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Atomic layer deposition of nickel manganese oxides

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1 Atomic layer deposition of nickel manganese oxides
Diploma thesis Manu Tenhunen

2 Outline of the presentation
Atomic layer deposition Ternary metal oxides ALD of ternary metal oxides Nickel manganese oxides Different structures ALD parameters Results Different measurements Conclusions Manu Tenhunen

3 Atomic layer deposition
Layer-by-layer deposition method Based on gas-to-surface chemical reactions Self-terminating Ideally very uniform films Manu Tenhunen

4 Ternary metal oxides Contain two metallic elements in addition to oxygen Numerous different structures Spinel, perovskite Many interesting functionalities Tunable stoichiometries Used in electrical applications Optoelectronic devices Electrolyte material for fuel cells Cathode material for high energy density devices Structures: trirutiles Functionalities: ferromagnetism, ferroelectricity Tunable stoichiometries -> tunable functionalities and properties Optoelectrics -> ITO indium tin oxide, transparent conductive coating, flexible displays Electrolyte (YSZ, yttrium-stabilized zirconia, Solid oxide fuel cells. Cathode, supercapacitors, li-ion batteries Manu Tenhunen

5 ALD of ternary metal oxides
Careful optimization of the reactor Difficulties getting adequate precursor gas concentrations High temperatures Bubblers etc. ”Travelling-wave” reactor type not optimal Manu Tenhunen

6 Nickel manganese oxides
Both nickel and manganese excellent as sole materials Cheap and abundant Good electrical properties NiO easy to deposit Three reported structures Spinel: NiMn2O4 Ilmenite: NiMnO3 Murdochite: Ni6MnO8 Have not been deposited with ALD before Electrical properties: conductance, capacitance Manu Tenhunen

7 Spinel NixMn3-xO4 Most researched structure
Cubic spinel when 0.4 ≤ x ≤ 2 and a tetragonal-distorted spinel when x is near zero Mn2+ occupies the tetrahedral sites of the spinel and Mn3+, Mn4+, and Ni2+ octahedral sites Possibly some Ni2+ and Mn3+ ions on tetrahedral sites Used as electrode material Electrode material in high density application. Usually with lithium Literature sources differ on the ions J. L. Baudour, F. Bouree, M. A. Fremy, R. Legros, A. Rousset, and B. Gillot, “Cation distribution and oxidation states in nickel manganites NiMn2O4 and Ni0.8Mn2.2O4 from powder neutron diffraction,” Phys. B Phys. Condens. Matter, vol. 180–181, no. PART 1, pp. 97–99, 1992. Manu Tenhunen

8 Ilmenite NiMnO3 Similar structure to perovskite but hexagonally packed instead of cubic packing All nickel and manganese in Ni2+ and Mn4+ forms on octahedral sites Applications in ORR/OER devices Catalyst in oxygen evolution and reduction reactions Alterning magnetic phases -> ferromagnetic D. Mehandjiev, E. Zhecheva, G. Ivanov, and R. Ioncheva, “Preparation and catalytic activity of nickel– manganese oxide catalysts with an ilmenite-type structure in the reactions of complete oxidation of hydrocarbons,” Appl. Catal. A Gen., vol. 167, no. 2, pp. 277–282, Feb Manu Tenhunen

9 Murdochite Ni6+2xMn1-xO8 Murdochite when 0 ≤ x ≤ 0.8 and structure of basic rock-salt (Fm-3m) when x is larger 4a positions are occupied by Mn4+ and Ni2+ ions, the 4b position is occupied by Ni3+ ions and vacancies The Ni2+ and Mn4+ ions are both octahedral coordinated by six oxygen ions No real Applications but researched in electrodes and as catalyst for oxygen evolution and reduction reactions H. Taguchi, S. Omori, M. Nagao, H. Kido, and M. Shimada, “Crystal Structure and Magnetic Properties of (Ni1-x]Mgx)6MnO8,” J. Solid State Chem., vol. 118, no. 1, pp. 112–116, Aug Manu Tenhunen

10 Experimental work ALD of nickel manganese oxides from Ni(thd)2 and Mn(thd)3 precursors Goal: depositing a spinel NiMn2O4 thin film F-120 ALD-reactor Ozone as oxygen suorce Crystal structures studied with grazing angle incidence x-ray diffraction (GIXRD) Heat-treatment in oven Manu Tenhunen

11 ALD parameters Dirk found the parameters for Ni(thd)2 beforehand
Mn(thd)3 was optimized Parameters: Sublimation temperatures Ni(thd)2, 130 °C Mn(thd)3, 110 °C Reaction chamber temperature 220 °C 2.5 s pulse times 8 s purge Manu Tenhunen

12 Results Depositions with first Mn-precursor batch showed only the pattern on NiO Manganese in amorphous form? Hump from glass substrate Manu Tenhunen

13 Results XRD of NiO from dirk Manu Tenhunen

14 Results Second batch of Mn(thd)3 precursor worked a lot better
New XRD-peaks appeared Second precursor batch was more fluffy and had yellowish tint. Manu Tenhunen

15 Results More maganese increased the intensity of spinel peaks
Manu Tenhunen

16 Results Powder XRD of nimno on right Manu Tenhunen 12.5.2017
A. Sagua, G. M. Lescano, J. A. Alonso, R. Martínez-Coronado, M. T. Fernández-Díaz, and E. Morán, “Neutron structural characterization, inversion degree and transport properties of NiMn2O4 spinel prepared by the hydroxide route,” Mater. Res. Bull., vol. 47, no. 6, pp. 1335–1338, Jun Manu Tenhunen

17 Results after heat-treatment
°C Annealing changed the crystal structures New XRD-peaks appear on NiO samples Different atmospheres had no effect (N2, O2, air) +1000c starts to destroy samples N2-atmosphere caused decay on the thin film surface. Visible spots. Manu Tenhunen

18 Results after heat-treatment
Ilmenite: ICDD file Only sample that showed ilmenite structure and only in 600 c temperature anneal Manu Tenhunen

19 Results after heat-treatment
XRD of hexanickelmanganese only differs by the (111) peak at 20 degrees Pretty common structure in the samples of the first batch after annealing Manu Tenhunen

20 Optical measurements The optical energy band gaps were calculated from absorbance measurements Initial measurements: 1:2 Ni-Mn: 3.0 eV 2:1 Ni-Mn: 3.5 eV MnO2: 2.8 eV More accurate measurements failed The reflectance and transmittance of the glass samples First with chem departments Hitachi and later with nanotalos perkinelmer lambda In line with literature Manu Tenhunen

21 Magnetic measurements
Zero-field-cooled (ZFC), field-cooled (FC) and magnetic hysteresis measurements Four samples Strong spinel structure Spinel with more intense peaks of NiO Spinel with some ilmenite structure Strong NiO pattern Turned out the strong NiO sample was not magnetic Physical Property Measurement System DynaCool from Quantum Design Manu Tenhunen

22 ZFC/FC measurements Measures the temperature when transition from ferromagnetism to paramagnetism happens Spinel and spinel/ilmenite samples: 70 – 80 K NiO/spinel sample: 140 – 150 K In literature 70 – 145 K Cooled to 5k and heated Menaka, N. Garg, S. Kumar, D. Kumar, K. V. Ramanujachary, S. E. Lofland, and A. K. Ganguli, “Nanostructured nickel manganese oxide: aligned nanostructures and their magnetic properties,” J. Mater. Chem., vol. 22, no. 35, p , 2012. Manu Tenhunen

23 Hysteresis measurements
Magnetic hysteresis loop reveals how the material behaves in changing magnetic field Spinel and spinel/ilmenite samples show typical behavior for ferromagnetic materials NiO/spinel shows higher coercivity, lower magnetization and does not reach saturation Attributed to NiO inpurities in literature Done in 10 kelvin A. Díez, R. Schmidt, A. E. Sagua, M. A. Frechero, E. Matesanz, C. Leon, and E. Morán Emilio, “Structure and physical properties of nickel manganite NiMn2O4 obtained from nickel permanganate precursor,” J. Eur. Ceram. Soc., vol. 30, no. 12, pp. 2617–2624, 2010. Manu Tenhunen

24 Conclusions Spinel NiMn2O4 thin films were succesfully deposited with ALD Also NiMnO3 and Ni6MnO8 structures with annealing Confirmed by XRD and magnetic measurements The ALD-reaction needs work Better Mn-precursor Different reactor configuration Manu Tenhunen

25 Thank you Any questions?
Manu Tenhunen

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