Spontaneous Crystallization of Perovskite Nanocrystals in Nonpolar Organic Solvents: A Versatile Approach for their Shape‐Controlled Synthesis

Huang, He; Li, Yanxiu; Tong, Yu; Yao, En‐Ping; Feil, Maximilian W.; Richter, A.; Döblinger, Markus; Rogach, Andrey L.; Feldmann, Jochen; Polavarapu, Lakshminarayana

doi:10.1002/anie.201906862

Cited by 98 publications

(113 citation statements)

References 35 publications

(31 reference statements)

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“…As schematically depicted in Figure 3, the morphology of NCs changed from 2D nanoplatelets to 1D nanorods as the concentration of FA-oleate increased. Similar to our previous work, [16] nanoplatelets were obtained at a lower concentration of FA. This suggests that anisotropic growth is favorable at a higher FA concentration when the ratio of FA/Pb remains low.…”

Section: Resultssupporting

confidence: 83%

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Facile Synthesis of FAPbI3 Nanorods

Huang

Wang

et al. 2019

Nanomaterials

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Metal halide perovskites are promising materials for a range of applications. The synthesis of light-emitting perovskite nanorods has become popular recently. Thus far, the facile synthesis of perovskite nanorods remains elusive. In this work, we have developed a facile synthesis to fabricate FAPbI 3 nanorods for the first time, demonstrating a high photoluminescence quantum yield of 35-42%. The fabrication of the nanorods has been made possible by carefully tuning the concentration of formamidine-oleate as well as the amount of oleic acid with pre-dissolved PbI 2 in toluene with oleic acid/oleylamine.

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Section: Resultssupporting

confidence: 83%

“…Figure 1a shows the synthetic process of FAPbI 3 NRs. The method used here is adapted from our previous publication [16]. In a typical synthesis, 60 µL of formamidine-oleate (0.1 M in OA) was added into 2 mL of PbI 2 precursor (0.01 M in toluene with OA and OLA) solution under vigorous stirring at room temperature.…”

Section: Methodsmentioning

confidence: 99%

Facile Synthesis of FAPbI3 Nanorods

Huang

Wang

et al. 2019

Nanomaterials

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“…In such a case, the advantage of using a single‐crystal precursor is lost. On the other hand, the (TEA) 2 (MA) 2 Pb 3 I 10 units in the poorly‐coordinating solvents can be well kept, since the addition of TOL can only solubilize the aromatic part through thiophene–benzene interaction and cause the formation of the colloidal templates, [ 45 ] like ligand‐assisted reprecipitation. With the help of HI, the DMAc:TOL mixed solvent can break down the large single‐crystal into colloidal clusters but retain phase purity regarding the layer thickness, with no observable intermediate phases.…”

Section: Resultsmentioning

confidence: 99%

“…The ITO‐coated substrates were sequentially cleaned with soap solution, water, acetone and isopropanol. The Cu:NiO x compact thin layer (50 nm) was fabricated by spin‐coating precursor solutions of Ni(NO 3 ) 2 ·6H 2 O doped with Cu(NO 3 ) 2 ·3H 2 O (2%) onto as‐cleaned ITO substrate at a rate of 3000 rpm for 90 s, [ 45 ] followed by heated in ambient air at 300 °C for 60 min. Then, the coated samples were transferred to a N 2 ‐filled glovebox for device fabrication.…”

Section: Methodsmentioning

confidence: 99%

Coordination Engineering of Single‐Crystal Precursor for Phase Control in Ruddlesden–Popper Perovskite Solar Cells

Qin

Zhong

Intemann

et al. 2020

Advanced Energy Materials

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efficiencies (PCE). [1,2] However, the intrinsic instability of 3D perovskite materials still remains unresolved. [3,4] Inert bulky organic cations can not only enhance their structural stability via strong interactions between covering organic cations and the [PbI 6 ] − units, but also block moisture from penetrating and corroding inner inorganic layers. [5,6] By incorporation of a larger cation into the 3D structure, the most common type is the (100)-oriented cutting direction, forming representative Ruddlesden-Popper perovskite (RPP) with a chemical formula (A′) 2 (A) n−1 Pb n I 3n+1 (A′ is a primary monovalent cations). [7,8] Unfortunately, the confinement effects of organic spacers also lead to a strong quantum and dielectric confinement in 2D perovskite. Moreover, the decreased conductivity of the organic layers prevents the carrier charge transport between perovskite quantum wells. [9] Thus, RPP exhibits a wider bandgap, a higher exciton binding energy (E b ), and lower charge mobility relative to the 3D perovskites, which results in poor efficiencies. Note that a weak quantum confinement would arise from an increase thickness of layers (n value), leading to a remarkable decrease in the optical bandgap, making it highly desirable to increase the number (n ≥ 4) of inorganic sheets between two adjacent organic spacers by forming quasi-2D structures. [10,11] In addition, through rational design 2D Ruddlesden-Popper perovskites (RPPs) have recently drawn significant attention because of their structural variability that can be used to tailor optoelectronic properties and improve the stability of derived photovoltaic devices. However, charge separation and transport in 2D perovskite solar cells (PSCs) suffer from quantum well barriers formed during the processing of perovskites. It is extremely difficult to manage phase distributions in 2D perovskites made from the stoichiometric mixtures of precursor solutions. Herein, a generally applicable guideline is demonstrated for precisely controlling phase purity and arrangement in RPP films. By visually presenting the critical colloidal formation of the single-crystal precursor solution, coordination engineering is conducted with a rationally selected cosolvent to tune the colloidal properties. In nonpolar cosolvent media, the derived colloidal template enables RPP crystals to preferentially grow along the vertically ordered alignment with a narrow phase variation around a target value, resulting in efficient charge transport and extraction. As a result, a recordhigh power conversion efficiency (PCE) of 14.68% is demonstrated for a (TEA) 2 (MA) 2 Pb 3 I 10 (n = 3) photovoltaic device with negligible hysteresis. Remarkably, superior stability is achieved with 93% retainment of the initial efficiency after 500 h of unencapsulated operation in ambient air conditions.

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“…They proposed that there was a high energy barrier between the precursors and nanocubes. [ 119 ] The use of room temperature synthesized PNCs in solar cells is not impossible but potentially requires finding suitable ligands to modulate the synthesis of the PNCs.…”

Section: Challengesmentioning

confidence: 99%

Metal Halide Perovskite Nanocrystal Solar Cells: Progress and Challenges

et al. 2020

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ultrasonication methods, [22] solvothermal approaches, [23] microwave-assisted synthesis, [24] and mechanical grinding. [25] PNCs not only inherit perovskite properties, but also possess the features of nanomaterials, such as their size-confinement effect and ease of processing as a colloidal ink, making PNCs suitable for incorporation into various electronic devices and compatible with printing techniques. [19,26] Moreover, nanoscale perovskites exhibit superior phase stability, particularly for CsPbI 3 and FAPbI 3 , due to their lattice construction and large surface energy. [27,28] Compared with traditional II-VI and III-V semiconductor nanocrystals, PNCs also exhibit unique properties. [29-32] Firstly, facile synthesis with inexpensive precursors can be conducted at room temperature with PNCs without inert gas protection. PNCs also have a bandgap ranging from the ultraviolet to nearinfrared, through which they can be easily tuned by size management and composition adjustment. Furthermore, they exhibit narrow bandwidth emission (<100 meV) over the entire visible range. PNCs also exhibit a fluorescence quantum yield near unity without additional passivation due to the defect-tolerance effect. Finally, they also demonstrate negligible self-absorption and Förster resonance energy transfer. These remarkable characteristics make PNCs more favorable than their bulk counterparts and traditional semiconductor nanocrystals. Thus, PNCs have promising applications in light-emitting diodes (LEDs), [33] lasers, [34] photodetectors, [35,36] and solar cells. [28] In 2016, Luther et al. first used CsPbI 3 PNCs to fabricate solar cells using a layer-by-layer approach. [28] The solar cell exhibited an extremely high open-circuit voltage (V OC) of 1.23 V, which was ≈85% of the Shockley-Queisser (S-Q) limited V OC , and a high power conversion efficiency (PCE) of 10.77%. This value was comparable to those of state-of-the-art PbS nanocrystal solar cells, [37] indicating the potential of PNC solar cells. To date, the highest PCE achieved by PNC solar cells has reached 17.39%. [38] Though PCEs have shown rapid, significant improvements, they are still limited compared to solar cells fabricated by bulk perovskite materials. Moreover, most studies on PNC solar cells have only been reported over the past two years. Research on PNC solar cells is still in its infancy, leaving substantial room for further improvement. Herein, we review the progress in the field of PNC solar cells. This review starts with detailing the unique advantages of PNCs. Next, we analyze current factors limiting their performance and Perovskite nanocrystal (PNC) solar cells have attracted increasing interest in recent years because of their excellent optoelectronic properties and unique advantages, which distinguish them from conventional nanocrystals and their bulk counterparts. This emerging type of photovoltaic is promising but faces many challenges regarding commercialization. Therefore, a comprehensive review is presented on the recent progress and current ch...

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Spontaneous Crystallization of Perovskite Nanocrystals in Nonpolar Organic Solvents: A Versatile Approach for their Shape‐Controlled Synthesis

Cited by 98 publications

References 35 publications

Facile Synthesis of FAPbI3 Nanorods

Facile Synthesis of FAPbI3 Nanorods

Coordination Engineering of Single‐Crystal Precursor for Phase Control in Ruddlesden–Popper Perovskite Solar Cells

Metal Halide Perovskite Nanocrystal Solar Cells: Progress and Challenges

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