Supporting Information for Formation of Al

Nanostructures on Alq3: An in Situ Grazing

Incidence Small Angle X-Ray Scattering Study
during RF Sputter Deposition
Shun Yu1,*, Gonzalo Santoro1, Kuhu Sarkar2, Benjamin Dicke1, Philipp Wessels3, Sebastian
Bommel1,4, Ralph Dhrmann1, Jan Perlich1, Marion Kuhlmann1, Ezzeldin Metwalli2, Johannes
F.H. Risch1, Matthias Schwartzkopf1, Markus Drescher3, Peter Mller-Buschbaum2, Stephan V.
Roth1,*
1 Deutsches Elektronen-Synchrotron (DESY), Notkestrae 85, D-22607 Hamburg, Germany
2 Lehrstuhl fr Funktionelle Materialien, Physik-Department, Technische Universitt Mnchen,
James-Franck-Str.1, D-85748 Garching, Germany
3 Institut fr Experimentalphysik, Universitt Hamburg, Luruper Chaussee 149, D-22761
Hamburg, Germany
4 Institut fr Physik, Humboldt-Universitt zu Berlin, Newtonstr. 15, D-12489 Berlin, Germany

To whom correspondence should be addressed: shun.yu@desy.de; stephan.roth@desy.de

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Experimental Methods
The experiments were carried out at the P03 MiNaXS beamline1 of the PETRA III storage
ring of DESY, Hamburg, Germany. The Alq3 film was prepared in a home-made Knudsen-type
organic deposition chamber. The thickness is about 205 nm, calibrated by X-ray reflectivity
(XRR). A home designed highly automated sputtering equipment (HASE) was used for the in situ
GISAXS measurement2. The deposition rate of Al is estimated to be 0.4 nm/min on the condition
of 150 W working power at Ar atmosphere of 1.4 10-2 mbar. In this work, the nominal Al
thickness (d) is converted by multiplying deposition time with this deposition rate. The incident
X-ray energy was 13 keV with the grazing incidence angle of 0.45. The sample to detector
distance (SDD) was 35181 mm. A Pilatus1M (DECTRIS Ltd., Switzerland) was used as
detector with an exposure time of 0.095 s in an exposure period of 0.1 s. If not mentioned
specifically, each detector image in this study is a summation of 10 experimental images,
corresponding to a total of 1 s exposure time. The entire sputtering process took about 41.5 min,
depositing a nominal Al thickness of 16.6 nm. The potential beam damage to the organic film
was fully considered and minimized by scanning the sample during deposition along the direction
horizontally perpendicular to the X-ray beam within a 5 mm region, repeatedly. The total
exposure time at every measured point is less than 4 s. As a result, no apparent beam damage is
observed either via optical microscope or by comparing the final scattering patterns between the
X-ray exposed and non-exposed regions.
Field emission scanning electron microscopy (FESEM, Zeiss Gemini NVision 40) images were
obtained with an accelerating voltage of 1 kV and at a low working distance (WD) of 1.3 mm.
The aperture size for all the measurements was kept at 7.5 m. The cross section FESEM image
was taken at the sample tilting of 60. All the FESEM images were processed using the software
ImageJ3.
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The software IsGISAXS was used to simulate the scattering patterns,4 using the refractive
indexes of Alq3 (chemical formula C27H18AlN3O3, density: tabulated values), Al and Si at 13
keV calculated via the website of the center for X-ray Optics.5 XRR fitting was done using
motofit software.6

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GISAXS data
Figure S1 shows an overview of vertical cuts (qz). Many small Kiessig fringe-like modulations
in the intensity can be observed, indicating a good roughness correlation between film and
substrate during the entire sputtering process.

Figure S 1 Vertical line cuts from the 2D GISAXS data (shifted along the intensity axis) for
selected sputtered Al thicknesses as indicated. The specular beam is blocked with a beam stop
(SBS).

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Figure S 2 Vertical line cuts from the 2D GISAXS data (shifted along the intensity axis) with
magnified Yoneda region. Red and blue mark the dominant intensity at different thicknesses. The
theoretical critical angle for Al and Alq3 are marked as vertical blue and red dashed lines.

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XRR
XRR is used to extract the thickness information. The thickness of the Alq3 film is 205 nm, of
the Al diffusion layer in Alq3 is 1.20.2 nm and of the Al+AlOx top layer is 14.20.2 nm.

Figure S 3 Top: X-ray reflectivity of oxidized sample (red points) shown together with its fit
(green line); Bottom: X-ray scattering length density (SLD) profile corresponding to this fit.

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Figure S 4 . Zoom-in of the XRR data. Number of the small modulation N = 12, with the total
difference qz = 0.037 -1. The Alq3 thin film is estimated via equation d = 2N/qz as 205 nm.

References:
(1)

Buffet, A.; Rothkirch, A.; Dhrmann, R.; Krstgens, V.; Abul Kashem, M. M.; Perlich, J.;
Herzog, G.; Schwartzkopf, M.; Gehrke, R.; Mller-Buschbaum, P.; et al. P03, the
Microfocus and Nanofocus X-Ray Scattering (Minaxs) Beamline of the PETRA III
Storage Ring: the Microfocus Endstation. J. Synch. Rad. 2012, 19, 64753.

(2)

Dhrmann, R.; Botta, S.; Buffet, A.; Santoro, G.; Schlage, K.; Schwartzkopf, M.; Bommel,
S.; Risch, J. F. H.; Mannweiler, R.; Brunner, S.; et al. A New Highly Automated Sputter
Equipment for in Situ Investigation of Deposition Processes with Synchrotron Radiation.
Rev. Sci. Instrum. 2013, 84, 043901043908.

(3)

Schneider, C. A.; Rasband, W. S.; Eliceiri, K. W. NIH Image to ImageJ: 25 Years of

Image Analysis. Nature Methods 2012, 9, 671675.

(4)

Lazzari, R. IsGISAXS: A Program for Grazing-Incidence Small-Angle X-Ray Scattering

Analysis of Supported Islands. J. Appl. Cryst. 2002, 35, 406421.

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(5)

Henke, B. L.; Gullikson, E. M.; Davis, J. C. X-Ray Interactions: Photoabsorption,

Scattering, Transmission, and Reflection at E = 50-30,000 eV, Z = 1-92. Atomic Data and
Nuclear Data Tables 1993, 54, 181342.

(6)

Nelson, A. Co-refinement of Multiple-Contrast Neutron/X-Ray Reflectivity Data Using

MOTOFIT. J. Appl. Cryst. 2006, 39, 273276.

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