Composition-tuned metal-organic thin-film structures based on photoswitchable azobenzene by ALD/MLD

Aida Khayyami; Anish Philip; Jenna Multia; Maarit Karppinen

doi:10.1039/d0dt02062a

Composition-tuned metal-organic thin-film structures based on photoswitchable azobenzene by ALD/MLD

Aida Khayyami, Anish Philip, Jenna Multia, Maarit Karppinen

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

27 Lataukset (Pure)

Abstrakti

We demonstrate the fabrication of in-situ crystalline thin films of various azobenzene (AZO) based metal-organic structures using the atomic/molecular layer deposition (ALD/MLD) technique; these are highly intriguing materials as azobenzene is one of the prototype organic molecules experiencing photoisomerization. Our Li-, Ca and Fe-AZO thin films deposited from Li(thd) (thd = 2,2,6,6-tetramethyl-3,5-heptanedione), Ca(thd)2, FeCl3 and azobenzene-4,4'-dicarboxylic acid precursors in the temperature range of 250-360 °C exhibit metal-AZO structures not known from bulk samples. In all these structures, the AZO linker molecules are free to undergo the characteristic trans-cis photoisomerization reaction upon UV (360 nm) irradiation. However, this lowers the degree of crystallinity. To address the issue, we investigate hetero-organic structures where TPA (terephthalic acid) is used as another linker component together with AZO. This allows the trans-cis reaction of the AZO moieties to occur without compromising the film crystallinity. Finally, we demonstrate the growth of MOF-on-MOF type Ca-ADA@Ca-TPA thin films also showing the efficient photoisomerization reaction.

Alkuperäiskieli	Englanti
Sivut	11310-11316
Sivumäärä	7
Julkaisu	Dalton Transactions
Vuosikerta	49
Numero	32
DOI - pysyväislinkit	https://doi.org/10.1039/d0dt02062a
Tila	Julkaistu - 18 elokuuta 2020
OKM-julkaisutyyppi	A1 Julkaistu artikkeli, soviteltu

Pääsy asiakirjaan

10.1039/d0dt02062a

d0dt02062aFinal published version, 2,39 MBLisenssi: CC BY-NC

Link to publication in Scopus

Sormenjälki Sukella tutkimusaiheisiin 'Composition-tuned metal-organic thin-film structures based on photoswitchable azobenzene by ALD/MLD'. Ne muodostavat yhdessä ainutlaatuisen sormenjäljen.

Projektit

2 Päättynyt

Uusia hybridimateriaaleja ALD/MLD:n avulla: perusteista sovelluksiin

Aleksandrova, I., Medina, E., Thomas, C., Karppinen, M., Haggren, A., Tiittanen, T., Multia, J., Ghazy, A., Mustonen, O., Khayyami, A., Revitzer, H., Sederholm, L., Johansson, L. & Madadi, M.

01/09/2016 → 24/09/2020

Projekti: Academy of Finland: Other research funding

Molecular-Layer-Engineered Inorganic-Organic Hybrid Materials

Hagen, D., Khayyami, A., Marin, G., Ghazy, A., Nisula, M., Johansson, L., Safdar, M., Krahl, F., Thomas, C., Medina, E., Tiittanen, T., Giedraityte, Z., Heiska, J., Lepikko, S., Karppinen, M., Haggren, A., Tripathi, T., Multia, J., Philip, A., Srivastava, D., Aleksandrova, I., Mustonen, O., Jin, H. & Ahvenniemi, E.

23/12/2013 → 24/05/2019

Projekti: EU: ERC grants

Laitteet

Raaka-aineiden tutkimusinfrastruktuuri

Maarit Karppinen (Manager)

Kemian tekniikan korkeakoulu

Laitteistot/tilat: Facility

Siteeraa tätä

Khayyami, A., Philip, A., Multia, J., & Karppinen, M. (2020). Composition-tuned metal-organic thin-film structures based on photoswitchable azobenzene by ALD/MLD. Dalton Transactions, 49(32), 11310-11316. https://doi.org/10.1039/d0dt02062a

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title = "Composition-tuned metal-organic thin-film structures based on photoswitchable azobenzene by ALD/MLD",

abstract = "We demonstrate the fabrication of in-situ crystalline thin films of various azobenzene (AZO) based metal-organic structures using the atomic/molecular layer deposition (ALD/MLD) technique; these are highly intriguing materials as azobenzene is one of the prototype organic molecules experiencing photoisomerization. Our Li-, Ca and Fe-AZO thin films deposited from Li(thd) (thd = 2,2,6,6-tetramethyl-3,5-heptanedione), Ca(thd)2, FeCl3 and azobenzene-4,4'-dicarboxylic acid precursors in the temperature range of 250-360 °C exhibit metal-AZO structures not known from bulk samples. In all these structures, the AZO linker molecules are free to undergo the characteristic trans-cis photoisomerization reaction upon UV (360 nm) irradiation. However, this lowers the degree of crystallinity. To address the issue, we investigate hetero-organic structures where TPA (terephthalic acid) is used as another linker component together with AZO. This allows the trans-cis reaction of the AZO moieties to occur without compromising the film crystallinity. Finally, we demonstrate the growth of MOF-on-MOF type Ca-ADA@Ca-TPA thin films also showing the efficient photoisomerization reaction.",

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AB - We demonstrate the fabrication of in-situ crystalline thin films of various azobenzene (AZO) based metal-organic structures using the atomic/molecular layer deposition (ALD/MLD) technique; these are highly intriguing materials as azobenzene is one of the prototype organic molecules experiencing photoisomerization. Our Li-, Ca and Fe-AZO thin films deposited from Li(thd) (thd = 2,2,6,6-tetramethyl-3,5-heptanedione), Ca(thd)2, FeCl3 and azobenzene-4,4'-dicarboxylic acid precursors in the temperature range of 250-360 °C exhibit metal-AZO structures not known from bulk samples. In all these structures, the AZO linker molecules are free to undergo the characteristic trans-cis photoisomerization reaction upon UV (360 nm) irradiation. However, this lowers the degree of crystallinity. To address the issue, we investigate hetero-organic structures where TPA (terephthalic acid) is used as another linker component together with AZO. This allows the trans-cis reaction of the AZO moieties to occur without compromising the film crystallinity. Finally, we demonstrate the growth of MOF-on-MOF type Ca-ADA@Ca-TPA thin films also showing the efficient photoisomerization reaction.

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