Analysis of the influence of substrate temperature on hydroxyapatite

deposited by laser ablation method using ArF laser

Waldemar Mróza, Marcin Jedyński*b, Zygmunt Szymańskib, Artur Prokopiuka, Sylwia Burdyńskaa
a
Military University of Technology, ul. Kaliskiego 2, 00-908 Warsaw, Poland
b
Institute of Fundamental Technological Research, ul. Świętokrzyska 21, 00-049 Warsaw, Poland

ABSTRACT

Hydroxyapatite layers (Ca10(PO4)6(OH)2) were deposited by means of laser ablation method using an ArF excimer laser
(193 nm). The influence of substrate temperature on the structure of deposited layers was studied. The layers were
deposited on Ti6Al4V titanium alloy which temperature varied from 250 OC to 700 OC. The characteristics of the
hydroxyapatite coatings were determined by means of Fourier Transform Infrared spectroscopy (FTIR). The obtained
spectra reveal that the presence and abundance of the PO4 absorption bands depend on the substrate temperature. The
topography of the deposited layers were analyzed with the use of an Atomic Force Microscope.

Keywords: Pulsed laser deposition, FTIR, AFM, hydroxyapatite

1. INTRODUCTION

Hydroxyapatite is an inorganic component of natural bone, therefore it plays an important role as a biocompatible
material used in medical applications such as thin coatings of titanium alloy implants for orthopedic surgery1. Among
many techniques pulsed laser deposition (PLD) is used for producing hydroxyapatite coatings. This method is
characterized by high deposition rate, possibility of precise controlling of the thickness of growing layer and its
crystallinity. The physical properties of deposited layer are controlled by changing conditions of PLD process. The
crucial PLD parameters are presence of an ambient gas and its pressure2, substrate temperature, fluence and repetition of
the laser pulse3. It was found that deposition at temperatures less than 400 OC resulted in amorphous films regardless of
the ambient gas. At temperatures greater than 400 OC films were either crystalline or amorphous, according to the gas
environment4.

The aim of this paper is to show the influence of substrate temperature on the physical properties of hydroxyapatite
coatings as well as their topography.

2. EXPERIMENTAL PROCEDURE

Hydroxyapatite coatings were deposited by means of pulsed excimer ArF laser operating at 193 nm. The laser pulse
width was 20 ns, the laser fluence 7 J/cm2 and repetition rate 50 Hz. The synthetic hydroxyapatite target was placed in
the central part of vacuum chamber and the angle of incidence of the laser beam was 40O. The hydroxyapatite was
deposited on Ti6Al4V titanium alloy substrates maintained at temperatures of 250 ± 50 OC, 400 ± 50 OC, 550 ± 50 OC
and 700 ± 50 OC, respectively. The substrates were situated at the distance of 4 cm from the target. The PLD process was
performed at presence of water vapor at a pressure of 17.5 Pa.

After PLD process the deposited layers were analyzed by FTIR as well as atomic force microscopy technique. The FTIR
spectra were registered with a resolution of 4 cm-1. For each spectrum 10 scans were made and summed in order to
improve signal to noise ratio.

*
jedynski@ippt.gov.pl

Laser Technology VIII: Applications of Lasers,

edited by Wieslaw L. Wolinski, Zdzislaw Jankiewicz, Ryszard S. Romaniuk,
Proc. of SPIE Vol. 6598, 65980B, (2007) · 0277-786X/07/$18 · doi: 10.1117/12.726542

Proc. of SPIE Vol. 6598 65980B-1

 3. EXPERIMENTAL RESULTS

Figure 1 depicts the absorption spectra of hydroxyapatite coatings deposited at different substrate temperatures. The band
at 610 cm-1 reflecting PO4 modes is visible in the spectra of layers deposited at every substrate temperature. This peak
becomes broader towards lower energy when the substrate temperature increases from 250 OC to 400 OC. The second
band at 480 cm-1 corresponding to PO4 mode appears at a temperature of 550 OC and is also present at 700 OC. Its
emergence indicates partial change of the phase structure of the obtained layers with the increase of the substrate
temperature. Since this peak is strictly assigned to the presence of crystalline as well as amorphous hydroxyapatite5 one
can conclude that the range of substrate temperature between 400 OC and 700 OC is most appropriate for the growth of
the hydroxyapatite layers.

270,
PO4 PO4 PO4 CO3

a)
Transmittance (a.u.)

b)

c)

d)

0,
400,
400 800 100 1200 1501600 200
2000 2800300 3600 4000
cm-
-1
cm

Fig. 1. Fourier spectra of deposited hydroxyapatite layers at different substrate temperatures: a) 250OC, b) 400OC, c) 550OC, d) 700OC.

The bands attributed to PO4 modes which appear around 950 cm-1, 980 cm-1 and 1130 cm-1 also change when the
substrate temperature increases. These bands are clearly visible in the spectra of the layers deposited at substrate
temperature of 250 OC and 400 OC. At higher temperatures the intensity of the peak at 980 cm-1 decreases in proportion
to the peaks at 950 cm-1 and 1130 cm-1. At a temperature about 700 OC the intensity of the peak at 950 cm-1 also
decreases. This reveals partial changing of the phase structure of the layers deposited at substrate temperatures lower and
higher than 550 OC. We also detected two bands around 1410 cm-1 and 1470 cm-1 in the spectra of all coatings. These
bands indicate the presence of CO3 group in the deposited layers. This reveals that one of the phases present in each
coating is biological apatite (Ca8.3(PO4)4.3(CO3-HPO4)1.7(OH)0.3).

Figure 2 shows two dimensional topography of 1 x 1 µm area of the hydroxyapatite layers along with the corresponding
phase maps. The hydroxyapatite coating obtained at 250 OC shows policrystalline structure which is clearly different
from amorphous structure obtained at room temperature6. The size of crystallites obtained at substrate temperature of 250

Proc. of SPIE Vol. 6598 65980B-2

O
C is about 100 nm. These crystallites are characterized by homogeneous arrangement on the surface. The phase map
indicates that in this case the deposited layer is dominated by only one phosphate phase. We assume that dominating
phase is OCP (Ca8(HPO4)2(PO4)4•5H2O) which is principal phase of layers deposited at substrate temperature of 150 OC
in the presence of water vapor7.
The topography of layer deposited at substrate temperature of 400 OC shows morphology different from the layer
deposited at 250 OC. It is visible that crystallites formed at a temperature of 400 OC are smaller and their arrangement is
not as homogeneous as in the case of 250 OC. In this case the comparable contribution of two material phases can be
seen. One of the phases is octacalcium phosphate phase and the second is biological apatite. This is proved by the
presence of CO3 absorption bands in the corresponding fourier spectrum.

0.2
0.200 /di 0.2 x O.200jjm dlv x 0.200 em/div xO.200nm/div

x 'j'
50.000 /di urn z 50.000 nm/div urn z 50.000 nm/div 50.000 nm/div

--
a) b) c) d)

-a— -.
-.

. •:; r-
o mum Lo

Fig .2. 3D-topography of 1 x 1 µm area of hydroxyapatite layers (upper images) along with corresponding phase maps (lower images)
registered at different substrate temperatures: a) 250 OC, b) 400 OC, c) 550 OC, d) 700 OC.

The layer deposited at 550 OC shows more homogeneous structure of the surface in contrast to the layer deposited at
400 OC but the size of the crystallites is the same in both cases. At the substrate temperature of 700 OC the coating grows
as a larger crystallites. Therefore from medical point of view its usefulness is poorer because on such surface osteoblasts
can not develop properly. The phase map indicates that the layer is dominated by only one material phase. One can
assume that this phase is biological apatite because the fourier spectrum obtained for the layer deposited at 700 OC is
similar to the spectrum obtained for the layers deposited at lower temperature.

4. CONCLUSIONS

In this work influence of substrate temperature on the structure of the deposited hydroxyapatite layer is presented. The
contribution of OCP phase in the deposited layers decreases with the increase of the substrate temperature while the
contribution of the biological apatite increases. This is proved by behavior of PO4, CO3 absorption bands of the fourier
spectra and the phase maps performed by atomic force microscopy. The optimum temperature for growth of the layer
with maximum content of hydroxyapatite and the size of crystallites which promote the development of osteoblasts
ranged from 400 OC to 550 OC.

ACKNOWLEDGMENTS

Financial partial support for this study by MNiI T00 004 29 and PBZ-KBN-100/T08/2003 is acknowledged.

Proc. of SPIE Vol. 6598 65980B-3

 REFERENCES

1. D. B. Chrisey, G. K. Hubler, Pulsed laser deposition of thin films, New York, 1994.
2. M. Jedyński, Z. Szymański, W. Mróz, A. Prokopiuk, M. Jelinek, T. Kocourek, Spectroscopic measurements of
plasma plume induced during the laser deposition of the hydroxyapatite, Czechoslovak Journal of Physics, 54, pp.
C397–C402, 2004.
3. B. Mayor, J. Arias, S. Chiussi, F. Garcia, J. Pou, B. Leon Fong, M. Perez-Amor, Calcium phosphate coatings grown
at different substrate temperatures by pulsed ArF-laser deposition, Thin Solid Films, 317, 363-366, 1998.
4. H. Zeng, R.L. William, M. Mirov, Structural and morphological study of pulsed laser deposited calcium phosphate
bioceramic coatings: influence of deposition conditions, laser parameters and target properties, Journal of Biomedical
Materials Research, 50, 248-258, 2000.
5. B. Major, T. Wierzchoń, W. Mróz, K. Haberko, R. Ebner, J. Bonarski, R. Major, A. Prokopiuk, Surface engineering
in formation of modern multiplayer structures-biofunctional hydroxyapatite coatings produced by pulsed laser
ablation and glow discharge nitriding multiplex method, Bulletin of the Polish Academy of Sciences, Technical
Sciences, 52, no. 4, 2004.
6. W. Mróz, Physics of deposition of hydroxyapatite layers by pulsed laser deposition methods, in Functional properties
of nanostructured materials, edited by Kassing R., NATO Science Series II Mathematics, Physics and Chemistry,
Vol. 223, 183-196, Springer 2006.
7. I. N. Mihailescu, Hydroxyapatite nanocomposite ceramics – new implant material for bone substitute, EUREKA
Workshop, Magurele and Sinaia 16-17 January 2006.

Proc. of SPIE Vol. 6598 65980B-4