What are perovskites?
Perovskite is a calcium titanium oxide mineral, with the chemical formula CaTiO3, discovered in the Ural Mountains of Russia by Gustav Rose in 1839 and named after Russian mineralogist Lev Perovski (1792–1856).
Perovskites are a class of materials with a similar structure that are easily synthesized and relatively low-cost. Perovskites are considered the future of solar cells and are also predicted to play a significant role in next-gen electric vehicle batteries, displays, sensors, lasers and much more.
Perovskites can have an impressive collection of interesting properties including “colossal magnetoresistance” - their electrical resistance changes when they are put in a magnetic field (which can be useful for microelectronics). Some Perovskites are superconductors, which means they can conduct electricity with no resistance at all. Perovskite materials exhibit many other interesting and intriguing properties. Ferroelectricity, charge ordering, spin dependent transport, high thermopower and the interplay of structural, magnetic and transport properties are commonly observed features in this family. Perovskites therefore hold exciting opportunities for physicists, chemists and material scientists.
What are LEDs?
A light-emitting diode (LED) is an electronic component that is essentially a two-lead semiconductor light source. It is a p–n junction diode that emits light upon activation by a voltage applied to the leads, which makes electrons recombine with electron holes within the device, releasing energy in the form of photons. This effect is called electroluminescence, and the color of the light is determined by the energy band gap of the chosen semiconductor.
LEDs’ advantages over incandescent light sources include lower energy consumption, longer lifetime, improved physical robustness, smaller size, and faster switching. Light-emitting diodes have become ubiquitous and are found in diverse applications in the aerospace and automotive industries, as well as in advertising, traffic signals, camera flashes and much more.
LEDs meant for general room lighting currently remain more expensive than fluorescent or incandescent sources of similar output, but are significantly more energy efficient.
What can perovskites do for LEDs?
Current high-quality LEDs are based on direct bandgap semiconductors, but making these devices is no easy task because they need to be processed at high temperatures and in vacuum, which makes them rather expensive to produce in large quantities. Perovskites that are direct-bandgap semiconductors could be real alternatives to other types of direct-bandgap materials for applications like color displays, since they are cheap and easy to make and can be easily tuned to emit light of a variety of colours.
Researchers have found that organometal halide-based perovskites (a combination of lead, organics and halogens that arrange into perovskite crystal structure in the solid state) could be very suitable for making optoelectronics devices, since they can be processed in solution and do not need to be heated to high temperatures. This means that large-area films of the these materials can be deposited onto a wide range of flexible or rigid substrates. The perovskites also have an optical bandgap that can be tuned in the visible to infrared regions, which makes them very promising for a range of optoelectronics applications. These materials also emit light very strongly, which makes them very suitable for making LEDs. The light emitted by the perovskites can be easily tuned, which could make them ideal for color displays and lighting, and in optical communication applications.
However, a major obstacle that perovskites will have to overcome in order to be used in LED-type devices is that electrons and holes only weakly bind in perovskite thin films. This means that excitons (electron-hole pairs) spontaneously dissociate into free carriers in the bulk recombination layer, leading to low photoluminescence quantum efficiency (PLQE), high leakage current and low luminous efficiency. This obviously impairs perovskites’ ability to create high-performance LEDs, and for perovskite materials to make a comparable impact in light emission, it is necessary to overcome their slow radiative recombination kinetics. Simply put, researchers will have to find ways of effectively confining electrons and holes in the perovskite so that they can “recombine” to emit light. Major progress is already being made in this field, and it seems that perovskites will indeed open the door to a low-cost, color-tunable approach to LED development.
Recent work in the field of perovskite-based LEDs
In July 2016, researchers at Nanyang Technological University in Singapore have fabricated high-performance green light-emitting diodes based on colloidal organometal perovskite nanoparticles. The devices have a maximum luminous efficiency of 11.49 cd/A, a power efficiency of 7.84 lm/W and an external quantum efficiency of 3.8%. This value is said to be about 3.5 times higher than that of the best colloidal perovskite quantum-dot-based LEDs previously made.
In March 2016, researchers at the University of Toronto in Canada and ShangaiTech University in China have succeeded in using colloidal quantum dots in a high-mobility perovskite matrix to make a near-infrared (NIR) light-emitting diode (LED) with a record electroluminescence power conversion efficiency of nearly 5% for this type of device. The NIR LED could find use in applications such as night vision devices, biomedical imaging, optical communications and computing.
In February 2016, researchers from the Universitat Jaume I and the Universitat de València have studied the interaction of two materials, halide perovskite and quantum dots, revealing significant potential for the development of advanced LEDs and more efficient solar cells. The researchers quantified the "exciplex state" resulting from the coupling of halide perovskites and colloidal quantum dots, both known separately for their optoelectronic properties, but when combined, these materials yield longer wavelengths than can be achieved by either material alone, plus easy tuning properties that together have the potential to introduce important changes in LED and solar technologies.
In December 2015, researchers at Pohang University in Korea are reportedly the first to develop a perovskite light emitting diode (PeLED) that could replace organic LED (OLED) and quantum dot LED (QDLED).
Organic/inorganic hybrid perovskite have much higher color-purity at a lower cost compared to organic emitters and inorganic QD emitters. However, LEDs based on perovskite had previously shown a limited luminous efficiency, mainly due to significant exciton (a complex of an electron and hole that can allow light emission when it is radiatively recombined) dissociation in perovskite layers. The research team overcame the efficiency limitations of PeLED and boosted its efficiency to a level similar to that of phosphorescent OLEDs. This increase was attributed to fine stoichiometric tuning that prevents exciton dissociation, and to nanograin engineering that reduces perovskite grain size, and concomitantly decreases exciton diffusion length. PeLED might be a game changer in the display and solid-state lighting industries, with significantly improved efficiency as well as advantages like excellent color gamut and low material cost.
In November 2015, Florida State researchers have developed a cheaper, more efficient LED, or light-emitting diode, using perovskites. The researchers spent months using synthetic chemistry to fine-tune the materials in the lab, creating a perovskite material capable of emitting a staggering 10,000 candelas per square meter when powered by 12 volts. The scientists say that such exceptional brightness owes, to a large extent, to the inherent high luminescent efficiency of this surface-treated, highly crystalline nanomaterial.
The latest perovskite LED news:
Researchers at Huazhong University of Science and Technology (HUST) in China, University of Toledo in the U.S, Monash University in Australia, Jilin University and Tsinghua University in China, the Dalian Institute in China and the University of Toronto in Canada have examined a lead-free double perovskite that exhibited stable and efficient white light emission. In its mechanism of action, the material produced self-trapped excitons (STEs) due to Jahn-Teller distortion of the AgCl6 octahedron in the excited state of the complex, observed when investigating exciton-phonon coupling in the crystal lattice.
The research team stated that a fifth of global electricity consumption is based on lighting, and efficient and stable white-light emission with single materials is ideal for such applications. Photon emission that covers the entire visible spectrum is, however, difficult to attain with a single material. Metal halide perovskites, for instance, have outstanding emission properties but contain lead, and so yield unsatisfactory stability. The perovskite in this study is, therefore, lead-free.
Researchers at the University of Cambridge have announced a new efficiency record for LEDs based on perovskite semiconductors, reportedly rivaling that of the best organic LEDs (OLEDs).
The team stated that compared to OLEDs, which are widely used in high-end consumer electronics, the perovskite-based LEDs can be made at much lower costs, and can be tuned to emit light across the visible and near-infrared spectra with high color purity.
Two papers have recently been published, reporting on perovskite-based LEDs. The efficiencies with which some perovskite LEDs (PLEDs) produce light from electrons already seem to rival those of OLEDs.
Both papers, by Cao et al. and Lin et al., have developed PLEDs that break an important technological barrier: the external quantum efficiency (EQE) of the devices, which quantifies the number of photons produced per electron consumed, is greater than 20%. There are several similarities between the devices reported by the two groups. Perhaps most notably, the active (emissive) perovskite layer is about 200 nanometres thick in both cases, and is sandwiched between two relatively simple electrodes. This design is called a planar structure, and is the most basic manifestation of diodes made from thin films of materials. The electrodes are appropriately modified to ensure that electrons and holes (quasiparticles formed by the absence of electrons in atomic lattices) are efficiently pumped into the perovskite. As in all LEDs, when electrons meet holes, they can release energy in the form of photons through a process known as radiative recombination.
A next-generation optical material based on perovskite nanoparticles can achieve vivid colors even on very large screens. Due to their high color purity and low cost advantages, it has also gained much interests in industry. A recent study including researchers with UNIST has introduced a simple technique to extract the three primary colors (red, blue, green) from this material.
This innovative work was led by Professor Jin Young Kim in the School of Energy and Chemical Engineering at UNIST. In the study, the research team introduced a simple technique that freely controls light emitting spectra by adjusting the anion halides in perovskite materials. The key is to adjust the anion halides by dissolving them in solvents to achieve red, blue and green lights. Application of this technique to LEDs can result in crystal-clear picture quality.
EPFL and AMI teams develop a method to replace one of the least stable components in perovskite solar cells
Researchers at the Adolphe Merkle Institute in Fribourg and the Ecole Polytechnique Fédérale de Lausanne have developed a new technique to replace one of the least stable components in perovskite solar cells, which could be a major step towards commercialization.
Perovskites are seen as promising thin-film solar-cell materials because they can absorb light over a broad range of solar spectrum wavelengths thanks to their tuneable bandgaps. Charge carriers (electrons and holes) can also diffuse through them quickly and over long lengths. The most efficient perovskite solar cells usually contain bromide and MA, which is thermally unstable. To overcome this problem, researchers tried replace MA with FA since it is not only more thermally stable but also has an optimal redshifted bandgap. Unfortunately, because of its large size, FA does distort the perovskite lattice and tends to produce a photoinactive “yellow” phase at room temperature. The other photoactive “black phase” can only be seen at high temperatures. However, the researchers in this new work have now found a way to stabilize the black phase of FA at room temperature.