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MAGMA : 23188 pp:126ðcol:fig::NILÞ PAGN:N:Manjunatha SCAN:Raj

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Journal of Magnetism and Magnetic Materials ] (]]]]) ]]]–]]]
www.elsevier.com/locate/jmmm
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Sintering prevention and phase transformation of FePt
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nanoparticles
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Y. Dinga, S.A. Majeticha,, J. Kimb, K. Barmakb, H. Rollinsc, P. Sidesd

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13 a
Physics Department, Carnegie Mellon University, Pittsburgh, PA 15213, USA

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b
MSE Department, Carnegie Mellon University, Pittsburgh, PA 15213, USA
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Idaho National Engineering and Environmental Laboratory, Idaho Falls, ID 83415, USA
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Chemical Engineering Department, Carnegie Mellon University, Pittsburgh, PA 15213, USA
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Abstract
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Two approaches attempted to overcome FePt nanoparticle sintering during the transformation to the high coercivity
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23 L10 phase, which currently limits the use of these nanoparticles in data storage media. High-pressure treatment of dilute
nanoparticle solutions failed to prevent sintering due to surfactant decomposition above 360 1C. By pre-annealing
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25 nanoparticle monolayers to decompose the surfactant, and then coating with an immiscible SiO2 matrix, sintering was
prevented with annealing temperatures up to 700 1C.
27 r 2004 Published by Elsevier B.V.
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PACS: ’; ’; ’
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Keywords: ’; ’; ’
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1. Introduction tropy L10 phase is thermodynamically more stable. 49

35 In direct synthesis of L10 phase, FePt nanoparti-
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Self-assembled FePt nanoparticle arrays have cles has been reported [2], but so far this method 51
37 been the subject of much interest due to their leads to polydisperse particles that cannot self-
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potential use as ultrahigh density magnetic storage assemble into arrays. Monodisperse FePt nano- 53
39 media [1]. A key advantage of the self-assembly particles as made are FCC, and must be annealed
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approach is the high degree of uniformity in the to high temperatures to induce the transformation. 55
41 grain size and position. In bulk phase FePt, the Unfortunately this annealing process sinters the
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chemically ordered high magnetocrystalline aniso- particles together, destroying the key advantage 57
43 over existing magnetic recording media. Sintering
Corresponding author. Tel.: +1-412-268-3105; fax: +1-
occurs because the surfactant coating around the 59
412-681-0648. particles decomposes at
400 1C. Without the
45 E-mail address: sm70@andrew.cmu.edu (S.A. Majetich).
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47 0304-8853/$ - see front matter r 2004 Published by Elsevier B.V.
doi:10.1016/j.jmmm.2004.07.011 63
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1 steric barrier, the particles coalesce at tempera-
tures sufficient for the L10 phase transformation
3 [3].
Here, we report the findings of two new
5 approaches to overcome this sintering problem.
In the first, high pressures were used to heat a
7 solution of the particles to high temperature, in
order to initiate the phase transformation while
9 the particles were well-separated. The high pres-
sure was used to prevent the liquid from evaporat-
11 ing while the temperature was increased. In the
second approach, particles were self-assembled
13 into monolayer arrays, and then heated to
moderate temperatures in order to decompose
15 the surfactant [4] without sintering. The arrays
were then over-coated with an immiscible silica
17 matrix, and annealed at higher temperatures to
transform the FePt into the L10 phase. Here
19 sintering is prevented by replacing the surfactant
coating with SiO2, which is chemically stable up to
21 700 1C, well above the L10 transformation tem-
perature [5].
23
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25 2. Experimental
27 Three nanometer FePt nanoparticles were pre-
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pared using standard high temperature chemical
29 methods [1]. The surfactant coating was a 1:1
mixture of oleic acid and oleylamine. The particles
31 were washed with ethanol, centrifuged, and redis-
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persed in hexane several times to improve the
33 monodispersity.
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Three nanometer FePt nanoparticles dissolved
35 in hexane were heated under high pressures using a
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specially designed stainless steel cell [6]. Two
37 samples from the same batch were heated to
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360 1C at
340 atm for 45 min and 450 1C at
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300 atm for 5 min, respectively.
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The high-pressure treated nanoparticles were
41 structurally and magnetically characterized to look
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for evidence of the FCC to L10 phase transforma-
43 tion and particle sintering. After high-pressure
treatment, more surfactant was added, and drops
45 of solution were evaporated on transmission
electron microscopy (TEM) grids. The samples
47 were observed using a 200 keV JEOL 2000 TEM.
Glancing angle X-ray diffraction (XRD) measure-
ments were made with a Philips X’Pert high- 49
resolution X-ray diffractometer operating at Cu
Ka radiation (l ¼ 0:154 nm), to look for the 51
development of the L10 phase and evidence of
line narrowing associated with grain growth. Here 53
the angle between the incident X-ray beam and the
sample surface was fixed at 61, and detector angle 55
2y was scanned from 101 to 1001. The particle
moment and coercivity were measured using a 57
quantum design superconducting quantum inter-
ference device (SQUID) magnetometer at 10 K. 59
To prepare over-coated monolayer arrays,
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particles were first dissolved in 1,1,1-trichlor- 61
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oethane (CH3CCl3), and then a droplet of the
solution was evaporated on oxidized Si wafers that 63
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had a 100 nm SiO2 surface layer. The oxidized Si
wafers were used to prevent silicide formation. The 65
sample was then annealed in a glass tube under
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vacuum (400 1C, 30 min) to decompose most of the 67
surfactant [3]. After this initial annealing stage at
400 1C, there was no measurable weight loss after 69
heating to higher temperatures. To prevent the
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FePt nanoparticles from oxidizing after the 71
surfactant decomposed, the wafer was temporarily
coated with eicosane (C20H42) for transfer to the 73
sputtering chamber. Eicosane is a solid at room
temperature but boils at a relatively low tempera- 75
ture. Its chemical structure makes it unlikely to
bind to the particle surface. The wafers were then 77
heated under vacuum (200 1C, 30 min) to thor-
oughly remove the eicosane. The base pressure of 79
the sputtering chamber was less than
5  107 Torr. A 2 min pre-sputtering process was 81
used to stabilize the RF plasma. Next, 100 nm
SiO2 layers were deposited by plasma sputtering of 83
a silica target, with 5 mTorr of flowing Ar. The
sputtering time was 1 h, at a rate of
0.03 nm/s to 85
ensure a smooth film. While 100 nm is too thick to
be usable for data storage media, excess silica was 87
used in these preliminary experiments to ensure
complete coverage. An excess of silica will not 89
matter for fundamental studies of the transforma-
tion temperature as a function of particle size. 91
Following the SiO2 over-coat, the wafers were then
annealed in flowing H2 for 30 min at different 93
temperatures, ranging from 400 to 700 1C.
In order to image the particles after processing, 95
and directly determine whether sintering had
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1 occurred, thinned Si3N4 TEM grids were also used
as substrates. The same procedure was used to
3 prepare particles on the Si3N4 grids, except that
20 nm SiO2 layer under-coats and over-coats were
5 used to retain electron transparency.
The room temperature coercivity of the over-
7 coated samples was measured after annealing by
an alternating gradient force magnetometer
9 (AGM). The particle morphology after annealing
was observed by TEM to see if the particles had
11 sintered.
Fig. 2 shows the magnetization curves of the 49
FePt nanoparticle solutions at 10 K. As made, the
particle moment is extremely low due to structural 51
disorder [4]. For the solution treated at 360 1C, the
magnetic moment increased by a factor of four, 53
but the coercivity was still
100 Oe. After treat-
ment at 450 1C, the coercivity increased to 55
1800 Oe, and the magnetization curve showed
clear saturation behavior expected for a ferro- 57
magnet.
XRD showed that the structure of the FePt 59
nanoparticles treated at 450 1C was mainly FCC,

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13 though there was evidence of a weak (1 1 0) peak 61

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from the L10 structure in the XRD glancing angle
15 3. Results and discussion scan (Fig. 3). The chemical order parameter S is 63

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17 After the high-pressure treatment at 360 1C and 65

340 atm for 45 min, the 3 nm FePt nanoparticles

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19 remained in solution, and did not respond to a 67
magnet. After heating to 450 1C at
300 atm for
21 5 min, most of the particles precipitated and 69
responded weakly to a magnet. Both samples were
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23 washed with ethanol and redispersed in hexane, in 71
order to improve the surfactant coating and
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25 monodispersity. Fig. 1 shows that the 3 nm FePt 73

particles treated at 360 1C were still able to self-
27 assemble into arrays. However, TEM showed that 75
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the particles treated at 450 1C were found to have Fig. 2. Magnetic moment at 10 K as a function of the applied
29 agglomerated and partly sintered together. The field, for 3 nm FePt nonoparticles treated at high pressure for 77
high pressure did not significantly change the various temperatures.
31 surfactant decomposition temperature [4]. Once 79
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the surfactant decomposed, interparticle collisions

33 caused agglomeration, even in dilute solution. The 81
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porous carbonaceous remnants of the decomposed

35 surfactant did not prevent sintering. 83
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Fig. 3. Glancing angle XRD pattern of FePt treated at various
temperatures and pressures. The broad peaks at around 201 are
45 from the excess surfactant. The peak at around 561 in 450 1C
93
pattern is from the off Bragg condition (3 1 1) diffraction of the
47 Fig. 1. TEM image of 3 nm FePt nanoparticle arrays formed Si substrate. The peak at around 321 in 450 1C pattern is from 95
from particles treated at 360 1C and
340 atm for 45 min. (1 1 0) diffraction of FePt L10 phase.
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1 widely used to characterize the degree of phase
transformation from FCC to L10 phase [7]. S is
3 defined by the following equation:
½I ð110Þ =I ð111Þ experimental
5 S2 ¼ ; ð1Þ
½I ð110Þ =I ð111Þ bulk
7 sure.
where I(hkl) is the intensity of the (hkl) diffraction
9 peak. From Fig. 3, S was estimated to be
0.3070.05, indicating that the ordering is far from
11 complete. Moreover, the narrowing of the FCC
diffraction peak widths at this temperature con-
13 firms the TEM observation of particle sintering
and grain growth. From these results alone, it is
15 unclear whether the transformation has begun
because the sample has reached a threshold
17 temperature, or because some particles have
sintered and reached a threshold size, above which
19 the L10 phase is most stable. A small fraction of
the transformed particles could dominate the
21 coercivity.
From Fig. 3, the calculated FCC lattice constant
23 a was 0.390 nm for the FePt treated at 360 1C and
0.383 nm for the FePt treated at 450 1C. In
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25 comparison, the lattice constant of bulk Pt is
0.392 nm and the lattice constant of bulk FCC
27 FePt is 0.382 nm [8]. This shift in the lattice
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constant following the heat treatment could be due
29 to changes in the chemical homogeneity. When a
FePt nanoparticle forms, a Pt seed forms first, and
31 then Fe deposits around the Pt cluster. Pt
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nucleates more readily, and in the absence of
33 Fe(CO)5, small Pt particles of
1 nm diameter are
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formed, even at much lower temperature. It is
35 unclear how much interdiffusion occurs during
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this deposition process. With minimal diffusion,
37 we would expect a Pt-rich core and an Fe-rich
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shell, with a gradient of composition. In the
39 extreme case, a 3 nm Fe50Pt50 nanoparticle would
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have a pure Pt core of 2.4 nm diameter and would
41 be surrounded by a 0.3 nm pure Fe shell. For the
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FCC structure with a lattice constant a
0.39 pffiffiffi nm,
43 the distance between nearest neighbors, ð 2=2Þa;
is only
0.3 nm, which means that the shell is just
45 one layer of Fe atoms. With more Pt in the particle
center, the average lattice constant determined by
47 XRD would be dominated by Pt and very close to
the 0.392 nm value of bulk Pt. Below temperatures
where there is significant atomic diffusion 49
(o400 1C), the atomic configuration won’t change
significantly. Once atomic diffusion begins, the 51
lattice constant would shift toward that of bulk
FePt. We have observed similar lattice spacings in 53
5 nm FePt particles annealed without high pres-
55
The surfactant coating was the key to keeping
particles from sintering, yet the organic surfactant 57
decomposes at about 400 1C even when treated
under high pressure. Even with the lowest feasible 59
transformation temperatures, the surfactant
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breakdown limits the high-pressure approach. 61
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SiO2 was chosen as an alternative barrier because
it is stable and does not react with Fe or Pt up to 63
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700 1C. Fig. 4 shows TEM images of 3 nm FePt
particles as initially self-assembled on a SiO2 65
surface, with the surfactant decomposed, and with
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a SiO2 over-coat after annealing at high tempera- 67
ture. This demonstrates that neither the annealing
at 400 1C nor the coating process sintered the 69
particles.
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Fig. 5 shows how the surfactant residue enables 71
particle sintering at high temperatures, in cases
where the particles were not thoroughly washed to 73
remove excess surfactant. Here, the sputtered SiO2
overcoats the remnants of excess surfactant 75
surrounding the particles. During the high tem-
perature anneal, a few of the particles grew in size 77
due to sintering. However, surrounding each of the
sintered particles, the TEM images show a diffuse 79
background associated with carbonaceous materi-
al. Presumably, the decomposed surfactant is 81
porous enough that particle sintering occurs.
Fig. 6 shows the room temperature coercivity of 83
the unagglomerated 3 nm FePt nanoparticle arrays
deposited on an oxidized Si wafer with a SiO2 85
overcoat and then annealed at different tempera-
tures. The results show that the 3 nm FePt 87
nanoparticle coercivity began to increase at
560 1C. The value of Hc for these particles is much 89
smaller than the thousands of Oersteds reported
for sintered FePt arrays. The small Hc of 3 nm 91
FePt particles could occur because the phase
transformation is incomplete, or because strains 93
from the SiO2 coating prevent full transformation.
However, it could also arise because the L10 phase 95
is not the stable state for very small particles. The
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Fig. 4. TEM images of FePt nanoparticles at different processing stages. All samples used thinned Si3N4 grids with a 20 nm base layer

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of sputtered SiO2. (a) A monolayer of surfactant-coated particles self-assembled by evaporating a drop of CH3CCL3 dispersion. The
17 length scale of the ordering is lower than on a standard carbon or SiO-coated grid, but the nearest neighbor separation is the same; (b)
65

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Part of the monolayer after decomposing the surfactant by a pre-annealing process, in which the grid is sealed in an evacuated ampoule
19 and heated in to 400 1C for 1 h. Note that the particle size and interparticle spacing are unchanged; (c) Part of the monolayer after 67
sputtering a layer of 20 nm SiO2, and then annealing at 600 1C for 30 min. The particle size and spacing are preserved by this process.
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Fig. 5. TEM image of annealed FePt particles with SiO2

35 overcoat showing some particle growth. Note that surrounding 83
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each of the larger particles is a diffuse halo due to the remnants

Fig. 6. Coercivity versus the maximum annealing temperature,
37 of excess surfactant. If excess surfactant remains, the sputtered 85
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SiO2 is unable to form an impervious barrier between the for 3 nm FePt particles on an oxidized Si wafer, over-coated
particles. At the high temperatures needed for the phase with SiO2 and annealed at different temperatures for 30 min.
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transformation, atomic diffusion is significant and sintering

will occur unless there is an immiscible barrier between the
41 particles. 4. Conclusions 89
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43 last hypothesis has been suggested previously,
based on annealing of FePt clusters deposited in
45 ultrahigh vacuum [9]. The threshold average size
for transformation to the L10 phase was 3.5 nm.
47 Further experiments on monodisperse particles
with larger sizes are underway.
Two new approaches were tried to overcome the 91
sintering problem in the FePt nanoparticle phase
transformation, high-pressure treatment and SiO2 93
over-coating. The results showed the important
connection between the surfactant decomposition 95
and sintering. The surfactant decomposition tem-
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1 perature was not significantly changed under high Department of Energy through the INEEL La- 29
pressure. Though the particles in solution were boratory Directed Research and Development
3 well separated, on average, once the surfactant (LDRD) Program under DOE Idaho Operations 31
decomposed, they sintered together. Measure- Office Contract DE-AC07-99ID13727.
5 ments confirmed that sintering occurred at tem- 33
peratures sufficient for the onset of the FCC to L10
7 FePt phase transformation. References 35
The SiO2 over-coating approach replaced the
9 surfactant with an inorganic silica coating. Here [1] S. Sun, C.B. Murray, D. Weller, L. Folks, A. Moser, 37
Science 287 (2000) 1989.
the particles did not sinter even when annealed at
[2] B. Jeyadevan, K. Urakawa, A. Hobo, N. Chinnasamy, K.
11 600 1C. The onset of the increase in coercivity Shinoda, K. Tohji, D. Djayaprawira, M. Tsunoda, M.
39
started at 560 1C. Compared with earlier results Takahashi, Jpn. J. Appl. Phys. 42 (2003) L350.

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13 with the same annealing temperature but without [3] Y. Ding, S. Yamamuro, D. Farrell, S.A. Majetich, J. Appl. 41

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the SiO2 coating to prevent sintering [1], we found Phys. 93 (2003) 7411.
15 a lower coercivity. There may be a minimum size [4] Y. Sahoo, H. Pizem, T. Fried, D. Golodnitsky, L. Burstein, 43
C.N. Sukenik, G. Markovich, Langmuir 17 (2001) 7907.

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for the transformation to the L10 phase. This [5] J.W. Harrell, S. Wang, D.E. Nikles, M. Chen, Appl. Phys.
17 approach is more promising for the formation of Lett. 79 (2001) 4393. 45
self-assembled FePt arrays for magnetic recording

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[6] The experimental set-up for the high-pressure treatment
19 media. studies consisted of a Shimadzu LC-10AT HPLC pump, a 47
high-pressure reactor (model MS-11, High Pressure Equip-
ment Company), a 1’’ tube furnace, pressure relief valve and
21 high-pressure valves and tubing. The sample temperature 49
Acknowledgments was monitored using a k-type thermocouple in contact with
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23 the sample. 51
We would like to thank Data Storage System [7] T. Shima, T. Moriguchi, S. Mitani, K. Takanashi, Appl.
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Phys. Lett. 80 (2002) 288.

25 Center (DSSC) at Carnegie Mellon University. 53
[8] PCPDFWIN v. 2.02, JCPDS-International Centre for
S.A.M. acknowledges support from the National Diffraction Data, 1999.
27 Science Foundation Grant ] CTS-0227645. [9] Y.K. Takahashi, T. Ohkubo, M. Ohnuma, K. Hono, J. 55
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H.W.R. acknowledges support from the US Appl. Phys. 93 (2003).

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