Kyung Min Lee

Beating the thermodynamic limit with photo-activation of n-doping in organic semiconductors

Chemical doping of organic semiconductors using molecular dopants plays a key role in the fabrication of efficient organic electronic devices. Although a variety of stable molecular p-dopants have been developed and successfully deployed in devices in the past decade, air-stable molecular n-dopants suitable for materials with low electron affinity are still elusive. Here we demonstrate that photo-activation of a cleavable air-stable dimeric dopant can result in kinetically stable and efficient n-doping of host semiconductors, whose reduction potentials are beyond the thermodynamic reach of the dimers effective reducing strength. Electron-transport layers doped in this manner are used to fabricate high-efficiency organic light-emitting diodes. Our strategy thus enables a new paradigm for using air-stable molecular dopants to improve conductivity in, and provide ohmic contacts to, organic semiconductors with very low electron affinity.

Electrical Stress Influences the Efficiency of CH3NH3PbI3 Perovskite Light Emitting Devices

Organic-inorganic hybrid perovskite materials are emerging as semiconductors with potential application in optoelectronic devices. In particular, perovskites are very promising for light-emitting devices (LEDs) due to their high color purity, low nonradiative recombination rates, and tunable bandgap. Here, using pure CH3 NH3 PbI3 perovskite LEDs with an external quantum efficiency (EQE) of 5.9% as a platform, it is shown that electrical stress can influence device performance significantly, increasing the EQE from an initial 5.9% to as high as 7.4%. Consistent with the enhanced device performance, both the steady-state photoluminescence (PL) intensity and the time-resolved PL decay lifetime increase after electrical stress, indicating a reduction in nonradiative recombination in the perovskite film. By investigating the temperature-dependent characteristics of the perovskite LEDs and the cross-sectional elemental depth profile, it is proposed that trap reduction and resulting device-performance enhancement is due to local ionic motion of excess ions, likely excess mobile iodide, in the perovskite film that fills vacancies and reduces interstitial defects. On the other hand, it is found that overstressed LEDs show irreversibly degraded device performance, possibly because ions initially on the perovskite lattice are displaced during extended electrical stress and create defects such as vacancies.

Phototriggered Depolymerization of Flexible Poly(phthalaldehyde) Substrates by Integrated Organic Light-Emitting Diodes

We demonstrate phototriggered depolymerization of a low ceiling temperature ( Tc) polymer, poly(phthalaldehyde) (PPHA), via internal light emission from integrated organic light-emitting diodes (OLEDs) fabricated directly on flexible PPHA substrates with silver nanowire electrodes. The depolymerization of the PPHA substrates is triggered by absorption of the OLED emission by a sensitizer that activates a photoacid generator via energetically favorable electron transfer. We confirm with Fourier-transform infrared spectroscopy that the photon doses delivered by the integrated OLED are sufficient to depolymerize the PPHA substrates. We determine this critical dosage by measuring the operating lifetimes of the OLEDs whose failure is believed to be due to significant mechanical softening during the liquefaction of decomposed phthalaldehyde monomers.

Redox-active molecules as electrical dopants for OLED transport materials (Conference Presentation)

Electrical doping of organic semiconductors increases conductivity and reduces injection barriers from electrode materials, both of which effects can improve the performance of organic light-emitting diodes (OLEDs). However, the low electron affinities of typical OLED electron-transport materials make the identification of suitable n-dopants particularly challenging; electropositive metals such as the alkali metals are not easily handled and form monoatomic ions that are rather mobile in host materials, whereas molecular dopants that operate as simple one-electron reductants must have low ionization energies, which leads to severe air sensitivity. This presentation will discuss approaches to circumventing this issue by coupling electron transfer to other chemical reactivity. In particular, dimers formed by certain highly reducing organometallic sandwich compounds and organic radicals can be handled in air, yet have effective reducing potentials, corresponding to formation of the corresponding monomeric cations and contribution of two electrons to the semiconductor, of ca. –2.0 V vs. ferrocene. These values fall a little short of what is required for typical OLED materials; approaches to further extending the doping reach of these dimers will be described. One such approach involving photoirradiation of a dimer:semiconductor blend leads to metastable doping of a material with a redox potential of –2.24 V, which allows the fabrication of efficient OLEDs in which even high-workfunction electrodes, such as indium tin oxide, can be used as electron-injection contacts.

Corrigendum: Beating the thermodynamic limit with photo-activation of n-doping in organic semiconductors

This corrects the article DOI: 10.1038/nmat5027.