Recent Advances in Spiro‐MeOTAD Hole Transport Material and Its Applications in Organic–Inorganic Halide Perovskite Solar Cells

Hawash, Zafer; Ono, Luis K.; Qi, Yabing

doi:10.1002/admi.201700623

“…So the V oc will increase linearly with the E g . [46] To check such an effect, the steady state efficiency of carbon-based Sb 2 (S,Se) 3 was also measured ( Figure S15, Supporting Information). So the main problem that prohibits the device PCE from a further improvement is the low J sc , which is mainly caused by the incomplete absorption.…”

Section: Wwwadvelectronicmatdementioning

confidence: 99%

Over 6% Certified Sb₂(S,Se)₃ Solar Cells Fabricated via In Situ Hydrothermal Growth and Postselenization

Wang

¹

,

Wang

²

,

Chen

³

et al. 2018

Adv Elect Materials

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eV), [1][2][3] remarkable absorption coefficient (≈10 5 cm −1 ), [4,5] excellent stability, and low-toxicity component. To promote the power conversion efficiency, many methods have been successfully applied to fabricate Sb 2 (S x ,Se 1-x ) 3 solar cells. For example, the rapid thermal evaporation (RTE) method [6] have been gathered many attentions for the fabrication of Sb 2 Se 3 solar cells. Recently, Tang and co-workers used a novel vapor transport deposition (VTD) way to refresh the recorded efficiency of Sb 2 Se 3 solar cell to 7.6%, [7] which has been made a great progress since Sb 2 Se 3 was successfully achieved a power conversion efficiency (PCE) of 0.03% in 2002. [8] On the other hand, Choi et al. have achieved a PCE of 7.5% [9] for Sb 2 S 3 by chemical bath deposition (CBD). Although the VTD and CBD methods have achieved impressive efficiency over 7%, a number of processing issues arise in these approaches. For example, VTD deposition processes are complex and expensive. While the nonvacuums CBD method also has weaknesses such as (i) the film prepared from CBD method is tend to be amorphous; [8,10] (ii) the Sb 2 S 3 film prepared by CBD method is antimony rich which results in a higher mean coordination number (MCN) than the stoichiometric Sb 2 S 3 . It will make it too rigid to flatten out after the annealing step; [11] (iii) the Sb 2 S 3 film prepared by CBD method inevitably includes impurities such as SbOCl, Sb 2 O 3 , and Sb 2 (SO 3 ) 3 . [12][13][14] Meanwhile, although the crystalline of the film fabricated by RTE or VTD is promising, the compactness of the absorber needs a further improvement. Thus, seeking for an effective and easy-handle nonvacuum approach to improve Sb 2 (S x ,Se 1-x ) 3 thin film solar cells is urgently needed.Since the hydrothermal method is a useful method in thin film preparation, the quality and homogeneity of the film deposited by this method is remarkable, which is expected to be able to solve the problem mentioned above and cut down the cost of fabrication. Liu et al. have taken this method to prepare the Sb 2 S 3 thin films, but there is no device reported. [15] In our previous work, double buffer layer was used to tune the band align and reduce recombination, which has achieved V oc as high as 792 mV based on hydrothermal derived Sb 2 (S x ,Se 1-x ) 3 solar cell. [16] But the thick buffer layer (60 nm TiO 2 + 60 nm CdS) inevitably increases the R s of device and decreases the transmittance as well, both of which will reduce J sc and PCE. Besides, the formation mechanism for Sb 2 S 3 thin films based Antimony sulfide-selenide Sb 2 (S,Se) 3 as a promising absorber material has drawn extensive attention owing to its rewarding photoelectric properties, low toxicity, and earth abundant components. Here, an available and highly effective method, in situ hydrothermal growth accompanied with postselenization, is successfully applied to fabricate Sb 2 (S,Se) 3 solar cells. The rationale for the preparation of Sb 2 S 3 precursors by the hydrothermal method is discussed, and ...

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“…[1][2][3][4] The currently reported certified power bis(trifluoromethanesulfonyl) imide (LiTFSI), which dopes the system with Li + cations, improving hole mobility up to two orders of magnitude. [13,20] Another common dopant that is usually combined with LiTFSI is 4-tert-butylpyridine (TBP). [13,20] Another common dopant that is usually combined with LiTFSI is 4-tert-butylpyridine (TBP).…”

Section: Introductionmentioning

confidence: 99%

“…[13] Based on previous publications about ionic dopants in disordered semiconductors, [18,19] some authors claim a hopping mechanism in the Spiro-OMeTAD layer for the charge transport between the available sites as well as the increase of the hole density provided by the p-doping. [13,21,22] Other dopants such as the Co complex FK209 (tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt (III) tri[bis(trifluoromethane) sulfonimide]) further increase the photovoltaic parameters when are doping the Spiro-OMeTAD layer in combination with LiTFSI and TBP, although the mechanism for this enhanced performance is still under debate. TBP is reported to improve several aspects of the Spiro-OMeTAD layers such as the homogeneity and the increase in the solubility of LiTFSI as well as preventing their accumulation and segregation.…”

Section: Introductionmentioning

confidence: 99%

“…[13,20] Another common dopant that is usually combined with LiTFSI is 4-tert-butylpyridine (TBP). [13] It is clear from the literature that a common strategy to enhance the charge transport properties of some SSHC is the addition of dopants in different relative concentrations. [13,21,22] Other dopants such as the Co complex FK209 (tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt (III) tri[bis(trifluoromethane) sulfonimide]) further increase the photovoltaic parameters when are doping the Spiro-OMeTAD layer in combination with LiTFSI and TBP, although the mechanism for this enhanced performance is still under debate.…”

Section: Introductionmentioning

confidence: 99%

“…TBP is reported to improve several aspects of the Spiro-OMeTAD layers such as the homogeneity and the increase in the solubility of LiTFSI as well as preventing their accumulation and segregation. [13,14] The most common issue is that ionic additives can contribute to the degradation of the perovskite film. [13] It is clear from the literature that a common strategy to enhance the charge transport properties of some SSHC is the addition of dopants in different relative concentrations.…”

Section: Introductionmentioning

confidence: 99%

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Enhanced Stability of Perovskite Solar Cells Incorporating Dopant‐Free Crystalline Spiro‐OMeTAD Layers by Vacuum Sublimation

Barranco

¹

,

López‐Santos

²

,

Idígoras

³

et al. 2019

Advanced Energy Materials

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The main handicap still hindering the eventual exploitation of organometal halide perovskite‐based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid‐state hole conductor (SSHC), i.e., the Spiro‐OMeTAD [2,2′,7,7′‐tetrakis (N,N‐di‐p‐methoxyphenyl‐amine) 9,9′‐spirobifluorene], and how its dopant‐free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution‐processed reference and after annealing in air up to 200 °C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the π–π stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light‐emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro‐OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X‐ray diffraction, grazing‐incidence small‐angle X‐ray scattering and grazing‐incidence wide‐angle X‐ray scattering, X‐ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy.

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Palladium, [ N , N ′‐1,2‐ethanediylidenebis[2,6‐dimethylbenzenamine‐κN]][(3,4‐ η )‐2,5‐furandione] ( ^DMP DAB–Pd–MAH)

Leitch,

Thomas

2024

Encyclopedia of Reagents for Organic Synthesis

0

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image [2721487‐84‐7] C 22 H 22 N 2 O 3 Pd (MW 468.85) InChI = 1S/C18H20N2.C4H2O3.Pd/c1‐13‐7‐5‐8‐14(2)17(13)19‐11‐12‐20‐18‐15(3)9‐6‐10‐16(18)4;5‐3‐1‐2‐4(6)7‐3;/h5‐12H,1‐4H3;1‐2H;/b19‐11+,20‐12+;; InChiKey = WHOQNDZHEHSRKP‐GAMUHHASSA‐N (palladium(0) compound used as a precursor to phosphine palladium(0) complexes, 1–5 and as a catalyst precursor for cross‐coupling reactions, 1,6 CH activation reactions, 7 and enantioselective allylation reactions 4,8 ) Alternative Names : (1 E ,2 E )‐ N 1, N 2‐bis(2,6‐dimethylphenyl)ethane‐1,2‐diimine 2,5‐dihydrofuran‐2,5‐dione palladium, [κ 2 ‐ N , N ′‐bis(2,6‐dimethylphenyl)ethan‐1,2‐diimine][ η 2 ‐maleic anhydride]palladium(0). Physical Data : m.p. 121 °C (dec). Solubility : fully soluble (≥20 mg mL −1 ) in acetone, dichloromethane, tetrahydrofuran (THF), 2‐methyltetrahydrofuran (MeTHF); partially soluble in toluene (5 mg mL −1 ), ethyl acetate (2.5 mg mL −1 ); poorly soluble (≤2 mg mL −1 ) in pentane, n ‐hexane, n ‐heptane, diethyl ether, tert ‐butylmethyl ether (TBME); insoluble in isopropanol (<1 mg mL −1 ); soluble but decomposes in acetonitrile, chloroform; poorly soluble and decomoposes in dimethylsulfoxide (DMSO), N,N ‐dimethylformamide (DMF), methanol, ethanol; insoluble in water. Form Supplied in : red/purple crystalline solid. Preparative Methods : commercially available. There are two reported procedures 1 for preparing DMP DAB–Pd–MAH by reacting N , N ′‐1,2‐ethanediylidenebis(2,6‐dimethylbenzenamine) ( DMP DAB) and maleic anhydride (MAH) 9 with either Pd 2 dba 3 ·CHCl 3 10 or “Pd(dba) 2 ” (actually Pd 2 dba 3 ·dba). 11 These palladium sources can be prepared from a variety of palladium(II) starting materials according to the method of Zalesskiy and Ananikov, 12 or purchased from commercial sources. Recystallization of crude “Pd(dba) 2 ” is not required, since purification of DMP DAB–Pd–MAH removes residual dba and colloidal palladium(0) (see below). N , N ′‐1,2‐ethanediylidenebis(2,6‐dimethylbenzenamine) ( DMP DAB) is prepared from glyoxal (40% wt/wt solution in water) and 2,6‐dimethylaniline in methanol with 13 or without 14 formic acid as a catalyst. Purification : colloidal palladium(0) can be removed from DMP DAB–Pd–MAH by dissolving the solid in a minimum amount of acetone, dichloromethane, or THF, followed by filtration through a bed of Celite ™ and subsequent solvent removal from the filtrate. Uncoordinated N , N ′‐1,2‐ethanediylidenebis(2,6‐dimethylbenzenamine) ( DMP DAB), maleic anhydride, and/or residual dibenzylideneacetone (dba) from the synthesis can be removed by slurrying solid DMP DAB–Pd–MAH in TBME (∼30 mL g −1 of solid), followed by filtration and washing with TBME. Analysis of Reagent Purity : 1 H NMR spectroscopic analysis is suitable for routine purity determination. In d 6 ‐acetone (solvent residual peak at 2.05 ppm), DMP DAB–Pd–MAH has diagnostic resonances at 8.55 ppm (s, 2 H ) for the N=CH–CH=N protons, 3.57 ppm (s, 2 H ) for the coordinated maleic anhydride, and 2.30 ppm (s, 12 H ) for the four Ar–CH 3 groups. Elemental analysis is also suitable for establishing bulk purity. Handling, Storage, and Precautions : solid DMP DAB–Pd–MAH is shelf‐stable when stored at room temperature in a closed container under ambient atmosphere.

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Recent Advances in Spiro‐MeOTAD Hole Transport Material and Its Applications in Organic–Inorganic Halide Perovskite Solar Cells

Cited by 360 publications

References 218 publications

Over 6% Certified Sb₂(S,Se)₃ Solar Cells Fabricated via In Situ Hydrothermal Growth and Postselenization

Over 6% Certified Sb₂(S,Se)₃ Solar Cells Fabricated via In Situ Hydrothermal Growth and Postselenization

Enhanced Stability of Perovskite Solar Cells Incorporating Dopant‐Free Crystalline Spiro‐OMeTAD Layers by Vacuum Sublimation

Palladium, [ N , N ′‐1,2‐ethanediylidenebis[2,6‐dimethylbenzenamine‐κN]][(3,4‐ η )‐2,5‐furandione] ( ^DMP DAB–Pd–MAH)

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Recent Advances in Spiro‐MeOTAD Hole Transport Material and Its Applications in Organic–Inorganic Halide Perovskite Solar Cells

Cited by 360 publications

References 218 publications

Over 6% Certified Sb2(S,Se)3 Solar Cells Fabricated via In Situ Hydrothermal Growth and Postselenization

Over 6% Certified Sb2(S,Se)3 Solar Cells Fabricated via In Situ Hydrothermal Growth and Postselenization

Enhanced Stability of Perovskite Solar Cells Incorporating Dopant‐Free Crystalline Spiro‐OMeTAD Layers by Vacuum Sublimation

Palladium, [ N , N ′‐1,2‐ethanediylidenebis[2,6‐dimethylbenzenamine‐κN]][(3,4‐ η )‐2,5‐furandione] ( DMP DAB–Pd–MAH)

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Product

Resources

About

Over 6% Certified Sb₂(S,Se)₃ Solar Cells Fabricated via In Situ Hydrothermal Growth and Postselenization

Over 6% Certified Sb₂(S,Se)₃ Solar Cells Fabricated via In Situ Hydrothermal Growth and Postselenization

Palladium, [ N , N ′‐1,2‐ethanediylidenebis[2,6‐dimethylbenzenamine‐κN]][(3,4‐ η )‐2,5‐furandione] ( ^DMP DAB–Pd–MAH)