Optical density spectra of amorphous diamond-like films of hydrogenated carbon modified with plati-num impurity (a-C : H) have been investigated. a-C : H  films were prepared by the method of ion 
plasma magnetron co-sputtering of graphite and platinum in argon-hydrogen atmosphere. Platinum con-tent in the films was varied from 0 to 9 at. %. In the optical spectra of a-C : H  films with different Pt 
content the peaks of resonance absorption in the range from 496 to 501 nm were found, whilst in the spec-trum of a-C : H films the absorption peak is absent. The appearance of these absorption peaks in a-C : H films is explained by resonance plasmon vibrations of free electrons in platinum nanocl usters. 
The average diameter of the Pt nanoclusters was estimated using electromagnetic theory of Mie, and it is 
~ 5 nm.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3638

Daineko, E.

Guseinov, N.

Maksimova, S.

Manabaev, N.

Mikhailova, S.

Muhametkarimov, E.

Prikhodko, O.

SocioEconomic Challenges Journal (Sumy State University)

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ 
Vol. 6 No 3, 03067(3pp) (2014) Том 6 № 3, 03067(3cc) (2014) 
 
 
The article was reported at the International Conference «The Advanced Technology, Equipment and Analytical Systems for Materials», Kursk, 13-14 May, 2014 
2077-6772/2014/6(3)03067(3) 03067-1  2014 Sumy State University 
Plasmon Resonance in а-С : Н Films Modified with Platinum Nanoclusters 
 
O. Prikhodko, N. Manabaev, N. Guseinov, S. Maksimova, E. Muhametkarimov,  
S. Mikhailova, E. Daineko 
 
Al-Farabi Kazakh National University, 71, Al-Farabi Str., 050038 Almaty, Kazakhstan 
 
(Received 19 May 2014; published online 15 July 2014) 
 
Optical density spectra of amorphous diamond-like films of hydrogenated carbon modified with plati-
num impurity (a-C : HPt) have been investigated. a-C : HPt films were prepared by the method of ion 
plasma magnetron co-sputtering of graphite and platinum in argon-hydrogen atmosphere. Platinum con-
tent in the films was varied from 0 to 9 at. %. In the optical spectra of a-C : HPt films with different Pt 
content the peaks of resonance absorption in the range from 496 to 501 nm were found, whilst in the spec-
trum of a-C : H films the absorption peak is absent. The appearance of these absorption peaks in  
a-C : HPt films is explained by resonance plasmon vibrations of free electrons in platinum nanoclusters. 
The average diameter of the Pt nanoclusters was estimated using electromagnetic theory of Mie, and it is 
~ 5 nm. 
 
Keywords: Amorphous diamond-like films of hydrogenated carbon (a-C : H) modified with platinum, Opti-
cal density, Nanoclusters, Plasmon resonance, Extinction section. 
 
 PACS numbers: 81.05.Uw, 68.55.Ln 
 
 
1. INTRODUCTION 
 
It is known that impurity of the metals weakly in-
teracted with carbon atoms can form the metal 
nanoclusters in the matrix of a-C : H films at certain 
conditions [1]. Those heterophase systems reveal non-
linear optical properties and, as a rule, plasmon reso-
nance absorption takes place [2, 3]. Among the metals 
chemically non-interacting with the a-C : H matrix Pt 
is of particular interest, since the structures with plat-
inum nanoclusters can be applicable in an air-hydrogen 
fuel cells [4]. 
The goal of this work was to study the optical prop-
erties of amorphous diamond-like carbon films modified 
with platinum nanoclusters (a-C : HPt). 
 
2. TECHNIQUE 
 
The a-C : HPt films were produced by the ion 
plasma magnetron sputtering of the combined poly-
crystalline graphite-platinum target in the atmosphere 
of argon-hydrogen gases mixture at deposition temper-
ature 200 С. 
The composition and morphology of the films were 
determined by scanning electron microscope Quanta 
3D 200i with energy-dispersive analysis. The results 
show that there are no unintentional impurities and 
the micron sized defects in studied films, and  
a-C : HPt films, as well as a-C : H films, are continu-
ous [5]. The concentration of Pt in a-C : H matrix 
reached 9 at. %. Optical properties of the films were 
studied using Spectrophotometer CF 2000 and Shi-
madzu UV2000. 
 
3. RESULTS AND DISCUSSION 
 
Figure 1 represents the optical density spectra D() 
of a-C : HPt films with different Pt content. It follows 
from fig. 1 that the presence of platinum impurity leads 
to significant increase of a-C : H the films optical densi-
ty. Moreover, in D() spectra of a-C : HPt films there 
are the distinct absorption peaks in the region from 496 
to 501 nm, whilst in the spectrum of a-C : H films such 
absorption peak is absent. The intensity of the absorp-
tion peaks increases with platinum concentration in 
the films. The detected absorption peaks can be  
explained by photons absorption of surface free elec-
trons of platinum clusters, i.e. resonance plasmon vi-
brations excitation. It should be noted that the same 
phenomenon was observed in materials containing iso-
lated nanoclusters of metals [6-8].  
The average diameter d of Pt nanoclusters in  
a-C : HPt films can be estimated from electromagnet-
ic theory of Mie [6, 7] using the half-width of resonance 
optical absorption peak Δ and characteristic wave-
length of plasmon resonance р 
 
 
2
f p
d
c
 
 


, (1) 
 
where νf is the electron velocity corresponding to the 
Fermi energy of the metal, c – is the velocity of light. 
 
 
 
Fig.1 – Optical density spectra of a-C : HPt films with Pt 
content (аt. %): 1 – 0; 2 – 4.6; 3 – 7.1; 4 – 9.0 
4 
λ, nm 
D
, 
o
p
ti
ca
l 
d
e
n
si
ty
 
 O. PRIKHODKO, N. MANABAEV, ET AL. J. NANO- ELECTRON. PHYS. 6, 03067 (2014) 
 
 
03067-2 
For the films with Pt content 4.6, 7.1 and 
9.0 at. % р is equal to 496, 498 and 501 nm, respective-
ly. The spectral position of the resonance peak and his 
half-width can be determined from D() spectra since 
the absorption coefficient α is proportional to optical 
density 
 
 D  – lgT  αlg(e), (2) 
 
where T is the optical transmission. According to the 
calculation, the average diameter of Pt nanoclusters in 
a-C : HPt films with 4.6, 7.1 and 9.0 at. % of plati-
num is~ 5 nm. 
Based on Mie theory the spectrum of resonance ab-
sorption in studied films can be calculated. Platinum 
nanoclusters are supposed to be embedded in amorphous 
diamond-like matrix. Let us estimate the extinction sec-
tionQext of  surface plasmon resonance under the assump-
tion of spherical shape of metal nanoclusters. In general, 
according to[9] Qextis determined from equation 
 
 
2
1
2
(2 1)Re( ),ext L L
L
Q L a b
k
 

    (3) 
 
where L – is the order of multipole excitation in nanopar-
ticle, k – wave vector, aL and bL are expressed through 
Riccati-Bessels cylindrical functions L
 
and L
 
and are 
called Mie coefficients [9]. In calculations L was assumed 
to be equal 1, which corresponds to dipole. 
 
 
( ) ( ) ( ) ( )
,
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
.
( ) ( ) ( ) ( )
L L L L
L
L L L L
L L L L
L
L L L L
m mx x mx x
a
m mx x mx x
mx x m mx x
b
mx x m mx x
   
   
   
   
 

 
 

 
 (4) 
 
Argument (mx) of functions in equation (4) is de-
termined from relation of optical constants of Pt metal 
particles and a-C : H matrix: mx  εPt / εa-C : H. Second 
argument x  |k|R, where R is the particle radius 
measured in nm.  
Usually a dielectric constant of metals is deter-
mined from Drude theory using known plasmon reso-
nance absorption energy ћωр and electron collisions 
frequency . For platinum ћωр  8,13 eV and 
  1,05·1013 s – 1.  
In its turn the optical extinction is linearly related 
to absorption coefficient :   Qext, where  is a densi-
ty of the particles in the film. Taking into account rela-
tion (2) we obtain  
 
 D  lg(e)Qext, (5) 
 
The last relation gives the opportunity to compare 
optical density of the films with extinction section. Fig-
ure 2 shows the results of extinction section calculation 
as a function of quantum energy. 
Good agreement the results of calculation with the po-
sition of the resonance absorption peak for a-C : HPt 
films at   498 nm (2.5 eV) (fig. 1) is obtained when the 
dielectric constant of а-С : Н films is equal to 4.8. 
Using the equations 3 and 4 one can obtain  
а-С : НPt films extinction section (optical density) 
dependence on photons energy and average metal 
nanoclusters radius (figure 3). 
 
 
 
Fig. 2 – Spectral dependency of extinction section for  
а-С : НPt films 
 
 
 
Fig. 3 – Thee xtinction sectionversus photons energy and 
average metal nanoclusters radius in а-С : НPt films 
 
It follows from fig. 3 that average metal nanoclus-
ters radius increasing leads to an increase in the plas-
mon resonance intensity and a slight shift of the reso-
nance absorption maximum to higher wavelengths.  
 
4. CONCLUSION 
 
In a-C : HPt films prepared by the ion plasma 
magnetron sputtering of the combined polycrystalline 
graphite-platinum target the optical absorption due to 
the excitation of surface plasmons in platinum 
nanoclusters was found in the region from 496 to 
501 nm. The a-C : HPt films with platinum nanoclus-
ters may be promising for a variety of applications). 
 
 
 
 
 
 
 
Ћω, eV 
R, nm 
Ћω, eV 
 PLASMON RESONANCE IN A-C : H FILMS… J. NANO- ELECTRON. PHYS. 6, 03067 (2014) 
 
 
03067-3 
REFERENCES 
 
1. V.I. Ivanov-Omskii, Proc. School of Advanced Material 
Science and Technology (Jesi-Ancona, Italy) (Ed. by 
D.G. Teer) (Franco Rusticelli, Timisoara: Sudara: 2000). 
2. S. Muto, T. Kubo, Y. Kurokawa, K. Suzuki, Thin Solid 
Films 322, 233 (1998). 
3. U. Kreibig, M. Vollmer, Optical Properties of Metal Clus-
ters. (Berlin: Springer: 1995). 
4. L. Li, L. Xu, Y. Wang, Mater. Lett. 57, 1406 (2003). 
5. O.Yu. Prikhodko, N.K. Manabaev, N. Guseynov, 
S. Maksimova, S. Mikhailova, G. Assanov, Adv. Mater. 
Res. 660, 47 (2013). 
6. D. Manikandan, S. Mohan, K.G. Nair, Mater. Res. Bull. 
38, 1545 (2003). 
7. D. Manikandan, S. Mohan, K.G.M. Nair, Physica B: Con-
dens. Matter. 325, 86 (2003). 
8. Sh.Sh. Sarsembinov, O.Yu. Prikhodko, A.P. Ryaguzov, 
S.Ya. Maksimova, E.A. Daineko, phys. status solidi c 7 
No 3-4, 805 (2010). 
9. A.L. Stepanov, Tech. Phys. 49 No 2, 143 (2004). 
 


English

Plasmon Resonance in а-С : Н Films Modified with Platinum Nanoclusters

Electronic Sumy State University Institutional Repository

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ Vol. 6 No 3, 03067(3pp) (2014) Том 6 № 3, 03067(3cc) (2014)   The article was reported at the International Conference «The Advanced Technology, Equipment and Analytical Systems for Materials», Kursk, 13-14 May, 2014 2077-6772/2014/6(3)03067(3) 03067-1  2014 Sumy State University Plasmon Resonance in а-С : Н Films Modified with Platinum Nanoclusters  O. Prikhodko, N. Manabaev, N. Guseinov, S. Maksimova, E. Muhametkarimov,  S. Mikhailova, E. Daineko  Al-Farabi Kazakh National University, 71, Al-Farabi Str., 050038 Almaty, Kazakhstan  (Received 19 May 2014; published online 15 July 2014)  Optical density spectra of amorphous diamond-like films of hydrogenated carbon modified with plati-num impurity (a-C : HPt) have been investigated. a-C : HPt films were prepared by the method of ion plasma magnetron co-sputtering of graphite and platinum in argon-hydrogen atmosphere. Platinum con-tent in the films was varied from 0 to 9 at. %. In the optical spectra of a-C : HPt films with different Pt content the peaks of resonance absorption in the range from 496 to 501 nm were found, whilst in the spec-trum of a-C : H films the absorption peak is absent. The appearance of these absorption peaks in  a-C : HPt films is explained by resonance plasmon vibrations of free electrons in platinum nanoclusters. The average diameter of the Pt nanoclusters was estimated using electromagnetic theory of Mie, and it is ~ 5 nm.  Keywords: Amorphous diamond-like films of hydrogenated carbon (a-C : H) modified with platinum, Opti-cal density, Nanoclusters, Plasmon resonance, Extinction section.   PACS numbers: 81.05.Uw, 68.55.Ln   1. INTRODUCTION  It is known that impurity of the metals weakly in-teracted with carbon atoms can form the metal nanoclusters in the matrix of a-C : H films at certain conditions [1]. Those heterophase systems reveal non-linear optical properties and, as a rule, plasmon reso-nance absorption takes place [2, 3]. Among the metals chemically non-interacting with the a-C : H matrix Pt is of particular interest, since the structures with plat-inum nanoclusters can be applicable in an air-hydrogen fuel cells [4]. The goal of this work was to study the optical prop-erties of amorphous diamond-like carbon films modified with platinum nanoclusters (a-C : HPt).  2. TECHNIQUE  The a-C : HPt films were produced by the ion plasma magnetron sputtering of the combined poly-crystalline graphite-platinum target in the atmosphere of argon-hydrogen gases mixture at deposition temper-ature 200 С. The composition and morphology of the films were determined by scanning electron microscope Quanta 3D 200i with energy-dispersive analysis. The results show that there are no unintentional impurities and the micron sized defects in studied films, and  a-C : HPt films, as well as a-C : H films, are continu-ous [5]. The concentration of Pt in a-C : H matrix reached 9 at. %. Optical properties of the films were studied using Spectrophotometer CF 2000 and Shi-madzu UV2000.  3. RESULTS AND DISCUSSION  Figure 1 represents the optical density spectra D() of a-C : HPt films with different Pt content. It follows from fig. 1 that the presence of platinum impurity leads to significant increase of a-C : H the films optical densi-ty. Moreover, in D() spectra of a-C : HPt films there are the distinct absorption peaks in the region from 496 to 501 nm, whilst in the spectrum of a-C : H films such absorption peak is absent. The intensity of the absorp-tion peaks increases with platinum concentration in the films. The detected absorption peaks can be  explained by photons absorption of surface free elec-trons of platinum clusters, i.e. resonance plasmon vi-brations excitation. It should be noted that the same phenomenon was observed in materials containing iso-lated nanoclusters of metals [6-8].  The average diameter d of Pt nanoclusters in  a-C : HPt films can be estimated from electromagnet-ic theory of Mie [6, 7] using the half-width of resonance optical absorption peak Δ and characteristic wave-length of plasmon resonance р   2f pdc  , (1)  where νf is the electron velocity corresponding to the Fermi energy of the metal, c – is the velocity of light.    Fig.1 – Optical density spectra of a-C : HPt films with Pt content (аt. %): 1 – 0; 2 – 4.6; 3 – 7.1; 4 – 9.0 4 λ, nm D, optical density  O. PRIKHODKO, N. MANABAEV, ET AL. J. NANO- ELECTRON. PHYS. 6, 03067 (2014)   03067-2 For the films with Pt content 4.6, 7.1 and 9.0 at. % р is equal to 496, 498 and 501 nm, respective-ly. The spectral position of the resonance peak and his half-width can be determined from D() spectra since the absorption coefficient α is proportional to optical density   D  – lgT  αlg(e), (2)  where T is the optical transmission. According to the calculation, the average diameter of Pt nanoclusters in a-C : HPt films with 4.6, 7.1 and 9.0 at. % of plati-num is~ 5 nm. Based on Mie theory the spectrum of resonance ab-sorption in studied films can be calculated. Platinum nanoclusters are supposed to be embedded in amorphous diamond-like matrix. Let us estimate the extinction sec-tionQext of  surface plasmon resonance under the assump-tion of spherical shape of metal nanoclusters. In general, according to[9] Qextis determined from equation   212(2 1)Re( ),ext L LLQ L a bk     (3)  where L – is the order of multipole excitation in nanopar-ticle, k – wave vector, aL and bL are expressed through Riccati-Bessels cylindrical functions L and L and are called Mie coefficients [9]. In calculations L was assumed to be equal 1, which corresponds to dipole.   ( ) ( ) ( ) ( ),( ) ( ) ( ) ( )( ) ( ) ( ) ( ).( ) ( ) ( ) ( )L L L LLL L L LL L L LLL L L Lm mx x mx xam mx x mx xmx x m mx xbmx x m mx x                 (4)  Argument (mx) of functions in equation (4) is de-termined from relation of optical constants of Pt metal particles and a-C : H matrix: mx  εPt / εa-C : H. Second argument x  |k|R, where R is the particle radius measured in nm.  Usually a dielectric constant of metals is deter-mined from Drude theory using known plasmon reso-nance absorption energy ћωр and electron collisions frequency . For platinum ћωр  8,13 eV and   1,05·1013 s – 1.  In its turn the optical extinction is linearly related to absorption coefficient :   Qext, where  is a densi-ty of the particles in the film. Taking into account rela-tion (2) we obtain    D  lg(e)Qext, (5)  The last relation gives the opportunity to compare optical density of the films with extinction section. Fig-ure 2 shows the results of extinction section calculation as a function of quantum energy. Good agreement the results of calculation with the po-sition of the resonance absorption peak for a-C : HPt films at   498 nm (2.5 eV) (fig. 1) is obtained when the dielectric constant of а-С : Н films is equal to 4.8. Using the equations 3 and 4 one can obtain  а-С : НPt films extinction section (optical density) dependence on photons energy and average metal nanoclusters radius (figure 3).    Fig. 2 – Spectral dependency of extinction section for  а-С : НPt films    Fig. 3 – Thee xtinction sectionversus photons energy and average metal nanoclusters radius in а-С : НPt films  It follows from fig. 3 that average metal nanoclus-ters radius increasing leads to an increase in the plas-mon resonance intensity and a slight shift of the reso-nance absorption maximum to higher wavelengths.   4. CONCLUSION  In a-C : HPt films prepared by the ion plasma magnetron sputtering of the combined polycrystalline graphite-platinum target the optical absorption due to the excitation of surface plasmons in platinum nanoclusters was found in the region from 496 to 501 nm. The a-C : HPt films with platinum nanoclus-ters may be promising for a variety of applications).        Ћω, eV R, nm Ћω, eV  PLASMON RESONANCE IN A-C : H FILMS… J. NANO- ELECTRON. PHYS. 6, 03067 (2014)   03067-3 REFERENCES  1. V.I. Ivanov-Omskii, Proc. School of Advanced Material Science and Technology (Jesi-Ancona, Italy) (Ed. by D.G. Teer) (Franco Rusticelli, Timisoara: Sudara: 2000). 2. S. Muto, T. Kubo, Y. Kurokawa, K. Suzuki, Thin Solid Films 322, 233 (1998). 3. U. Kreibig, M. Vollmer, Optical Properties of Metal Clus-ters. (Berlin: Springer: 1995). 4. L. Li, L. Xu, Y. Wang, Mater. Lett. 57, 1406 (2003). 5. O.Yu. Prikhodko, N.K. Manabaev, N. Guseynov, S. Maksimova, S. Mikhailova, G. Assanov, Adv. Mater. Res. 660, 47 (2013). 6. D. Manikandan, S. Mohan, K.G. Nair, Mater. Res. Bull. 38, 1545 (2003). 7. D. Manikandan, S. Mohan, K.G.M. Nair, Physica B: Con-dens. Matter. 325, 86 (2003). 8. Sh.Sh. Sarsembinov, O.Yu. Prikhodko, A.P. Ryaguzov, S.Ya. Maksimova, E.A. Daineko, phys. status solidi c 7 No 3-4, 805 (2010). 9. A.L. Stepanov, Tech. Phys. 49 No 2, 143 (2004).  

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Plasmon Resonance in а-С : Н Films Modified with Platinum Nanoclusters

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