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Prying Apart Ruddlesden−Popper Phases: Exfoliation into Sheets and Nanotubes for Assembly of Perovskite Thin Films
Protonated Ruddlesden−Popper tantalates and titanotantalates H2[A n - 1B n O3 n +1] (A = Na, Ca, Sr, La; B = Ta, Ti) that have acidic interlayer protons were exfoliated using tetra(n-butyl)ammonium hydroxide (TBA+OH-). H2CaNaTa3O10 forms both single sheets and tubular “scrolls” when reacted to make...
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Published in: | Chemistry of materials 2000-11, Vol.12 (11), p.3427-3434 |
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Main Authors: | , |
Format: | Article |
Language: | English |
Subjects: | |
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Online Access: | Get full text |
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Summary: | Protonated Ruddlesden−Popper tantalates and titanotantalates H2[A n - 1B n O3 n +1] (A = Na, Ca, Sr, La; B = Ta, Ti) that have acidic interlayer protons were exfoliated using tetra(n-butyl)ammonium hydroxide (TBA+OH-). H2CaNaTa3O10 forms both single sheets and tubular “scrolls” when reacted to make TBA x H2 - x CaNaTa3O10 colloids. In contrast, TBA x H2 - x A2Ta2TiO10 and TBA x H2 - x ALaTi2TaO10 (A = Ca, Sr) form sheets exclusively. The n = 2 tantalate TBA x H2 - x SrTa2O7 forms high aspect ratio scrolls, as well as smaller amounts of sheets. In contrast to the analogous tantalates, the Ruddlesden−Popper titanates and titanoniobates have weakly acidic interlayer protons and exfoliate only to a limited extent. TBA x H2 - x SrNb2O7 forms sheets exclusively, whereas TBA x H2 - x Ca2Nb2TiO10 forms both sheets and scrolls. The n = 3 titanate H2La2Ti3O10 exfoliates into sheets using n-butylamine, and Na2La2Ti3O10·xH2O forms sheets when exfoliated with TBA+OH-. When reacted with O-(2-aminopropyl)-O ‘-(2-methoxyethyl) polypropylene glycol 500, H2La2Ti3O10 exfoliates into monodisperse 20 × 100 nm scrolls. The exfoliated tantalates and titanotantalates can be electrostatically adsorbed to a Si/SiO2/PDDA [PDDA = poly(diallyldimethylammonium chloride)] surface, forming perovskite monolayers. Above pH 9.5, TBA x H2 - x SrLaTi2TaO10 sheets tile to densely cover a Si/SiO2 surface derivatized with 4-aminobutyldimethylmethoxysilane (4-ABDMMS) and two bilayers of poly(sodium styrenesulfonate) (PSS) and poly(allylamine hydrochloride) (PAH). The exfoliated titanates and titanoniobates generally do not adhere to polycationic surfaces. |
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ISSN: | 0897-4756 1520-5002 |
DOI: | 10.1021/cm000495r |