NanaShuchued Materials. Vol. 5. No. 6. pp. 607-613.

1995
Elsevia Science Ltd
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NANOCRYSTALLINE METALLIC POWDERS AND FILMS

PRODUCED BY THE POLYOL METHOD

L.K. Kurihara, G.M. Chow and P.E. Schoen

Code 6930, Laboratory for Molecular Interfacial Interactions

Center for Bio/Molecular Science and Engineering
Naval Research Laboratory, Washington, D. C. 20375

(Accepted June 1995)

Abstract-The polyol method has been extended to synthesize metallic powders of Ru, Rh,
Sn, Re, W, P&Au, Fe-Cu, Co-&, Ni-Cu, in addition to powders of Fe, Co,Ni, Cu, Pd andAg which
were previously prepared by others using this method. This method can also be used to deposit
nanocrystalline metallicfilms on a variety of substrates, including PyrexTM,KaptonTM, Teflon-,
aluminum nitride, carbonfibers and aluminafibers. This can be a viable catalyst-free methodfor
the deposition of conductive metallic films on non-conductive substrates.

INTRODUCTION

Nanostructured powders and films (with particle diameters in the range of l-100 nm) have
many potential electronic, magnetic and structural applications (1). Among the various prepara-
tive techniques used, chemical routes (2) offer the advantages of molecular or atomic level control
and efficient scale-up for processing and production. Fine metallic powders of Co, Cu, Ni, Pb and
Ag (3-8) have been prepared using the polyol method. In this process, the metal precursor(s) are
suspended or dissolved in a polyol such as ethylene glycol. The resultant glycol-metal precursor
mixture is then heated to reflux and the metallic moieties precipitated out of solution. These
particles were micron and submicron in size, and consisted of single elements (3-8). Depending
on the type of metallic precursors used in the reaction, additional reducing agents were often used
(7,8).
More recently, we have reported a detailed study on the synthesis, structure and magnetic
properties of nanocomposite powders of Co-Cu prepared using this polyol method (9). In this
communication, we report that the polyol process can be used (i) to prepare a variety of metallic
powders with nanoscale crystal&s of single.elements, or of alloys and composites; and (ii) to
deposit metallic films on different substrates. Specifically, nanocrystalline powders of Fe, Co, Ni,
Cu, Ru, Rh, Pd, Ag, Sn, Re, W, Pt, Fe-Cu, Co-01 and Ni-Cu have been made, and nauocrystalline
metallic films of Co, Ni, Rh, Re, W, Pt and Au have been deposited on many substrates, including

607
608 LK KURIHARA,
GM CHOW
AND PE SCHOEN

PyrexTM, KaptonTM, TeflonTM, aluminum nitride, carbon fibers and alumina fibers (10). Film
deposition on non-conductive surfaces using this polyol process is a new approach to low-
temperature (< 200°C), non-vacuum metallization of nonconductive surfaces, which has been
conventionally accomplished by catalyst-assisted electroless plating. This polyol method is a
simple, single-step process for preparing nanostructured powders and coatings.

EXPERIMENTAL

The general procedure for the synthesis of different metallic powders and films involved
suspending the corresponding metal precursors in ethylene glycol or tetraethylene glycol and
subsequently bringing the resulting mixture to refluxing temperature (generally between 120 to
200°C) for 1 - 3 hr. During this reaction time, the metallic moieties precipitated out of the mixture.
The metal-glycol mixture was cooled to room temperature, filtered, and the collected precipitate
was dried in air. For film deposition, substrates were immersed in the reaction mixture. The
substrates were used in the “as-received” conditions, without preparative surface treatment. The
reaction times cited in this study were taken from when heat was initially applied to the solution
mixture. The reaction temperature was measured using a thermocouple inserted in a glass port
which was submerged in the solution. The crystal structure of the powders and films was studied
using X-ray diffraction (XRD). Line broadening of XRD peaks was used to estimate the average
crystallite size. The morphology was investigated using scanning electron microscopy (SEM) and
transmission electron microscopy (TIM) (accelerating voltage of 300 kV).

DISCUSSION OF RESULTS

Table 1 shows processing parameters and results of the polyol method used to prepare
metallic powders and films. Examples of XRD results for several metallic films are shown in
Figure 1. Figure 2 shows comparative XRD spectra of the as-synthesized powders of Ni, Cu and
an alloy of N&&75. For this system of Ni and Cu, diffraction peaks of Ni2sCu75 were found to
obey Vegard’s law and the formation of a solid solution was confirmed. These results indicate that
alloys can be synthesized from solution with atomic level mixing. For immiscible metals such as
the CuxCuloo_x system ( 4 I x I49 at.% ), it was found that a composite was formed (9).
The effects of processing temperature and reaction time on crystallite size were studied using
the single element system Cu. Crystallite sizes, as expected, increased both with temperature and
time, ranging from 10 to 80 nanometers (Figure 3). However, it was pointed out (4) that the mean
size of the polyol-derived metallic particles usually decreases as the reaction temperature
increases, since the number of nuclei that form in the process increases with increasing tempera-
ture. In our work with copper, this relationship between the size and processing temperature was
not observed. Others (4,8) have prepared copper particles with diameters within the 0.46- 1.82
micron range by reducing CuO in a polyol/sorbitol mixture. They controlled the mean particle size
by adding NaOH, which was believed to enhance the rate of reduction of the dissolved Cu species.
The particle size of the copper particles without the addition of NaOH was found to be 1.32-4.23
micron range. In our work, we found that nanoscale Cu particles could be formed without the use
 NANOCRYSTALLINE
METALLICPOWDERSANDFILMSPRODUCED
BYTHEPOLYOLMETHOD 609

TABLE 1
Synthesis Parameters and Products of the Polyol Reactions
(The range of crystallite size is given when it is concentration dependent.)

copper (II) acetate

*keys: K = Kapton, P = Pyrex , T = Teflon, G = graphite, A = alumina, S = sapphire, F = Fiber

610 LK KURIHARA,
GM CHOW
ANDPE SCHOEN

20 30 40 50 60 70 80
20
Figure 1. XRLI spectra of as-deposited films of Au, Pt, Pd, Rh and Ru.

._.._....,__..
_.......
.._.._,,_ .__......_....
.’ .._.,.._..
_....._._._...__..___...................... ^.......

40 45 50 55 60 65 70 75 80

20
Figure 2. XRD spectra of as-deposited powders of Ni, Cu and Ni2sCu75.
 NAN~CAYSTALLINE
METALLICPOWDERSANDFILMSPRODUCED
BYTHE POLYOLMETHOD 611

80

60

40

20

0
130 140 150 160 170 180 190 200
Processing Temperature (“C)

Figure 3. The effects of increasing processing temperature and time on

the crystallite size of Cu powders.

of additives. The morphologies of some of the powders and films prepared in this study are
revealed in the SEM and TEM micrographs shown in Figures 4a and b. Figure 4a shows a TEM
micrograph of a nanostructured W film, and the nanoscale particles of the film exhibited a
crystallite size of about 12 nm (see Table 1). The SEM micrograph of Ni on a KaptonTMsubstrate
is shown in Figure 4b.
The adhesion of the deposited films on different substrates was also qualitatively examined
using adhesive tape peel test. They were found to adhere to the substrates and were not removed
by the tape. It is noted that many of the substrates used in this study contain surface oxygen
moieties, and it is reasonable to assume that the adhesion occurs through metal-oxygen interac-
tions. However, the adhesion of metallic films to TeflonTM surfaces may involve a different
mechanism, since TeflonTMdoes not contain oxygen species on the surface and the conditions of
plating were not harsh enough to cause defluorination. In this case, adhesion is believed to be due
to mechanical interlocking with the textured surface of TeflonTM.
In summary, we have communicated that the polyol approach is a versatile and simple
method to prepare many different kinds of nanocrystalline powders and films. This is a
catalyst-free process for depositing metallic films and coatings on non-conducting surfaces.
Research is currently underway to understand the chemistry of the polyol reactions for different
materials, the nucleation and growth of powders and films, the adhesion of metallic films to various
surfaces, and the properties of the powders and films.
612 LK KURIHARA,GM CHOWANDPE SCHOEN

Figure 4. The morphologies of various deposited materials: (a) TEM micrograph of a W

film; (b) SEM micrograph of a Ni film on a KaptonTMsubstrate.

ACKNOWLEDGMENT

This work was supported by an ONR 6.2 program. LKK was supported by an ASEE
postIdoctoral fellowship. We are also grateful for the assistance of R.K. Everett and S.H. Lawrence
both OfNlu.

REFERENCES

1. see for example, Research Opportunities for Materials with Ultrafine Microstructures, National
Materials Advisory Board, National Research Council, National Academy Press (1989); N.
I&nose, Y. Ozaki and S. Kashu, Superjine Particle Technology, Springer-Verlag, London, (1992);
H. Gleiter, Nanostmct. Mater. 1, 1 (1992).
 NAN~CRYSTALLINE
METALLICPOWDERSANDFILM PRODUCED
BYTHE POLYOLMETHOD 613

2. see for example, Molecularly Designed UltrajinelNanostructured Materials, eds. K.E. Gonsalves,
G.M. Chow,T.D.Xiao andR.C. Cammarata,MaterialsResearchSociety SymposiumProceedings,
m( 1994); G.M. Chow, K.E. Gonsalves, in Nanostructured Materials: Synthesis. Properties and
Uses. eds. A.S. Edelstein, R.C. C ammarata, (IOP Publishing Ltd., England), in press.
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6. C. Ducamp-Sanguesa, R. Herrera-Urbina and M. Figlarz, Solid State Chem. lQ& 272 (1992).
7. C. Ducamp-Sanguesa, R. Herrera-Urbina and M. Figlarz, Solid State Ionics f&f&, 25 (1993).
8. F. Fievet, F. Fievet-Vincent, J.P. Lagier, B. Dumont and M. Figlarz, J. Mater. Chem. 3,627 (1993).
9. G.M.Chow,L.K.Kurihara,K.M.Kemner,P.E.Schoen,W.T. Elam,A. Ervin, S.Keller,Y.D.Zhang,
J. Budnick and T. Ambrose, J. Mater. Res. lQ, 1546 (1995).
10. L.K. Kurihara, G.M. Chow and PE. Schoen, “ Synthesis of Metallic Powders and Films using a
Polyol Process”, Patent disclosure, U.S. Navy Case No. 76,572 (1994), application pending.