Modifying optical properties of reduced/graphene oxide with controlled ozone and thermal treatment in aqueous suspensions

Md Tanvir Hasan, Brian J. Senger, Price Mulford, Conor Ryan, Hung Doan, Zygmunt Gryczynski, Anton V. Naumov

Research output: Contribution to journalArticleResearchpeer-review

8 Citations (Scopus)

Abstract

Graphene possesses a number of advantageous properties, however, does not exhibit optical emission, which limits its use in optoelectronics. Unlike graphene, its functional derivative, graphene oxide (GO) exhibits fluorescence emission throughout the visible. Here, we focus on controlled methods for tuning the optical properties of GO. We introduce ozone treatment of reduced graphene oxide (RGO) in order to controllably transform it from non-emissive graphene-like material into GO with a specific fluorescence emission response. Solution-based treatment of RGO for 5-45 min with ∼1.2 g l-1 ozone/oxygen gas mixture yields a drastic color change, bleaching of the absorption in the visible and the stepwise increase in fluorescence intensity and lifetime. This is attributed to the introduction of oxygen-containing functional groups to RGO graphitic platform as detected by the infrared spectroscopy. A reverse process: controllable quenching of this fluorescence is achieved by the thermal treatment of GO in aqueous suspension up to 90C. This methodology allows for the wide range alteration of GO optical properties starting from the dark-colored non-emissive RGO material up to nearly transparent highly ozone-oxidized GO showing substantial fluorescence emission. The size of the GO flakes is concomitantly altered by oxidation-induced scission. Semi-empirical PM3 theoretical calculations on HyperChem models are utilized to explore the origins of optical response from GO. Two models are considered, attributing the induced emission either to the localized states produced by oxygen-containing addends or the islands of graphitic carbon enclosed by such addends. Band gap values calculated from the models are in the agreement with experimentally observed transition peak maxima. The controllable variation of GO optical properties in aqueous suspension by ozone and thermal treatments shown in this work provides a route to tune its optical response for particular optoelectronics or biomedical applications.

Original languageEnglish
Article number065705
JournalNanotechnology
Volume28
Issue number6
DOIs
StatePublished - 10 Feb 2017

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Graphite
Ozone
Oxides
Graphene
Suspensions
Optical properties
Heat treatment
Fluorescence
Oxygen
Optoelectronic devices
Bleaching
Gas mixtures

Keywords

  • absorption
  • fluorescence
  • fluorescence lifetime
  • graphene oxide
  • oxidation
  • ozone
  • reduced graphene oxide

Cite this

Hasan, Md Tanvir ; Senger, Brian J. ; Mulford, Price ; Ryan, Conor ; Doan, Hung ; Gryczynski, Zygmunt ; Naumov, Anton V. / Modifying optical properties of reduced/graphene oxide with controlled ozone and thermal treatment in aqueous suspensions. In: Nanotechnology. 2017 ; Vol. 28, No. 6.
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abstract = "Graphene possesses a number of advantageous properties, however, does not exhibit optical emission, which limits its use in optoelectronics. Unlike graphene, its functional derivative, graphene oxide (GO) exhibits fluorescence emission throughout the visible. Here, we focus on controlled methods for tuning the optical properties of GO. We introduce ozone treatment of reduced graphene oxide (RGO) in order to controllably transform it from non-emissive graphene-like material into GO with a specific fluorescence emission response. Solution-based treatment of RGO for 5-45 min with ∼1.2 g l-1 ozone/oxygen gas mixture yields a drastic color change, bleaching of the absorption in the visible and the stepwise increase in fluorescence intensity and lifetime. This is attributed to the introduction of oxygen-containing functional groups to RGO graphitic platform as detected by the infrared spectroscopy. A reverse process: controllable quenching of this fluorescence is achieved by the thermal treatment of GO in aqueous suspension up to 90C. This methodology allows for the wide range alteration of GO optical properties starting from the dark-colored non-emissive RGO material up to nearly transparent highly ozone-oxidized GO showing substantial fluorescence emission. The size of the GO flakes is concomitantly altered by oxidation-induced scission. Semi-empirical PM3 theoretical calculations on HyperChem models are utilized to explore the origins of optical response from GO. Two models are considered, attributing the induced emission either to the localized states produced by oxygen-containing addends or the islands of graphitic carbon enclosed by such addends. Band gap values calculated from the models are in the agreement with experimentally observed transition peak maxima. The controllable variation of GO optical properties in aqueous suspension by ozone and thermal treatments shown in this work provides a route to tune its optical response for particular optoelectronics or biomedical applications.",
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Modifying optical properties of reduced/graphene oxide with controlled ozone and thermal treatment in aqueous suspensions. / Hasan, Md Tanvir; Senger, Brian J.; Mulford, Price; Ryan, Conor; Doan, Hung; Gryczynski, Zygmunt; Naumov, Anton V.

In: Nanotechnology, Vol. 28, No. 6, 065705, 10.02.2017.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Modifying optical properties of reduced/graphene oxide with controlled ozone and thermal treatment in aqueous suspensions

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AU - Senger, Brian J.

AU - Mulford, Price

AU - Ryan, Conor

AU - Doan, Hung

AU - Gryczynski, Zygmunt

AU - Naumov, Anton V.

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AB - Graphene possesses a number of advantageous properties, however, does not exhibit optical emission, which limits its use in optoelectronics. Unlike graphene, its functional derivative, graphene oxide (GO) exhibits fluorescence emission throughout the visible. Here, we focus on controlled methods for tuning the optical properties of GO. We introduce ozone treatment of reduced graphene oxide (RGO) in order to controllably transform it from non-emissive graphene-like material into GO with a specific fluorescence emission response. Solution-based treatment of RGO for 5-45 min with ∼1.2 g l-1 ozone/oxygen gas mixture yields a drastic color change, bleaching of the absorption in the visible and the stepwise increase in fluorescence intensity and lifetime. This is attributed to the introduction of oxygen-containing functional groups to RGO graphitic platform as detected by the infrared spectroscopy. A reverse process: controllable quenching of this fluorescence is achieved by the thermal treatment of GO in aqueous suspension up to 90C. This methodology allows for the wide range alteration of GO optical properties starting from the dark-colored non-emissive RGO material up to nearly transparent highly ozone-oxidized GO showing substantial fluorescence emission. The size of the GO flakes is concomitantly altered by oxidation-induced scission. Semi-empirical PM3 theoretical calculations on HyperChem models are utilized to explore the origins of optical response from GO. Two models are considered, attributing the induced emission either to the localized states produced by oxygen-containing addends or the islands of graphitic carbon enclosed by such addends. Band gap values calculated from the models are in the agreement with experimentally observed transition peak maxima. The controllable variation of GO optical properties in aqueous suspension by ozone and thermal treatments shown in this work provides a route to tune its optical response for particular optoelectronics or biomedical applications.

KW - absorption

KW - fluorescence

KW - fluorescence lifetime

KW - graphene oxide

KW - oxidation

KW - ozone

KW - reduced graphene oxide

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