Multiple-Noncovalent-Interaction-Stabilized Layered Dion–Jacobson Perovskite for Efficient Solar Cells

Lv, Guangwei; Li, Ling; Lu, Da-Yong; Xu, Zhiyuan; Dong, Yixin; Li, Qiaohui; Chang, Zhaorong; Yin, Wan‐Jian; Liu, Yongsheng

doi:10.1021/acs.nanolett.1c01505

Cited by 66 publications

(70 citation statements)

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“…[ 23–25 ] Recently, several aromatic diammonium cations such as pyridinium‐based aromatic spacers (3AMP, 4AMP), phenyl‐based aromatic spacer (PDMA) and thiophene‐based aromatic spacer (ThDMA) have been developed as organic spacers in 2D DJ PSCs to enhance the device performance. [ 23,26–30 ] These single aromatic ring‐based bulky spacers used so far still cannot directly contribute to the optoelectronic properties due to their short conjugation length and lack of specific functionality. With extensive π‐electron delocalization along the conjugated backbone, the conjugated multiple‐ring aromatic diammonium spacers could enhance charge transport and reduce the dielectric mismatch in 2D perovskites in comparison with that using single‐ring aromatic spacers.…”

Section: Introductionmentioning

confidence: 99%

“…[23][24][25] Recently, several aromatic diammonium cations such as pyridinium-based aromatic spacers (3AMP, 4AMP), phenyl-based aromatic spacer (PDMA) and thiophene-based aromatic spacer (ThDMA) have been developed as organic spacers in 2D DJ PSCs to enhance the device performance. [23,[26][27][28][29][30] These single aromatic ringbased bulky spacers used so far still cannot directly contribute 2D Dion-Jacobson (DJ) perovskites have become an emerging photovoltaic material with excellent structure and environmental stability due to their lacking van der Waals gaps relative to 2D Ruddlesden-Popper perovskites. Here, a fused-thiophene-based spacer, namely TTDMAI, is successfully developed for 2D DJ perovskite solar cells.…”

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confidence: 99%

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Highly Efficient and Stable Dion−Jacobson Perovskite Solar Cells Enabled by Extended π‐Conjugation of Organic Spacer

et al. 2021

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in dramatically improved environmental and structural stability. [2,3] However, the exciton binding energy of layered phases in 2D perovskites could be as high as 300 meV although this value could be reduced with the increased thickness of inorganic layer, resulting in relatively inferior photovoltaic performance compared to 3D perovskite solar cells (PSCs). [13] Thus, it is urgent to develop more efficient organic spacers as well as device engineering to obtain both highly efficient and stable 2D PSCs for future industry application.Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) structures are two main archetypes of layered 2D perovskites to date. [14][15][16][17][18][19] The general formula of a 2D RP and DJ perovskite is (L′) 2 A n−1 M n X 3n+1 and (L″)A n−1 M n X 3n+1 , where L′ and A are monovalent cations, L″ is a divalent organic cation, M is a divalent metal cation, X is a halide ion, and n is the number of corner-sharing [MX 6 ] 4− octahedral slabs. [5] Typically, a van der Waals gap exist in organic spacers between adjacent inorganic [MI 6 ] 4octahedron slabs in 2D RP perovskites. [1] 2D RP perovskites have been shown enhanced stability, while the weak interlayer interactions in 2D RP perovskites with obvious van der Waals gaps cannot sufficiently stabilize their layered structure. In contrast, charge transport and stability could be enhanced in 2D DJ perovskites, where the neighboring inorganic slabs were bridged by diammonium spacers, resulting in shortened interslab distance and eliminated van der Waals gap. [1] So far, the aliphatic diammonium spacers, such as 1,4-butanediamine (BDA) and 1,3-propanediamine (PDA), have been studied in 2D DJ perovskite devices with promising photovoltaic performance. [20][21][22] However, the electrically insulating aliphatic diammonium spacers could block efficient charge transport due to their low dielectric constant. [23] In comparison with the aliphatic spacers, the aromatic spacers typically exhibit a larger dielectric constant and better conductivity due to the delocalized π-electrons along the molecular backbone, which could weaken the dielectric confinement effect by reducing dielectric mismatch between corner-sharing inorganic slabs and adjacent organic spacer layer. [23][24][25] Recently, several aromatic diammonium cations such as pyridinium-based aromatic spacers (3AMP, 4AMP), phenyl-based aromatic spacer (PDMA) and thiophene-based aromatic spacer (ThDMA) have been developed as organic spacers in 2D DJ PSCs to enhance the device performance. [23,[26][27][28][29][30] These single aromatic ringbased bulky spacers used so far still cannot directly contribute 2D Dion-Jacobson (DJ) perovskites have become an emerging photovoltaic material with excellent structure and environmental stability due to their lacking van der Waals gaps relative to 2D Ruddlesden-Popper perovskites. Here, a fused-thiophene-based spacer, namely TTDMAI, is successfully developed for 2D DJ perovskite solar cells. It is found that the DJ perovskite using TTDMA spacer with extended π-conjuga...

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Highly Efficient and Stable Dion−Jacobson Perovskite Solar Cells Enabled by Extended π‐Conjugation of Organic Spacer

et al. 2021

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“…However, the spin orbital coupling (SOC) in organic molecules is generally too weak to effectively break the spin-prohibition of the triplet-singlet transitions, thereby resulting in poor quantum yield for phosphorescence emission. [4] Recently, 2D hybrid organicinorganic perovskites (2D HOIPs) have emerged as promising light-emitting materials with much improved environmental stability, [5,6] superior optoelectronic properties, [7,8] accessible and cost-effective fabrication. [9] Unlike 3D HOIPs, large-sized organic cations can incorporate into the 2D HOIPs as the organic spacers.…”

Section: Introductionmentioning

confidence: 99%

Two‐Dimensional Perovskites with Tunable Room‐Temperature Phosphorescence

Zhou

et al. 2022

Adv Funct Materials

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Functional materials with room-temperature phosphorescence (RTP) are highly desired for optoelectronic and bio-imaging applications. Currently, most inorganic RTP materials require exceedingly expensive rare metals. Although organic materials have the advantages of low cost and facile fabrication, their quantum yields are quite poor due to low efficiency in the intersystem crossing process. 2D hybrid organic-inorganic perovskites (2D HOIPs), however, entail the virtue of both inorganic and organic RTP materials, thereby capable of strong and persistent phosphorescence for making future-generation RTP materials. Herein, an effective screening approach is presented to search for 2D HOIPs as efficient RTP materials. The guidelines for this high-throughput screening include the Dexter-type energy transfer mechanism, the computed excited-state properties, and the molecular morphing operators. Moreover, the structural stability of the 2D HOIPs is assessed by using a newly proposed tolerance factor. Overall, 539 candidates are identified as promising 2D HOIP materials for RTP. In particular, four 2D HOIPs, namely, (thNfuEA) 2 PbBr 4 , (selBthEA) 2 PbBr 4 , (selBfuEA) 2 PbBr 4 , and (BselBthEA) 2 PbBr 4 , are predicted to possess robust room-temperature stability, suitable energy level and proper frontierorbital alignment, thus hold high potential for functional optoelectronic applications.

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“…Methods to produce diamine organic ligands, beyond those that are commercially available, require multiple steps. , For example, synthesis beginning with a single-ring aromatic amine will likely utilize bulky butyloxy carbonyl (−Boc) groups to protect the reactive amine groups. Functional groups such as −Br can be installed using a subsequent bromination reaction.…”

Section: Resultsmentioning

confidence: 99%

Rigid Conjugated Diamine Templates for Stable Dion–Jacobson-Type Two-Dimensional Perovskites

et al. 2021

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Hybrid organic–inorganic perovskites (HOIPs) have garnered widespread interest, yet stability remains a critical issue that limits their further application. Compared to their three-dimensional (3D) counterparts, two-dimensional (2D)-HOIPs exhibit improved stability. 2D-HOIPs are also appealing because their structural and optical properties can be tuned according to the choice of organic ligand, with monovalent or divalent ligands forming Ruddlesden–Popper (RP) or Dion–Jacobson (DJ)-type 2D perovskites, respectively. Unlike RP-type 2D perovskites, DJ-type 2D perovskites do not contain a van der Waals gap between the 2D layers, leading to improved stability. However, bifunctional organic ligands currently used to develop DJ-type 2D perovskites are limited to commercially available aliphatic and single-ring aromatic ammonium cations. Large conjugated organic ligands are in demand for their semiconducting properties and their potential to improve materials stability further. In this manuscript, we report the design and synthesis of a new set of larger conjugated diamine ligands and their incorporation into DJ-type 2D perovskites. Compared with analogous RP-type 2D perovskites, DJ 2D perovskites reported here show blue-shifted, narrower emissions and significantly improved stability. By changing the structure of rings (benzene vs thiophene) and substituents, we develop structure–property relationships, finding that fluorine substitution enhances crystallinity. Single-crystal structure analysis and density functional theory calculations indicate that these changes are due to strong electrostatic interactions between the organic templates and inorganic layers as well as the rigid backbone and strong π–π interaction between the organic ligands themselves. These results illustrate that targeted engineering of the diamine ligands can enhance the stability of DJ-type 2D perovskites.

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Multiple-Noncovalent-Interaction-Stabilized Layered Dion–Jacobson Perovskite for Efficient Solar Cells

Cited by 66 publications

References 68 publications

Highly Efficient and Stable Dion−Jacobson Perovskite Solar Cells Enabled by Extended π‐Conjugation of Organic Spacer

Highly Efficient and Stable Dion−Jacobson Perovskite Solar Cells Enabled by Extended π‐Conjugation of Organic Spacer

Two‐Dimensional Perovskites with Tunable Room‐Temperature Phosphorescence

Rigid Conjugated Diamine Templates for Stable Dion–Jacobson-Type Two-Dimensional Perovskites

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