38th International Conference of IMAPS-CPMT Poland

Rzeszw - Czarna, 21-24 September 2014

Composition analysis of epitaxial NbTiN films

for superconductor photon detectors
Sylwia Przywska 1, Marek Guziewicz 2, Marcin Juchniewicz 2, Renata Kruszka 2,
Edyta Piskorska-Hommel 3, Jarosaw Domagaa 4, Alexandru Marin5,
Petre Osiceanu5, Andriej Klimov2, Jan Bar2, Wojciech Sysz2 ,
1

Faculty of Physics, Warsaw University of Technology, ul. Koszykowa 75, 00-662 Warsaw, Poland;
2
Institute of Electron Technology, al. Lotnikow 32/46, 02-668 Warsaw, Poland;
3
Institute of Solid State Physics, University of Bremen, Otto-Hahn-Allee, 28359 Bremen,
4
Institute of Physics, PAS, al. Lotnikow 32/46, 02-668 Warsaw, Poland
5
Institute of Physical Chemistry, Spl. Independentei 202, Bucharest, Romania
Abstract:
We report the characterization of the ultrathin NbTiN films for SSPDs. The higher
quality of the ultrathin superconducting films in comparison to niobium nitride, as far as the
fabrication technology of single photon detectors is concerned, was demonstrated. The films
deposited on Al2O3 single crystals shown excellent both superconducting and structure properties.
New results based on XPS studies of NbTiN films reveal presence of some contaminations like
carbon and oxygen. The following XPS peaks were examined: Nb 3d, Ti 2p, O 1s, N 1s, C 1s and
Al 2p. Compounds of NbN, NbTiN and some Nb-oxides have been revealed. The NbTiN films
with thickness of 4 nm, grown on the Al2O3 and post-grown annealed at 1000oC in Ar, reach
critical temperature of 14K. Moreover, the films disclose the best superconducting properties extremely high critical current density of 12106 A/cm2.
Key words: Superconductor, NbN, XPS, single-photon detector

1.

INTRODUCTION

Superconducting single-photon detectors (SSPDs) are able to detect single optical photons, these have
relatively high quantum efficiency and low dark counts rate and low jitter. The detectors are expected
to play a leading role in such applications as optical quantum information processing, satellite
communications and medical diagnostics, especially as detectors of singlet oxygen luminescence in
photodynamic therapy. Construction of a detector includes 100 nm wide stripes patterned in an
ultrathin NbN or NbTiN film. They are biased on a subcritical current. The absorption of a photon
generates a hot spot that grows until a resistive region is formed across the nano-stripe, thus, produced
a detectable voltage pulse. The higher quality of ultrathin superconducting NbTiN films in comparison
to NbN films was demonstrated. High epitaxial quality of NbTiN films grown on the Al2O3 substrates
was proved by HRXRD in our previous work [1,2], but film composition was not cleared because of
problems regarding to composition study on so ultrathin films. New results for NbTiN and NbN films
that based on X-ray photoelectron spectroscopy (XPS) studies reveal presence of contaminations such
as carbon and oxygen.The quantitative composition analyses of NbTiN films as well as detection
parameters of SSPD made with the NbTiN film are here presented.

2.

TECHNOLOGY OF SUPERCONDUCTIONG FILMS

The NbTiN films were grown by high-temperature reactive radio-frequency magnetron sputtering
using 1000C system from the Surrey Nanosystems Ltd. The films were deposited from a 3-inch
diameter Nb and Ti targets at DC power of 220 W on Nb and of 80 W on Ti, respectively, in N2Ar
plasma at temperature of 850oC. Al2O3(0001) and Si(001) are used as substrates. The thicknesses of

38th International Conference of IMAPS-CPMT Poland

Rzeszw - Czarna, 21-24 September 2014

the studied layers was 4 nm. To improve superconducting properties of the films Rapid Thermal
Annealing (RTA) was conducted at 1000oC in Ar for 10 min [1].

3.

XPS STUDIES

3.1. Quantitative analysis of film composition

XPS investigations of NbTiN films deposited on Si and Al2O3 were performed on samples assigned
NbTiN 11Si and NbTiN 11sh, respectively. The XPS spectra were recorded by means PHI Quantera
SXM which is the state of the art Scanning XPS Microprobe equipment in Bucharest. The studied
films were cleaned in-situ by sputtering using Ar+ at 500 eV. Analysis of XPS spectra concerns
following peaks: Nb 3d, Ti 2p, O 1s, N 1s, C 1s and Al 2p or Si 2p. The XPS quantification is
performed by assigning quantification regions, subtracting the background from each region. We used
two methods of background subtracting: Spline Shirley (used for titanium peaks), which requires
setting up several nodes, necessary for the Shirley algorithm, and Shirley (used for other component
peaks). Percentage atomic concentration parameter is computed from the raw peak area divided by the
Relative Sensitivity Factor (RSF), which is extracted from the given library for every peak identified
by a region. The atomic concentration Xi is computed using the formula:

X i = 100

Ai

(1)

i=1 Ai

where Ai (i = 1, 2, ) are the adjusted intensities, which are determined from the measured intensity Ii,
the transmission function Ti evaluated for electrons of recorded energy E, the relative sensitivity factor
Ri for the transition i and the escape depth compensation exponent n. The adjusted intensities are
defined by eq. 2 as follows:

Ai = 100

Ii
T (E )E n Ri

(2).

Multiplying Xi by the atomic mass of the components and normalising to 100% we can get mass %
concentration. For quantitative analysis of Nb 3d and Ti 2p peaks we used the procedure given in
papers [3, 4]. The intensity ratio of doublets 2p3/2 and 2p1/2 peaks are constrained to be at a ratio of
2:1, the intensity ratio of 3d3/2 and 3d5/2 doublets are constrained to be at a ratio of 2:3. FWHM of
the peaks in doublets are forced to be alike, except for the Ti doublets in TiO2,because of CosterKroning effect, where FWHM of the 2p1/2 peak is broader than FWHM of the 2p3/2 peak.
The values of binding energy applied in our study are the average Binding Energy (BE) data from the
NIST XPS database, or the values taken from the paper [3]. The binding energies, which are used in
this work are shown in the table 1. The doublet splitting was constrained as we used the available
literature data.
Tab. 1. Binding energies E(eV) of Nb and Ti components [3] applied in our XPS spectra simulations.
Peak

NbN

Nb2O5

NbN(1-x)O(x)

NbNO/NbCO Nb2N(2-y)O(3-y)

TiO

TiN

Ti2O3

TiO2

3d5/2

203.7

207.5

204.8

205.9

206.9

3d3/2

206.5

209.9

206.8

208.8

209.5

2p1/2

460.9

461.8

462.3

464.3

3.2. Composition of NbTiN films

Samples NbTiN11sh and NbTiN11Si were taken under the investigation. Based on full XPS spectrum
and using the formula (1) we computed atomic % concentrations for the samples and included in
Tab.2. The concentrations of components change slowly with the sputtering time. As expected the
concentration of carbon suddenly decreases after the first sputtering step, then the falling trend
maintains slowly. Concentration of oxygen is gradually decreasing with the etching time, while Al
2

38th International Conference of IMAPS-CPMT Poland

Rzeszw - Czarna, 21-24 September 2014

concentration increases slowly with the time, so we can suppose that oxygen is bonded with metals,
more intensely on surface, while the Al signal relates to the sapphire substrate. Analyzing the Nb3d
peak shown in Fig.1a., there are visible doublets 3d5/2, and 3d3/2 of the following components: NbN,
Nb2O5, NbN1-xOx, Nb2N2-yO3-y, and NbNO with NbCO (which are not bonded together, but differences
in their binding energy are too small to subtract their spectra). In the Ti2p peak there are visible
doublets 2p3/2, and 2p1/2 which can be assigned to the following components: TiO, TiN, Ti2O3 and
TiO2. The relative ratio of the noted components changes with the sputtering time. The obtained data
for distribution of mass conc. of Nb and Ti compounds is presented in Tab. 3.
Tab. 2. At.% composition of the NbTiN11sh film before and after sputtering etching of the surface.
Sputtering time

Nb

Ti

Al

25.0

1.8

20.9

17.2

33.2

1.9

0.1 min

39.1

2.0

21.5

26.4

8.5

2.4

0.3 min

43.7

2.4

17.2

28.6

5.1

2.8

0.5 min

45.5

3.0

14.0

30.00

3.3

3.9

a)

b)
30
35
25

Counts x102

Counts x103

30
25
20
15

20
15
10

10
5
5
0

0
216

212

208

204

200

468

464

Binding energy [eV]

460

452

456

Binding energy [eV]

Fig. 1. An example of Nb3d (a) and Ti2p (b) peaks from XPS spectra measured on the NbTiN 11sh sample asdeposited on sapphire substrate.

Tab. 3. Distribution of mass % concentration of compounds identified in the NbTiN 11sh film as-dep.
Sputtering
time

NbN Nb2O5

As rec

21.7

15.5

34.6

10.0

18.1

17.5

0,2 min

27.9

20.4

43.5

8.2

16.6

30.1

30.5

22.8

0,5 min

33.1

17.3

47.1

2.5

7.2

29.6

28.9

34.3

NbN(1-x)Ox

NbNO/NbCO

Nb2N(2-y) O(3-y)

TiO

TiN

Ti2O

TiO2

11.8

41.9

28.8

Although, as expected, the NbN atomic concentration level is very high, our data shows that there is
substantial amount of NbN(1-x)Ox. The concentration levels of NbN as well as NbN(1-x)Ox is increasing
with the sputtering time. The concentration of Nb2O5 is mostly visible at the surface of the sample,
then its level decreases with the time. The NbNO/NbCO concentration ratio, which indicates the level
of contamination of our sample, is decreasing with the sputtering time. Undoubtedly, Nb2N (2-y)O(3-y) is
present only on the surface of the sample. The titanium components on the surface are mostly oxides,
but the TiN mass concentration increases with the sputtering time. In the case of NbTiN film annealed
at 1000oC (NTN11shW) we calculated based on XPS measurements similar at. % concentration of Nb
and Ti, but oxygen contamination is strongly present on the top. Moreover, N at. % concentration on
the film surface is strongly reduced and in turn, it is increased to the level in the original NbTiN film

38th International Conference of IMAPS-CPMT Poland

Rzeszw - Czarna, 21-24 September 2014

after surface cleaning by the Ar+ etching for 2 min. Above results confirm presence of oxidized
surface on both the as-dep. - and annealed NbTiN film, and show differences in at.% concentrations.

4.

PHOTODETECTOR QUANTUM EFFICIENCY CHARACTERIZATION

The system quantum efficiency (SQE) of the fabricated SSPD, based on the NbTiN film deposited on
the sapphire substrate with post annealing , was estimated. For this, the dependence of the detector
photon count rate on laser pulse intensity was measured. The SQE was determined as a ratio of the
detector count rate to the number of photons, emitted by the laser within a linear part of observed
dependence. The laser was operated at 10 MHz repetition rate. Linear dependence indicates that
detector is in single photon absorption regime (Fig.3a). A plateau region indicates the background
noise level which is due to so-called dark counts. The measurement of critical temperature TC, relied
on measuring of the detector resistance as function of temperature. Fig. 3b shows the such
dependence of the normalized resistance where TC =14K was registered. Measurements of current
density on similar NbTiN film disclosed extremely high critical current density of 12106 A/cm2
which is the best value, up to now, known for superconducting films.
a)

b)

Fig. 3. Photon count rate dependence on the laser intensity measured on the SSPD manufactured with the NbTiN
film (a); measurement of critical temperature for the NbTiN film (NTN11shW after RTA) (b).

5. CONCLUSIONS
Quantitative analysis of atomic concentrations on 4 nm thick NbTiN film was performed by XPS
investigations. The film includes 3 at.% conc. of Ti. A deficiency of N concentration is observed in the
film because of some oxides formed on the surface. Concentration levels of Nb-, Ti nitrides as well as
contaminants like TiOx, NbN(1-x)Ox, and Nb-oxides were evaluated. TbTiN films deposited on Al2O3
and RTA annealed are the superior material for SSPD, as confirmed by measurements of SSPD SQE.
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