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Epitaxial growth and thermoelectric properties of Mg3Bi2 thin films deposited by magnetron sputtering
Malmö University, Faculty of Technology and Society (TS), Department of Materials Science and Applied Mathematics (MTM). Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, Linköping.ORCID iD: 0000-0002-2857-5135
Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, Linköping SE-581 83, Sweden.ORCID iD: 0000-0002-2696-4372
Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
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2022 (English)In: Applied Physics Letters, ISSN 0003-6951, E-ISSN 1077-3118, Vol. 120, no 5, article id 051901Article in journal (Refereed) Published
Abstract [en]

Mg3Sb2-based thermoelectric materials attract attention for applications near room temperature. Here, Mg-Bi films were synthesized using magnetron sputtering at deposition temperatures from room temperature to 400 °C. Single-phase Mg3Bi2 thin films were grown on c-plane-oriented sapphire and Si(100) substrates at a low deposition temperature of 200 °C. The Mg3Bi2 films grew epitaxially on c-sapphire and fiber-textured on Si(100). The orientation relationships for the Mg3Bi2 film with respect to the c-sapphire substrate are (0001) Mg3Bi2‖(0001) Al2O3 and [112⎯⎯2¯0] Mg3Bi2‖[112⎯⎯2¯0] Al2O3. The observed epitaxy is consistent with the relatively high work of separation, calculated by the density functional theory, of 6.92 J m−2 for the Mg3Bi2 (0001)/Al2O3 (0001) interface. Mg3Bi2 films exhibited an in-plane electrical resistivity of 34 μΩ m and a Seebeck coefficient of +82.5 μV K−1, yielding a thermoelectric power factor of 200 μW m−1 K−2 near room temperature.This work was supported financially by the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU No. 2009 00971), the Knut and Alice Wallenberg Foundation through the Wallenberg Academy Fellows program (No. KAW-2020.0196), the Swedish Research Council (VR) under Project Nos. 2016-03365 and 2021-03826, the National Key Research and Development Program of China under Grant No. 2018YFB0703600, the National Natural Science Foundation of China under Grant No. 51872133, the Guangdong Innovative and Entrepreneurial Research Team Program under Grant No. 2016ZT06G587, and the Tencent Foundation through the XPLORER PRIZE, Guangdong Provincial Key Laboratory Program (No. 2021B1212040001) from the Department of Science and Technology of Guangdong Province. The computations were performed on resources provided by the Swedish National Infrastructure for Computing (SNIC) at National Supercomputer Centre (NSC) partially funded by the Swedish Research Council through Grant Agreement No. 2018-05973.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2022. Vol. 120, no 5, article id 051901
National Category
Condensed Matter Physics
Identifiers
URN: urn:nbn:se:mau:diva-49952DOI: 10.1063/5.0074419ISI: 000752314600003Scopus ID: 2-s2.0-85124696742OAI: oai:DiVA.org:mau-49952DiVA, id: diva2:1635374
Funder
Vinnova, 2009 00971Knut and Alice Wallenberg Foundation, 2020.0196Swedish Research Council, 2016-03365Swedish Research Council, 2018-05973Swedish Research Council, 2021-03826Available from: 2022-02-06 Created: 2022-02-06 Last updated: 2024-08-23Bibliographically approved
In thesis
1. Thermoelectric properties of Mg3SbxBi2−x thin films
Open this publication in new window or tab >>Thermoelectric properties of Mg3SbxBi2−x thin films
2024 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Thermoelectric materials produce an electrical potential when exposed to a temperature gradient. The lack of moving parts makes thermoelectric devices quiet and reliable, and therefore often used for off-grid energy generation. When deposited in the form of thin films, the surface to volume ratio is far larger than for bulk materials, granting them some useful attributes due to quantum electron confinement and phonon-scattering effects. Mg_3Sb_xBi_2-x is a thermoelectric material with good properties close to room temperature. This thesis explores the transport properties of Mg_3Sb_xBi_2-x thin films deposited using dc magnetron sputtering. 

Mg_3Bi_2 films were synthesized between room temperature and 400 C -- a relatively low deposition temperature of 200 C proved to be necessary for single crystal growth to avoid loss of Mg due to its relatively high vapor pressure. Results from energy-dispersive X-ray spectroscopy and X-ray diffraction confirm the loss of Mg at 300 C and above, while at room temperature the film was polycrystalline. The epitaxy was confirmed using X-ray pole figures and computer simulation based on density functional theory. The thermoelectric properties were measured between room temperature and 200 C. Mg_3Bi_2 is a semimetal with low electrical resistivity. The power factor   , where S is the Seebeck coefficient and ρ is the electrical resistivity, had a peak value of 200 µWm^-1K^-2 at room temperature. Through measuring the carrier concentration and mobility, it has been confirmed that the decrease in power factor as the temperature increases is due to the bipolar effect -- the small bandgap of the material being insufficient to prevent the minority carrier excitation. The electrons and holes neutralize, decreasing the net current, and therefore limiting the Seebeck coefficient. Decreasing the bipolar effect may be possible by increasing the majority carrier concentration and enlarging the band gap of the material. 

Mg_3Sb_2 is a semiconductor -- it has significantly higher electrical resistivity and Seebeck coefficient as compared to Mg_3Bi_2. Alloying both materials together can result in a semiconducting material with appreciably lower thermal conductivity. This is especially important for Mg_3Bi_2 which as a semimetal has high thermal conductivity. Furthermore, the increase in Sb content increases the energy gap and shifts the bipolar effect, making the material more suitable for higher temperatures. It must be noted that low band gap is more desirable for room temperature materials than for high temperature thermoelectrics. Five Mg_3Sb_xBi_2-x samples were synthesized at 200 C with x ranging from 0.00 to 1.19. Sample characterization included composition, crystal structure and transport properties. An Sb peak has been observed in X-ray diffraction results for x ≥ 1. The precipitation of Sb due to minute deficiency of Mg in those samples can affect the properties -- the focus of the study became x < 1 instead. Higher Sb content results in a more polycrystalline structure, higher band gap, electrical resistivity and Seebeck coefficient. For room temperature implementations, high Bi content is advantageous. This work has prospects for further study of Mg_3Sb_xBi_2-x based thin films and their synthesis on flexible substrates, which are often sensitive to higher temperatures.

Abstract [sv]

Termoelektriska material kan omvandla temperaturgradienter till elektrisk spänning. Termoelektriska anordningar innehåller inga rörliga delar och är därför tysta och pålitliga, de används därför ofta för att generera elektricitet utanför elnätet. Det höga förhållandet mellan yta och volym för tunna filmer gör att vissa förmånliga kvantmekaniska effekter kan utnyttjas. Mg_3Sb_xBi_2-x är ett termoelektriskt material med goda egenskaper nära rumstemperatur. I detta arbete undersöks syntes och karakterisering av tunna filmer av Mg_3Sb_xBi_2-x tillverkade genom dc magnetron sputtring. Epitaxiell tillväxt av icke-dopade tunna filmer av p-typ är av vikt för fördjupad förståelse av fundamentala fysikaliska processer relaterade till Mg_3Bi_2-baserade tunna filmer. 

Tunna filmer av Mg_3Bi_2 har producerats vid olika temperaturer mellan rumstemperatur och 400 C. En relativt låg temperatur, 200 C, visade sig vara nödvändig för att åstadkomma enkristaller, högre temperaturer ledde till förluster av Mg på grund av dess relativt höga ångtryck. Resultat från röntgenspektroskopi och röntgendiffraktion bekräftar förlust av Mg vid temperaturer över 300 C samt att filmen blev polykristallin vid deponering i rumstemperatur. Epitaxiell tillväxt bekräftades genom polfigurer och täthetsfunktionalteori modellering. De termoelektriska egenskaperna mättes mellan rumstemperatur och 200 C. Mg_3Bi_2 är en halvmetall med låg elektrisk resistans. Materialets så kallade effektfaktor   , där S är Seebeck-koefficienten och   är resistansen, nådde sitt högsta värde 200 µWm^-1K^-2  vid rumstemperatur. Genom att mäta koncentrationen av laddningsbärarna och dess mobilitet kunde det bekräftas att minskningen av effektfaktorn med ökande temperatur beror på den bipolära effekten. Detta yttrar sig genom att det smala bandgapet i materialet är inte tillräckligt för att undvika excitation av minoritetsbärare vid högre temperatur. Genom att öka bandgapet kan den bipolära effekten minskas. 

Mg_3Sb_2 är en halvledare och har därför betydligt högre resistans och Seebeck-koefficient än Mg_3Bi_2. Genom att legera dessa material med varandra fås ett halvledande material med betydligt lägre termisk ledningsförmåga. Detta är speciellt viktigt för Mg_3Bi_2, som är en halvmetall och därför har hög termisk ledningsförmåga. Genom att öka halten Sb ökas även bandgapet och motverkar därmed den bipolära effekten vilket gör materialet mer lämpat för högre temperaturer. Små bandgap är mer lämpade för rumstemperaturtillämpningar än för tillämpningar vid höga temperaturer. Fem prover av Mg_3Sb_xBi_2-x, där x ligger mellan 0.00 och 1.19, synteserades. Dess komposition, kristallstruktur och transportegenskaper karaktäriserades. En diffraktionstopp från Sb kunde observeras för x ≥ 1. Utfällningar av Sb på grund av små förluster av Mg i de proverna kan påverka de termoelektriska egenskaperna, studien fokusserades därför på x < 1 istället. En högre halt av Sb resulterar i en polykristallin film med högre bandgap, resistans och Seebeck-koefficient. För rumstemperaturtillämpningar är det fördelaktigt med en högre halt av Bi. Den här studien möjliggör vidare undersökningar av Mg_3Sb_xBi_2-x filmer deponerade på flexibla substrat som ofta är känsliga för höga temperaturer. 

Place, publisher, year, edition, pages
Malmö: Malmö University Press, 2024. p. 28
Series
Studies in Applied Physics
National Category
Physical Sciences
Identifiers
urn:nbn:se:mau:diva-70562 (URN)10.24834/isbn.9789178775118 (DOI)978-91-7877-510-1 (ISBN)978-91-7877-511-8 (ISBN)
Presentation
2024-09-13, C377, Orkanen, Malmö University, Nordenskiöldsgatan 10, Malmö, 09:00 (English)
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Supervisors
Available from: 2024-08-23 Created: 2024-08-23 Last updated: 2024-11-04Bibliographically approved

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Sadowski, GrzegorzMusic, Denis

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