讲稿20. 有机发光二极管-第八部分

1、1,Organic LEDs part 8,Exciton Dynamics in Disordered Organic Thin Films Quantum Dot LEDs,Handout on QD-LEDs: Coe et al., Nature 420, 800 (2002).,April 29, 2003 Organic Optoelectronics - Lecture 20b,2,Exciton Dynamics in Time Dependant PL,3,Dynamic Spectral Shifts of DCM2 in Alq3, Measurement performed on doped DCM2:Alq3 films Excitation at =490 nm (only DCM2 absorbs), DCM2 PL red shifts 20 nm over 6 ns ,Wavelength nm ,4,Time Evolution of 4% DCM2 in Alq3 PL Spectrum,5,Electronic Processes in Mole

2、cules,density of available S1 or T1 states,6,Time Evolution of DCM2 Solution PL Spectra,7,Spectral Shift due to, Exciton Diffusion Intermolecular Solid State Interactions ,8,Excitonic Energy Variations,9,Exciton Distribution in the Excited State (S1 or T1), Time Evolved Exciton Thermalization ,EXCITON DIFFUSION LEADS TO REDUCTION IN FWHM,10,11,12,13,Time Evolution of Peak PL in Neat Thin Films,14,Parameters for Simulating Exciton Diffusion,observed radiative lifetime (),Normalized Integrated Spe

3、ctral Intensity,Frster radius (RF), Assign value for allowed transfers:, Assume Gaussian shape of width, wDOS Center at peak of initial bulk PL spectrum Molecular PL spectrum implied,excitonic density of states (gex(E),15,Fitting Simulation to Experiment Doped Films, Good fits possible for all data sets RF decreases with increasing doping, falling from 52 to 22 wDOS also decreases with increasing doping, ranging from 0.146 eV to 0.120 eV,16,Fitting Simulation Neat Films, Spectral shift observed

4、in each material system Molecular dipole and wDOS are correllated: lower dipoles correspond to less dispersion Even with no dipole, some dispersion exists Experimental technique general, and yields first measurements of excitonic energy dispersion in amorphous organic solids,17,Temporal Solid State Solvation,upon excitation both magnitude and direction of lumophore dipole moment can change FOR EXAMPLE for DCM: 1 0 20 Debye ! from 5.6 D to 26.3 D ,following the excitation the environment surround

5、ing the excited molecule will reorganize to minimize the overall energy of the system (maximize Eloc),18,Exciton Distribution in the Excited State (S1 or T1), Time Evolved Molecular Reconfiguration ,DIPOLE-DIPOLE INTERACTION LEADS TO ENERGY SHIFT IN DENSITY OF EXCITED STATES,log(Time),19,Fusion of Two Material Sets,Hybrid devices could enable LEDs, Solar Cells, Photodetectors, Modulators, and Lasers which utilize the best properties of each individual material.,Efficient,Organic Semiconductors,F

6、lexible,Emissive,Fabrication of rational structures has been the main obstacle to date.,20,Inorganic Nanocrystals Quantum Dots,Quantum Dot SIZE,Synthetic route of Murray et al, J. Am. Chem. Soc. 115, 8706 (1993).,21,Fusion of Two Material Sets,Quantum Dots,Organic Molecules,22,Integration of Nanoscale Materials Quantum Dots and Organic Semiconductors,ZnS overcoating shell (0 to 5 monolayers),Oleic Acid or TOPO caps,Synthetic routes of Murray et al, J. Am. Chem. Soc. 115, 8706 (1993) and Chen, et

7、 al, MRS Symp. Proc. 691,G10.2.,Trioctylphosphine oxide,Tris(8-hydroxyquinoline) Aluminum (III),3-(4-Biphenylyl)-4-phenyl-5- tert-butylphenyl-1,2,4-triazole,N,N-Bis(naphthalen-1-yl)- N,N-bis(phenyl)benzidine,N,N-Bis(3-methylphenyl)- N,N-bis-(phenyl)-benzidine,23,1. A solution of an organic material, QDs, and solvent 2. is spin-coated onto a clean substrate. 3. During the solvent drying time, the QDs rise to the surface 4. and self-assemble into grains of hexagonally close packed spheres.,Organic

8、 hosts that deposit as flat films allow for imaging via AFM, despite the AFM tip being as large as the QDs.,Phase segregation is driven by a combination of size and chemistry.,Phase Segregation and Self-Assembly,24,As the concentration of QDs in the spin-casting solution is increased, the coverage of QDs on the monolayer is also increased.,Monolayer Coverage QD concentration,25,CdSe(ZnS)/TOPO,PbSe/oleic acid,QD-LED Performance,26,Full Size Series of PbSe Nanocrystals from 3 nm to 10 nm in Diamet

9、er,27,Design of Device Structures,QDs are poor charge transport materials.,Isolate layer functions of maximize device performance,1. Generate excitons on organic sites. 2. Transfer excitons to QDs via Frster or Dexter energy transfer. 3. QD electroluminescence.,Phase Segregation.,But efficient emitters,Use organics for charge transport.,Need a new fabrication method in order to be able to make such double heterostructures:,28,A general method?,Phase segregation occurs for different 1) organic hosts: TPD, NPD, and poly-TPD. 2) solvents: chloroform, chlorobenzene, and mixtures with toluene. 3) QD core materials: PbSe, CdSe, and CdSe(ZnS). 4) QD capping molecules: oleic acid and TOPO. 5) QD core size: 4-8nm. 6) substrates: Silicon, Glass, ITO. 7) Spin parameters: speed, acceleration and time., This process is robust, but further exploration is needed to broadly generaliz

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