Graded-index films using aluminium oxynitrides

Francis Placido, Joim Russell* and Zhenhui Gou

University ofPaisley, Physics Department, High St, Paisley PAl 2BE, Scotland
*now at DRA, Malvern, Malvem WR14 3P5, Worcestershire, England

ABSTRACT

High quality coatings of aluminium oxynitrides have been deposited by reactive RF sputtering of aluminium
in argon/oxygen/nitrogen atmospheres. Graded-index films in which the refractive index changes
continuously with thickness over the range 1 .6 - 2.0 have been produced by varying the oxygen and nitrogen
content ofthe growing film. Computer control ofthe gas flow rates has allowed the reproducible production
oflaser rejection filters having optical densities greater than 4 and rejection wavelengths which can be chosen
from < 300 to > 1 100 nm. Scanning electron microscopy has shown that films when broken, tend to fracture
preferentially at one particular composition. Depth profiling chemical analysis of the films has been carried
out using X-ray photoelectron spectroscopy (XPS), showing clearly that the desired sinusoidal composition
variations with depth (rugate) has been achieved in these films.
Keywords: RE sputtering, graded-index, oxynitrides, rugate, laser rejection, XPS.

1. INTRODUCTION

Inhomogeneous films in which the refractive index varies with thickness have been a subject of great interest
for a number ofyears. There have however been many more papers dealing with theory''° than experimental
realisations ofsuch fi1ms1114. The obvious advantages to be gained by the optical filter designer if materials
with suitable properties can be found and produced without too much difficulty are a strong incentive to
continue the search. The ideal material would be one whose refractive index could be varied continuously
over a large range although the so-called "digital" technique in which a high-low pair is used to approximate
a continuous index range has been used with success. Previous attempts to produce continuously variable
films have used RF power variation to vary the stoichiometry/density of the growing film13, ion-assisted
deposition (J\J)11 and plasma enhanced chemical vapour deposition (PECVD)14. Of these, PECVD would
seem to produce the best quality films.

The present paper concentrates on the growth of aluminium oxynitride films where the composition is varied
continuously from A12O3 to A1N through intermediate compositions A1ON . This material has a number of
highly desirable properties being hard, wear-resistant, adhering strongly to a variety of substrates, transparent
to around 9 microns with low absorption, resistant to chemical attack (when fully dense) and offering a
potential refractive index range of 1 .7 (A1203 bulk) to 2.2 (A1N bulk) . A1N has been grown by PECVD with
rather exotic precursors15 but there appear to be no reports ofgrowth ofthe oxynitrides by PECVD. The oxide
and nitride of aluminium have been grown by reactive RF sputtering and although the oxide is easier to form
than the nitride, there seems to be no reason why the oxynitrides should not be successfully grown by this
method. For such a promising material as aluminium oxynitride there seems to be little reported work since
the TAD work of Hwangbo et al11. We present here results of room temperature deposition of aluminium
oxynitrides with a refractive index range of 1.6 to 1.98 by reactive RF sputtering of aluminium in

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 argonloxygenlnifrogen atmospheres. This technique has been used to produce high quality rugate filters, in
which the refractive index is varied sinusoidally with thickness, and the results are compared with theoretical
predictions.

2. EXPERIMENTAL DETAILS

The present work uses a rather standard experimental setup consisting of a cryo-pumped vacuum chamber
(CVC1O4) with water cooled stainless steel walls, 1kW RF power supply, 8" circular magnetron, 99.999%
aluminium target, electronic grade Ar, 02, N2 (BOC), 0 —f 10 sccm and 0 — 100 sccm mass flow controllers
(Tylan), turbo-pumped RGA (Leda-Mass) and in-house software varying and monitoring the mass flow
controllers. We have not found it necessary to have any form of feedback control and the mass flow
controllers run in a completely open-loop fashion. This works very reliably and reproducibly for single-line
rugates, although it may prove necessary to have some feedback control for more complicated filters. There
is no deliberate heating ofthe substrates during deposition and the chamber temperature seldom rises above
60° C during extended runs. We have predominantly used glass microscope slides as substrates but have also
used fused silica, silicon and polycarbonate with success.

3. ALUMINIUM OXYNITRIDE FILMS

Strongly adherent films have been produced with 800 W RF power, 3mtorr chamber pressure and Ar flow
rates of 80 sccm and 02/N2 flow rates in the range of 0 > 9 seem. The oxygen and nitrogen flows are varied
sinusoidally in antiphase. Measurements of the refractive index of homogeneous films on glass have been
successfully made using mode coupling by frustrated total internal reflection (Metricon). These
measurements show that transparent films with refractive indices in the range of 1 .58 to 1 .99 can be made
with the above parameters. At target-substrate distance ofaround 4", deposition rates of 100 — 400 nm/hour
were obtained, with the higher deposition rates being obtained at low oxygen flow rates. At high nitrogen/low
oxygen (N2 > 9 sccm, Q < 0.5 sccm) the films had a pale yellow tinge and XRD measurements showed
diffraction peaks ofAlN, indicating that such films are at least partially crystalline. Films with 02 flow rates
larger than 0.5 sccm showed no diffraction peaks and appeared to be amorphous.

4. RUGATE FILTERS

Rugate filters, in which the refractive index varies sinusoidally with film thickness, have received much
attention in the literature1114. The spectral response is that of a rejection filter, having high transmission
everywhere except a narrow region centred on wavelength, ?. Southwell4 has shown that a refractive index
variation given by

n(z) = mean
+ sin( rnea + d) (1)

where 11niean is the average refractive index, orange is the refractive index range and the geometrical
thickness of one sinusoidal cycle, t0, is

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 t0 = o (2)
2nmean

leads to a rejection filter centred on and with a bandwidth of

L= range (3)
mean

Such filters have applications in laser goggles for protection of humans and laser rejection filters for
instruments, as general purpose laser mirrors, and in head-up displays. Ifthe side bands can be controlled then
they may also compete with holographic filters in the new generations of compact Raman spectrometers.
Equn. 2 shows that the centre wavelength is varied by changing the physical thickness of one cycle and Equn
3 shows that the bandwidth can be varied by changing the refractive index range of the sinusoid. In addition
the optical density at ? is dependent on the number of cycles deposited. The phase factor in Equn. (1) is
important in determining the magnitudes and positions of the sidebands which are observed with this type
of filter'4. Figure 1 shows how the transmission at ? varies with the number of cycles deposited for the
following parameters, which are in a range appropriate to our aluminium oxynitride films.

nmean I nrange (nm) to (nm)

1.78 0.36 392 110

The calculations for Figure 1 have been performed for a coating on a finite thickness glass substrate
immersed in air; the phase ofthe sine wave is = 0. It can be seen that optical densities of4 (which
seems to be a benchmark figure) can be obtained for the above film parameters with 35 deposited cycles,
corresponding to a film thickness of 3 .85 i.

Figure 2 shows the experimental realisation (full line) of such a filter on glass. After measurement of the
transmission the films are broken and the thickness measured on a Hitachi 541 00 field emission scanning
electron microscope (SEM). The microscope magnification for the particular operating conditions is
calibrated against polystyrene spheres. The dotted line in Fig. 2 is a calculated spectrum, using the
measured cycle thickness and the measured to calculate nean from Equn. 2 and adjusting '1range for a
good fit to the spectral width. The calculation takes into account the glass absorption, but assumes the
oxynitride films to be dispersion free. The fit to the side lobes is very sensitive to the assumed starting
phase of the sine wave as mentioned earlier but is also sensitive to the end layer at the film-air boundary
(the end phase of the sine wave in a sense). The spectrum in Fig. 2 has 35.4 cycles and has been
adjusted for a good fit to the sidelobes.

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 We have made similar filters with ranging from 300 to 1 100 nm and with up to 70 deposited cycles. The
centre wavelength is predictable and reproducible when the deposition parameters (target-substrate distance,
RF power, gas flow rates, chamber pressure) are unchanged, being dependent only on the deposition time for
one cycle.The visual quality ofthe deposited films is generally very good but sometimes there are obvious
particles in the film which act as scatterers. These are readily observed by SEM in cross-sections ofthe films
and seem to be entirely related to the initial cleanliness of the substrates. This and other features of the film
cross-sections are discussed in more detail in the following section.

5. SCANNING ELECTRON MICROSCOPE OBSERVATIONS

The films are broken after scoring the glass side with a diamond and cross sections are examined at 2 -7 KeV
on the Hitachi 54100 as mentioned earlier. This simple procedure leads to much better images than mounting
and polishing the cross sections. An oblique angle view of a cross-section on glass is shown in Figure 3.
Colunmar growth is seen but the remarkable feature is the "Giant Causeway" appearance due to preferential
cracking of the film. Figure 4 shows even more clearly that the film has cracked at the same point in each
cycle and the 50 cycles which were deposited can be easily counted (the lowest layer is glass). This is
invariably seen at some point in films broken in this way and is a very convenient feature since it makes it
easy to count and measure the thickness and uniformity ofthe deposited cycles. Since such features are not
observed in polished cross-sections we believe that they are caused by the breaking of the glass and propose
that the regular occurrence is due to the crystalline nature of the films at high nitrogen content, producing
larger stresses at this point in each cycle.

Particulate contamination ofthe films can be seen in the film cross-section of Figure 5.The conical shaped
particle to the right is typical of the contamination seen in these films. The conical particles appear to be
aluminium oxynitride, showing the same growth features as the films themselves, but seem to originate at
some defect or speck of dirt on the substrate. Certainly the number of such defects observed is related to the
care taken in cleaning the substrates. The top of another conical particle can be seen to the left of centre in
Fig. 5 along with some fracturing ofthe film in its neighbourhood. This is seen to better effect in the oblique
view of another film in Fig. 6. In this case a particle has been completely torn out of the film apparently
taking some layers with it and leaving an amphitheatre ofterraced cycles behind.

6. X-RAY PHOTOELECTRON SPECTROSCOPY

It is very difficult to be sure that these films are truly varying continuously in composition and hence
refractive index since alternating layers ofAl2O3 and A1N with thicknesses close to quarter waves can show
similar optical performance. We have used X-ray Photoelectron Spectroscopy16 (XPS) to measure the
aluminium, oxygen and nitrogen variation with depth (so far in only one film). The results of these
measurements are very encouraging, showing that the oxygen 1 s and nitrogen is peaks vary sinusoidally and
in antiphase with depth from the surface. The aluminium 2p peak on the other hand is of constant height but
varies in energy with depth. This is consistent with the composition ofthe film varying continuously from
aluminium oxide to aluminium nitride. The observed Al 2p chemical shift varies by around 2.9 eV which is
remarkably similar to the variation found by Hwangbo et who made a range ofhomogeneous aluminium
oxynitride films with different compositions. Since the aluminium peak is a single peak varying in position
rather than two peaks with varying heights we share the conclusion of Hwangbo et al11 that aluminium
oxynitrides are continuously variable compounds rather than a mixture of phases of A12O3 and A1N.

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 7. CONCLUSIONS

We have demonstrated that reactive RF sputtering of aluminium in argonlogygen/nitrogen mixtures can

produce thin films with a range ofrefractive index which is close to the range expected from the bulk indices.
Furthermore the composition of these films can be varied continuously during deposition by varying the
oxygen/nitrogen flow rates. Coupled with the excellent optical properties, hardness and adherence of these
films, aluminium oxynitride would appear to be an ideal candidate for graded-index filters and the multitude
of applications arising from this type of material.

8. REFERENCES

1.R. Jacobsson, "Optical properties of a class of inhomogeneous thin films," Optica Acta, i, 3 09-323,
(1963).
2. E. Delano, "Fourier synthesis ofmultilayer filters," J. Opt. Soc. Am. 7, 1529-1533, (1967).
3 . J. A. Dobrowolski and D. Lowe. "Optical thin film synthesis program based on the use of Fourier
transforms," App!. Opt. U, 3039-3050, (1978).
4. W. H. Southwell, "Spectral response calculations ofrugate filters using coupled-wave theory," J. Opt. Soc.
Am. A., 1558-1564, (1988).
5. B. G. Bovard, "Derivation ofa matrix describing a rugate dielectric thin film," Appi. Opt. 2, 1998-2005,

(1988).
6. R. R. Willey, "Rugate broadband antireflection coating design," SPIE 1 168-26, San Diego, (1989).
7. P. G. Verly, J. A. Dobrowolski, W. J. Wild, and R. L. Burton, "Synthesis ofhigh rejection filters with the
Fourier transform method," App!. Opt. 2, 2864-2867, (1989).
8. R. R. Willey, "Basic nature and properties ofinhomogeneous antireflection coatings," in In homogeneous
and Quasi-inhomogeneous Optical Coatings, Jerzy A. Dobrowolski, Pierre G. Verly, Editors, Proc SPIE
2046, 69-77, (1993).
9. A. K. Tikhonravov, "Mathematical aspects of the synthesis of inhomogeneous coatings," in
Inhomogeneous and Quasi-inhomogeneous Optical Coatings, Jerzy A. Dobrowolski, Pierre G. Verly, Editors,
Proc SPIE 2046, 18-29, (1993).
1 0. J. A. Dobrowolski and A. V. Tikhonravov, "Series of optimal and near-optimal solutions to an
antireflection problem", in Inhomogeneous and Quasi-inhomogeneous Optical Coatings, Jerzy A.
Dobrowoiski, Pierre G. Verly, Editors, Proc SPIE 2.Q4, 62-68, (1993).
1 1 . C. K. Hwangbo, L. J. Lingg, J. P. Lehan, H. A. Macleod and F. Suits, "Reactive ion assisted deposition

ofaluminium oxynitride thin films," Appi Opt. Z, 2779-2784, (1989)

12. M. F. Ouellette, R. V. Lang, K. L. Yan, R. W. Bertram and R. S. Owles, "Experimental studies of
inhomogeneous coatings for optical applications", J. Vac. Sci. Technol. A9, 1188-1192, (1991).
13. A. F. Jankowski, L. R. Schrawyer and P. L. Peny, "Reactive sputtering ofmolybdenum-oxide gradient-
index filters," J. Vac. Sci. Technol. A9, 1 184-1 187, (1991).
14. S. Lim, J. H. Ryu, J.F. Wager and T. K. Plant, "Rugate filters grown by plasma-enhanced chemical vapour
deposition," Thin Solid Films, 245, 141-145, (1993).
15. J. N. Kidder, J. S. Kuo, A. Ludviksson, T. P. Pearsall, J. W. Rogers, J. M. Grant, L. R. Allen and S. T.
Hsu, "Deposition of A1N at lower temperatures by atmospheric metalorganic chemical vapour deposition
using dimethylethylamine alane and ammonia," J. Vac. Sci. Technol. fl 711-715, (1995).
16. Experimental techniques centre (ETC), Brunel University, Uxbridge, Middlesex UB8 3PH, England.

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 Cycle thickness t0=iio nm
Centre wavelength 0 = 391.6 mn
Average refractive index n an 1.78 Incident medium nO =1
Range of refractive index n range 0.36 Substrate sn = 1.5
Phase shift of sine wave =0 Exit Medium nO = 1

5.5

4.5

z 3.5

2.5

C
2

I .5

0.5

0
0 5 10 15 20 25 30 35 40

NUMBER OF CYCLES

Fig 1; Optical density vs Number of cycles deposited for a sine-wave rugate.

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 No of cycles
Centre wavelength
Cycle thickness
Filter thickness
Phase of sme wave
110.60

= 5.03
Average refractive index mean = 1.78
ncycles = 35.40

tfi3.9O 10 nm

Range of refractive index range = 0.38

3
= 393.74
nm
nm
1.8

1.6

1.4
0
i/i 50
Geometric Thickns

Incident medium nO = 1.00

Substrate Sn = 1.51
100

Exit Medium nO = 1.00

zC

300 320 340 360 380 400 420 440 460 480 500

WAVELENGTH

Fig 2; Transmission of an experimental rugate on glass with calculated spectrum

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 Fig 3; Oblique view of film on glass

Fig 4; Film on glass. Cross-section showing 50 cycles

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 Fig 5; Particulate contamination in film

Fig 6; Hole where particle has been removed and terraces

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 Counts

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