Lohaus, Christian (2019)
The Fermi Level in
Hematite - Doping, Band Alignment, and Charge Transitions.
Technische Universität Darmstadt
Dissertation, Erstveröffentlichung
Kurzbeschreibung (Abstract)
In this work the position of the Fermi level in hematite (Fe2O3) is being manipulating and the accessible range of Fermi level positions within the optical band gap is being determined. This range directly translates to the photovoltage that a semiconducting material like Fe2O3 can generate and thereby gives an answer why usually the photovoltages of hematite based devices fall short of predicted values based on the value of the optical band gap. In order to study the Fermi level position of RF-magnetron sputtered hematite thin films the samples were being investigated by XPS and UPS without leaving the UHV conditions in advance, thus guarantying clean surfaces. The phase and other structural properties of the thin films after deposition and manipulation were investigated by Raman spectroscopy and XRD. Optical transmission and reflectance measurements and electrical investigations gave insight into the functional properties of the thin films. The manipulation of the position of the Fermi level was achieved with several techniques. First, by utilizing a self-designed co-sputtering setup, doping elements were incorporated during the sputter deposition into the hematite thin films. The doping elements of choice were the p-type dopant magnesium as well as the n-type dopants silicon and zirconium. In addition, manipulation of the Fermi level was achieved by contact formation on the surface of hematite thin films. Dedicated interface experiments to materials such as ITO, RuO2, Al2O3, and NiO gave further insight into the accessible Fermi level positions. Finally, the behavior of the Fermi level in hematite while being in contact with molecular species (oxygen, water, OH-, peroxides) was being studied as well. The results show accessible Fermi level positions from 0.3eV to 1.75eV above the valence band maximum. This range of about 1.5 eV is far less than the optical band gap which is about 2.2 eV and is in good agreement with the low photovoltages that are usually reported for hematite (or other transition metal oxides) based devices. The upper value of 1.75 eV was achieved by several different techniques and is identified to be a fundamental limit to the Fermi level due to pinning. The origin of this pinning is found to be the charge transition from Fe3+ to Fe2+. In other words, instead of generating free charge carriers in the conduction band the electrons are being trapped at an iron site and are positioned much lower in energy. This trapping has already been discussed in literature as polarons and has been identified to be the leading cause for slow charge carrier transport. This work extents the understanding of polarons in hematite and other transition metal oxides by identifying these quasi-particles as reasons for energetic limitations preventing large photovoltages. In addition, it was shown that the polaron state which is positioned within the optical band gap of hematite acts as an effective band edge. Using the results from interface experiments a new assignment of the band edge position on an absolute energy scale is possible and it is shown that electrochemical Mott-Schottky plot analysis have positioned the band edges too low. However, charge transfer from hematite to the hydrogen redox level in water is still not possible as the electrons are trapped within the lower lieing polaron state.
Typ des Eintrags: | Dissertation | ||||
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Erschienen: | 2019 | ||||
Autor(en): | Lohaus, Christian | ||||
Art des Eintrags: | Erstveröffentlichung | ||||
Titel: | The Fermi Level in Hematite - Doping, Band Alignment, and Charge Transitions | ||||
Sprache: | Englisch | ||||
Referenten: | Jaegermann, Prof. Dr. Wolfram ; Clemens, Ass.-Prof. Oliver | ||||
Publikationsjahr: | 2019 | ||||
Ort: | Darmstadt | ||||
Datum der mündlichen Prüfung: | 7 Februar 2019 | ||||
URL / URN: | https://tuprints.ulb.tu-darmstadt.de/8541 | ||||
Kurzbeschreibung (Abstract): | In this work the position of the Fermi level in hematite (Fe2O3) is being manipulating and the accessible range of Fermi level positions within the optical band gap is being determined. This range directly translates to the photovoltage that a semiconducting material like Fe2O3 can generate and thereby gives an answer why usually the photovoltages of hematite based devices fall short of predicted values based on the value of the optical band gap. In order to study the Fermi level position of RF-magnetron sputtered hematite thin films the samples were being investigated by XPS and UPS without leaving the UHV conditions in advance, thus guarantying clean surfaces. The phase and other structural properties of the thin films after deposition and manipulation were investigated by Raman spectroscopy and XRD. Optical transmission and reflectance measurements and electrical investigations gave insight into the functional properties of the thin films. The manipulation of the position of the Fermi level was achieved with several techniques. First, by utilizing a self-designed co-sputtering setup, doping elements were incorporated during the sputter deposition into the hematite thin films. The doping elements of choice were the p-type dopant magnesium as well as the n-type dopants silicon and zirconium. In addition, manipulation of the Fermi level was achieved by contact formation on the surface of hematite thin films. Dedicated interface experiments to materials such as ITO, RuO2, Al2O3, and NiO gave further insight into the accessible Fermi level positions. Finally, the behavior of the Fermi level in hematite while being in contact with molecular species (oxygen, water, OH-, peroxides) was being studied as well. The results show accessible Fermi level positions from 0.3eV to 1.75eV above the valence band maximum. This range of about 1.5 eV is far less than the optical band gap which is about 2.2 eV and is in good agreement with the low photovoltages that are usually reported for hematite (or other transition metal oxides) based devices. The upper value of 1.75 eV was achieved by several different techniques and is identified to be a fundamental limit to the Fermi level due to pinning. The origin of this pinning is found to be the charge transition from Fe3+ to Fe2+. In other words, instead of generating free charge carriers in the conduction band the electrons are being trapped at an iron site and are positioned much lower in energy. This trapping has already been discussed in literature as polarons and has been identified to be the leading cause for slow charge carrier transport. This work extents the understanding of polarons in hematite and other transition metal oxides by identifying these quasi-particles as reasons for energetic limitations preventing large photovoltages. In addition, it was shown that the polaron state which is positioned within the optical band gap of hematite acts as an effective band edge. Using the results from interface experiments a new assignment of the band edge position on an absolute energy scale is possible and it is shown that electrochemical Mott-Schottky plot analysis have positioned the band edges too low. However, charge transfer from hematite to the hydrogen redox level in water is still not possible as the electrons are trapped within the lower lieing polaron state. |
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Alternatives oder übersetztes Abstract: |
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URN: | urn:nbn:de:tuda-tuprints-85416 | ||||
Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 500 Naturwissenschaften | ||||
Fachbereich(e)/-gebiet(e): | 11 Fachbereich Material- und Geowissenschaften 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Fachgebiet Oberflächenforschung |
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Hinterlegungsdatum: | 31 Mär 2019 19:55 | ||||
Letzte Änderung: | 31 Mär 2019 19:55 | ||||
PPN: | |||||
Referenten: | Jaegermann, Prof. Dr. Wolfram ; Clemens, Ass.-Prof. Oliver | ||||
Datum der mündlichen Prüfung / Verteidigung / mdl. Prüfung: | 7 Februar 2019 | ||||
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