recombined with a hole, each process involving only one carrier), is generally referred to as monomolecular recombination.

In organic semiconductors, a recombination centre can for instance be a trapped hole, localised in a deep state; it can induce a monomolecular recombination with a mobile electron. Even knowing this, it still feels like bimolecular recombination, doesn’t it? ;-)

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Comment on Primary Photoexcitation in Polymer:Fullerene Blends

17. March 2008

It seems that one prominent discussion in organic photovoltaics has officially ended, the one about the primary photoexcitation in disordered organic solar cells being excitons (with a binding energy clearly above 100meV) or free charges (with excitons having binding energies in the range of the thermal energy, i.e. <<100meV). Hwang, Moses and Heeger, have just published a paper on polymer:fullerene blends [Hwang 2008] where they describe the charge generation as

Mobile carriers are generated via a two-step process: initial ultrafast charge separation to an intermediate charge transfer (CT) bound state, followed by the transfer of carriers onto the bicontinuous networks.

They explicitly mention

[...] indicating ultrafast dissociation of the singlet excitons at the polymer-PCBM interface and the build-up of the initial CT state.

The paper is nice but in itself not that remarkable, except that previously, Moses and Heeger always claimed the primary photoexcitation to be free charges instead of bound excitons. Their measurements yielded exciton binding energies in the range of the thermal energy, i.e., no donor acceptor interface being necessary for charge separation. To quote an older paper [Moses 2000],

Thus, carriers are photoexcited directly and not generated via a secondary process from exciton annihilation.

Now I have to mention that in the new paper they use P3HT:PCBM, and in the old one MEH-PPV:PCBM. But as they do not mention this in the new paper, I assume that either I missed something, or they changed their point of view concerning the primary photoexcitation.

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Comments on Estimates on the Efficiencies of Organic Tandem Solar Cells

16. March 2008

Ideally, tandem solar cell made of a series connection of two subcells work as follows. tandem.png Both sub cells generate their own photocurrent by absorbing light and generating charges (as described for single layer cells in here), and have their own open-circuit voltage. Of course, as the two cells are connected in series, they influence each other. The photogenerated holes of cell 1 are extracted by the ITO, but where to the electrons go? They have to recombine with photogenerated holes from cell 2: that is what the intermediate recombination layer is for. If the photocurrent of sub cells 1 and 2 is initially unbalanced, the electric field is redistributed, such that the photocurrent becomes balanced… at a lower value, approximately determined by the worse of the two cells. The open-circuit voltage is aproximately the sum of both sub cells’ open circuit voltages. Of course, in cases of field redistribution, that does not quite hold true. So, what approximately happens in a tandem solar cell of subcells 1 and 2:

  • open circuit voltage Voc = Voc1 + Voc2
  • short circuit current Isc = min(Isc1, Isc2)
  • fill factor is more difficult, but as a rough guide lets stick to the minimum of both as well

So for an ideal tandem solar cell, complementary absorption ranges, and balanced photocurrents are needed.

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