3 mayo 2014

Polarones

Resumen
An exciton is an excited quasiparticle in a solid, which is formed by a
Coulomb-bound electron-hole pair. It is more prominent in organic
semiconductors as compared to their inorganic counterparts: as the
dielectric constant is lower in organics, the screening length is larger. In
this case, the name Frenkel exciton is applied, whereas the weakly bound
type is called Wannier-Mott. (J)

A polaron pair (PP) is a Coulomb bound pair of a negative and a positive
polarons, situated on different molecules. Usually, polaron pairs are the
intermediate step from an exciton to a pair of free polarons far enough
apart not to feel the attraction of one another and therefore important in
order to understand photogeneration in organic semiconductors. (J)

An exciplex is just an exciton which is located at the interface of its host molecular material indeed it still
resides on one molecule as indicated in the image. Due to the influence of the surface, the exciplex
experiences a different environment as compared to a bulk exciton.

A polaron is a charge, i.e., an electron or a hole, plus a distortion of the charges 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.





two polarons on a single chain or polaron pair (PP) model. (B)

Charges on polymer chains connected with a chain distortion appear in the case of holes
as (hole) polarons (Ps, charge +e and spin 1/2). The polaron is just a radical ion (spin 1/2)
associated with a lattice distortion and the presence of localized electronic states in the
gap referred to as polaron states.

(T) When a second electron is removed from the polymer chain, we have two polarons,
a bipolaron (BP) formation. (B) Bipolarons have been considered for a long time as the
doubly charged states (BPs, +2e)



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A)
Our treatment assumes that current is governed solely by generation and recombination at the heterojunction
and that both processes proceed through the polaron pair PP intermediate state.
PhysRevB.82.155305.pdf
(F:\RESPALDOS\Doc\Doctorado\DOCTORADO\Avance marzo - mayo 2014)

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B)
52099169-061-Physical-and-Chemical-Aspects-of-Organic-Electronics.pdf
(F:\Libros y Solucion\Doctorado)

Another proposed mechanism is connected with the doubly charged state of polymer chains, formation and
dissociation of bipolarons. (pg. 317)

Charges on the polymer chains occur as polarons (P) since a chain distortion appears due to electronphonon
coupling. For a long time, bipolarons (BP) [7, 8] have been considered as doubly charged and spin-less states of
the polymer chains. (pg. 317)

two polarons on a single chain or polaron pair (PP) model. Giving a consistent explanation of optical data,
the latter was proposed to be preferable compared with the BP model. (pg. 317)

Another possibility would be transport of carriers (polarons) connected with formation/dissociation of
bipolarons (a second order reaction). (pg. 319)

the doubly charged state of the polymer chain formed by the polaronpolaron reaction is a bipolaron or a
polaron pair. (pg. 319)

...second order polaron reaction leading to bipolarons. (pg. 331)

16.5 Equilibrium of Polarons With Doubly Charged States of the Polymer Chain (pg. 331)

Charges on polymer chains connected with a chain distortion appear in the case of holes as (hole) polarons
(Ps, charge +e and spin 1/2). (pg. 331)

Bipolarons have been considered for a long time as the doubly charged states [7, 8] (BPs, +2e) (pg. 331)

..formation of doubly charged polymer chain states by polaron pair collision and dissociation of
the doubly charged species,... (pg. 331)

Alternatives to the bipolaron have been discussed earlier and especially the two polarons on
a single chain or polaron pair (PP) model [9] (PPs, +2e) (pg. 332)


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C)

Bipolarons or Polaron Pairs in Conducting Polymers.pdf
(C:\Datos\RESPALDOS\DOC\Avance marzo - mayo 2014)
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D)

















(pg. 335)



Figure 16.11 Equilibrium concentrations of Ps, BPs, and PPs as functions of the electrochemical
potential for different equilibrium constants, zero at midgap position, oxidation potential
E
1
=1V, m = 6.

16.6.1 Formation and Dissociation of Bipolarons (pg. 339)

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E)
Brutting_Physics of Organic Semiconductors_352740550X.pdf
(F:\Libros y Solucion\Doctorado)

3.2 Charge Carrier Transport (pg. 6)



(pg. 7)



(pg. 131)

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F)
Device Physics of Organic (libro).pdf
(F:\Libros y Solucion\Doctorado)

Figure 3.7: The evolution of the energy levels of a molecular solid from single-molecule levels.
Gaps are decreased due to a polarization effect of the surrounding. Also excited states are
plotted on a separate scale, where the ground state S0 is placed at the position of the HOMO.
Disorder leads to a broadening of the levels.


(pg. 51)

3.2 Energy and charge transport in organic semiconductors (pg. 51)

Energy (exciton) and charge (polaron) transport in a highly ordered molecular crystal and at
low temperatures are comparable to the processes in conventional semiconductors described
in the previous chapter. These quasi-particles are coherently transported in energy bands with
a crystal momentum k.

3.2.1 Exciton transport
An excited state can be transfered to a neighboring molecule. The excited state is then called
an exciton, which provides an energy transport by migration. Such an exciton can be
delocalized in case of strong intermolecular interactions as present in a highly crystalline solid.
It is then called a Wannier exciton. This is not the case in the studied disordered materials,
where the exciton is mainly located on one molecule and can be treated as a neutral quasi-
particle with polaronic nature, called Frenkel exciton.

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G)
0507.Organic Photovoltaics. Mechanisms, Materials, and Devices (Optical Engineering) by Sam-
Shajing Sun.pdf
(F:\Libros y Solucion\Doctorado)
Devices based on a single polymer face two insurmountable challenges to produce a viable
solar cell. First, absorption of light does not directly generate charge carriers (electronhole
pairs or oppositely charged polarons). The primary photogenerated state is a neutral exciton
with a binding energy of several tenths of an electron volt.

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H)
Solar cell device physics Stephen J. Fonash.pdf

the multi-particle core-electron interactions in which the cores polarize to shield an electron s
charge give rise to multi-particle solutions to the overall Schrdinger equation which are called
polarons. Multi-particle electronelectron interactions can give rise to solutions termed
excitons. Polarons and excitons are examples of multi-particle states . (pg. )

(b) Excitons
Single -crystal, multicrystalline, and microcrystalline solids can also harbor
the solutions to the Schrdinger equation that are known as polarons and excitons. (pg. 24)

Polarons are generally only of any significance in crystals with some degree of ionicity. 1
Excitons are of much more interest, since they are a multi-particle phenomenon that can be
involved in the light absorption process in solar cell materials. Specifically, excitons are multi-
electron solutions that may be viewed as an electron bound to a hole via Coulombic attraction.

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http://www.springerimages.com/Images/RSS/1-
10.1007_978-1-4614-0742-3_1-4

Fig 5 Polaron and bipolaron states: (a) positive polaron, (b)
negative polaron, (c) positive bipolaron and (d) negative
bipolaron











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J)
http://blog.disorderedmatter.eu/2008/04/15/polaron-
polaron-pair-exciton-exciplex/

A polaron is a charge, i.e., an electron or a hole, plus a
distortion of the charges 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.

A polaron pair (PP) is a Coulomb bound pair of a negative and a positive polarons, situated on
different molecules. Usually, polaron pairs are the intermediate step from an exciton to a pair
of free polarons far enough apart not to feel the attraction of one another and therefore
important in order to understand photogeneration in organic semiconductors.

An exciton is an excited quasiparticle in a solid, which is formed by a Coulomb-bound electron-
hole pair. It is more prominent in organic semiconductors as compared to their inorganic
counterparts: as the dielectric constant is lower in organics, the screening length is larger. In
this case, the name Frenkel exciton is applied, whereas the weakly bound type is called
Wannier-Mott. Thus, in organic materials, the two charges feel a strong mutual attraction, and
usually reside on one molecule.

An exciplex is just an exciton which is located at the interface of its host molecular material
indeed it still resides on one molecule as indicated in the image. Due to the influence of the
surface, the exciplex experiences a different environment as compared to a bulk exciton. This
leads to photoluminescence which is slighlty red shifted. Also, the lifetime can be prolonged in
comparison to the bulk exciton, as it is stabilised by the surface states.

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K)
http://www.nature.com/nmat/journal/v7/n9/fig_tab/nmat2252_F1.html

Following formation of a polaron pair
(PP), it may either dissociate into free
charge carriers, or recombine through
an exciton state. Here, we focus on the
transition between polaron pairs with
triplet and singlet content. Two
possible mechanisms of moving from
PP
S
to PP
T
are illustrated: the first is
through incoherent spin-lattice
relaxation, the second by coherently
driving the pair between the singlet
and triplet configuration using pulsed
electron spin resonance. Electrically
neutral, bound singlet or triplet
excitons (SE, TE) do not contribute to
the current through the device, and
decay radiatively or non-radiatively.

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L)
http://www.nature.com/ncomms/2013/130802/ncomms3286/fig_tab/ncomms3286_F1.html

From
Tuning organic magnetoresistance in polymer-fullerene blends by controlling spin reaction
pathways ; P. Janssen, M. Cox, S.H.W. Wouters, M. Kemerink, M.M. Wienk
& B. Koopmans ; Nature Communications 4, Article number: 2286 doi:10.1038/ncomms3286


Figure 1: Unified picture of relevant particles and their spin-dependent reactions.
(a) Possible polaron pairs in an organic semiconductor as a function of energy. Free charges can
form precursor pairs in a singlet (S) 1( ) or triplet (T) 3( ) configuration. From this pair state, the
precursor pair can either recombine into a S or T exciton (in the case of an eh pair), a S
bipolaron (in the case of a bipolaron pair) or dissociate back into free carriers again. Because of
hyperfine fields (hf) the S and T precursor pairs can mix and an external magnetic field can
suppress this mixing. The magnetic field-dependent transitions between the pair states are
indicated with curved arrows. The energy levels and possible mixing mechanisms of a CTS are
also included in the diagram (shaded area). Electrons and holes are interchangeable in this
diagram. (b) The characteristic low (red) and high (blue) field lineshapes of the (i) bipolaron, (ii)
eh and (iii) tripletpolaron mechanism, all according to explicit calculations using a density
matrix formalism.



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M)
Bipolarons or Polaron Pairs in Conducting Polymers.pdf
(C:\Datos\RESPALDOS\DOC\Avance marzo - mayo 2014)
http://download.springer.com/static/pdf/269/art%253A10.1134%252FS1023193506110024.p
df?auth66=1399493482_7788ff3fe1811e2db2afb1e178180c84&ext=.pdf

Charges on the polymer chains appear as polarons (Ps) since due to electronphonon coupling
a chain distortion appears.

bipolarons (BPs) [5] occur also as charged states of the polymer chains.

Concerning equilibrium and kinetics the [] -dimer (on two adjacent chains) and two polarons
on a single chain are basically equivalent and denoted here as polaron pair (PP).

Charges on a polymer chain due to oxidation or charge injection at a contact lead primarily to
hole polarons Ps+ (charge +e, spin 1/2).

We denote the concentrations of Ps, BPs, and PPs by c
P
, c
BP
and c
PP
.


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N)
52099169-061-Physical-and-Chemical-Aspects-of-Organic-Electronics.pdf
(F:\Libros y Solucion\Doctorado)

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O)
Numerical simulations OSC.pdf
(C:\Datos\RESPALDOS\DOC)



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P)
Bipolarons or Polaron Pairs in Conducting Polymers.pdf (C:\Datos\RESPALDOS\DOC\Avance
marzo - mayo 2014)





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Q)
Polaron Pairs in P3HT-PCBM Composite.pdf
(C:\Datos\RESPALDOS\DOC\Avance marzo - mayo 2014)
http://download.springer.com/static/pdf/750/art%253A10.1007%252Fs00723-012-0401-
2.pdf?auth66=1399493746_306f5b6353ea6719551ca4ed103c67af&ext=.pdf

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R)








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S)
m 6 a 10 , monomer units

c
P
: concentrations of Ps (polarones)
c
BP
: concentrations of BPs (bipolarones)
c
PP
: concentrations of PPs (pares de polarones)
c
0
: concentration of neutral segments
c
S
:segment concentration
c
mon
= mc
S
: monomer concentration
= 1 g/cm
3
, mass density
mw = 166 , molecular weight
con m = 6
c
S
= 5 x 10
20
cm
-3


c
mon
= mc
S
= (6) (5 x 10
20
cm
-3
) = 3 x 10
21
cm
-3


c
0
= c
P
Y
1


c
P
= c
BP
Y
2


Yi = exp -f(E-Ei)

E1 : standard potentials for the first oxidation step
E2 : standard potentials for the second oxidation step
- eE = F : electrochemical potential is connected with the Fermi energy
1/f = k T /e
c
S
= c
0
+ c
P
+ c
BP

K
BP
= exp f(E1 E2) = (c
BP
c
0
/ c
P
2
)
equi.


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http://en.wikipedia.org/wiki/Polymer_solar_cell
animacin

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http://www.amazon.com/Handbook-Organic-Conductive-Molecules-Polymers/dp/0471968137
Handbook of Organic Conductive Molecules and Polymers

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http://www.chem.wisc.edu/courses/341/handouts/ACR_1985_18_309.pdf
Polarons , bipolarons and solitons in conducting polymers.pdf
C:\Datos\RESPALDOS\DOC

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T)








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U)
http://www.nature.com/pj/journal/v17/n1/pdf/pj198517a.pdf
charge storage in conducting polymers, soliton, polaron and bipolaron.pdf
C:\Datos\RESPALDOS\DOC

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http://www.amazon.com/Solitons-Polarons-Conducting-Polymers-L/dp/997150054X
Solitons and Polarons in Conducting Polymers [Paperback]
by L. Yu

http://books.google.com.mx/books?id=l1uaDjUxvpcC&pg=PA267&lpg=PA267&dq=J.L.+Bredas,
+R.R.+Chance,+R.+Silbey,+Phys.+Rev.+B26+(1982)+5843&source=bl&ots=vXOPWEYkH1&sig=3ll
iOL_g9TBCQkHFiD2dF5WVtcs&hl=es&sa=X&ei=6j96U9TAIMeiqAaJiIGwCw&ved=0CDYQ6AEwA
g#v=onepage&q=J.L.%20Bredas%2C%20R.R.%20Chance%2C%20R.%20Silbey%2C%20Phys.%20
Rev.%20B26%20(1982)%205843&f=false

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http://books.google.com.mx/books?id=6GRovXHas_MC&pg=PA841&lpg=PA841&dq=J.L.+Bred
as,+R.R.+Chance,+R.+Silbey,+Phys.+Rev.+B26+(1982)+5843&source=bl&ots=FNRwD_3ztk&sig=
L-
jy0SmaLNSMNLJJo7RklmaRVpQ&hl=es&sa=X&ei=6j96U9TAIMeiqAaJiIGwCw&ved=0CFkQ6AEw
Bw#v=onepage&q=J.L.%20Bredas%2C%20R.R.%20Chance%2C%20R.%20Silbey%2C%20Phys.%2
0Rev.%20B26%20(1982)%205843&f=false

Handbook of Conducting Polymers, Second Edition,
editado por Terje A. Skotheim

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PhysRevB.82.155305.pdf
(C:\Datos\RESPALDOS\DOC\Avance marzo - mayo 2014)
Ideal diode equation for organic heterojunctions. I. Derivation and application