ThC.4.

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Photoluminescence of ion beam sputtered

HfO2/Al2O3 and HfO2/SiO2 mixtures
Thimotheus Alig, Stefan Günster, Detlev Ristau
Laser Zentrum Hannover e.V., Hollerithallee 8, 30419 Hannover, Germany
t.alig@lzh.de

Abstract: Energy levels of ion beam sputtered hafnia mixed with alumina or silica
were investigated by photoluminescence at 193 nm. The emission spectra originating from
interstitial defects and oxygen vacancies were correlated to residual optical properties.
OCIS codes: 310.6860, 310.3840, 300.6280

1. Introduction
High laser induced damage threshold and low absorption losses in the ultraviolet wavelength range lead to a wide
dissemination of hafnia in optical thin films. Nevertheless the application of conventionally sputtered hafnia is limited
by absorption and scattering losses in complex coatings of high thickness. Objective of this work is the identification
of responsible energy levels in hafnia to enable a further optimization of the high index material. For this purpose ion
beam sputtered hafnia single layers were modified by adding alumina or silica and characterized regarding refractive
indices, extinction coefficients, total scattering and photoluminescence from the ultraviolet to the infrared wavelength
range.
Compositions of oxide and fluoride layer materials enable customized settings of optical and mechanical properties
towards reduced absorption losses and higher resistance to laser irradiation. Applied in rugate filters and graded index
antirefection coatings material mixtures offer new design prospects for optical components. Stenzel et al. presented a
wide range of optical and mechanical properties of mixed oxide coatings prepared by magnetron sputtering, ion beam
sputtering, plasma ion assisted deposition and electron beam evaporation [1]. A study of luminescent defects in hafnia
thin films made with different deposition techniques was conducted by Ciapponi et al. [2].

2. Experimental details
Single layer mixtures of hafnia, alumina and silica of about 500 nm thickness were deposited on Quartz substrates
by ion beam sputtering [3]. The metallic targets were sputtered by a radio frequency pumped ion source in a reactive
oxygen atmosphere at pressure levels around 10−4 mbar. The production of material compounds in the deposition
system was realized by means of zone targets partially sputtered by argon ions.

Fig. 1. Photoluminescence setup for the investigation in energy levels of ion beam sputtered
HfO2 /Al2 O3 and HfO2 /SiO2 mixtures. The photoluminescence was excited under 45 ◦ by an ex-
cimer laser at 193 nm and analyzed perpendicular to the film surface in a fiber coupled spectrometer.
 ThC.4.pdf Optical Interference Coatings (OIC) 2016 © OSA 2016

Table 1. Optical properties of ion beam sputtered HfO2 /Al2 O3 and HfO2 /SiO2 mixtures for the
investigation in energy levels determined by spectrophotometer and Fast Total Scattering facility [4].
Composition n k Scattering Composition n k Scattering
1064 nm 355 nm 532 nm 1064 nm 355 nm 532 nm
[ 10−4 ] [ppm] [ 10−4 ] [ppm]
HfO2 1.97 54 132 HfO2 1.97 54 132
71% HfO2 / 29% Al2 O3 1.86 30 47 82% HfO2 / 18% SiO2 1.87 34 31
28% HfO2 / 72% Al2 O3 1.74 8 24 40% HfO2 / 60% SiO2 1.64 13 26
Al2 O3 1.64 7 47 SiO2 1.47 18 30

To characterize the single layer systems the refractive indices were determined from spectrometric measurements
(Perkin Elmer L900) in transmission and reflectance mode (see Table 1). The material compositions were calculated
by the Lorentz-Lorenz theory based on the refractive indices. Further investigations of the single layer systems show
a decrease of extinction coefficient and total scattering by adding alumina or silica.
The photoluminescence of the material mixtures was generated by an excimer laser and analyzed in a fiber coupled
spectrometer (HORIBA Scientific iHR320). The excitation of the thin films was conducted at 193 nm with a pulse
energy of approximately 3.5 mJ and a repetition rate of 200 Hz. The irradiation was performed in nitrogen atmosphere
at room temperature. The emission spectra were measured perpendicular to the film surface (see Fig. 1).

3. Results and discussion

Photoluminescence of the ion beam sputtered HfO2 /Al2 O3 and HfO2 /SiO2 mixtures was measured and extend from
the ultraviolet to the infrared wavelength range (see Fig. 2). The intensities were normalized to the highest peak to
compensate for the optical properties at 193 nm and alignment errors of the single layer systems. Measurement artifacts
at multiple of 193 nm were detected by the spectrophotometer and originate from the pump light scattered by the thin
films containing mainly hafnia.
The photoluminescence of hafnia is basically limited to the visible wavelength range showing two peaks in the range
of 445 and 530 nm. Toshihide et al. previously reported the appearance of the former peak at plasma enhanced chemical
vapor deposited hafnia and zirconia films [5]. Moreover calculations of Foster et al. attributed the corresponding energy
level to atomic and molecular interstitial defects and oxygen vacancies in monoclinic hafnia [6].
Photoluminescence [normalized]

Photoluminescence [normalized]

Hafnia Hafnia

71% Hafnia / 29% Alumina 82% Hafnia / 18% Silica

28% Hafnia / 72% Alumina 40% Hafnia / 60% Silica

Alumina Silica

250 500 750 1000 1250 250 500 750 1000 1250
Wavelegth [nm] 1 Wavelenth [nm] 1

Fig. 2. Normalized photoluminescence of ion beam sputtered HfO2 /Al2 O3 and HfO2 /SiO2 mixtures
for the investigation in energy levels. The photoluminescence was excited by an excimer laser and
analyzed in a fiber coupled spectrometer.
 ThC.4.pdf Optical Interference Coatings (OIC) 2016 © OSA 2016

Two peaks around 330 and 640 nm and a plateau from 400 to 500 nm characterizing the photoluminescence spectra
of silica. Fluorescence spectroscopy on Quartz by Leclerc et al. results in a similar red fluorescence band and was
associated with nonbridging oxygen hole centers [7]. The photoluminescence of alumina shows the highest peak
around 430 nm limited by two humps in the range of 350 and 600 nm. The luminescence spectra of the blended single
layer systems show features of both basic materials and can be described as a superposition.

4. Conclusion
Energy levels of ion beam sputtered hafnia layers containing alumina and silica were analyzed by photoluminescence
measurements generated with ultraviolet photons. Several emission bands obtained from hafnia and silica could be
brought into agreement with previous experiments and originate from interstitial defects and oxygen vacancies. The
transformation of photoluminescence spectra from hafnia to alumina or silica is accompanied by a decrease of absorp-
tion losses determined by spectrometric measurements in transmission and reflectance mode. To further associate the
emission bands of basic materials and compositions an investigation of thermal annealing effects is necessary.

5. Acknowledgments
The work was performed in the framework of the project “Cell-UV”. The project Cell-UV is carried out in the frame-
work of the European program “Eurostars”. The financial support of the German partners by the Federal Ministry of
Education and Research (EUROSTARS E! 7721 - CELL-UV) is gratefully acknowledged.

References
1. O. Stenzel, S. Wilbrandt, M. Schürmann, N. Kaiser, H. Ehlers, M. Mende, D. Ristau, S. Bruns, M. Vergöhl, M.
Stolze, M. Held, H. Niederwald, T. Koch, W. Riggers, P. Burdack, G. Mark, R. Schäfer, S. Mewes, M. Bischoff,
M. Arntzen, F. Eisenkrämer, M. Lappschies, S. Jakobs, S. Koch, B. Baumgarten, and A. Tünnermann, ”Mixed
oxide coatings for optics,” Appl. Opt. 50, C69-C74 (2011).
2. Alessandra Ciapponi, Frank R. Wagner, Stéphanie Palmier, Jean-Yves Natoli and Laurent Gallais, ”Study of
luminescent defects in hafnia thin films made with different deposition techniques,” Journal of Luminescence:
Elsevier, (2009, December).
3. Wei, David T., Harold R. Kaufman, and Cheng-Chung Lee. ”Ion beam sputtering.” Thin Films for Optical
Systems,](Flory, FR, ed.) (1995): 133.
4. Kadkhoda, P., et al. ”Fast total scattering facility for 2D inspection of optical and functional surfaces.” SPIE
Europe Optical Metrology. International Society for Optics and Photonics, 2009.
5. Ito, Toshihide, et al. ”Similarities in photoluminescence in hafnia and zirconia induced by ultraviolet photons.”
Journal of applied physics 97.5 (2005): 054104.
6. Foster, Adam S., et al. ”Vacancy and interstitial defects in hafnia.” Physical Review B 65.17 (2002): 174117.
7. Leclerc, N., et al. ”Transient absorption and fluorescence spectroscopy in fused silica induced by pulsed KrF
excimer laser irradiation.” Applied physics letters 59.26 (1991): 3369-3371.