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  4. Ion and Trap Induced Dynamic Phenomena in Salt Semiconductor Devices
 
doctoral thesis

Ion and Trap Induced Dynamic Phenomena in Salt Semiconductor Devices

Diethelm, Matthias  
2021

State-of-the-art organic light-emitting diodes (OLEDs) used in commercial display technology are complex multilayer structures. In contrast, the light-emitting electrochemical cell (LEC) can be built from a single emissive layer sandwiched between two electrodes. Due to the presence of mobile ions - intermixed with the active material - the single layer can perform all the tasks that take place in an OLED, i.e., electrical charge injection, transport, exciton formation, and radiative recombination. Therefore, LECs have the potential to be fabricated by low-cost solution coating and printing processes. While the structure is simple, the simultaneous occurrence of electronic and mobile ionic charge introduces a complex device functionality. Basic operation principles have been discussed for years in the field and consensus has been reached on the electrochemical doping model. The focus of this thesis is to unravel the interplay of electronic and ionic charges in LECs and to highlight the boundaries and gaps of the firmly established electrochemical doping model. Used methods and conclusions are not restricted to the polymer-based LECs and can be applied to various systems with combined electronic and ionic conduction, as demonstrated for perovskite LEDs. First, effects of ion concentration and active layer thickness variation in the super yellow (SY) polymer LEC (PLEC) are investigated, which play a critical role on the performance. The dependence on the layer thickness reveals the often-overlooked microcavity/Purcell effect, which leads to a strong dependence of the optical outcoupling efficiency on the emitter position (EP) within the active layer. For thicker PLECs, a continuous change of the emission colour during operation provides a direct visual indication of a moving EP. Drift-diffusion simulation of the electrical measurements pinpoints the EP shift to ion dynamics and demonstrates that the only precondition for this event to occur is unequal cation and anion mobilities. Quantitative ion profiles reveal that the movement of ions stops when the intrinsic zone stabilizes, confirming the relation between ion movement and EZ shift. The unresolved origin of device degradation after the ionic steady state has been reached leads to the study of the SY polymer LED (PLED) with the idea to isolate the electronic from ionic effects. Response of PLEDs to electrical driving and breaks covering the timescale from microseconds to (a few) hours reveals a surprisingly slow response of electron traps. Subsequently, the characteristic response of the electron traps to electrical breaks is identified in the PLEC as well. Further investigation by electroabsorption measurement finds that hole trap formation limits the device lifetime, in the exact same manner as for PLEDs. The methodology to unravel dynamic processes due to mobile ions, electronic charges and trap development is applied to perovskite light-emitting diodes (PeLEDs). The application of the optical model based on the microcavity effect to the PeLED is discussed. Experimental thickness variation of the TPBi transport layer of a CsPbBr3 based PeLED indicates the validity of the optical model. A transient voltage pulse reveals an emission feature within the time range of ionic mobility. Transient drift-diffusion simulation is able to describe the observed emission increase as a result of ionic movement.

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Type
doctoral thesis
DOI
10.5075/epfl-thesis-8881
Author(s)
Diethelm, Matthias  
Advisors
Nüesch, Frank  
•
Hany, Roland  
Jury

Prof. Christophe Ballif (président) ; Prof. Frank Nüesch, Dr Roland Hany (directeurs) ; Prof. Mohammad K. Nazeeruddin, Prof. Henk J. Bolink, Prof. L. Jan Anton Koster (rapporteurs)

Date Issued

2021

Publisher

EPFL

Publisher place

Lausanne

Public defense year

2021-11-15

Thesis number

8881

Total of pages

197

Subjects

light-emitting electrochemical cell

•

optical model

•

super yellow

•

mobile ion

•

drift-diffusion model

•

emitter position

•

polymer light emitting diode

•

charge trap dynamics

•

degradation

•

perovskite LED

EPFL units
URSIMX  
Faculty
STI  
School
IMX  
Doctoral School
EDMX  
Available on Infoscience
October 28, 2021
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/182597
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