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Synthesis and x-ray characterization of sputtered bi-alkali antimonide

photocathodes

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Synthesis and x-ray characterization
of sputtered bi-alkali antimonide
photocathodes
Cite as: APL Mater. 5, 116104 (2017); https://doi.org/10.1063/1.5010950
Submitted: 02 February 2017 . Accepted: 20 October 2017 . Published Online: 10 November 2017

M. Gaowei , Z. Ding, S. Schubert, H. B. Bhandari, J. Sinsheimer, J. Kuehn, V. V. Nagarkar, M. S. J.

Marshall, J. Walsh, E. M. Muller, K. Attenkofer , H. J. Frisch , H. Padmore, and J. Smedley

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© 2017 Author(s).
 APL MATERIALS 5, 116104 (2017)

Synthesis and x-ray characterization of sputtered

bi-alkali antimonide photocathodes
M. Gaowei,1,a Z. Ding,2 S. Schubert,3 H. B. Bhandari,4 J. Sinsheimer,2
J. Kuehn,5 V. V. Nagarkar,4 M. S. J. Marshall,4 J. Walsh,1 E. M. Muller,2
K. Attenkofer,1 H. J. Frisch,6 H. Padmore,3 and J. Smedley1
1 Brookhaven National Laboratory, Upton, New York 11973, USA
2 StonyBrook University, Stony Brook, New York 11794, USA
3 Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
4 Radiation Monitoring Devices, Watertown, Massachusetts 02472, USA
5 Helmholtz-Zentrum Berlin, Berlin 12489, Germany
6 University of Chicago, Chicago, Illinois 60637, USA

(Received 2 February 2017; accepted 20 October 2017; published online 10 November 2017)

Advanced photoinjectors, which are critical to many next generation accelerators,

open the door to new ways of material probing, both as injectors for free electron
lasers and for ultra-fast electron diffraction. For these applications, the nonunifor-
mity of the electric field near the cathode caused by surface roughness can be the
dominant source of beam emittance. Therefore, improving the photocathode rough-
ness while maintaining quantum efficiency is essential to the improvement of beam
brightness. In this paper, we report the demonstration of a bi-alkali antimonide pho-
tocathode with an order of magnitude improved roughness by sputter deposition
from a K2 CsSb sputter target, using in situ and operando X-ray characterizations.
We found that a surface roughness of 0.5 nm for a sputtered photocathode with a
final thickness of 42 nm can be achieved while still yielding a quantum efficiency
of 3.3% at 530 nm wavelength. © 2017 Author(s). All article content, except where
otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/1.5010950

Alkali antimonide photocathodes have been the standard option for low visible light photodetec-
tors and image intensifiers for decades. These materials are relatively easy to grow and more resistant
against contamination than other options (e.g., Cs:GaAs).1–4 Recently they have been investigated
for use as high-current, low emittance electron sources for next generation accelerator applications
such as Linac Coherent Light Source II (LCLS-II).5 These applications require high quantum effi-
ciency (QE) and long operational lifetime, just as photodetectors do, but also require good correlation
of the emitted electrons (e.g., low beam emittance). Unfortunately, while traditional growth meth-
ods produce cathodes with a peak quantum efficiency in excess of 30%, these films are very rough
and this roughness impacts the beam emittance.6–8 In this paper, we present results from a bi-alkali
antimonide photocathode with an order of magnitude improved surface roughness by sputter depo-
sition from a pre-fabricated K2 CsSb sputter target. A roughness of 0.5 nm for the sputtered cathode
has been achieved while yielding sufficient quantum efficiency (QE) (peak QE over 20% at 220
nm and green QE over 3% at 530 nm). The method is controllable and reproducible in film stoi-
chiometry, and the sputter target used for this experiment yields over 25 cathodes without depletion.
Film quality is monitored by in situ and operando X-ray techniques including X-ray fluorescence
spectroscopy (XRF), X-ray diffraction (XRD), and X-ray reflectivity (XRR). Detailed post-analysis
from these techniques along with the resulting spectral response is also reported. This advancement
provides future opportunity for significantly lower emittance photocathodes with equally improved
brightness.

a Electronic mail: mgaowei@bnl.gov

2166-532X/2017/5(11)/116104/7 5, 116104-1 © Author(s) 2017

116104-2 Gaowei et al. APL Mater. 5, 116104 (2017)

The central enabling advancement is the fabrication of a stoichiometrically controlled alkali

antimonide sputter target from which the photocathode was grown. The alkali antimonide sputter
target was fabricated at Radiation Monitoring Devices (RMD), Inc. The K2 CsSb compound weigh-
ing 10 g was chemically synthesized from the elemental raw materials of cesium, potassium, and
antimony. The as-prepared alkali antimonide was sintered into a sputter target format measuring
∼48 mm (1.9 in.) in diameter and ∼2 mm in thickness, as shown in Fig. 1(a). The target was bonded to
a metal backing plate using Nanofoil® (http://www.indium.com/nanofoil/) and subsequently loaded
into a Meivac RF sputter gun apparatus located in a self-contained vacuum system with an ion pump
and a gate valve to isolate it from the glove box where the target was synthesized. It is important
to note that the target was prepared in an inert environment and was loaded into the sputter gun
without exposure to ambient moisture or oxygen. The RF sputter gun with the target was shipped
in 10 9 Torr vacuum to the beamline, where it was attached to the operando photocathode growth
chamber. The X-ray powder diffraction studies performed on the synthesized compound show the
K2 CsSb crystalline cubic phase, as confirmed by ICDD PDF#03-065-4162 in the Joint Committee on
Powder Diffraction Standards (JCPDS) and NIST Crystal database. These data have been previously
reported.9
The cathode growth was carried out in a UHV deposition chamber with the K2 CsSb sputter
gun attached. The sputter growth was performed in a noble gas environment (Ar or Ne) with a
partial pressure of 20–30 mTorr. The gas passes through an inert gas purifier to reach 10 10 Torr
partial pressure for water and oxygen. The sputter target was mounted approximately 45◦ below
the sample rotation plane, and when in position, the distance between the target and the substrate
was 13 cm. All films were grown using a RF power of 10 W–20 W in order to reach 0.1–0.2 Å/s
growth rate for K2 CsSb for better operando observation and characterization of the growth process.
The target was cleaned by sacrificial sputtering for ∼1 h prior to the film growth in order to remove
possible degraded surface layer resulting from the transport and installation. Post-cesiation was done
by thermal evaporation using cesium getter sources manufactured by SAES. The Cs sources were
mounted on a manipulator that could bring the sources perpendicular to the sample normal and
∼6.5 cm from the sample surface. The position of the sputter gun and the Cs sources is illustrated in
Fig. 1(c).
The in situ film growth and real-time characterization were carried out at beamline G3 of
the CHESS light-source facility at Cornell University. The incident X-ray beam was 11.3 keV
(λ = 1.097 Å) with a photon flux of approximately 1014 photons/s which is a relatively high flux
enabling fast diffraction scanning and improved signal from off-axis XRR features. The experiments
are performed with a beam 0.5 mm wide and 0.75 mm high. The XRR and XRD measurements were
carried out using a 4-axis diffractometer with two Pilatus 100 K X-ray cameras mounted downstream
for image collection [labeled cam 1 and cam 2 in Fig. 1(c)]. XRR measurements were performed

FIG. 1. (a) The K2 CsSb sputter target measuring 1.9 in. (∼48 mm) in diameter and ∼2 mm thick, bonded to a backing plate.
The target was fabricated at RMD, Inc. (b) K2 CsSb sputter target during deposition. (c) Schematic diagram of the in situ and
operando X-ray characterization setup.
116104-3 Gaowei et al. APL Mater. 5, 116104 (2017)

by scanning the 2θ angle from 0◦ to 6◦ , and XRD measurements were performed by scanning the2θ
range from 5◦ to 30◦ . During growth, the X-ray beam was kept at a grazing incident angle of 1.4◦ from
the sample surface. Cam 1 was positioned so that the center of the camera was 2.5◦ with respect to the
incident beam in the sample rotation plane and 100 cm away from the sample. Cam 2 was positioned
approximately 25 cm from the sample and 45◦ above the sample rotation plane. An XRF signal was
collected by a vortex multi-cathode X-ray detector [labeled cam 3 in Fig. 1(c)] mounted 45◦ with
respect to the sample surface normal and approximately 25 cm away from the sample to measure the
stoichiometry during growth. A laser with a wavelength of 532 nm was positioned approximately
25 cm from the cathode surface; the diameter of the laser spot on the surface was about 1 mm with
an angle of incidence of 45◦ . The photocurrent was measured with a Keithley 6517B electrometer.
Deposition rates were recorded using an INFICON front load quartz crystal film thickness monitor
(QCM).
Substrates used for this experiment were Si(100) wafers cut to 1 cm × 2 cm rectangles. Substrates
were ultrasonically cleaned in acetone and isopropanol, followed by hydrofluoric acid (48%) dipping
to remove the oxidized layer. Substrates were transferred into the chamber through a vacuum loadlock,
heated to 600 ◦ C for 3 h to remove possible surface contamination, and then cooled down to 90 ◦ C for
film growth. Chamber base pressure was 1.5 × 10 10 Torr with the major component being N2 /CO
(>50%). The partial pressure of both water and oxygen was lower than 10% of the base pressure.
During substrate heating, the partial pressure of water rose temporally to 10 9 Torr and the total
pressure of the chamber was ∼5 × 10 9 Torr. XRF, XRR, and XRD scans were performed to confirm
that the substrate is pristine before growth. A target film thickness of 25 nm of K2 CsSb was sputtered
onto the substrates, and samples were further cooled down to 70 ◦ C, followed by Cs deposition in
order to maximize the photocurrent at 532 nm. After each growth step, an XRF spectrum was taken
to record stoichiometry and θ-2θ scans were taken to determine the crystal structure and texture, film
thickness, and roughness. Spectral response was measured for each sample using an optical system
which consisted of a Laser Driven Light Source (LDLS) and a Cornerstone monochromator. With
this setup, we were able to measure the QE over an incident wavelength ranging from 220 nm to
700 nm (1.77 eV–5.63 eV).
Figure 2(a) shows the XRF spectrum of a cathode grown on a Si(100) substrate. The red
curve represents the cathode immediately after sputtering in Ne and the dark curve is the final
cathode spectrum after Cs deposition, indicating the relative composition of K, Sb, and Cs. The
XRF spectra were analyzed using the software package PyMCA,10 where the mass concentration
for selected elements was calculated from fitting the experimental curve and then normalized to
the atomic fractions for K, Sb, and Cs. Elemental mass concentrations for both films are shown
in the inset table in Fig. 2(a). From the XRF analysis, we found that the sputter films were rich
in Sb and deficient in alkalis compared to the desired K2 CsSb stoichiometry. Such deviation from
the stoichiometric ratios can be explained by the combination of non-stoichiometric distribution
within the target and different sputter yields for the K, Cs, and Sb elements for current sputter
parameters.11 An excess of Cs in the stoichiometry was observed for the finished cathode com-
pared to the ideal ratio of K:Cs:Sb = 2:1:1, with the final composition being K0.84 Cs1.75 Sb. It
has been reported previously that the K–Cs–Sb cathode finished with a cesiation step tended to
form a Cs enriched surface termination that has a lower electron affinity at the cathode-vacuum
interface.6
The XRF spectra for cathodes sputtered in Ar and Ne plasma are compared in Fig. 2(b). Both
curves are normalized using the Sb peaks. It is prominent that the Ar sputtered film has a higher
alkali/antimony ratio than that of the Ne sputtered photocathode. The inset table in Fig. 2(b) shows
that in Ar sputtered films, there are 1.75 alkali atoms per Sb atom, while in the Ne sputtered film,
this ratio is 1.24, comparing to an ideal ratio of 3. It is also observed that in the Ar sputtered film the
K/Cs ratio is 1.7, while in the Ne sputtered film, this ratio is much closer to the ideal K/Cs ratio of 2.
Such a discrepancy can be explained by the different ion bombardment energy carried by single Ar+
and Ne+ ions, resulting in different sputter yields for the 2 gases.11
The experimental XRR data for each growth step for the same sample along with the fitting
results are listed in Fig. 3. Raw data were fitted by GenX based on Parratt’s recursion method and
Nevot’s model, which is widely used for the simulation and fitting of XRR curves of thin films.12
116104-4 Gaowei et al. APL Mater. 5, 116104 (2017)

FIG. 2. X-ray fluorescence (XRF) spectra of (a) cathode immediately after sputtering in Ne (red) and after Cs deposition
(dark); (b) cathode sputtered in Ar (red) and Ne (dark), showing the relative composition of each element. The inset tables
present the normalized atomic fraction for each element calculated from curve fitting.

Table I lists the fitted film thickness and surface roughness with uncertainties. The XRR results
from the as-sputtered film shows clear oscillations up to 5◦ . After Cs deposition, oscillations become
denser yet still observable up to 3◦ , indicating a well-maintained surface morphology through the
growth process. The fitting of experimental curves yields a rms surface roughness of ∼0.52 nm for a
23.4 nm thick sputtered film and ∼0.4 nm for the finished photocathode with a final thickness of
41.7 nm. This is remarkably smooth given that the measured roughness is on the order of the
unit cell lattice parameter for KCs2 Sb (∼0.88 nm).13 The increased film thickness is a result of
lattice expansion on the formation of antimonide from the added Cs reacting with the excess Sb
in the sputtered film.14 The fitting of the oscillations in the sputtered layer mismatches at higher
angles, which suggests a variation of film thickness across the sample. This also explains the
larger uncertainty in the film thickness estimation. The intrinsic emittance from a similarly smooth
alkali antimonide photocathode (roughness 0.6 nm) has been calculated to be 0.14 µm/mm rms at
20 MV/m,15 which gives an plausible estimation of the emittance from the sputtered cathode in this
experiment.
The in situ XRD patterns of this sample were compared with simulated powder diffraction
patterns calculated using the cubic structure and lattice parameters established in Ref. 13, namely,
8.61 Å for K2 CsSb and 8.88 Å for KCs2 Sb. The missing of diffraction peaks in the XRD scan
116104-5 Gaowei et al. APL Mater. 5, 116104 (2017)

FIG. 3. X-ray reflectivity (XRR) of the sputtered cathode, where the photocathode thickness was ∼23 nm, followed by the
deposition of Cs. The persistence of oscillations is a testament to the film quality.

in Fig. 4(a) indicates an amorphous structure of the as sputtered layer (∼23 nm) under our growth
conditions. After Cs deposition, crystallinity was barely observable. The weak peak at 2θ = 20.16◦
in Fig. 4(a) was identified as the (220) peak of KCs2 Sb (comparing with the calculated value of
20.12◦ ), which also matches the stoichiometry observed in the fluorescence spectrum. A thicker film
grown with the same parameters indicated that for a thicker sputtered layer, weak crystallinity can
be observed. In Fig. 4(b), the peaks observed at 12.67◦ and 25.27◦ for a 49.6 nm sputtered cathode
on Si(100) are the (111) and (222) peaks from the cubic phase of K2 CsSb.16 The appearance of the
symmetry-forbidden (111) peak indicates a significant lattice distortion, e.g., weak crystallinity. After
adding Cs to this thick sputtered layer, the intensity of the (111) peak dropped significantly, indicating
a better formation of the cubic lattice, while the (222) peak shifted towards the lower angle by 0.15◦ ,
indicating a slight increase in the lattice constant, a sign of phase transformation from K2 CsSb to
KCs2 Sb.
The spectral response measurement between 220 nm and 700 nm for the sputtered cathode is
presented in Fig. 5, with a peak QE (at 220 nm) of 23.5% and a QE of 3.3% in the green (530 nm).
This growth procedure was repeated several times off the beamline and the QE at 530 nm ranged from
3% to 3.8%. From the evidence based on the XRF and XRD results, we have a reason to believe that
the cathodes grown with our method are closer to KCs2 Sb instead of K2 CsSb. The investigation of the
electronic structures and the optical properties of these two materials shows that compared to K2 CsSb,
KCs2 Sb has a smaller bandgap but a higher absorption of green light (530 nm).17 Such properties
of KCs2 Sb might result in a similar green QE and a lower quantum yield in the UV compared to
K2 CsSb photocathodes. A commercial K2 CsSb cathode from Photonis, Inc., was measured in the
same geometry and the spectral response (dark curve in Fig. 5) yields in a green QE of 4.6%. The QE
difference could rise from the difference in stoichiometry and the rougher surface of cathodes grown

TABLE I. The thickness and surface roughness results of the sputtered cathode and the final cathode after cesiation, compared
with a sequentially grown bi-alkali photocathode from Ref. 6.

Sample Thickness (Å) Roughness (Å)

Si substrate N/A 3.27 (0.03, 0.009)

Sputtered cathode 234.2 (13.75, 14.47) 5.17 (0.22, 0.15)
Post-Cs deposition 417 (13.81, 11.27) 4.19 (0.08, 0.03)
CsK2 Sb cathode from sequential growth 400–500 2506
116104-6 Gaowei et al. APL Mater. 5, 116104 (2017)

FIG. 4. The XRD spectrum of sputtered layers of thickness (a) 23.4 nm and (b) 49.6 nm, with subsequent cesiation steps.
XRD results indicate the amorphous nature of the sputtered cathodes.

sequentially. As discussed previously, this could result in a larger surface area hence higher electron
emission current.
In summary, a novel method for creating a low surface roughness photocathode material was
presented. Direct sputtering of bi-alkali antimonide photocathodes was prepared by sputter deposi-
tion using a pre-synthesized K2 CsSb target. The growth processes were monitored using in situ and
operando XRF, XRR, and XRD measurements to optimize the optical performance of the photo-
cathode. The sputtered bi-alkali cathode material achieved 0.5 nm surface roughness and remained a
smooth surface after Cs deposition. With the final cesiation, the cathode reached a sufficient QE of
3.3% in the green. Although the measured green QE of the sputtered cathode was lower than that of
sequentially grown K2 CsSb photocathodes, the excellent smooth surface of this cathode will result in
an emittance that has much smaller field dependence, which is crucial for future accelerator applica-
tions. The composition and the crystal structure in the films can be further improved via optimization
of the composition of the target and a better understanding of relative elemental sputter yields. The
sputter target we used for this experiment yields over 25 cathodes without depletion. The operation
from an already stoichiometric target makes the cathode growth process fast and reproducible. This
method may be the optimal method of growing low emittance, ultrasmooth alkali antimonide cath-
odes in a simple and reproducible manner. As a follow up of this work, there are plans underway to
operate a sputtered cathode in a photoinjector to test cathode emittance vs applied field, which is the
critically needed data in the community.

FIG. 5. Quantum efficiencies of a sputtered photocathode on Si(100) substrate (red curve) and a commercial K2 CsSb Photonis
photocathode (dark curve). The QE difference could rise from the difference in stoichiometry and the rougher surface (hence
a larger surface area) of cathodes grown sequentially, as discussed previously.
 116104-7 Gaowei et al. APL Mater. 5, 116104 (2017)

The authors would like to thank Arthur Woll, Howie Joress, and beamline staff from Cornell
University for their support of our work at CHESS. This work is funded by U.S. Department of Energy,
under No. KC0407-ALSJNT-I0013 and SBIR Grant Nos. DE-SC0017202 and DE-SC0017693. The
use of CHESS is supported by the NSF and the NIH/NIGMS under NSF Award Nos. DMR-0936384
and DMR-1332208.
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