Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals

Luo, Yanqi; Khoram, Parisa; Brittman, Sarah; Zhu, Zhuoying; Lai, Barry; Ong, Shyue Ping; Garnett, Erik C.; Fenning, David P.

doi:10.1002/adma.201703451

Cited by 94 publications

(121 citation statements)

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“…In this study, ion migration was studied as function of applied voltage. [82] Without bias, the distribution is homogeneous and, as expected, a ratio of ≈3 is detected. [101][102][103] Elemental composition maps were obtained by synchrotron-based nano-XRF with 250 nm resolution.…”

Section: Wwwadvancedsciencenewscomsupporting

confidence: 75%

“…[81] The two major developments of these techniques, according to West et al, [80] are the possibility to use lens-less imaging methods, [80,82] and the high-resolution in optics, enabling X-ray spot sizes down to 11 nm in nanoprobe beamlines. Likewise, synchrotron measurements have a large penetration depth of several micrometers.…”

Section: Synchrotron-based Mapping Techniquesmentioning

confidence: 99%

Section: Elements Homogenization and Stoichiometrymentioning

confidence: 99%

“…Luo et al [82] investigated the elemental composition (by synchrotron-based XRF) and photoluminescence mapping (µ-PL) (see Section 6.1) changes by applying an electric field to single crystals of bromide perovskite MAPbBr 3 . Luo et al [82] investigated the elemental composition (by synchrotron-based XRF) and photoluminescence mapping (µ-PL) (see Section 6.1) changes by applying an electric field to single crystals of bromide perovskite MAPbBr 3 .…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

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Imaging and Mapping Characterization Tools for Perovskite Solar Cells

Hidalgo

Castro‐Méndez

Correa‐Baena

2019

Advanced Energy Materials

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define the perovskite structure, decreases below 0.8 and orthorhombic, rhombohedral, or tetragonal structures tend to form. For large A-cations, layered 2D [3] and 1D [4] chain structures can be formed, e.g., Ruddlesden-Popper, Aurivillius, and Dion-Jacobson phases. Both 3D and 2D perovskites have gained the attention of the solar cell community.Lead halide perovskites are outstanding semiconductors with impressive optoelectronic properties, such as high absorption coefficient, tunable band gap, and long charge carrier lifetimes. Despite having such impressive properties, there is still a need for deeper understanding of the degradation mechanisms of the perovskite materials in order to make PSCs viable for outdoor applications and commercialization. [5,6] Currently, a major challenge facing perovskites is their long-term stability, due to their sensitivity to temperature, moisture, oxygen, and ultraviolet (UV) light. [6] Furthermore, chemical and electronic stability, compositional, and crystal homogeneity in the absorber layer of PSCs are parameters that allow us to understand and ensure the maximum PCE and long-term durability of the devices.Imaging and mapping characterization techniques allow researchers to obtain insights of the nano-and microscale features related to their chemical and electronic properties, which in turn limit PSC performance and long-term durability. This review will focus on the progress of the imaging and mapping techniques that have been used understanding and designing perovskite materials. This comprehensive review will span from basic morphology characterization methods, such as scanning electron microscopy (SEM) to advanced, synchrotron-based characterization using X-ray microscopy, such as X-ray fluorescence for compositional mapping, and X-ray beam induced current (XBIC) for electric performance mapping. Different imaging and mapping tools allow for correlations of different physical, chemical, optical and electrical features in space and time. These characterization techniques have helped explain phenomena that govern perovskite materials, including chemical and electrical properties and how they relate to solar cell performance. The following table summarizes the different imaging and mapping characterization techniques and their use for PSCs research.Perovskite solar cells (PSCs) have attracted much attention as efficiencies have gone beyond 24%. To achieve these impressive numbers, the PSC scientific community is working to improve the perovskite optoelectronic properties. Imaging and mapping characterization techniques have been widely used to understand the fundamental properties that allow lead halide perovskites to achieve high performance. In this review, these techniques are evaluated, from simple tools, such as electron microscopy, to more complex systems that include atomic force microscopy, synchrotron-based X-ray mapping, and ultrafast and photoluminescence mapping. These tools have helped understand lead halide perovskites and their impressive optoelectronic prope...

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confidence: 75%

Section: Synchrotron-based Mapping Techniquesmentioning

confidence: 99%

Section: Elements Homogenization and Stoichiometrymentioning

confidence: 99%

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

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Imaging and Mapping Characterization Tools for Perovskite Solar Cells

Hidalgo

Castro‐Méndez

Correa‐Baena

2019

Advanced Energy Materials

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“…72 In the case of bromide perovskites, it was concluded that high V Br concentrations result in a lower radiative recombination efficiency and a consequent decrease in PLQY. 75 In the case of CsPbBr 3 , using a small excess of CsBr precursor (compared to PbBr 2 ) results in decreased V Br concentration and, thus, an enhanced PLQY. 76 The different nature of halide vacancies in perovskites is also evident in lead-free Cs 2 AgInBr 6 and Cs 2 TlBiBr 6 double perovskites (elpasolites), where halide vacancies have been reported both as shallow (Cs 2 AgInBr 6 ) and deep (Cs 2 TlBiBr 6 ), respectively.…”

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confidence: 99%

Zero-Dimensional Cesium Lead Halides: History, Properties, and Challenges

Akkerman

Abdelhady

Manna

2018

J. Phys. Chem. Lett.

221

247

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Over the past decade, lead halide perovskites (LHPs) have emerged as new promising materials in the fields of photovoltaics and light emission due to their facile syntheses and exciting optical properties. The enthusiasm generated by LHPs has inspired research in perovskite-related materials, including the so-called “zero-dimensional cesium lead halides”, which will be the focus of this Perspective. The structure of these materials is formed of disconnected lead halide octahedra that are stabilized by cesium ions. Their optical properties are dominated by optical transitions that are localized within the individual octahedra, hence the title “‘zero-dimensional perovskites”. Controversial results on their physical properties have recently been reported, and the true nature of their photoluminescence is still unclear. In this Perspective, we will take a close look at these materials, both as nanocrystals and as bulk crystals/thin films, discuss the contrasting opinions on their properties, propose potential applications, and provide an outlook on future experiments.

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The Relationship between Chemical Flexibility and Nanoscale Charge Collection in Hybrid Halide Perovskites

Luo

Aharon

Stückelberger

et al. 2018

Adv Funct Materials

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Hybrid organometal halide perovskites are known for their excellent optoelectronic functionality as well as their wide-ranging chemical flexibility. The composition of hybrid perovskite devices has trended toward increasing complexity as fine-tuned properties are pursued, including multielement mixing on the constituents A and B and halide sites. However, this tunability presents potential challenges for charge extraction in functional devices. Poor consistency and repeatability between devices may arise due to variations in composition and microstructure. Within a single device, spatial heterogeneity in composition and phase segregation may limit the device from achieving its performance potential. This review details how the nanoscale elemental distribution and charge collection in hybrid perovskite materials evolve as chemical complexity increases, highlighting recent results using nondestructive operando synchrotron-based X-ray nanoprobe techniques. The results reveal a strong link between local chemistry and charge collection that must be controlled to develop robust, high-performance hybrid perovskite materials for optoelectronic devices.applications including solar cells, [1,2] lightemitting diodes, [3] lasers, [4] and photodetectors. [5] The exceptional minority carrier diffusion lengths in these materials [6,7] lead to nearly 100% internal quantum efficiency [8] which results in high charge-carrier collection efficiency and high external luminescence efficiency in electron-photon conversion devices. [9] Particularly in the field of photovoltaics (PV), their extraordinary material properties [10][11][12] have enabled perovskite solar absorbers to achieve large improvements in device performance in the past 8 years. The perovskite crystal structure is shown in Figure 1a, where the A-site is CH 3 NH 3 + (MA, methylammonium), the B-site is Pb 2+ , and the X-site is I − following the general perovskite formula ABX 3. After demonstration of a device with 3.8% power conversion efficiency (PCE) by Miyasaka and co-workers in a dye-sensitized solar cell architecture using CH 3 NH 3 PbI 3 , [13] a breakthrough in perovskite photovoltaics occurred in 2012 when the first allsolid-state hybrid perovskite devices were shown by Kim et al., [14] improving the chemical stability of the perovskite and enabling device performance to exceed beyond 9% using CH 3 NH 3 PbI 3 perovskites. With intense investigation of perovskite material properties from research groups all over the world, including bandgap engineering by halide mixing [15,16] and device optimization using A-site mixing, [9,17] the record PCE of hybrid perovskite solar cells reached 22.7% in 2017 after achieving 22.1% PCE in 2015 [18] using a mixture of formamidinium lead iodide (CH(NH 2 ) 2 PbI 3 ) with 5% loading of methylammonium lead bromide (CH 3 NH 3 PbBr 3 ) chemistry. [19,20] Surpassing 22% PCE by leveraging the chemical flexibility of the perovskite structure brought hybrid perovskite solar cells on par in efficiency with most polycrystalline solar absor...

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Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals

Cited by 94 publications

References 50 publications

Imaging and Mapping Characterization Tools for Perovskite Solar Cells

Imaging and Mapping Characterization Tools for Perovskite Solar Cells

Zero-Dimensional Cesium Lead Halides: History, Properties, and Challenges

The Relationship between Chemical Flexibility and Nanoscale Charge Collection in Hybrid Halide Perovskites

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