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b University of Tartu, Institute of Physics, Department of Materials Science, EE-51014 Tartu, Estonia
c National Institute of Chemical Physics and Biophysics, EE-12618 Tallinn, Estonia
d Department of Physics, Brandenburg University of Technology, D-03046 Cottbus, Germany
Iron oxide and magnesium-doped iron oxide films were grown by atomic layer deposition in the temperature range of 350500 C
from ferrocene, (dimethylaminomethyl)ferrocene, magnesium -diketonate, and ozone. Phase composition of the films depended on
the deposition temperature, as magnetite and/or maghemite tended to form instead of hematite upon lowering the temperature. Iron
oxide layers were also mixed with magnesium oxide by alternate deposition of MgO and Fe2 O3 which also favored the formation of
magnetite or maghemite structure prior to hematite. Scanning electron microscopy implied the smoothening of the films after doping
with magnesium oxide. Magnetometry was used to study the effects of temperature and doping levels on the magnetic properties of
the films.
2012 The Electrochemical Society. [DOI: 10.1149/2.004303jss] All rights reserved.
Manuscript submitted September 17, 2012; revised manuscript received December 3, 2012. Published December 20, 2012.
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
earlier study devoted to a gas phase deposition of iron oxide, transition from maghemite to hematite was reported, occurring between
350 and 400 C.56 In the latter study, the major peak appeared at ca.
30.5 and was attributed to the 220 reflection of -Fe2 O3 . Most of the
other peaks were attributed to iron hydroxide, which do not match with
the peaks observed in the present study, neither does the formation of
hydroxides seem likely in the water-free process provided at that high
temperature. Similarly, the peaks at 30.5 and 35.5 have been assigned
as 220 and 311 of -Fe2 O3 in a study on the iron oxide nanostructures
obtained in a solvothermal process30 as well as by a wet chemical
method.17 The presence of maghemite can thus be considered, although the main reflection, i.e. that at 26.103 , which could be significant while distinguishing between magnetite and maghemite, was not
apparent in most of the patterns recorded in the present study as well as
in the reference given. Traces of that peak (PDF card 039-1346) may
be recognized in the iron oxide film as-deposited at 375 C (Fig. 1,
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
= 425 C
Fe 2p XAS, TEY
non-doped
Mg 0.02 at.%
Mg 0.2 at.%
Mg 0.38 at.%
710
720
730
740
photon energy, eV
Figure 5. X-ray absorption spectra, measured in total electron yield mode,
of non-doped and doped films grown at 425 C from CpFeC5 H4 CHN(CH3 )2 .
The legend indicates the magnesium (oxide) content in the films measured by
EDX.
the films grown using ferrocene (not shown). Such films consisted
of columns, grains or pillars formed, possibly, on continuous base
layer with large voids between the pillars. Already small amounts
of magnesium oxide (Mg/Fe = 0.02) caused some increase in the
density of the pillars/grains and decrease in the width of the voids
(Fig. 6, 2nd panel from top). Further increase in the relative amount of
MgO resulted in the formation of quite continuous film surfaces and
also smoothening of the film surface visible even by naked eye, as
mentioned above. Moreover, the addition of MgO also had a marked
effect on the film thickness. Application of quite low amounts of
MgO enhanced the growth resulting in higher total thickness of the
films. Increment in the number of MgO deposition cycles, on the other
hand, reduced the film growth rate. For instance, using MgO:Fe2 O3
cycle ratio of 20:100 resulted in films with thickness nearly two times
lower than that of non-doped Fe2 O3 films. The surfaces of the films
grown to thicknesses below 7080 nm at temperatures below 400 C
remained smoother without no particular features which could indicate the formation of separated columns or large grains on the surface
(not shown).
Fig. 7 represents cross-sectional SEM and EDX mapping images
taken from an iron oxide film deposited on 3D substrates. One can
conclude, that the films could be grown conformally into trenches
with aspect ratio 1:20 using the same cycle time parameters as those
applied for the growth on planar substrates. EDX allowed one to detect
signals from iron along with the depth of the trenches, including the
bottom area. Distribution of oxygen could be mapped as well.
Magnetometry. Magnetic properties of non-doped films.Magnetization vs. magnetic field measurements revealed that the as deposited
and annealed films both exhibit saturated hysteresis loops at room
temperature, while magnetization was found to be enhanced in films
annealed in hydrogen. Coercivity, HC , and saturation magnetization,
S , determined from the hysteresis curves expectedly tended to increase with the decrease in measurement temperature. No systematic
dependences of both HC and S on the film thickness were observed,
though.
The films grown at high temperatures, 500 C, from ferrocene were
defined consisting completely of hematite, as described above. These
films possessed S as low as 20 emu/cm3 in as-deposited state and no
measurable HC (not shown). After FGA, the magnetization-versusfield (M-H) curves (not shown) demonstrated that S increased by
approximately an order of magnitude and HC was measurable up
to 500 Oe at room temperature. This means that although no phase
changes were noticed upon annealing by GIXRD (Fig. 1), some weak
reduction must have been occurred. The rest of the samples magnet-
Figure 6. Bird-eye scanning electron microscopy images of Fe2 O3 (topmost panel) and Fe3 O4 -MgO films (2nd to 4th panel from top) grown using different cycle sequences indicated by labels. The films were grown from
CpFeC5 H4 CHN(CH3 )2 at 425 C. Film thicknesses and Mg to Fe atomic ratios
are also given by labels.
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
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state, and, correspondingly, 410, 410 and 750 Oe after annealed. The
S was 222228 and 206217 emu/cm3 in the as-deposited and annealed films, respectively. Thus, both HC and S were increased after
adding a minor amount of MgO pulses.
The films grown from CpFeC5 H4 CHN(CH3 )2 at 425 C (XRD results in Fig. 2) also possessed magnetic properties influenced by MgO.
Comparing the non-doped 163 nm thick Fe2 O3 with lightly doped
183 nm thick sample (Table II), one could detect noticeable increase
in S upon adding MgO, whereas the coercivities remained comparable. Both HC and S expectedly increased after annealing. Further, after stronger doping (Mg/Fe = 0.23 and 0.38) the coercivities still remained quite comparable, but S was dropped markedly.
The effect of annealing remained the same. Drop in the S might
partially be explained by the drop in the film growth rate and, consequently, reduced thickness and, partially, by the possible formation of magnesium-rich phase, magnesioferrite, in addition to magnetite/maghemite. In any case, it seems that, at elevated substrate temperatures, it would be useful to keep the Mg content as low as possible,
below Mg to Fe ratio of 0.1, in order to get smooth films and stronger
magnetization.
The films grown from CpFeC5 H4 CHN(CH3 )2 at 375 C also
demonstrated properties influenced by MgO-doping (Fig. 8). The HC
tended to decrease upon the increase in the Mg content. In the nondoped and as-deposited films the HC ranged from 485 to 1950 Oe
between 300 and 10 K (not shown). In the films with Mg/Fe atomic
ratio of 0.017 the HC was in the range of 3001260 Oe between 300
and 10 K. Upon further increase in the Mg content to Mg/Fe ratio
of 0.062 the HC was decreased, being in the range of 150460 Oe
between 300 and 10 K (Fig. 8). The annealing procedure again decreased the HC (Fig. 8). On the other hand, S was increased with the
Mg content up to a certain limit. One could see that high amounts of
magnesium may not be advantageous in terms of increasing both HC
and S , maybe due to the formation of an additive ternary phase, e.g.
magnesioferrite, in the film bulk.
Curie temperatures (ferro-/ferri-paramagnetic transitions) were
found to be in the range of 820895 K, determined from zero-fieldcooled high temperature magnetization curves. The Curie temperatures were not systematically dependent on the iron precursor used,
growth temperature and not even noticeably on the film composition,
varying between 820 and 895 K. The Curie temperature of magnetite
and Neel temperature of hematite bulk materials are about 850 and
Table I. Precursors, growth temperatures (Tgrowth ), thicknesses, compositions (Mg/Fe), coercitivities (HC ), saturation magnetization values (C )
and Curie temperatures (TC ) of some representative films investigated in this study.
S , emu/cm3
HC , Oe
precursors
Tgrowth
thickness
state
300 K
100 K
10 K
300 K
100 K
10 K
TC ,K
FeCp2 NMe2
450 C
705 nm
FeCp2
400 C
246 nm
FeCp2 NMe2
375 C
262 nm
375 C
425 nm
0.017
375 C
411 nm
0.062
as-dep
FGA
as-dep
FGA
as-dep
FGA
as-dep
FGA
as-dep
FGA
425
330
300
135
485
325
300
260
150
200
900
750
600
230
1200
500
830
310
330
210
1175
800
780
250
1950
850
1260
580
460
380
104
375
62
360
193
346
200
280
491
274
107
372
64
381
205
356
207
282
496
289
107
370
65
386
206
359
209
283
497
291
870
860
860
895
850
840
845
840
830
820
Table II. Growth cycle sequences, thicknesses, Mg/Fe ratios, coercivities, and saturation magnetization values of doped films grown at 425 C,
measured at room temperature. The deposition cycle times were 1.00.52.00.5 s.
Cycle sequencing
500 Fe2 O3
100 Fe2 O3 + 4 [3 MgO + 100 Fe2 O3 ]
100 Fe2 O3 + 4 [20 MgO + 100 Fe2 O3 ]
100 Fe2 O3 + 4 [30 MgO + 100 Fe2 O3 ]
0
0.021
0.23
0.38
200
180
170
235
340
360
420
330
217
260
224
193
344
496
220
391
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
Figure 8. Representative magnetization versus external field curves of doped iron oxide films deposited from CpFeC5 H4 CHN(CH3 )2 at 375 C. Mg/Fe atomic
ratios, film thicknesses, hysteresis parameters and measurement temperatures are given by labels. Annealing was carried out in forming gas at 450 C for
30 min. (Color online)
and annealed states compared to those in non-doped oxide. Magnetization was somewhat increased in doped films in as-deposited
state to 217 emu/cm3 , but remained lower, 60 emu/cm3 , after annealing. After further increase in Mg/Fe ratio to 0.043 in a film grown
to thickness of 59 nm with cycle ratio of 5:100, the HC was even
more decreased. The measured values in the as-deposited films were
140 and 1250 Oe at 300 and 10 K, respectively, and 280 and 950 Oe in
the annealed films. The S values were decreased to 6065 emu/cm3
in the as-deposited films, and were increased to 190200 emu/cm3 after FGA. Curie temperatures in all these films were between 840 and
850 K. The optimization of the film composition and thickness would
need more detailed process parametrization in the future studies.
Both Raman and XAS measurements in the present study have
revealed features characteristic of magnetite whereas at least Raman
also referred to the maghemite. The films grown in this study at
elevated temperatures, and consisting of hematite, did not exhibit
enhanced magnetization, though.
Summary
Fe2 O3 /Fe3 O4 films were grown by atomic layer deposition on
planar and three-dimensional SiO2 /Si substrates using FeCp2 and
CpFeC5 H4 CHN(CH3 )2 , as metal precursors, and O3 as oxygen precursor in the substrate temperature range of 350500 C. The precursor
pulse and purge times were kept below 2.5 seconds. Application of
FeCp2 enabled reliable formation of the films at 400 C and higher
temperatures, whereas CpFeC5 H4 CHN(CH3 )2 allowed the reduction
of the growth temperature by about 50 degrees. The films deposited
at 450500 C consisted of major hematite phase, whereas in the films
grown at 375400 C the formation of magnetite or maghemite became
more likely. Several films were annealed in forming gas in order to
study the possibility to partially reduce the hematite and give rise to the
formation of magnetite. The significance of the reduction increased
with the decrease in the deposition temperature.
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
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Acknowledgments
Dr. Petr Brazda is acknowledged for critical reading the
manuscript. The work was partially supported by Finnish Center
of Excellence in Atomic Layer Deposition (Academy of Finland),
Estonian Ministry of Education and Research (targeted projects
SF0180042s07 and SF0690029s09), Estonian Science Foundation
(grant no. ETF8440), Estonian Center of Excellence in Research
Project TK117T High-technology Materials for Sustainable Development, and the European Community - Research Infrastructure Action under the FP6 Structuring the European Research Area Program
(through the Integrated Infrastructure Initiative Integrating Activity
on Synchrotron and Free Electron Laser Science)
References
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ECS Journal of Solid State Science and Technology, 2 (3) N45-N54 (2013)
41. X. Meng, M. Ionescu, M. N. Banis, Y. Zhong, H. Liu, Y. Zhang, S. Sun, R. Li, and
X. Sun, J. Nanopart. Res., 13, 1207 (2011).
42. J. Bachmann, J. Jing, M. Knez, S. Barth, H. Shen, S. Mathur, U. Gosele, and
K. Nielsch, J. Am. Chem. Soc., 129, 9554 (2007).
43. K. Pitzschel, J. M. M. Moreno, J. Escrig, O. Albrecht, K. Nielsch, and J. Bachmann,
ACS Nano, 3, 3463 (2009).
44. O. Nilsen, M. Lie, S. Foss, H. Fjellvag, and A. Kjekshus, Appl. Surf. Sci., 227, 40
(2004).
45. M. Lie, H. Fjellvag, and A. Kjekshus, Thin Solid Films., 488, 74 (2005).
46. R. Mantovan, M. Georgieva, M. Perego, H. L. Lu, S. Cocco, A. Zenkevich, G. Scarel,
and M. Fanciulli, Act. Phys. Pol., A, 112, 1271 (2007).
47. T. Suntola, Thin Solid Films, 216, 84 (1992).
48. M. Putkonen, L.-S. Johansson, E. Rauhala, and L. Niinisto, J. Mater. Chem., 9, 2449
(1999).
49. R. A. Waldo, Microbeam Analysis, San Francisco Press, San Francisco, CA, p. 310
(1988).
50. D. Schmeisser, P. Hoffmann, and G. Beuckert, Materials for Information Technology, Devices, Interconnects and Packaging, Engineering Materials and Processes;
Springer: New York, 2005.
51. M. Tallarida and D. Schmeisser, Semicond. Sci. Technol., 27, 074010 (2012).
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