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Formation of quaternary Zn(AlxGa1−x)2O4 epilayers driven by thermally induced interdiffusion between spinel ZnGa2O4 epilayer and Al2O3 substrate
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-5879-3264
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.
National Yang Ming Chiao Tung University, Hsinchu, 30010, Taiwan.
National United University, Miaoli, 36063, Taiwan.
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2023 (English)In: Materials Today Advances, ISSN 2590-0498, Vol. 20, article id 100422Article in journal (Refereed) Published
Abstract [en]

Zinc aluminogallate, Zn(AlxGa1−x)2O4 (ZAGO), a single-phase spinel structure, offers considerable potential for high-performance electronic devices due to its expansive compositional miscibility range between aluminum (Al) and gallium (Ga). Direct growth of high-quality ZAGO epilayers however remains problematic due to the high volatility of zinc (Zn). This work highlights a novel synthesis process for high-quality epitaxial quaternary ZAGO thin films on sapphire substrates, achieved through thermal annealing of a ZnGa2O4 (ZGO) epilayer on sapphire in an ambient air setting. In-situ annealing x-ray diffraction measurements show that the incorporation of Al in the ZGO epilayer commenced at 850 °C. The Al content (x) in ZAGO epilayer gradually increased up to around 0.45 as the annealing temperature was raised to 1100 °C, which was confirmed by transmission electron microscopy (TEM) and energy dispersive x-ray spectroscopy. X-ray rocking curve measurement revealed a small full width at half maximum value of 0.72 °, indicating the crystal quality preservation of the ZAGO epilayer with a high Al content. However, an epitaxial intermediate �–(AlxGa1−x)2O3 layer (� - AGO) was formed between the ZAGO and sapphire substrate. This is believed to be a consequence of the interdiffusion of Al and Ga between the ZGO thin film and sapphire substrate. Using density functional theory, the substitution cost of Ga in sapphire was determined to be about 0.5 eV lower than substitution cost of Al in ZGO. Motivated by this energetically favorable substitution, a formation mechanism of the ZAGO and AGO layers was proposed. Spectroscopic ellipsometry studies revealed an increase in total thickness of the film from 105.07 nm (ZGO) to 147.97 nm (ZAGO/AGO) after annealing to 1100 °C, which were corroborated using TEM. Furthermore, an observed increase in the direct (indirect) optical bandgap from 5.06 eV (4.7 eV) to 5.72 eV (5.45 eV) with an increasing Al content in the ZAGO layer further underpins the formation of a quaternary ZAGO alloy with a tunable composition.

Place, publisher, year, edition, pages
Elsevier, 2023. Vol. 20, article id 100422
Keywords [en]
Zinc aluminogallate; Ellipsometry; Semiconductors; Annealing; Interdiffusion; Bandgap
National Category
Condensed Matter Physics Inorganic Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-197989DOI: 10.1016/j.mtadv.2023.100422ISI: 001081449100001OAI: oai:DiVA.org:liu-197989DiVA, id: diva2:1798900
Note

Funding agencies;This research was funded by Vetenskapsrådet (2018–04198), Energimyndigheten (46658-1), and Stiftelsen Olle Engkvist Byggmästare (197–0210), STINT (MG2019-8485), and Stiftelsen för Strategisk Forskning (2009-00971). The Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU 2009-00971) is acknowledged for financial support. We acknowledge the support from Wafer Works Corporation, National Science and Technology Council (Taiwan) (112-2218-E-A49-024-MBK, 112-2622-8-A49-013-SB, MOST 111-2923-E-A49 -003 -MY3), and MAtek (2021-T-006).

Available from: 2023-09-20 Created: 2023-09-20 Last updated: 2023-11-03
In thesis
1. Optical studies of AlN and GaO based nanostructures using Mueller matrix spectroscopic ellipsometry
Open this publication in new window or tab >>Optical studies of AlN and GaO based nanostructures using Mueller matrix spectroscopic ellipsometry
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis explores the diverse optical properties manifested when light interacts with various materials, with an emphasis on circular polarization- and bandgaprelated phenomena. The studies in this work are centered around Mueller matrix spectroscopic ellipsometry, with the objective of synthesizing and characterizing nanostructured and high-quality thin films to expand our understanding of the optical properties arising from their underlying structure and electronic transitions, respectively.

Papers I, II, and III of the research address the optical properties associated with circular polarization, emphasizing the importance of the morphology and structure of the sculptured thin films used. To clarify this, AlN-based chiral sculptured thin films are synthesized using glancing angle deposition and magnetron sputtering. The discussion explores the impact of different growth parameters on the morphology and crystal structure of the films. By examining these thin film samples, it is shown how their structure and crystallographic orientation can be designed to reflect narrow spectral bands of circularly polarized light at specific wavelengths. The research also tackles how thin films preferentially reflect one handedness of circularly polarized light over the other with a high degree of circular polarization. A combination of theoretical and experimental studies offers insights into the nuances of growth and light-material interactions, particularly in complex photonic structures.

Papers IV and V investigate the optical properties that arise from electronic transitions in thin films, focusing on the complex dielectric function and optical bandgap phenomena. These properties are explored using high-quality single crystalline homogenous thin films of ZnGaO, grown using metal-organic chemical vapor deposition. Various formalisms to calculate bandgap values are evaluated for their precision and applicability. The modified Cody formalism stands out as the preferred choice due to its ability to provide the most linear region for extrapolating bandgap energy values. Through both theoretical calculations and experiments, a critical analysis is provided on the evolution of the crystal structure and optical properties of these thin films when exposed to elevated temperatures. These findings explain the interplay between the structural characteristics of thin films and their subsequent influence on bandgap properties.

Altogether, this thesis provides a fundamental understanding of the structural and intrinsic properties of materials that govern light-matter interactions. This research paves the way for the further development of thin film-based polarization filters and advanced optoelectronic device technologies.

Abstract [sv]

Detta arbete utforskar optiska egenskaper som manifesteras när ljus interagerar med olika material. Avhandlingens tonvikt ligger på generation av cirkulärpolariserat ljus samt bandgapsrelaterade egenskaper. Studierna är centrerade kring spektroskopisk Mueller-matrisellipsometri, med målet att syntetisera och karakterisera nanostrukturerade och högkvalitativa tunna filmer. Detta för att utöka förståelsen av de optiska fenomen som uppstår från deras underliggande struktur respektive elektroniska övergångar.

Artikel I, II och III i avhandlingen är relaterade till optiska polarisationsstudier och belyser betydelsen av morfologi och struktur hos optiska och fotoniska material. För att studera detta syntetiserar vi AlN baserade kirala skulpterade tunna filmer med hjälp av magnetronsputtring vid små infallsvinklar (glancing angle deposition) och diskuterar inverkan av olika tillväxtparametrar på filmernas morfologi och kristallstruktur. Genom att studera detta visar vi hur struktur och kristallografiska orientering kan skräddarsys för att reflektera smala spektrala band av där ljuset har hög grad av cirkulär polarisation. Vi visar även hur de tunna filmerna selektivt reflekterar den ena polarisationsriktningen (vänster/höger) beroende på det inkommande ljusets infallsvinkel och våglängd. Genom en serie teoretiska och experimentella studier ger vi detaljerad insikt i hur de studerade nanostrukturerna samverkar med ljus.

Artikel IV och V undersöker de optiska egenskaperna som härrör från elektroniska övergångar i tunna filmer, med fokus specifikt på dielektricitetsfunktionen och optiska bandgapsfenomen. Dessa egenskaper studeras med för högkvalitativa enkristallina och homogena tunna filmer av ZnGaO, syntetiserade med metallorganisk CVD-teknik (Chemical Vapour Deposition). Vi utvärderar olika formalismer för att beräkna bandgapsvärden och bedömer deras noggrannhet och tillämpbarhet. Den modifierade Cody formalismen framhålls som bästa val på grund av dess egenskap att tillhandahålla den mest linjära regionen för att extrapolera fram värden på bandgapsenergierna. Med hjälp av teoretiska beräkningar och experiment analyserar vi även utvecklingen de tunna filmernas kristallstruktur och optiska egenskaper när de värms upp till höga temperaturer. Resultaten förklarar samspelet mellan de strukturella egenskaperna och kopplingen till bandgapsvärdena.

Sammantaget ger denna avhandling en grundläggande förståelse för strukturella och inneboende egenskaper hos material som styr samverkan mellan ljus och materia. Denna forskning banar väg för vidareutveckling av tunnfilmsbaserade polarisationsfilter och avancerade optoelektroniska komponenter.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2023. p. 43
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 2354
Keywords
GLAD, MMSE, PVD, III-nitrides, Oxides, Anisotropy, Bandgap
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:liu:diva-198144 (URN)10.3384/9789180753777 (DOI)9789180753760 (ISBN)9789180753777 (ISBN)
Public defence
2023-10-27, NOBEL BL32, B Building, Campus Valla, Linköping, 09:15 (English)
Opponent
Supervisors
Note

Funding agencies: This work was funded by Nanyang Technological University and Linköping University joint Ph.D. programme on Materials and Nanoscience Engineering (DnrLiU-2015-01061), Vetenskapsrådet (2018-04198), Stiftelsen för Strategisk Forskning (2009-00971), Energimyndigheten (grant number 46658-1), Stiftelsen Olle Engkvist Byggmästare (grant number 197-0210), and Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU 2009-00971).

Available from: 2023-09-26 Created: 2023-09-26 Last updated: 2023-10-03Bibliographically approved

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Chang, Jui-CheGueorguiev, Gueorgui KostovMagnusson, RogerBirch, JensJärrendahl, KennethHsiao, Ching-Lien

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