Magnetic timeofflight photoelectron spectrometer for massselected negative cluster

ions
O. Cheshnovsky, S. H. Yang, C. L. Pettiette, M. J. Craycraft, and R. E. Smalley

Citation: Review of Scientific Instruments 58, 2131 (1987); doi: 10.1063/1.1139475

View online: http://dx.doi.org/10.1063/1.1139475
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 Magnetic time..of..flight photoelectron spectrometer for mass-selected
negative cluster ions
o. Cheshnovsky,a) S. H. Yang,b) C. l. Pettiette,b) M. J. Craycraft,b)
and R. E. Smalley
Rice Quantum Institute and Department of Chemistry, Rice University, Houston, Texas 77251
(Received 6 July 1987; accepted for publication 22 July 1987)

Design considerations and initial results are presented for a new type of time-of-flight
photoelectron spectrometer which is particularly suited to the study of cold metal and
semiconductor cluster anions prepared in a supersonic molecular beam. The desired cluster is
extracted from the molecular beam, mass-selected after an initial time-of-flight, and
decelerated as it enters the photoelectron spectrometer. Photoelectrons ejected from the duster
by an ArF excimer laser are collected with> 98% efficiency in an intense pulsed magnetic
field of carefully controlled divergence. This divergent field parallelizes the photoelectron
trajectories and maps smoothly onto a low, uniform magnetic field which guides the electrons
along a 234-cm flight tube leading to a microchannel-plate detector. The strong magnetic fields
and simple, open design provide excellent rejection of stray photoelectrons in a clean,
ultrahigh-vacuum environment The UPS spectrum of Si20 ,- is given as an example.

INTRODUCTION apparatus described below a more typical negative cluster

Cluster beams provide an intriguing possibility of studying
the evolution of bulk surface properties starting at the sim-
plest diatomic molecule, and building up larger and larger
clusters one atom at a time. In such studies, one of the most
informative possible spectroscopies is expected to be ultra-
violet photoelectron spectroscopy (UPS) since this is one of
the very few techniques that is equally applicable to atoms
and molecules at one extreme, and the true bulk surface on
the other. 1-3 It would be extremely useful, therefore, to have
a UPS spectrometer which could cleanly show the spectrum
of each cluster, mass-selected from all others, and done with
sufficiently high photon energies to permit the measurement
of the full "valence-band structure" of the duster.
A major advance towards such a goal was achieved sev-
eral years ago when techniques were developed to prepare
cold beams of the negative duster ion. 4 Using pulsed time-
of-flight and mass-gating techniques,4,5 any desired negative
cluster ion could be extracted from the pulsed supersonic
beam, mass selected, and transmitted with high efficiency to
the detachment region of a photoelectron spectrometer. But
it was clear that no conventional photoelectron spectrom-
eter would be up to the task.
There are two key problems in performing UPS studies
of pulsed negative cluster beams. First is low signaL Since
the cluster beams are pulsed with a very low duty cycle
(10 -4), pulsed lasers must be used to generate the photo-
electrons. Even if superintense negative ion cluster beams
could be generated, one could not afford to have more than
105 duster ions in the detachment region of the photoelec-
tron spectrometer simply because of the unacceptable space-
charge effects on the photoelectron energies. While 10 5 ions
per pulse is an extremely intense cluster beam, in a conven-
tional photoelectron spectrometer this would be equivalent
to a neutral target gas density of only 3 X 10-- 11 Torr. In the
ion count in the roughly I-cm 3 detachment region of the
UPS spectrometer is only 103 • One must, therefore, use rath-
er intense laser pulses to achieve a high yield of photoelec-
trons, and these photoelectrons must be collected with high
efficiency and energy analyzed so as to accumulate the entire
UPS spectrum from each laser shot.
The second key problem-background photoelectron
noise-stems from the solution of the first. With intense de-
tachment lasers and high photoelectron collection efficien-
cies, extraordinary measures must be taken to avoid the ex-
periment being totally swamped in stray photoelectron
signaL In order to do truly ultraviolet photoelectron spec-
troscopy, it is necessary to use detachment lasers which are
well above the work function of all surfaces in the spectrom-
eter. Photoelectrons from these surfaces must be avoided
both because of the signals they produce, and because of
distortions in the spectrometer resolution caused by local
stray fields arising from the space charge. And since the neg-
ative cluster target density is equivalent to less than 10 - 12
Torr, it is clear that ultrahigh-vacuum technology will be
required to keep stray photoelectron signals from the back-
ground gas at acceptable levels.
In an impressive paper published by Kruit and Read a
few years ago, 6 a new type of time-of-flight photoelectron
spectrometer was introduced. It involved the use of a diver-
gent magnetic field to collect the photoelectrons with high
efficiency and a lower, guiding magnetic field which directed
them down a flight tube for time-of-flight analysis. Although
the idea of using diverging magnetic fields in a photoelectron
spectrometer had been discussed before by a number of re-
searchers,7 the Kruit and Read paper was the first detailed
illustration of the high-resolution capabilities of such a de-
sign. An alternative magnetic time-of-flight design with a
cylindrical (1/?-) field was introduced a short time later by
Siegbahn and co-workers 8 ; it also featured quite impressive

2131 Rev. Sci.lnstrum. 56 (11), November 1987 0034-6148/871112131-01$01.30 @ 1987 American Institute of Physics 2131

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 resolution potential at high collection efficiency.
The intriguing aspect of the Kruit and Read design from
this viewpoint of cluster UPS is that both of the above men-
tioned key problems are solved-at least in principle. As ori-
ginally published, the high magnetic field of their design pro-
vided 2rr sr collection efficiency and excellent resolution in a
time-of-flight mode. The seeds of a solution to the second
problem stem from the good imaging properties of their
spectrometer. Photoelectrons in the detachment region are
forced to travel along field lines, and only for a small central
region in the source region do these lines map smoothly onto
the detector at the end of the flight tube. All surfaces in the
source region of this spectrometer are in portions where the
field lines diverge away from the detector. In principal,
therefore, the Kruit and Read design should permit excel-
lent rejection of stray photoelectrons.
In practice, however, the Kruit and Read design was
unacceptable for pulsed cluster UPS: the ferromagnets in the
source region do not provide a sufficiently large open space
to readily achieve the necessary ultrahigh vacuum, and it
would be impossible to avoid unacceptable levels of scattered
light when using VUV lasers. Simply scaling up the overall
size of the Kruit and Read apparatus by a factor of 5 or so
would have solved these problems to some extent, but as
described below, we have found a somewhat cleaner (and
smaller) solution.
I. DESIGN AND IMPLEMENTATION
Figure 1 is a schematic drawing of the current version of
this new photoelectron spectrometer. The pulsed negative
cluster ion beam is shown entering the apparatus from the
top of the schematic. The supersonic beam apparatus which
generates these cluster ions has been described in earlier pub-
FIG. 1. Horizontal cross section of the photoelectron spectrometer: 1.
Pulsed mass gate. 2. Pulsed decelerator. 3. Water-cooled pulsed solenoid. 4.
Laser interaction zone. The laser beam and the baffle arms are perpendicu-
lar to the page. 5. In-line dual microchannel-plate ion detector. 6. Photo-
electron Hight tube, 234 em long. 7. Low field guiding solenoid. 8. mu metal
shielding. 9. Cryogenic pump. Note that both oftbe solenoids are outside of
the vacuum chamber.
2132 Rev. Sci.lnstrum., Vol. 55, No. ii, November 1981
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lications from this group,4.5 but aside from the fact the clus-
ter ions are traveling at roughly 840-900 eV as they enter the
UPS chamber, this supersonic cluster source is of only peri-
pheral interest to the present discussion. As this cluster ion
pulse enters the UPS spectrometer, it passes through a triad
afflat grids [numbered (1) in the schematic J which serve as
a computer-controlled mass gate. Since the cluster ions had
been pulse extracted from the supersonic beam, they have
become separated according to mass during their flight. The
first and last grids of the mass gate are held at ground poten-
tial while the central one is normally kept at - 1000 V. As
the particular cluster to be studied approaches this mass
gate, the central grid is dropped to ground potential for a
short time 0-2 ms) while this desired cluster passes
through.
As will be clear from the simulations and results pre-
sented in the next section, for good UPS resolution it is criti-
cal to remove as much of the translational energy from the
negative cluster ions as possible. This is accomplished by the
pulsed decelerator assembly shown in Fig. 1 just below the
mass gate (see label 2). As the cluster ion packet emerges
from the mass gate, this assembly is maintained at a decel-
eration potential of (typically) - 810 V, slowing the clus-
ters down to below 100 e V as they pass through the first grid
of this decelerator assembly. As shown in the figure, the
clusters then travel in a field-free region for 3 cm prior to
passage through the final grid of the assembly. During this
time the potential of the decelerator assembly is dropped to
ground, via computer control, so that the decelerated clus-
ters enter into the UPS chamber without reacceleration. A
pair of microchannel plates (5) mounted directly in the
flight path of these cluster ions is used to monitor them at
high sensitivity while the cluster source is being optimized
and a particular cluster selected for study.
The photodetachment region of the spectrometer is lo-
cated in the center of the schematic at a point indicated by
the cross (4). As the clusters drift through this region, the
detachment laser beam is fired (not shown in the figure, but
perpendicular to the page). Since the objective of this design
is to permit VUV lasers to be used, extensive careful baffling
arrangements were provided both on the laser input and exit
arms of the apparatus. To be consistent with the URV vacu-
um criteria of the apparatus, porous blackened surfaces such
as graphite or anodized aluminum were not used. Instead,
these baffles were assembled from sharp, electroformed
nickel cones (actually molecular beam skimmers) together
with a variety of aperture stops. UV grade fused silica win-
dows mounted with a 15° offset angle were used on both
entrance and exit baffle tubes. The intent of the laser in-
put/output design was to achieve what we term "third-order
baffling": meaning that no light should be able to hit a criti-
cal surface in the detachment region of the spectrometer
without having first suffered at least three successive reflec-
tions.
It THE SPECTROMETER
The details of the laser photodetachment region of the
new UPS spectrometer are shown more clearly in Fig. 2. As
Photoelectron spectrometer 2132

:. "._~_._Zhw,-·-·r
FIG. 2. An expanded view of the main parts of the photoelectron spectrom-
eter. Superimposed are the magnetic field lines generated by the two sole-
noids. The labels have the same meaning as in Fig. 1.
indicated here with dashed lines, this is a region of strong
and highly divergent magnetic fields. The strongest field is
produced by a pulsed electromagnet [label (3 ) in Fig. 2] . As
seen in the figure, this magnet is actually mounted outside
the vacuum wall in a cylindrical mount which extends to
within 1.5 cm of the center of the chamber where the laser
photodetachment occurs. Note that this magnet mount has a
central hole (1.0-cm Ld., 3.0-cm length) facing the detach-
ment region. The purpose ofthis hole is to ensure that in the
vicinity of the detachment laser there is no metal surface for
which the local magnetic field maps onto the photoelectron
detector. The only surfaces of this pulsed magnet mount ex-
posed to the vacuum are smooth, highly electropolished 304
stainless steel.
The pulsed electromagnet was prepared from 350 turns
of A WG 24 magnet wire wound on a water-cooled copper
core, producing a coil 1.2-cm i.d., 3.4-cm o.d. and 1.5 cm in
length. To improve heat dissipation the wires were embed-
ded in high thermal conductivity epoxy (Aluminum putty,
Devcon, Inc.) during the winding process. In practice, a
current of 25 A is pulsed through the magnet with a pulse
duration of 3 ms. Due to the inductance of the coil ( - 2 mH)
and its consequently slow response time, it is necessary to
turn on the magnet at least 2.5 ms before the detachment
laser is fired. This magnet, along with the rest of the appara-
tus is pulsed for a complete repetition of the experiment ten
times a second. With these current settings the magnet gen-
erates a peak magnetic field at its center of 5000 G. At the
laser detachment region, 1.5 em down axis from the face of
the magnet, this field has dropped to 450 G.
In such a strong magnetic field, the photoelectrons are
tightly constrained to follow the local field lines. In order to
channel these photoelectron trajectories down the time-of-
flight drift tube (7), a weak (1-3-G) static field is produced
by a long solenoid magnet mounted coaxially along the full
234-cm length of the flight tube. This in turn is shielded from
2133 Rev. SCi.lnstrum., Vol. 58, No. 11, November 1987
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stray magnetic fields in the laboratory by a double barrier of
"mu" metal (Eagle Magnetics Co-nectic) (label NO.8 in
Fig. 1).
At the end of the flight tube the electrons pass through a
high-transmission Mo mesh and are accelerated towards an
electron detector which consists of triply staged microchan-
ne! plates. The resultant signal is then amplified and record-
ed with lOons resolution on a transient digitizer (Transiac
2001) triggered by a fast photo diode monitoring the detach-
ment laser pulse. The digitized time-of-flight signal is then
further analyzed by a microcomputer to discriminate single
photoelectron events from stray electrical noise. For the ex-
periments described below, the time-of-flight photoelectron
spectra were typically accumulated through 104 laser shots
with about 105 photoelectron events.
This high magnetic field design differs considerably
from that of Kruit and Read in that here the electrons are
detached in a region which is quite far "downhill" from the
peak of the strong magnetic field. There are three key advan-
tages in this. First, the collection efficiency is now greater
than 98%-the magnetic mirror effect ensures that virtually
all photoelectrons are directed to the detector. Second, there
is now no need for any magnetic structure between the de-
tachment region and the flight tube, eliminating the prob-
lems of cooling, scattered light, and vacuum quality that
would otherwise be encountered. Third, with this large open
design no photoelectron ever comes closer than 0.5 cm to a
surface (and most never get closer than 1 em). The result is
that small-scale surface patch potentials on the inside of the
apparatus do not strongly affect the photoelectron time of
flight. There is, therefore, no need to coat the inside surfaces
with graphite and suffer the consequent reduction in vacu-
um quality. Aside from a few Macar insulators in the struc-
tures that support the mass gate and decelerator and quartz
bakeout lamps, an surfaces inside this UPS apparatus are
smooth, electropolished stainless steel. All magnets are ex-
ternal to the vacuum chamber and can be removed during
baking.
Throughout the design much care was taken regarding
the positioning of surfaces within the magnetic field. Al-
though it would have been easier to generate the high field
with a ferromagnetic core in the pulsed solenoid (or simply
use a pennanent magnet), this option was not taken because
then the field lines would pass through the ferromagnetic
materiaL In such a case it would have been impossible to
avoid the existence ofIarge surfaces for which the local field
lines map directly onto the photoelectron detector.
Instead, a simple helical copper solenoid was used. This
has the critical advantage that the field lines (which can be
calculated exactly) all pass through the center of the coil-a
center which is purposely kept open to the vacuum (i.e., the
central hole in the magnet mount seen in Figs. 1 and 2). Only
at the very back surface of this central hole do the field lines
mapping from the detector encounter a metal surface. But
even photoelectrons detached from this surface by stray la-
ser light are rarely seen by the detector. Except for the
roughly 2 % which start pointed almost exactly along a local
field line, the bulk of the photoelectrons from this rear sur-
face of the central hole will be reflected by the magnetic field
Photoelectron spectrometer 2133
 as it converges to a peak of 5000 G on the way out to the
detector.
In order to maintain the best possible vacuum in the
UPS chamber, a single 20-cm-Ld. cyropump is used (9)
(cn Cryogenics). After bakeout, the chamber typically op-
erates at roughly 1 X 10 - 10 Torr. The partial pressure of
high molecular weight condensable gases which can be two-
photon ionized by the UPS laser is expected to be two orders
of magnitude lower in such cryopumped systems. The nega-
tive cluster beam input flight tube is differentially pumped
by a 130 1 s - I turbopump, and a liquid-nitrogen cryotrap,
and typically operates near 1 X 10 - 9 Torr.
III. RESOLUTION-GENERAL CONSIDERATIONS
Several factors-some of them specific to the experi-
ment of UPS of negatively charged clusters-govern the re-
solution in our photoelectron spectrometer. In what follows
we shall try to evaluate their relative contribution.
By far, the most crucial limitation stems from the finite
velocity of the negatively charged ions, VI' Since the de-
tached electrons are collected from nearly a 41T solid angle,
the velocity of the detached electron in the cluster center of
mass, V e , will range between ve + vJ and ue - V[ in the labo-
ratory frame. One can thus assume a velocity spread of 2VI
for the electron, The resultant energy spread can be ex-
pressed as
dEe = mevedve = (2m,Ee )0.5 2(2E[/m[ )0.5
= 4[(m e /m I )(Ee E 1 )]0.5 , (1)
where E e and E I denote the kinetic energies of the electron in
the center of mass and of the clusters, respectively, while me
and m I denote the masses. For this reason we have deceler-
ated the ions prior to the detachment. Limited by the kinetic
energy spread of the cluster (which is intrinsic to our time-
of-flight mass spectrometer) the typical deceleration in the
experiments was 80 eV. On deceleration to 20-eV kinetic
energy the electron signal decreased by about one order of
magnitude. In Fig. 3 we present the expected energy spread
in the photoelectron spectrum due to the ion velocity effect,
as expressed in Eq. (1), for 100- and 1000-amu clusters at
the kinetic energies of 80 and 20 eV, respectively.
We shall now consider effects which are intrinsic to the
magnetic design of the spectrometer. As shown by Kruit and
Read 1 the degree of parallelization of the electrons on their
entry to the drift tube is given by
8 /.max - ' -1(Bf IB i )0.5
- Sin , (2)
where B; is the magnetic field at the detachment zone while
Bf is the uniform magnetic field in the drift tube. 8 j ;max de-
notes the maximum angle between the electron velocity and
the drift tube propagation axis. The intrinsic limit on the
resolution in the magnetic design can be then approximated
as
(3)
Ee B;
Typically, Bi equals 450 G while Bf equals 2.2 G. This im-
plies an upper limit of about 1:200 in energy resolution for
2134 Rev. ScLlnstrum., Vol. 58, No. 11, November 1987
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0.3
0.1
:>
.2
c:
0
~
g
Q)
a::
.01
.003
.I ID 10
Electron K.E. (eV)
FIG. 3. The limits on the resolution of tile magnetic time-of-flight electron
spectrometer, as imposed by several experimental factors, as a function of
the electron kinetic energy. The four top lines represent the expected energy
spread for 100- and IOOO-amu clusters due to two different kinetic energies
[see Eq. (I) J. Tile first number in the labels denotes the cluster mass (in
amu) while the second denotes the kinetic energy (in eV ). The broken tine
represents the energy spread due to the finite alignment time of the electrons
along the flight tube direction. The dotted line represents the intrinsic ener-
gy spread of the photoelectron as imposed by the ratio of the magnetic field
in the detachment zone and in the flight tube, respectively [see Eq. (3) J.
our current spectrometer, No effort was taken to improve
the field ratio as it is the other effects, described above and
below, which restrict our resolution. The energy spread as
implied by Eq. (3) is represented in Fig. 3 by the dotted line.
There is a finite time upon which the electrons are redi-
rected along the magnetic field lines of the drift tube. It is
zero for the electrons which are directed along the propaga-
tion axis and is the longest for these electrons which are
directed away from the flight tube and are reflected back by
the magnetic field via a "magnetic mirror" mechanism. Un-
der the adiabatic approximation, the reflection or redirec-
tion time is proportional to E e- 0.5 and depends on the initial
direction of the electrons and on the distribution of the mag-
netic fields. The time spread of isotropically detached elec-
trons in a given magnetic field is thus proportional to E e- o.s.
We have calculated this time spread with the simulation
program which is described below. For our distribution of
magnetic fields the spread equals 45 ns*E - o,S(eV). The
flight time in the drift region is also proportional to E 0.5, so
the relative resolution due to the parallelization does not
depend on the energy of the electrons. With our flight tube of
234 em, the relative energy spread due to parallelization
amounts to about 1:43. It is represented by the broken line in
Fig. 3.
The spread in the time of parallelization can be mini-
mized by designing a magnetic structure with a rapid spatial
divergence in the magnetic field. We have limited ourselves
in this respect because it would be contradictory to our in-
tention of keeping the surfaces near the detachment region
away from the intense UV laser beam. Instead we have used
a relatively long flight tube of 234 em so that the paralleliza-
tion effect will not dominate our spectra.
Two other potential causes for spoiling the resolution,
the finite excitation time ( ~ 10 ns) and finite volume of exci-
Photoelectron spectrometer 2134
 tation (about O.5-cm diameter of the detachment laser OBSERVED SIMULATIONS
beam), are negligible in our experimental setup and will not
be discussed here.

~l
A a
IV. SIMULATED AND OBSERVED PERFORMANCE
One of the virtues of this photoelectron spectromete.r \
design is that the magnetic fields from both the pulsed and

~
!/)
static solenoids can be calculated directly. With this infor- I-
Z
mation and direct measures of the dimensions of the appara- ::>
o
(.)
tus, it is straightforward to prepare a full computer simula-
z
tion of the photoelectron time of arrival distribution. The
computational scheme of this simulation code was much the
oa:
I-
u
IJ
same as that described in Sec. 2.2 of the paper by Kruit and W
..J
W
Read. oI- c
Photoelectrons detached with a given kinetic energy o
J:
and direction in the source region of the spectrometer propa- c.. I
I
gate under influence of the local Lorenz force, F = e(vXB). i
It is calculated at each point, and the trajectory for the next
IV
,
small time interval is approximated as a section of a helix of
appropriate diameter around a guiding axis paranel to the
local magnetic field line. Such a scheme was found to be
quite efficient and accurate even when implemented on a
smaIl personal computer (IBM PC-AT).
!
j\
d

3 4 2
Since this photoelectron spectrometer was designed "
from the start for application to negative cluster ions, the FLIGHT TIME (psecl
computer code takes into account both the velocity of the
FIG. 4. Simulated (right panel) and observed (left panel) time·of-flight
cluster ion prior to detachment and the angular dependence
spectra of photoelectrons detached from eu - ions by a 2.33-eV laser (the
of photoelectron ejection upon the polarization of the de- second harmonics of a Nd/YAG). The electron affinity of a copper atom is
tachment laser beam. Copies of this simulation code are 1.23 eV so that the kinetic energy of the electron equals 1.10 eV. The labels
available from the authors. refer to detachment from (a) a copper ion with 900-eV kinetic energy as the
laser beam is polarized perpendicularly to the velocity vector of the ions.
The right-hand panel of Fig. 4 shows the results of this The lower three spectra refer to a collinear polarization at (b) 900-, (c)
computer program for the simulated time-of-flight photo- 250-, and (d) 20-eV kinetic energy. Note the dramatic influence ufthe de·
electron arrival time distribution of the negative ion of the celeration on the resolution.
copper atom detached by a laser of 2.33-eV photon energy
(the second harmonic of a Nd:YAG laser). The electron
affinity of the copper atom is 1. 23 e V9 resulting in 1.1O-eV
kinetic energy for the electron in the ion center of mass. The leI to the velocity vector ofthe eu - parent ion beam). In this
top simulation (a) assumed a Cu·· ion translational energy configuration the bulk of the photoelectrons are initially di-
of 900 e V, and assumed the detachment laser polarization to rected along the direction of motion of the Cu· ion, and the
be parallel to the central magnetic axis of the spectrometer. splitting in the laboratory-frame energy of the forward and
The bulk of the width in the arrival time distribution here backward directed halves is now quite clear. Spectra (c) and
actually has little to do with the intrinsic resolution of the (d) show how both the splitting and effective resolution im-
spectrometer. It is simply due to the fact that the photoelec- prove as the Cu ... ion beam is decelerated to 250, and then to
tron velocity in the laboratory frame is directly affected by 20 eV, respectively.
the original velocity of the parent ion. Since> 98% of all Efficient deceleration of the parent negative ion is quite
photoelectrons are collected, regardless of the direction of clearly one of the most vital factors in determining the effec-
their initial velocity vectors, the full effect of this ion velocity tive resolution of this UPS spectrometer, This is an unavoid-
is seen in the time-of-flight spectrum. For the simulation of able aspect of any spectrometer design that collects a large
spectrum (a) the angular distribution of the initial velocity solid angle of the detached photoelectrons. However, note
vectors in the center of mass frame was assumed to follow a that the calibration and the testing ofthe spectrometer were
cos 2 c/J functional form, where ¢; is the angle between the elec- performed on the Cn - atom. The actual resolution for clus-
tric vector of the detachment laser and the velocity vector of ters is typically better due to their higher mass, as implied by
the detached electron. The limits of the time-of-flight distri- Eq.O).
bution shown here correspond to photoelectron velocities of The left-hand panel of Fig. 4 shows actual results from
Ve + V J and Ve -- VI' respectively. the new magnetic photoelectron spectrometer for Cu -- pho-
As seen in the simulated spectrum (b) the intensity dis- todetachment with the second-harmonic beam of a
tribution changes drastically when the laser is polarized per- Nd:Y AG laser, under beam energy and polarization condi-
pendicular to the central axis of the spectrometer (but paral- tions corresponding to the simulations on the right. The ex-

2135 Rev. Sc!.lnstrum., Vol. 58, No. 11, November 1987 Photoelectron spectrometer 2135

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 cellent agreement between experiment and simulation is par-
ticularly impressive when it is realized there are no
adjustable parameters being used here. The only inputs to
the simulation were the measured dimensions of the appara-
tus and the currents flowing in the two magnetic solenoids.
Similarly, excellent agreements between observed spec-
tra and direct simulations were obtained for Cu - with a
variety of detachment laser wavelengths (355, 256, and 193
nm). Such excellent agreement with ab initio predictions is
testament to the simplicity and reliability of the spectrom-
eter design.
Vo APPL.ICATIONS
The real test of any new scientific apparatus, of course, is
how effectively it handles the task for which it was intended.
In this case the prime objective was to permit routine UPS
measurements of the "band structure" of mass-selected neg-
ative cluster ions. Our first example of such an application
has been the study ofthe UPS of clusters of silicon and ger-
manium taken with an ArF excimer laser at 6.4-eV photon
energy. Initial results of this study have been summarized
elsewhere. 1O We have also successfully measured with this
apparatus the UPS spectra oflarge carbon and copper clus-
ters. \l.12
One example is shown here in Fig. 5 which presents the
first observation of the photoelectron spectrum of the 20th
cluster of silicon, Si 20 -, obtained with the new spectrometer
using an ArF detachment laser. Comparison with UPS spec-
tra of other silicon clusters in this size range reveals that this
20th cluster is quite unique: the small hump in the 3-4-eV
region is seen only in Si20 - . This is strong evidence that the
neutral Si20 cluster is a particularly stable species with a
closed shell electronic structure and a substantial HOMO-
LUMO "band" gap. This is a particularly intriguing result
since it may be evidence that the 20th cluster has the struc-
ture of a dodecahedron.
The high rejection efficiency of the surface photoelec-
trons was dramatically verified in these experiments. Typi-
3.0 2.0 1.0 0.0
BINDING ENERGY (eV)
FIG. 5. Ultraviolet photoelectron spectrum of mass-selected Si,-o obtained at
193 nrn (6.42eV). The spectrum was taken with 10 000 laser shots at 10Hz
with an average signal of five counts per shut. Background signal averaging
to about one count per shot was subtracted 011 alternate shots. Typical laser
pulse energy was 100 flJ.
2136 Rev. ScLlnstrum., Vol. 58, No. 11, November 1987
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193.0.65.67 On: Mon, 22 Dec 2014 10:34:26
cally, the background photoelectron signal amounted to less
than one count per 100 f-tJ of the 6.4-eV laser shot. As we
turned the pulsed solenoid off, the electron detector was
practically flooded with thousands of surface photoelectrons
per laser shot.
VI. PROSPECTIVES
As discussed above, and quite vividly demonstrated in
Fig. 3, the most critical factors limiting the resolution of this
photoelectron spectrometer are the translational energy of
the parent cluster ion beam itself and the finite time of direct-
ing the electrons along their trajectories in the flight tube.
We do not expect to decelerate the ions much further be-
cause oftheir initial energy spread and because of the spatial
spread resulting from the intense deceleration. However a
conceivable solution to the ion velocity problem can be
achieved, by sacrificing collection efficiency, with a some-
what different configuration of the spectrometer. It involves
a geometry where the flight tube is collinear with an ion
beam and a hollow solenoid. The detachment zone is located
on the ion trajectories before they reach the solenoid. In such
a case only some fraction of the forward-going electrons will
be transmitted by the solenoid [see Eq. (2) and Ref. 5 J. It
can be easily shown that in such a configuration the velocity
spread of the monoenergetic electrons in the center of mass
will be gi ven by
dv = 2v 1* (collection efficiency) , (4)
while the collection efficiency is given by
collection efficiency = 0.5 [1 - (l - B;lB max )05] ,
(5)
where Bmax is the maximum magnetic field of the solenoid.
Notice that our present 2VI velocity spread and collection
efficiency are consistent with the above relations.
As we aim to work with higher photon energies, the
influence of the alignment time on the resolution will be-
come dominant (see Fig. 3). This problem can and will be
solved by the lengthening of the flight tube or by trying a
more compact solenoid structure in which the spatial change
in the magnetic field is faster. We do not anticipate any con-
sequent decline in the collection efficiency because of the
very efficient guiding of the long solenoid coil.
One obvious limitation on the highest photon energy for
the investigation of negatively charged clusters is the avail-
ability of sufficiently intense laser sources above 7.9 eV (the
F J laser). Frequency tripling in metal vapors seems now like
the most promising technique. 13 Other obstacles have to do
with the background noise. As discussed above, the strong
magnetic field at the detachment zone serves well to dis-
criminate against stray electrons from the surrounding sur-
faces. Although this background can be further reduced by
more careful light baffling and a higher magnetic field at the
detachment region, one does not anticipate substantially
more surface photoelectrons at higher photon energies. The
photon energies are already well above the work function of
stainless steel.
However, photon energies higher than about 12 eV can
induce efficient one-photon ionization of such species as O 2
Photoelectron spectrometer 2136
 and H 20 in the background gas surrounding the detachment
zone. These processes can effectively mask the UPS spectra
of our 10 -12_Torr cluster beams. We suspect the attempt to
pass this 12-e V energy limit will become the next major chal-
lenge in the developing technology of UPS of negatively
charged cluster beams.
ACKNOWLEDGMENTS
The authors would like to acknowledge J. M. Alford
and R. T. Laaksonen for their help in the trajectory simula-
tions. Development of UPS capability in this group has thus
far been primarily supported by internal Rice University
funds and the Robert A. Welch Foundation. Support for
semiconductor cluster research from the U.S. Army Re-
search Office is gratefully acknowledged. Major portions of
the cluster beam and associated laser app-aratus used here
were supported by the Department of Energy and National
Science Foundation in projects focused on bare metal clus-
ters and chemisorbed clusters, respectively.
0)Department of Chemistry, Tel-Aviv University, 69978 Tel-Aviv, Israel.
b) Robert A. Welch Foundation Predoctorai Fellow.
'J. W. Rabalais, Principles of Ultraviolet Photoelectron Spectroscopy (Wi-
2137 Rev, SCi,lnstrurn., Vol. 58, No.11, November 1987
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193.0.65.67 On: Mon, 22 Dec 2014 10:34:26
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Photoelectron spectrometer 2137