Exciton Diffusion. Exciton Diffusion

Exciton Diffusion Exciton Energy transfer Exciton Diffusion. Photoluminescence measurement. Photocurrent measurement Handout on Photocurrent Response: Bulovic and Forrest., Chemical Physics 210, 13 (1996). Handout on Solar Cells and Photodetectors: Peumans, Bulovic, and Forrest., Appl. Phys. Lett. 76, 2650 (2000) & 76, 3855 (2000). @ MIT March 4, 2003 Organic Optoelectronics - Lecture 8 1

Energy Transfer dopant molecules (generate luminescence) host molecules How does an exciton in the host transfer to the dopant? Energy transfer processes: 1. Radiative transfer 2. Förster transfer 3. Dexter transfer 2

Radiative energy transfer Transfer of excitation energy by radiative deactivation of a donor molecular entity and reabsorption of the emitted light by an acceptor molecular entity. The probability of transfer is given approximately by: Pr, t [ A] xj Where J is the spectral overlap integral, [A] is the concentration of the acceptor, and x is the specimen thickness. This type of energy transfer depends on the shape and size of the vessel utilized. Same as trivial energy transfer. Quoted from IUPAC Compendium of Chemical Terminology compiled by Alan D. McNaught and Andrew Wilkinson (Royal Society of Chemistry, Cambridge, UK). 3

Förster transfer - resonant dipole-dipole coupling - donor and acceptor transitions must be allowed very fast <10-9 s R O < 100Å Donor Acceptor (dye) Donor * Acceptor Donor Acceptor * typically singlet- singlet transitions 4

Förster transfer - Example Alq 3 LUMO Alq 3 (DONOR) DCM LUMO ABSORPTION PL 200 300 400 500 600 700 800 900 Wavelength [nm] FÖRSTER ENERGY TRANSFER DCM HOMO DCM (ACCEPTOR) Alq 3 HOMO ABSORPTION EL DCM2 in Alq 3 200 300 400 500 600 700 800 900 Wavelength [nm] Alq 3 low DCM2 high DCM2 for efficient transfer donor emission and acceptor absorption must overlap 5

Förster excitation transfer (dipole-dipole) excitation transfer) A mechanism of excitation transfer which can occur between molecular entities separated by distances considerably exceeding the sum of their van der Waals radii. It is described in terms of an interaction between the transition dipole moments (a dipolar mechanism). The transfer rate constant kd A is given by: k D A = K 2 J8.8 10 4 6 n ϖr Where K is an orientation factor, n the refractive index of the medium, ω the radiative lifetime of the donor, r the distance (cm) between donor (D) and acceptor (A), and J the spectral overlap (in coherent units cm 6 mol -1 ) between the absorption spectrum of the acceptor and the florescence spectrum of the donor. The critical quenching radium r 0, is that distance at which kd A is equal to the inverse of the radiative lifetime. 28 mol Quoted from IUPAC Compendium of Chemical Terminology compiled by Alan D. McNaught and Andrew Wilkinson (Royal Society of Chemistry, Cambridge, UK). 6

Förster transfer Rate Equations 2π 2 K ET = (2π/ħ) <D,A* H DA Pda D*,A> = Z fd ( Fa ( E) h 2 g D (E) g A (E) de Energy transfer rate (K ET ) depends on the overlap integral FOR DIPOLE-DIPOLE INTERACTION: KET ( R ) = τ R R 1 0 6 g A (E) g D (E) ALLOWED TRANSITIONS: 1 D * + 1 A 1 D + 1 A * 1 D * + 3 A(T n ) 1 D + 3 A * (T m ) g A (E) (Adapted from Blasse & Grabmaier) 7

Dexter transfer diffusion of excitons from donor to acceptor Wigner-Witmer spin conservation rules A + B C + D total spin of reactants: (S A +S B ),(S A +S B -1),..., S A -S B total spin of products: (S C +S D ),(S C +S D -1),..., S C -S D reaction allowed if two sequences have a number in common only singlet-singlet, triplet-triplet allowed speed? Donor Acceptor ( eg. phosphorescent dye ) Donor * Acceptor Donor Acceptor * ~ 10Å 8

Dexter excitation transfer (electron exchange excitation transfer) Excitation transfer occurring as a result of an electron exchange mechanism. It requires an overlap of the wave functions of the energy donor and the energy acceptor. It is the dominant mechanism in triplet-triplet energy transfer. The transfer rate constant, k ET, is given by: 2 ket [ h ( 2π )] P J exp[ 2r L] where r is the distance between donor (D) and acceptor (A), L and P are constants not easily related to experimentally determinable quantities, and J is the spectral overlap integral. For this mechanism the spin conservation rules are obeyed. Quoted from IUPAC Compendium of Chemical Terminology compiled by Alan D. McNaught and Andrew Wilkinson (Royal Society of Chemistry, Cambridge, UK). 9

Nonradiative Energy Transfer Förster, Coulombic (long range ~30-100 Å) Dexter, e - exchange (short range ~6-20 Å) D * A D * A SINGLET-SINGLET SINGLET-SINGLET & TRANSFER TRIPLET-TRIPLET TRANSFER D A * 10

Cascade Energy Transfer Laser Threshold Energy ~ 0.1 µj/cm 2 Absorbance and photoluminescence spectra of the host material and fluorescent dyes. The host material is 2-(4-biphenylyl)-5-(4-tbutylphenyl)-1,3,4-oxadiazole(PBD); the dyes are coumarin 490(C490), DCMII and LDS821. The spectra for PBD are from a pure film whereas the other spectra are from solid solutions of the material in polystyrene. Normalized absorbance of PBD, and stimulated emission spectra from this material alone, and when doped with dyes. Curve: (a) PBD only; (b) 0.6% C490 in PBD; (c) 0.6% C490 + 0.9% DCMII in PBD (d) 0.6% C490 + 0.9% DCMII + 0.6% + LDS821 in PBD. Adapted from Figure 1 and 2 from Berggren, et al., Nature 389, 466 (1997). 11

Luminescent Organic Film on a Si p-n Junction "Escape Cone" cone A UV 1 Visible 7 Quantum Efficiency of Photoresponse 1 0.1 0.01 Coated η i = 35 % η i = 25 % Uncoated Alq 3 on Si p-n junction d = 0.52 µm η i = i 0.30 0.30 ± 0.05 0.05 300 400 500 600 Wavelength [nm] Adapted From: Garboze et al, Journal of Applied Physics, vol 80, pg 4644, 1996 2 calculated improvement 10.9% Photocurrent [a.u.] 2 1 0 3 cone B Film p-si n-si 4 5 6 AR coating in Visible Downconverter in UV Conventional Si Solar Cell Si Cell coated with 100% PL Efficient Organic Film 200 400 600 800 1000 Wavelength [nm] 12

Diffusion of Excitons PL Internal Efficiency [%] 40 30 20 10 0 Alq 3 exciton diffusion length ~ 10 nm PL efficiency of Alq 3 on glass 0.01 0.1 1 Film Thickness [µm] If energy transfer occurs between the donor and acceptor molecules of the same species, the term energy migration is used. The four general methods used to measure diffusion of excitons are: bulk quenching, surface quenching, bimolecular recombination, and photoconduction ABSORPTION PL Alq 3 200 300 400 500 600 700 800 900 Wavelength [nm] Adapted From: Garboze et al, Journal of Applied Physics, vol 80, pg 4644, 1996 Small overlap between Alq 3 absorption and luminescence results in a small Förster radius of ~12 Å Since the size of Alq 3 molecules is ~10 Å Förster energy transfer can facilitate exciton diffusion 13

Photosynthetic Machinery of Purple Bacteria energy transfer often occurs in biological systems exciton transport followed by exciton dissociation (RESULTING IN STABLE TRANSMEMBRANE CHARGE SEPARATION) V. Sundström, et al., J. Phys. Chem. B 103, 2327 (1999). Light-induced electron transport ATP synthesis in a photosynthetic bacterium http://www.nobel.se/chemistry/ educational/poster/1988/ 14

Schematic picture of a photosynthetic reaction center from the bacterium Rhodopseudomonas virdis. The polypeptide chains are drawn as ribbons of different colors for the four different protein subunits. Image from http://www.bio.anl.gov/ The reaction center is composed of four protein subunits. Two of these, the L and M subunits, each form five membranespanninghelices. The structure shows the precise arrangement in the L and M subunits of the photochemically active groups two chlorophyll molecules forming a dimer, two monomeric chlorophylls, two pheophytin molecules (these lack the central magnesium ion of chlorophyll), one quinone molecule, called QA (a second quinone molecule, QB, is lost during the preparation of the reaction center) and one iron ion (Fe). The L and M subunits and their chromophores are related by a twofold symmetry axis that passes through the chlorophyll dimer and the iron. A third subunit, H, without active groups and located on the membrane inner surface, is anchored to the membrane by a protein helix. The remaining subunit, a cytochrome with four heme groups (related to the blood pigment hemoglobin), binds at the outer surface of the membrane. Photosynthesis and respiration are based on the transfer of electrons between donor and acceptor molecules bound to biological membranes sheet-like structures composed of lipids and proteins which surround the cells and their inner compartments. The photosynthetic reactions in plants take place in the inner membranes of the chloroplasts, the organelles which contain the chlorophyll. Some bacteria have a simpler form of photosynthesis, to some extent similar to that in plants but without the ability to form oxygen. In all types of photosynthesis, the light energy absorbed by chlorophyll is transferred to membrane-bound protein-pigment complexes, known as reaction centers. In these complexes the light energy initiates electron-transfer reactions which are coupled to the translocation of hydrogen ions across the membrane. The resulting ph gradient is utilized by another membrane-bound protein, ATPase, to synthesize ATP, a compound used as a fuel in energy-demanding biological processes. In cell respiration, too, electron transport is coupled to proton translocation and ATP synthesis. From http://www.nobel.se/chemistry/educational/poster/1988/ 15

Single Layer Organic PV Cells PTCDA V 11.96 Å In PTCDA 17.34 Å ITO z 3.21Å Glass x y Incident Light 16

Photocurrent Generation LIGHT ABSORPTION EXCITON GENERATION EXCITON DIFFUSION E EXCITON DISSOCIATION CARRIER SEPARATION CARRIER TRANSPORT DELIVERY TO EXTERNAL CIRCUIT 17

Photocurrent, Photovoltage, Absorption Photocurrent measured at 0V external bias 25pA 10µV 500 nm PTCDA Thin Film photon flux = 5 x 10 14 cm -2 s -1 5x10 5 Photocurrent / Photovoltage 20pA 15pA 10pA 5pA 8µV 6µV 4µV 2µV Photo - I Photo - V α 4x10 5 3x10 5 2x10 5 1x10 5 α [cm -1 ] In V PTCDA 0A 0V 2.0 2.2 2.4 2.6 2.8 3.0 0 ITO Glass Energy [ev] Incident Light 18

Photocurrent Dependence on Electric Field Different photocurrent response for positive and negative applied bias positive field (In +, ITO -) negative field (In -, ITO +) 10-1 V/µm 10-1 Yield [%] 10-2 10-3 1.00 0.40 0.20 0.10 0.04 0.01 2.0 2.5 3.0 Energy [ev] Yield [%] 10-2 10-3 V/µm 1.00 0.40 0.10 0.04 0.01 0.00 2.0 2.5 3.0 Energy [ev] 19