University of Puerto Rico at Cayey

Diana Mara Rosario Torres Wilfredo Otao Ph.D. RISE Program

Abstract:
The project is directed toward the fabrication of a calcium phosphate/hydroxyapatite (HA) nanocoating deposited on silicon and functionalized to overcome existing barriers of biomedical coatings commercially used with metallic implants. The calcium phosphate crystalline phase hydroxyapatite (HA) is a bioactive material with important clinical applications. HA is the main constituent of bone and teeth and shows the best bioactivity among the calcium phosphate ceramics. It has the ability to attach directly to living tissue without any intervening fibrous tissue and it is osteoconductive, forming a uniquely strong interface. The goal for this semester was the deposition of the HA thin films at different pressures and time using magnetron sputtering. A UHV Torus magnetron was used to successfully deposit calcium phosphate from a commercial hydroxyapatite (HA) target, at pressures between 5, 10 and 15 mTorr, 100 Watts of rf sputtering power, a substrate temperature of 500C and 100% argon gas. The samples showed the same surface morphology as previous ones deposited using another target. The deposition configuration was optimized to obtain a good deposition rate. A first batch of samples was sent to UPRMayaguez where their ability to grow bone-forming cells is being studied.
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Background and Significance

CaP

crystalline phase Hydroxyapatite (Ca10(PO4)6(OH)2, HA). 9Main constituent of bone and teeth 9Is a bioactive material 9Important clinical applications Deposition 9Vacuum process 9Deposition of coatings 9Excellent adhesion of coating

Sputtering

Previous Research
A

UHV Torous Magnetron was used for the deposition of calcium phosphate from an HA Commercial target.
HA

Deposition Parameters:
9600C substrate temperature
Lin (Cps)
0.05

(0 02 )

(2 11 ) 00 ) H

H A

HA_54

(3

HA_53 HA_52 HA_51

9Pressures between 5-20 mTorr 9100% Ar gas 9100 watts of rf sputtering power

HA_50 HA_49

0 19.1 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

41

2-Theta - Scale
HA 49 - File: HA_49.raw - Type: 2Th alone - Start: 19.337 - End: 41.050 - Step: 0.100 - Step time: 800 Operations: Y Scale Add 3.000 | Background 1.000,1.000 | Fourier 4.997 x 1 | Displacement 0.583 | Import HA 50 - File: HA_50.raw - Type: 2Th alone - Start: 19.337 - End: 41.050 - Step: 0.100 - Step time: 800 Operations: Y Scale Add 1.000 | Y Scale Add -2.000 | Y Scale Add -2.000 | Y Scale Add 7.000 | Y Scale A HA 51 - File: HA_51.raw - Type: 2Th alone - Start: 19.337 - End: 41.050 - Step: 0.100 - Step time: 800 Operations: Y Scale Add 20.000 | Background 1.000,1.000 | Displacement 0.583 | Import HA 52 Frame: HA_52.unw Frame: HA_52.unw - File: HA_52.raw - Type: 2Th alone Operations: Y Scale Add 2.000 | Y Scale Add 2.000 | Y Scale Add 22.000 | Background 1.000,1.000 | Impo

HA 53 Frame: HA_53.unw Frame: HA_53.unw - File: HA_53.raw - Type: 2Th alone Operations: Displacement 0.333 | Y Scale Add 32.000 | Background 1.000,1.000 | Import HA 54 Frame: HA_54.unw Frame: HA_54.unw - File: HA_54.raw - Type: 2Th alone Operations: Displacement 0.250 | Y Scale Add 40.000 | Displacement 0.417 | Background 1.000,1.000 | Im 09-0432 (I) - Hydroxylapatite, syn - Ca5(PO4)3(OH) - Y: 15.46 % - d x by: 1.000 - WL: 1.54056

Films presented a X-ray diffraction pattern consistent with the hydroxyapatite phase.

Problem
Hydroxyapatite

coating used on medical implants has problems of adhesion and longevity.

Hypothesis
Magnetron Sputtering will produce an hydroxypatite coating with good adhesion and crystallinity.

Controlled balance system

Target Substrate

Objectives
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Deposit hydroxyapatite (HA) thin films using the controlled balance sputtering system The thin films will be deposited from a HA target and using in-situ heating. Deposition parameters such as deposition pressure and sputtering time will be varied to control the composition and crystallinity of the films.

Methodology
a) Deposit HA - Thin films prepared at 5, 10, and 15 mTorr of 100% argon gas and substrate temperature of 500C. b) Characterization- morphology - Surface morphology studied with the SEM. c) Send samples to UPR Mayaguez for study of bone cells adhesion and proliferation on HA surface.

Data:
Sample HA #79 HA #80 HA #81 HA #82 Base Pressure (torr) 1.1x10-6 1.6x10-6 1.4x10-6 1.7x10-6 Thermocouple Calibration Sent to UPR Mayaguez for cell growth Pressure (mtorr) 5 5 10 15 Flow Ar (sccm) 74 74 172 284 Heating No 5A-9V 5A-9V 5A-9V Presputtering time (min) 5 5 5 5 Sputtering time (min) 60 120 120 120 dc Bias (V) 94 124 235 212 30 Thickness 55 Comments

HA #84

HA #85 HA #86 HA #87

2.3x10-6 2.0x10-6 1.6x10-6 substrate distance reduced

5 10 15

73 166 284

509C ~5A 509C ~5A 509C ~5A

120 120 120

128 142 160

140

71

HA #88

3.7x10-6

74

No

21.5

85 CaP deposition in new configuration 5A in T, not desired Temperature

HA #89

1.2x10-6

No

180

217

HA #90 HA #91

1.9x10-6 1.3x10-6

10 15

177

No 5A

2 5

180 180

140-160 166

149 298

HA#92

15.x10-6

77

5A-3hrs.

360

145-150

557

After 3 hrs the heater was turned off

Photos:

HA 92 at 5 mTorr (sputtering time 360 min)

Conclusion:
Impurities were acting as nuclei for the heterogeneous nucleation of nanograins observed at the surface and preventing the nucleation of the HA crystalline phase. Deposition process parameters can be used to produce HA films with controlled crystallinity.

Future Projections
Synthesis of a highly crystalline HA coating on silicon and Ti6Al4V substrates, with defined control of the crystalline phase(s), and with excellent adhesion to the coated surface. Begin to deposit in titanium.

References
x Personal Communication: Juan M. Figueroa Thesis Proposal for the UPR Cayey Honor Program. x Robert K. Waits, Thin Film Deposition and Pattering, American Society Monograph Series, Harland. Vacuum

x W. Otao, V. M. Pantojas, J. M. Figueroa, D. Hernndez and A. Rodrguez-Navarro, Magnetron sputtering deposition of calcium phosphate films with nanoscale grain morphology in their surface, in Mechanics of Biological and Bio-Inspired Materials, edited by K. Katti, C. Hellmich, C. Viney, and U. Wegst ( Mater. Res. Soc. Symp.Proc. Volume 975E, Warrendale, PA, 2007) paper #0975DD06-08.

Acknowledgements
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NAMAS LAB. y RISE Program