Dynamics in blue emitting metal halide perovskites for light emitting diodes

• Main Author: Karlsson, Max
• Other Authors: Sum Tze Chien
• Format: Thesis-Doctor of Philosophy
• Language: English
• Published: Nanyang Technological University 2023
• Subjects: Science::Physics::Optics and light; Engineering::Materials::Photonics and optoelectronics materials
• Online Access: https://hdl.handle.net/10356/166337
• Institution: Nanyang Technological University

Lighting comprises a large part of the global electricity consumption as of today, and the use of lighting in illumination and displays is only projected to grow. It is therefore imperative to meet this energy demand, not only by means of greener energy production, but also with materials that are both more efficient to fabricate as well as to use. Low cost and energy efficient light sources therefore play an important role in minimizing further greenhouse emissions from the way we choose to live. Metal halide perovskites are a group of semiconductors that have received a great amount of attention during the past years due to impressive - and continuously increasing - performance as active materials implemented in solar cells and light emitting diodes. This is due to highly desirable optoelectronic properties combined with low-cost, solution-processable fabrication methods. Simple bandgap-tunability is easily achieved by compositional and dimensional engineering, allowing perovskite emission to span a broad wavelength region from ultraviolet to near infrared. As with previous technologies, attaining stable, bright, and pure blue light has proven difficult also in metal halide perovskites. This thesis investigates some of the challenges in achieving blue emission in mixed-halide and mixed-dimensional perovskites for light-emitting-diode applications. Mixed-halide alloying provides the most straightforward way of tuning the bandgap of perovskites. Unfortunately, mixed bromide/chloride-perovskites (used to achieve blue light) suffer from both spectral and temporal instabilities, as well as severe luminescence quenching at the large chloride contents necessary for blue emission. The spectral instability arises from a segregation of halides into regions of differing halide content, and hence different bandgap, resulting in a shift in emission color during operation. Although the origins of the poor temporal stability of perovskite light emitting diodes are manifold, one of the main problems are the low barriers for halide migration under the applied electric field during operation, rapidly degrading the device properties. We first find that compositional heterogeneities, stemming from rapid uncontrolled film growth, both lowers the threshold for further halide segregation as well as serves as centers for non-radiative recombination, resulting in reduced luminescence yield. We show that by carefully moderating the crystallization dynamics it is possible to achieve films with a homogeneous composition, thereby mitigating the negative effects arising from material inhomogeneities. We identify means of how growth environment, stoichiometric tuning and chelating additives can be used to favorably control film formation and provide guidelines that can be more widely applied in the fabrication of perovskite films and devices. We continue by investigating the role of Br/Cl-alloying on device efficiency and stability in green to blue emitting perovskite LEDs. We find that chloride incorporation, while having only a minor impact on efficiency at moderate levels, detrimentally affects device stability even in small amounts. We ascribe this phenomenon to an increased mobility of halogen ions in the mixed-halide lattice resulting from an increased chemically and structurally disordered landscape with reduced migration barriers. We assign this as the major obstacle towards stable blue-emitting mixed-halide perovskite light emitting diodes. In the last work we investigate blue emitting mixed-dimensional Ruddlesden-Popper perovskites (RPPs) comprising of multiple-quantum-well-structures of varying bandgap. Successful implementation in LEDs has been attributed to efficient carrier funneling from large bandgap (donor) regions to low bandgap regions (acceptors) resulting in improved luminescence yields due to trap state filling from the locally increased carrier density. However, due to the enhanced carrier concentrations in acceptor domains, Auger recombination quickly outcompetes radiative recombination mechanisms already at moderate pump fluences or carrier injection densities in RPPs. We show that by moderating the inter-well carrier transfer, while at the same time providing adequate defect passivation, high quantum yields can be maintained even at large carrier densities. We thereby show that RPPs can support a large density of carriers without compromising luminescence efficiency, paving the way for their use in high brightness applications by engineering the funneling and recombination processes in these materials. The work in this thesis provides new insights on various dynamical processes in metal halide perovskites aimed at light emitting applications. The hope is that it will contribute toward the understanding of these systems and help in bringing these materials closer to practical use.