In this work nanowires of magnetic metals (Co,Ni and Fe) were obtained via matrix synthesis, using etched track polymer template. The new data on electrodeposition of Ni was obtained. Two effects- the growth rate decrease (while the growing metal nanowires are filling the pores) and current density in-crease were investigated and discussed.
The results of X-rays analysis obtained using synchrotrone source demonstrated the dependence of structure and composition of nanowires on the deposition voltage. Mossbauer spectroscopy was used for in-vestigation of Fe samples. The obtained data are in good agreement with X-rays results.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3526

Bedin, S.A.

Berezkin, V.V.

Frolov, K.V.

Korotkov, V.V.

Kudryavtsev, V.N.

Mchedlishvili, B.V.

Sulyanov, S.N.

Zagorskiy, D.L.

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 2 No 2, 02PCN41(3pp) (2013) 
 
 
2304-1862/2013/2(2)02PCN41(3) 02PCN41-1  2013 Sumy State University 
Matrix Synthesis of Magnetic Nanowires 
 
D.L. Zagorskiy1,*, V.V. Korotkov1,2,†, V.N. Kudryavtsev2, S.A. Bedin1,3, S.N. Sulyanov1, K.V. Frolov1,  
V.V. Berezkin1, B.V. Mchedlishvili1 
 
1 Institute of Crystallography of RAS, 59, Leninskiy Ave., 119333 Moscow, Russia 
2 Mendeleyev University of Chemical Technology of Russia, 9, Miusskaya sq., 125047 Moscow, Russia 
3 Moscow State Pedagogical University, 1, Malaya Pirogovskaya street, 119992 Moscow, Russia 
 
(Received 19 June 2013; published online 03 September 2013) 
 
In this work nanowires of magnetic metals (Co,Ni and Fe) were obtained via matrix synthesis, using 
etched track polymer template. The new data on electrodeposition of Ni was obtained. Two effects- the 
growth rate decrease (while the growing metal nanowires are filling the pores)  and current density in-
crease  were investigated and discussed. 
The results of X-rays analysis obtained using synchrotrone source demonstrated the dependence of 
structure and composition of nanowires on the deposition voltage. Mossbauer spectroscopy was used for in-
vestigation of Fe samples. The obtained data are in  good agreement with X-rays results. 
 
Keywords: Template synthesis, Electrodeposition, Nanowires, Synchrotron spectroscopy, Mossbauer spec-
troscopy. 
 
  PACS number: 61.46. Km 
 
 
                                                          
* dzagorsky@gmail.com 
† vk-1@yandex.ru 
1. TEMPLATE SYNTHESIS 
 
The matrix synthesis is known as one of the most 
perspective ways of production of nanomaterials. The 
main goal of this technique is to fill the pores with 
required substance. One of the best porous matrix ver-
sion is track membrane. The track membrane applica-
tion as porous matrix advantage is possibility to control 
the main geometric parameters of porous system at the 
stage of virgin film irradiation and at the stage of track 
chemical etching stage [1]. It is possible to fill the pores 
of track membrane with various materials. Among 
these materials, metals are most prospective. It must 
be noted that the electrodeposition (metal plating) is 
well-studied technological process, widely used in in-
dustry, but its peculiarities in the low volumes are 
investigated insufficiently.  
Most promising metals are magnetic ones – the ob-
tained ensembles of magnetic nanowires could be used 
as sensors, as the media for magnetic memory. Moreo-
ver, these samples are of great scientifical interest due 
to the possibility to vary the geometry of the samples 
on nanometer scale. In this work the Co, Ni and Fe 
electrodeposition into   track membranes pores with 
diameters in range from 0.1 mcm to 0.5 mcm was car-
ried out. (It could be mentioned that our first results for 
application of such nanowires as ion emitters were 
given in [2,3], for obtaining of Co and Ni nanowires are 
given in [4,5,6]).  Here the metals deposition was done 
in potentiostatic regimes and the dependence of current 
on time was measured. The obtained results for Ni are 
given in Fig.1 – they are in a good accordance with the 
data for Co [4]. 
Two effects are of great interest here: the growth 
rate decrease (while the growing metal nanowires are 
filling the pores)  and current density increase (to com-
pare with a flat surface). 
In order to explain the first effect we should note 
that two processes competition takes place in the 
growth of metal replicas in narrow pores – the decrease 
of unfilled pore section length and the decrease of elec-
trolyte concentration in narrow channels (because of 
slow ion transport, so called diffusion limits). The first 
effect results in electrical resistance decrease while the 
second one – to its increase.  It is clearly that growth 
slowdown proves the second process dominance. This 
conclusion is suggested with the fact that this effect is 
maximal for narrow pores and/or under high overvolt-
age. 
The increase of current density was observed in 
metal replicas growth in matrix pores. It must be noted 
that increase of effective electrolyte conductivity in the 
track membranes pores was observed earlier. This fact 
was explained with gel layer formation at the pore 
surface [7, 8]. It may be suggested that current density 
increase defined in work presented can be explained 
with gel layer existing at pore surface. The one's high 
conductivity results in increase of measured conductivi-
ty by several times with compare to standard one. 
The production of Fe nanowires was also investigat-
ed. The influences of solution mixing, overvoltage and 
temperature on the process were studied.  
 D.L. ZAGORSKIY, V.V. KOROTKOV, V.N. KUDRYAVTSEV ET AL. PROC. NAP 2, 02PCN41 (2013) 
 
 
02PCN41-2 
 
 
 
Fig. 1 – I-t curves for deposition of Ni for different pores diameters (500, 200, and 100 nm) and for different potentials:1: -700 
mV,2: -650 mV, 3: -600 mV, 4: -550 mV, 5: -500 mV. 
 
2. STRUCTURE INVESTIGATIONS 
 
 Structure investigations were done for Fe, Co and 
Ni samples using synchrotrone source (“Belok” station 
of the Synchrotrone in Kurchatov institute, wavelength 
0,09811 nm). Measurement technique described in [9]. 
The obtained results are given in Fig. 2 and 3. 
 
 
 
Fig. 2 – X-ray spectra of Fe-samples. Growing voltages: 1: -
750 mV, 2: -900 mV, 3: -1050 mV and 4 – control sample (dep-
osition of Fe on flat surface). 
 
In all cases two types of peaks could be indicated: a 
substrate (copper) lines and the lines of the metal de-
posited into the pores. For iron samples, increasing of 
deposition voltage leads to decreasing of iron lines in-
tensity; for the highest voltage (1050 mV) iron was not 
detected. For nickel samples the trend is the same (see 
spectra 2 and 3 in Fig E), but the effect is not so signifi-
cant. For cobalt samples two type of phases were de-
tected – cubic and hexagonal. 
 
 
 
Fig. 3 – X-ray spectra of Ni-samples. Growing voltages: 1 – for 
large pores, 2: -550 mV, 3: -750 mV and 4 – control sample 
(deposition of Ni on flat surface). 
 
3. MOSSBAUER SPECTROSCOPY 
 
Iron samples were investigated by Mossbauer spec-
troscopy. This technique was used for template-
synthesized Fe nanowires before (see for example [6] and 
previous papers of these authors), but all of these exper-
iments were carried out for the wires grown in the POA 
(porous oxide aluminium) matrixes. In our experiments 
matrix and growth parameters were quite different. We 
investigated Fe nanowires grown inside the 100 nm 
pores (etched tracks in PET film) under three different 
overpotentials (overvoltages) from -600 to -900 mV. 
The Mössbauer absorption spectra from 57Fe nuclei 
were recorded at the temperature 295 K using a stand-
0
10
20
30
40
50
60
70
80
90
0 500 1000 1500 2000 2500
C
u
rr
e
n
t,
 m
A
 
Time, s 
3 
4 
5 
1 
0
10
20
30
40
50
60
70
80
90
0 500 1000 1500 2000 2500
C
u
rr
e
n
t,
 m
A
 
Time, s 
3 
4 
5 
1 
0
10
20
30
40
50
60
70
80
90
0 500 1000 1500 2000 2500
Time, s
C
u
rr
e
n
t,
 m
A
1
2
3
4
500 nm 200 nm 
100 nm 
 MATRIX SYNTHESIS OF MAGNETIC NANOWIRES PROC. NAP 2, 02PCN41 (2013) 
 
 
02PCN41-3 
ard MS-1104Em spectrometer (University Rostov-on-
Don, Russia), operating in the constant acceleration 
mode. The vibrating source of γ-quanta [57Co(Rd)] was 
at room temperature. Isomer shifts were measured 
relative to the reference α-Fe sample (18-μm-thick iron 
foil annealed in hydrogen) at room temperature. Com-
puter processing of spectra was carried out using Uni-
vem MS software. The room temperature Mössbauer 
spectra for three samples are shown in Fig. 4 – for -600 
mV, in Fig.5 – for -750 mV and in Fig. 6 – for -900 mV. 
 
 
 
Fig. 4 – Mossbauer spectra of the sample grown at -600 mV. 
 
 
 
Fig. 5 – Mossbauer spectra of the sample grown at -750 mV. 
 
 
Fig. 6 – Mossbauer spectra of the sample grown at -900 mV. 
(Additional peaks appeared in the middle). 
 
In the first case we have sextet-spectra consists of 6 
peaks with intensity ratio 3:2:1:1:2:3.This ratio is typi-
cal for the polycrystalline or powder pure α-Fe sample 
with disoriented domains magnetization without any 
texture. At the same time, increasing of  overvoltage 
(next sample, Fig 5) leads to changing of the peaks 
intensity – now it is approximately 3:1:1:1:1:3. The 
computer data processing revealed in this case the 
presence of one magnetic sextet corresponding magnet-
ic ordered α-Fe phase. It could be connected with orien-
tation of iron domain magnetization (approx. 37o to 
direction of γ-quanta). And in the third case (Fig.6 – 
the highest overvoltage) additional paramagnetic dou-
blet indicates the appearance of some additional phases 
(probably oxides FeO and α-Fe2O3 or sulphides).  
These Mossbauer spectra and structure data for Fe 
and are in good agreement: the process at low voltage 
gave the perfect crystalline wires (no impurities, no 
magnetization). At the same time, the increasing of 
overvoltage (and therefore the acceleration of nan-
owires growth) leads to formation of the wires with 
anisotropy  and/or with impurities. 
 
ACKNOWLEDGMENTS.  
 
This work was supported by Grants OFN B-65 and RFBR 
13-08-01448. We are also thankful to Dr. P. Yu. Apel for mem-
brane preparations and for discussions. 
 
 
REFERENCES 
 
1. C.R. Martin Science 266, 1961 (1994). 
2. V.A. Oleinikov, D.L. Zagorski, S.A. Bedin, A.A. Volosnikov, 
P.A. Emelyanov, Y.P. Kozmin, B.V. Mchedlishvili, Radia-
tion Measurements 43, 635 (2008). 
3. Zagorskiy D.L., Bedin S.A., Oleinikov V.A., Polyakov N.B., 
Rybalko O.G., Mchedlishvili B.V. Radiation measure-
ments, 44 №9-10, 1123 (2009). 
4. V. Korotkov, V. Kudravtsev, D. Zagorskiy, S. Bedin, Elec-
troplating and Surface treatment., XIX №4, 23 (2011). 
5. D. Zagorskiy, S. Bedin, V. Korotkov, V. Kudravtsev,  
P. Ershov, A. Vilenski, 1-th International Conference “Na-
nomaterials: Application and Properties”, Alushta, 
Ukraine,. Book of Abs., 359 (2011). 
6. D.L. Zagorskiy, V.V. Korotkov, S.A. Bedin, S.N. Sulyanov, 
K.V. Frolov, A.I. Vilenski, B.V.  Mchedlishvili, Proc. NAP, 
1 №1, 01PCN41-1 (2012). 
7. V.V. Berezkin, O.A. Kiseleva, A.N. Nechaev, V.D. Sobolev, 
N.V. Churaev Colloid Journal, 56 No3, 319 (1994) (in 
Russain). 
8. K.G. Sabbatovski, A.I. Vilenski, V.D. Sobolev,  
Yu.K. Kochnev, B.V. Mchedlishvili Colloid Journal 74, N3, 
353 (2012)(in Russain). 
9. S. Sulyanov, H. Boysen, C. Paulmann, E. Sulyanova,  
A. Rusakov, Z. Kristallogr. Proc. 1, 175 (2011). 
10. Q.-F. Zhan, J.-H.Gao, Y.-Q.Liang, N.-L.Di, Z.-H.Cheng. 
Phys. Rev. B 72, 024428 (2005). 
 
 


Matrix Synthesis of Magnetic Nanowires

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 2 No 2, 02PCN41(3pp) (2013)   2304-1862/2013/2(2)02PCN41(3) 02PCN41-1  2013 Sumy State University Matrix Synthesis of Magnetic Nanowires  D.L. Zagorskiy1,*, V.V. Korotkov1,2,†, V.N. Kudryavtsev2, S.A. Bedin1,3, S.N. Sulyanov1, K.V. Frolov1,  V.V. Berezkin1, B.V. Mchedlishvili1  1 Institute of Crystallography of RAS, 59, Leninskiy Ave., 119333 Moscow, Russia 2 Mendeleyev University of Chemical Technology of Russia, 9, Miusskaya sq., 125047 Moscow, Russia 3 Moscow State Pedagogical University, 1, Malaya Pirogovskaya street, 119992 Moscow, Russia  (Received 19 June 2013; published online 03 September 2013)  In this work nanowires of magnetic metals (Co,Ni and Fe) were obtained via matrix synthesis, using etched track polymer template. The new data on electrodeposition of Ni was obtained. Two effects- the growth rate decrease (while the growing metal nanowires are filling the pores)  and current density in-crease  were investigated and discussed. The results of X-rays analysis obtained using synchrotrone source demonstrated the dependence of structure and composition of nanowires on the deposition voltage. Mossbauer spectroscopy was used for in-vestigation of Fe samples. The obtained data are in  good agreement with X-rays results.  Keywords: Template synthesis, Electrodeposition, Nanowires, Synchrotron spectroscopy, Mossbauer spec-troscopy.    PACS number: 61.46. Km                                                             * dzagorsky@gmail.com † vk-1@yandex.ru 1. TEMPLATE SYNTHESIS  The matrix synthesis is known as one of the most perspective ways of production of nanomaterials. The main goal of this technique is to fill the pores with required substance. One of the best porous matrix ver-sion is track membrane. The track membrane applica-tion as porous matrix advantage is possibility to control the main geometric parameters of porous system at the stage of virgin film irradiation and at the stage of track chemical etching stage [1]. It is possible to fill the pores of track membrane with various materials. Among these materials, metals are most prospective. It must be noted that the electrodeposition (metal plating) is well-studied technological process, widely used in in-dustry, but its peculiarities in the low volumes are investigated insufficiently.  Most promising metals are magnetic ones – the ob-tained ensembles of magnetic nanowires could be used as sensors, as the media for magnetic memory. Moreo-ver, these samples are of great scientifical interest due to the possibility to vary the geometry of the samples on nanometer scale. In this work the Co, Ni and Fe electrodeposition into   track membranes pores with diameters in range from 0.1 mcm to 0.5 mcm was car-ried out. (It could be mentioned that our first results for application of such nanowires as ion emitters were given in [2,3], for obtaining of Co and Ni nanowires are given in [4,5,6]).  Here the metals deposition was done in potentiostatic regimes and the dependence of current on time was measured. The obtained results for Ni are given in Fig.1 – they are in a good accordance with the data for Co [4]. Two effects are of great interest here: the growth rate decrease (while the growing metal nanowires are filling the pores)  and current density increase (to com-pare with a flat surface). In order to explain the first effect we should note that two processes competition takes place in the growth of metal replicas in narrow pores – the decrease of unfilled pore section length and the decrease of elec-trolyte concentration in narrow channels (because of slow ion transport, so called diffusion limits). The first effect results in electrical resistance decrease while the second one – to its increase.  It is clearly that growth slowdown proves the second process dominance. This conclusion is suggested with the fact that this effect is maximal for narrow pores and/or under high overvolt-age. The increase of current density was observed in metal replicas growth in matrix pores. It must be noted that increase of effective electrolyte conductivity in the track membranes pores was observed earlier. This fact was explained with gel layer formation at the pore surface [7, 8]. It may be suggested that current density increase defined in work presented can be explained with gel layer existing at pore surface. The one's high conductivity results in increase of measured conductivi-ty by several times with compare to standard one. The production of Fe nanowires was also investigat-ed. The influences of solution mixing, overvoltage and temperature on the process were studied.   D.L. ZAGORSKIY, V.V. KOROTKOV, V.N. KUDRYAVTSEV ET AL. PROC. NAP 2, 02PCN41 (2013)   02PCN41-2    Fig. 1 – I-t curves for deposition of Ni for different pores diameters (500, 200, and 100 nm) and for different potentials:1: -700 mV,2: -650 mV, 3: -600 mV, 4: -550 mV, 5: -500 mV.  2. STRUCTURE INVESTIGATIONS   Structure investigations were done for Fe, Co and Ni samples using synchrotrone source (“Belok” station of the Synchrotrone in Kurchatov institute, wavelength 0,09811 nm). Measurement technique described in [9]. The obtained results are given in Fig. 2 and 3.    Fig. 2 – X-ray spectra of Fe-samples. Growing voltages: 1: -750 mV, 2: -900 mV, 3: -1050 mV and 4 – control sample (dep-osition of Fe on flat surface).  In all cases two types of peaks could be indicated: a substrate (copper) lines and the lines of the metal de-posited into the pores. For iron samples, increasing of deposition voltage leads to decreasing of iron lines in-tensity; for the highest voltage (1050 mV) iron was not detected. For nickel samples the trend is the same (see spectra 2 and 3 in Fig E), but the effect is not so signifi-cant. For cobalt samples two type of phases were de-tected – cubic and hexagonal.    Fig. 3 – X-ray spectra of Ni-samples. Growing voltages: 1 – for large pores, 2: -550 mV, 3: -750 mV and 4 – control sample (deposition of Ni on flat surface).  3. MOSSBAUER SPECTROSCOPY  Iron samples were investigated by Mossbauer spec-troscopy. This technique was used for template-synthesized Fe nanowires before (see for example [6] and previous papers of these authors), but all of these exper-iments were carried out for the wires grown in the POA (porous oxide aluminium) matrixes. In our experiments matrix and growth parameters were quite different. We investigated Fe nanowires grown inside the 100 nm pores (etched tracks in PET film) under three different overpotentials (overvoltages) from -600 to -900 mV. The Mössbauer absorption spectra from 57Fe nuclei were recorded at the temperature 295 K using a stand-01020304050607080900 500 1000 1500 2000 2500Current, mA Time, s 3 4 5 1 01020304050607080900 500 1000 1500 2000 2500Current, mA Time, s 3 4 5 1 01020304050607080900 500 1000 1500 2000 2500Time, sCurrent, mA1234500 nm 200 nm 100 nm  MATRIX SYNTHESIS OF MAGNETIC NANOWIRES PROC. NAP 2, 02PCN41 (2013)   02PCN41-3 ard MS-1104Em spectrometer (University Rostov-on-Don, Russia), operating in the constant acceleration mode. The vibrating source of γ-quanta [57Co(Rd)] was at room temperature. Isomer shifts were measured relative to the reference α-Fe sample (18-μm-thick iron foil annealed in hydrogen) at room temperature. Com-puter processing of spectra was carried out using Uni-vem MS software. The room temperature Mössbauer spectra for three samples are shown in Fig. 4 – for -600 mV, in Fig.5 – for -750 mV and in Fig. 6 – for -900 mV.    Fig. 4 – Mossbauer spectra of the sample grown at -600 mV.    Fig. 5 – Mossbauer spectra of the sample grown at -750 mV.   Fig. 6 – Mossbauer spectra of the sample grown at -900 mV. (Additional peaks appeared in the middle).  In the first case we have sextet-spectra consists of 6 peaks with intensity ratio 3:2:1:1:2:3.This ratio is typi-cal for the polycrystalline or powder pure α-Fe sample with disoriented domains magnetization without any texture. At the same time, increasing of  overvoltage (next sample, Fig 5) leads to changing of the peaks intensity – now it is approximately 3:1:1:1:1:3. The computer data processing revealed in this case the presence of one magnetic sextet corresponding magnet-ic ordered α-Fe phase. It could be connected with orien-tation of iron domain magnetization (approx. 37o to direction of γ-quanta). And in the third case (Fig.6 – the highest overvoltage) additional paramagnetic dou-blet indicates the appearance of some additional phases (probably oxides FeO and α-Fe2O3 or sulphides).  These Mossbauer spectra and structure data for Fe and are in good agreement: the process at low voltage gave the perfect crystalline wires (no impurities, no magnetization). At the same time, the increasing of overvoltage (and therefore the acceleration of nan-owires growth) leads to formation of the wires with anisotropy  and/or with impurities.  ACKNOWLEDGMENTS.   This work was supported by Grants OFN B-65 and RFBR 13-08-01448. We are also thankful to Dr. P. Yu. Apel for mem-brane preparations and for discussions.   REFERENCES  1. C.R. Martin Science 266, 1961 (1994). 2. V.A. Oleinikov, D.L. Zagorski, S.A. Bedin, A.A. Volosnikov, P.A. Emelyanov, Y.P. Kozmin, B.V. Mchedlishvili, Radia-tion Measurements 43, 635 (2008). 3. Zagorskiy D.L., Bedin S.A., Oleinikov V.A., Polyakov N.B., Rybalko O.G., Mchedlishvili B.V. Radiation measure-ments, 44 №9-10, 1123 (2009). 4. V. Korotkov, V. Kudravtsev, D. Zagorskiy, S. Bedin, Elec-troplating and Surface treatment., XIX №4, 23 (2011). 5. D. Zagorskiy, S. Bedin, V. Korotkov, V. Kudravtsev,  P. Ershov, A. Vilenski, 1-th International Conference “Na-nomaterials: Application and Properties”, Alushta, Ukraine,. Book of Abs., 359 (2011). 6. D.L. Zagorskiy, V.V. Korotkov, S.A. Bedin, S.N. Sulyanov, K.V. Frolov, A.I. Vilenski, B.V.  Mchedlishvili, Proc. NAP, 1 №1, 01PCN41-1 (2012). 7. V.V. Berezkin, O.A. Kiseleva, A.N. Nechaev, V.D. Sobolev, N.V. Churaev Colloid Journal, 56 No3, 319 (1994) (in Russain). 8. K.G. Sabbatovski, A.I. Vilenski, V.D. Sobolev,  Yu.K. Kochnev, B.V. Mchedlishvili Colloid Journal 74, N3, 353 (2012)(in Russain). 9. S. Sulyanov, H. Boysen, C. Paulmann, E. Sulyanova,  A. Rusakov, Z. Kristallogr. Proc. 1, 175 (2011). 10. Q.-F. Zhan, J.-H.Gao, Y.-Q.Liang, N.-L.Di, Z.-H.Cheng. Phys. Rev. B 72, 024428 (2005).   

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