Sjoerd Hoogland

Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals

Large-crystal perovskite films The performance of organic-inorganic hybrid perovskite planar solar cells has steadily improved. One outstanding issue is that grain boundaries and defects in polycrystalline films degrade their output. Now, two studies report the growth of millimeter-scale single crystals. Nie et al. grew continuous, pinhole-free, thin iodochloride films with a hot-casting technique and report device efficiencies of 18%. Shi et al. used antisolvent vapor-assisted crystallization to grow millimeter-scale bromide and iodide cubic crystals with charge-carrier diffusion lengths exceeding 10 mm. Science, this issue p. 522, p. 519 Solution processing techniques enable the growth of high-quality, large-area perovskite crystals for solar cells. The fundamental properties and ultimate performance limits of organolead trihalide MAPbX3 (MA = CH3NH3+; X = Br– or I–) perovskites remain obscured by extensive disorder in polycrystalline MAPbX3 films. We report an antisolvent vapor-assisted crystallization approach that enables us to create sizable crack-free MAPbX3 single crystals with volumes exceeding 100 cubic millimeters. These large single crystals enabled a detailed characterization of their optical and charge transport characteristics. We observed exceptionally low trap-state densities on the order of 109 to 1010 per cubic centimeter in MAPbX3 single crystals (comparable to the best photovoltaic-quality silicon) and charge carrier diffusion lengths exceeding 10 micrometers. These results were validated with density functional theory calculations.

Ultrasensitive solution-cast quantum dot photodetectors.

Solution-processed electronic and optoelectronic devices offer low cost, large device area, physical flexibility and convenient materials integration compared to conventional epitaxially grown, lattice-matched, crystalline semiconductor devices. Although the electronic or optoelectronic performance of these solution-processed devices is typically inferior to that of those fabricated by conventional routes, this can be tolerated for some applications in view of the other benefits. Here we report the fabrication of solution-processed infrared photodetectors that are superior in their normalized detectivity (D*, the figure of merit for detector sensitivity) to the best epitaxially grown devices operating at room temperature. We produced the devices in a single solution-processing step, overcoating a prefabricated planar electrode array with an unpatterned layer of PbS colloidal quantum dot nanocrystals. The devices showed large photoconductive gains with responsivities greater than 103 A W-1. The best devices exhibited a normalized detectivity D* of 1.8 × 1013 jones (1 jones = 1 cm Hz1/2 W-1) at 1.3 µm at room temperature: todays highest performance infrared photodetectors are photovoltaic devices made from epitaxially grown InGaAs that exhibit peak D* in the 1012 jones range at room temperature, whereas the previous record for D* from a photoconductive detector lies at 1011 jones. The tailored selection of absorption onset energy through the quantum size effect, combined with deliberate engineering of the sequence of nanoparticle fusing and surface trap functionalization, underlie the superior performance achieved in this readily fabricated family of devices.

Colloidal-quantum-dot photovoltaics using atomic-ligand passivation

Colloidal-quantum-dot (CQD) optoelectronics offer a compelling combination of solution processing and spectral tunability through quantum size effects. So far, CQD solar cells have relied on the use of organic ligands to passivate the surface of the semiconductor nanoparticles. Although inorganic metal chalcogenide ligands have led to record electronic transport parameters in CQD films, no photovoltaic device has been reported based on such compounds. Here we establish an atomic ligand strategy that makes use of monovalent halide anions to enhance electronic transport and successfully passivate surface defects in PbS CQD films. Both time-resolved infrared spectroscopy and transient device characterization indicate that the scheme leads to a shallower trap state distribution than the best organic ligands. Solar cells fabricated following this strategy show up to 6% solar AM1.5G power-conversion efficiency. The CQD films are deposited at room temperature and under ambient atmosphere, rendering the process amenable to low-cost, roll-by-roll fabrication.

Hybrid passivated colloidal quantum dot solids

Colloidal quantum dot (CQD) films allow large-area solution processing and bandgap tuning through the quantum size effect. However, the high ratio of surface area to volume makes CQD films prone to high trap state densities if surfaces are imperfectly passivated, promoting recombination of charge carriers that is detrimental to device performance. Recent advances have replaced the long insulating ligands that enable colloidal stability following synthesis with shorter organic linkers or halide anions, leading to improved passivation and higher packing densities. Although this substitution has been performed using solid-state ligand exchange, a solution-based approach is preferable because it enables increased control over the balance of charges on the surface of the quantum dot, which is essential for eliminating midgap trap states. Furthermore, the solution-based approach leverages recent progress in metal:chalcogen chemistry in the liquid phase. Here, we quantify the density of midgap trap states in CQD solids and show that the performance of CQD-based photovoltaics is now limited by electron-hole recombination due to these states. Next, using density functional theory and optoelectronic device modelling, we show that to improve this performance it is essential to bind a suitable ligand to each potential trap site on the surface of the quantum dot. We then develop a robust hybrid passivation scheme that involves introducing halide anions during the end stages of the synthesis process, which can passivate trap sites that are inaccessible to much larger organic ligands. An organic crosslinking strategy is then used to form the film. Finally, we use our hybrid passivated CQD solid to fabricate a solar cell with a certified efficiency of 7.0%, which is a record for a CQD photovoltaic device.

Efficient and stable solution-processed planar perovskite solar cells via contact passivation

Passivating traps in perovskites Low-temperature processing of planar organic-inorganic perovskite solar cells made through solution processing would allow for simpler manufacturing and the use of flexible substrates. However, materials currently in use form interfaces with charge carrier trap states that limit performance. Tan et al. used chlorine-capped TiO2 colloidal nanocrystal films as an electron-selective layer, which limited interface recombination in solution-processed solar cells. Such cells achieved certified efficiencies of 19.5% for active areas of 1.1 cm2. Science, this issue p. 722 Chlorine-capped TiO2 nanocrystal films processed below 150°C effectively passivate detrimental carrier trap states. Planar perovskite solar cells (PSCs) made entirely via solution processing at low temperatures (<150°C) offer promise for simple manufacturing, compatibility with flexible substrates, and perovskite-based tandem devices. However, these PSCs require an electron-selective layer that performs well with similar processing. We report a contact-passivation strategy using chlorine-capped TiO2 colloidal nanocrystal film that mitigates interfacial recombination and improves interface binding in low-temperature planar solar cells. We fabricated solar cells with certified efficiencies of 20.1 and 19.5% for active areas of 0.049 and 1.1 square centimeters, respectively, achieved via low-temperature solution processing. Solar cells with efficiency greater than 20% retained 90% (97% after dark recovery) of their initial performance after 500 hours of continuous room-temperature operation at their maximum power point under 1-sun illumination (where 1 sun is defined as the standard illumination at AM1.5, or 1 kilowatt/square meter).

Perovskite energy funnels for efficient light-emitting diodes

Organometal halide perovskites exhibit large bulk crystal domain sizes, rare traps, excellent mobilities and carriers that are free at room temperature-properties that support their excellent performance in charge-separating devices. In devices that rely on the forward injection of electrons and holes, such as light-emitting diodes (LEDs), excellent mobilities contribute to the efficient capture of non-equilibrium charge carriers by rare non-radiative centres. Moreover, the lack of bound excitons weakens the competition of desired radiative (over undesired non-radiative) recombination. Here we report a perovskite mixed material comprising a series of differently quantum-size-tuned grains that funnels photoexcitations to the lowest-bandgap light-emitter in the mixture. The materials function as charge carrier concentrators, ensuring that radiative recombination successfully outcompetes trapping and hence non-radiative recombination. We use the new material to build devices that exhibit an external quantum efficiency (EQE) of 8.8% and a radiance of 80 W sr-1 m-2. These represent the brightest and most efficient solution-processed near-infrared LEDs to date.

Air-stable n-type colloidal quantum dot solids.

Colloidal quantum dots (CQDs) offer promise in flexible electronics, light sensing and energy conversion. These applications rely on rectifying junctions that require the creation of high-quality CQD solids that are controllably n-type (electron-rich) or p-type (hole-rich). Unfortunately, n-type semiconductors made using soft matter are notoriously prone to oxidation within minutes of air exposure. Here we report high-performance, air-stable n-type CQD solids. Using density functional theory we identify inorganic passivants that bind strongly to the CQD surface and repel oxidative attack. A materials processing strategy that wards off strong protic attack by polar solvents enabled the synthesis of an air-stable n-type PbS CQD solid. This material was used to build an air-processed inverted quantum junction device, which shows the highest current density from any CQD solar cell and a solar power conversion efficiency as high as 8%. We also feature the n-type CQD solid in the rapid, sensitive, and specific detection of atmospheric NO2. This work paves the way for new families of electronic devices that leverage air-stable quantum-tuned materials.

Fast, sensitive and spectrally tuneable colloidal-quantum-dot photodetectors

Solution-processed semiconductors are compatible with a range of substrates, which enables their direct integration with organic circuits, microfluidics, optical circuitry and commercial microelectronics. Ultrasensitive photodetectors based on solution-process colloidal quantum dots operating in both the visible and infrared have been demonstrated, but these devices have poor response times (on the scale of seconds) to changes in illumination, and rapid-response devices based on a photodiode architecture suffer from low sensitivity. Here, we show that the temporal response of these devices is determined by two components--electron drift, which is a fast process, and electron diffusion, which is a slow process. By building devices that exclude the diffusion component, we are able to demonstrate a >1,000-fold improvement in the sensitivity-bandwidth product of tuneable colloidal-quantum-dot photodiodes operating in the visible and infrared.

Planar-integrated single-crystalline perovskite photodetectors

Hybrid perovskites are promising semiconductors for optoelectronic applications. However, they suffer from morphological disorder that limits their optoelectronic properties and, ultimately, device performance. Recently, perovskite single crystals have been shown to overcome this problem and exhibit impressive improvements: low trap density, low intrinsic carrier concentration, high mobility, and long diffusion length that outperform perovskite-based thin films. These characteristics make the material ideal for realizing photodetection that is simultaneously fast and sensitive; unfortunately, these macroscopic single crystals cannot be grown on a planar substrate, curtailing their potential for optoelectronic integration. Here we produce large-area planar-integrated films made up of large perovskite single crystals. These crystalline films exhibit mobility and diffusion length comparable with those of single crystals. Using this technique, we produced a high-performance light detector showing high gain (above 104 electrons per photon) and high gain-bandwidth product (above 108 Hz) relative to other perovskite-based optical sensors.

Enhanced mobility-lifetime products in PbS colloidal quantum dot photovoltaics.

Colloidal quantum dot (CQD) photovoltaics offer a promising approach to harvest the near-IR region of the solar spectrum, where half of the suns power reaching the earth resides. High external quantum efficiencies have been obtained in the visible region in lead chalcogenide CQD photovoltaics. However, the corresponding efficiencies for band gap radiation in the near-infrared lag behind because the thickness of CQD photovoltaic layers from which charge carriers can be extracted is limited by short carrier diffusion lengths. Here, we investigate, using a combination of electrical and optical characterization techniques, ligand passivation strategies aimed at tuning the density and energetic distribution of charge trap states at PbS nanocrystal surfaces. Electrical and optical measurements reveal a more than 7-fold enhancement of the mobility-lifetime product of PbS CQD films treated with 3-mercaptopropionic acid (MPA) in comparison to traditional organic passivation strategies that have been examined in the literature. We show by direct head-to-head comparison that the greater mobility-lifetime products of MPA-treated devices enable markedly greater short-circuit current and higher power conversion efficiency under AM1.5 illumination. Our findings highlight the importance of selecting ligand treatment strategies capable of passivating a diversity of surface states to enable shallower and lower density trap distributions for better transport and more efficient CQD solar cells.