Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids
Electronically-induced desorption from solid Ar pre-irradiated by a low-energy electron beam was investigated by activation spectroscopy methods—photon-stimulated exoelectron emission and photon-stimulated luminescence in combination with spectrally-resolved measurements in the VUV range of the...
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Цитувати: | Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids / G.B. Gumenchuk, I.V. Khyzhniy, A.N. Ponomaryov, M.À. Bludov, S.À. Uyutnov, A.G. Belov, E.V. Savchenko, V.E. Bondybey // Физика низких температур. — 2008. — Т. 34, № 3. — С. 309–313. — Бібліогр.: 23 назв. — англ. |
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irk-123456789-1168562017-05-17T03:03:41Z Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids Gumenchuk, G.B. Khyzhniy, I.V. Ponomaryov, A.N. Bludov, M.À. Uyutnov, S.À. Belov, A.G. Savchenko, E.V. Bondybey, V.E. Кpаткие сообщения Electronically-induced desorption from solid Ar pre-irradiated by a low-energy electron beam was investigated by activation spectroscopy methods—photon-stimulated exoelectron emission and photon-stimulated luminescence in combination with spectrally-resolved measurements in the VUV range of the spectrum. Desorption of vibrationally excited argon molecules Ar₂ *(ν) from the surface of pre-irradiated solid Ar was observed for the first time. It was shown that desorption of «hot» Ar₂ *(ν) molecules is caused by recombination of self-trapped holes with electrons released from traps by visible-range photons. The possibility of optical stimulation of the phenomenon is evidenced. 2008 Article Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids / G.B. Gumenchuk, I.V. Khyzhniy, A.N. Ponomaryov, M.À. Bludov, S.À. Uyutnov, A.G. Belov, E.V. Savchenko, V.E. Bondybey // Физика низких температур. — 2008. — Т. 34, № 3. — С. 309–313. — Бібліогр.: 23 назв. — англ. 0132-6414 PACS: 79.20.La;72.20.Jv;79.75.+g http://dspace.nbuv.gov.ua/handle/123456789/116856 en Физика низких температур Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine |
collection |
DSpace DC |
language |
English |
topic |
Кpаткие сообщения Кpаткие сообщения |
spellingShingle |
Кpаткие сообщения Кpаткие сообщения Gumenchuk, G.B. Khyzhniy, I.V. Ponomaryov, A.N. Bludov, M.À. Uyutnov, S.À. Belov, A.G. Savchenko, E.V. Bondybey, V.E. Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids Физика низких температур |
description |
Electronically-induced desorption from solid Ar pre-irradiated by a low-energy electron beam was investigated
by activation spectroscopy methods—photon-stimulated exoelectron emission and photon-stimulated
luminescence in combination with spectrally-resolved measurements in the VUV range of the spectrum.
Desorption of vibrationally excited argon molecules Ar₂ *(ν) from the surface of pre-irradiated solid Ar
was observed for the first time. It was shown that desorption of «hot» Ar₂ *(ν) molecules is caused by recombination
of self-trapped holes with electrons released from traps by visible-range photons. The possibility of
optical stimulation of the phenomenon is evidenced. |
format |
Article |
author |
Gumenchuk, G.B. Khyzhniy, I.V. Ponomaryov, A.N. Bludov, M.À. Uyutnov, S.À. Belov, A.G. Savchenko, E.V. Bondybey, V.E. |
author_facet |
Gumenchuk, G.B. Khyzhniy, I.V. Ponomaryov, A.N. Bludov, M.À. Uyutnov, S.À. Belov, A.G. Savchenko, E.V. Bondybey, V.E. |
author_sort |
Gumenchuk, G.B. |
title |
Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids |
title_short |
Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids |
title_full |
Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids |
title_fullStr |
Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids |
title_full_unstemmed |
Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids |
title_sort |
optically-stimulated desorption of «hot» excimers from pre-irradiated ar solids |
publisher |
Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України |
publishDate |
2008 |
topic_facet |
Кpаткие сообщения |
url |
http://dspace.nbuv.gov.ua/handle/123456789/116856 |
citation_txt |
Optically-stimulated desorption of «hot» excimers from
pre-irradiated Ar solids
/ G.B. Gumenchuk, I.V. Khyzhniy, A.N. Ponomaryov, M.À. Bludov,
S.À. Uyutnov, A.G. Belov, E.V. Savchenko, V.E. Bondybey
// Физика низких температур. — 2008. — Т. 34, № 3. — С. 309–313. — Бібліогр.: 23 назв. — англ. |
series |
Физика низких температур |
work_keys_str_mv |
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first_indexed |
2025-07-08T11:12:37Z |
last_indexed |
2025-07-08T11:12:37Z |
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1837077014530490368 |
fulltext |
Fizika Nizkikh Temperatur, 2008, v. 34, No. 3, p. 309–313
Short Notes
Optically-stimulated desorption of «hot» excimers from
pre-irradiated Ar solids
G.B. Gumenchuk1,2, I.V. Khyzhniy1, A.N. Ponomaryov2, M.À. Bludov1,
S.À. Uyutnov1, A.G. Belov1, E.V. Savchenko1, and V.E. Bondybey2
1
B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine
47 Lenin Ave., Kharkov 61103, Ukraine
E-mail: savchenko@ilt.kharkov.ua
2
Lehrstuhl für Physikalische Chemie II TU München, 4 Lichtenbergstraße, Garching 85747, Germany
Received September 5, 2007
Electronically-induced desorption from solid Ar pre-irradiated by a low-energy electron beam was in-
vestigated by activation spectroscopy methods — photon-stimulated exoelectron emission and photon-stim-
ulated luminescence in combination with spectrally-resolved measurements in the VUV range of the spec-
trum. Desorption of vibrationally excited argon molecules Ar
2
�( )� from the surface of pre-irradiated solid Ar
was observed for the first time. It was shown that desorption of «hot» Ar
2
�( )� molecules is caused by recombi-
nation of self-trapped holes with electrons released from traps by visible-range photons. The possibility of
optical stimulation of the phenomenon is evidenced.
PACS: 79.20.La Photon- and electron-stimulated desorption;
72.20.Jv Charge carriers: generation, recombination, lifetime, and trapping;
79.75.+g Exoelectron emission.
Keywords: photon stimulated desorption, electron stimulated desorption, exoelectron emission.
1. Introduction
Desorption from rare gas crystals has been studied un-
der excitation by ions [1,2], electrons [3,4] and photons
[5,6]. Desorbing particles are ground state atoms, excited
atoms, excited molecules and ionic species. Desorption
stimulated by electronic excitation of the crystal was first
observed in experiments on the diffraction of slow elec-
trons [7]. The basis of this phenomenon is the conversion
of electronic excitation energy into kinetic energy of at-
oms caused by the localization of excitations near the sur-
face of the crystal.
When a rare gas solid (RGS) is irradiated by ionizing
radiation with excitation energy higher than the forbidden
energy gap, electron-hole pairs are produced. Electrons
behave like free particles in RGS (except He), while holes
are self-trapped in a short period of time — 10–12 s [8].
Let us consider the desorption from RGS on the exam-
ple of solid Ar. Excimer molecules in Ar lattice are pro-
duced due to self-trapping of excitons or due to recombi-
nation of self-trapped holes with electrons followed by
the formation of self-trapped excitons. The transition of
the excited molecule to the repulsive part of the ground
state term is accompanied by emission of the broad
M-band with a maximum at 9.7 eV:
Ar2
+
+ e � Ar2
�
� Ar + Ar + �E + h� (9.7 eV).
This recombination reaction of self-trapped holes with
electrons stimulates the desorption of Ar atoms from solid
Ar to the vacuum. The energy �E released in this process
is approximately 1 eV (~0.5 eV per atom). This value is
enough for an atom to overcome the energy barrier and es-
cape from the sample to the vacuum in case recombina-
tion occurs on the surface of the crystal — the excimer
dissociation mechanism of desorption [9,10].
Excited Ar atoms desorb from the surface of solid Ar
because of repulsive interaction between an excited elec-
tron and surrounding atoms of a regular lattice caused by
negative electron affinity of crystalline Ar [8] — the
so-called «cavity-ejection» mechanism [9]. The partial
contribution of excited atoms to the desorption was dis-
tinguished in [4,6] and was shown to be stimulated by di-
rect generation of excitons in the crystal. In [11] a mecha-
© G.B. Gumenchuk, I.V. Khyzhniy, A.N. Ponomaryov, M.À. Bludov, S.À. Uyutnov, A.G. Belov, E.V. Savchenko, and V.E. Bondybey,
2008
nism of desorption of excited atoms from solid Ar under
low-energy electron beam excitation was discussed. Ex-
periments were performed using luminescence VUV
spectroscopy. It was shown that nonthermalised excitons
play the main role in the transport of excitation energy to
the surface.
The desorption of «hot» molecules from rare gas sol-
ids was observed before only during excitation of the
crystals. Electronically induced desorption of vibratio-
nally hot molecules from surfaces of solid Ar [12] and Ne
[13,14] was identified by observation of luminescence
stemming from a plume of sputtered particles under exci-
tation. Excimer desorption from solid Ar under selective
excitation in the range of 10–35 eV was studied in [15].
Excitation spectra of the W-band demonstrated that pri-
mary creation of excitonic states is necessary for ejection
of Ar excimers and electron-hole recombination stimu-
lates this process as well. The formation of excimers is
caused by the self-trapping of excitons in the lattice due
to exciton-phonon interaction. Desorption of hot mole-
cules Ar
2
�( )�
from solid Ar can occur via different mecha-
nisms. First one is the «cavity–ejection» mechanism ope-
rating in RGS with negative electron affinity [8,9]. In
solid Ar it causes repulsion between excited particles and
surrounding atoms of regular lattice. Therefore a cavity
around Ar2
� is formed. Thus excimers formed on the sur-
face of the sample are pushed out to the vacuum. Another
mechanism is concerned with lattice rearrangements in
the vicinity of excimer. Appearance of the dimer in the in-
terstitial position is followed by its shift along the n direc-
tion in the lattice. The electronic excitation energy is
transferred to a specific motion of the dimer. This motion
can result in desorption of excimer when the described
process occurs on the surface. The energy needed for such
dimer motion can also be released in the lattice in the
course of the vibronic relaxation. A theoretical investiga-
tion [16] showed that in a system with strong local vib-
ration the energy release proceeds in a jump-like mul-
tiphonon process.
In case of pre-irradiated rare gas solids initial states of
relaxation cascades are self-trapped holes in molecu-
lar-type configuration Rg2
+and trapped electrons. It was
found recently in a molecular dynamics study of energy
transfer in solid Ar that the energy can be transferred over
long distances from the excitation site [17]. Desorption of
atoms in the ground state induced by charge recombina-
tion in the bulk of the crystal can take place via the
so-called crowdion mechanism, suggested in [18] to ex-
plain anomalous low-temperature desorption of Ar atoms
from solid Ar pre-irradiated by an electron beam.
Crowdions are non-linear waves of atomic displace-
ments, which propagate through the crystal to compara-
tively long distances (~100 of lattice constants). These
quasi-particles can exist in solid Ar, as was shown in [19],
and can take part in the desorption of atoms from the sam-
ple transmitting energy to the sample surface. The authors
calculated the energy needed for the creation of crowdion
to be 0.3 eV, which is lower than that released due to the
radiative decay of the excited dimer Ar2
� . This process is
the main stimulating factor for desorption of Ar atoms at
temperatures much lower than the characteristic sublima-
tion temperature for solid Ar (30 K).
In this article we present the first observation of a
nontrivial post-irradiation phenomenon — desorption of
vibrationally «hot» excimers Ar2
* from solid Ar pre-irra-
diated by an electron beam.
2. Experiment
Before the experiment the gas inlet system was
pumped and degassed by heating under pumping. The
samples were condensed from the gas phase under iso-
baric conditions (P = 10–7 mbar) on a metal substrate
cooled by a closed-cycle 2-stage Leybold RGD 580 cryo-
stat to the temperature 9 K. High purity Ar (99,999%) was
used. The base pressure in the vacuum chamber was
5�10–8 mbar. A typical sample thickness was 100 �m. The
samples were irradiated with an electron beam to generate
electron-hole pairs. We used electrons of 500 eV energy
and the current density of 30 �Acm–2. The dose of irradia-
tion was increased with exposure time.
To register cathodoluminescence spectra of solid Ar a
VUV monochromator was used. We performed spectrally
resolved measurements in the VUV range to detect emis-
sion from the bulk of the crystal and from the desorbing
particles. The measurements of luminescence intensity
were performed in a photon-counting mode. After the irra-
diation was finished the yields of afterglow and after-
emission of electrons were measured. The emission of
electrons from pre-irradiated samples was detected with an
Au-coated Faraday plate kept at a small positive potential
+9 V. It was positioned in front of the sample at the dis-
tance of 10mm. The current from the Faraday plate was
amplified by a FEMTO DLPCA 100 current amplifier.
For experiments on photon stimulated exoelectron
emission we used a Coherent 899-05 dye laser pumped
with an Ar-ion laser and tuned to 633 nm wavelength. The
power of the laser beam was 4 mW. The sample heating
under laser light did not exceed 0.5 K. In photo-induced
recombination luminescence experiments a vacuum
monochromator was tuned to the wavelength correspond-
ing to the W-band of solid Ar. Then the pre-irradiated
sample was exposed to a He–Ne laser beam of 4 mW
power and 632,8 nm wavelength.
3. Results and discussion
During irradiation of the samples of solid Ar by an
electron beam the spectra of cathodoluminescence were
310 Fizika Nizkikh Temperatur, 2008, v. 34, No. 3
G.B. Gumenchuk et al.
recorded. The luminescence spectrum of nominally pure
solid Ar under irradiation with an electron beam consists
of features that originate from the bulk and surface-re-
lated features. The most intense luminescence is caused
by the radiative decay of molecular-type self-trapped
excitons Ar2
� in the bulk of the sample. This broad
so-called M-band is formed due to transitions of excimers
from 1 3,
� u
� states to the ground state 1
� g
� and its intensity
is much higher than that of other features in the spectrum.
In Fig. 1 the cathodoluminescence spectrum of solid Ar in
the range of interest (10.7–11.8 eV) under irradiation by
low-energy electrons is presented. The well-known
M-band is not shown here. Band c is ascribed to
atomic-type excitons self-trapped on defect sites in the
bulk of the sample and is analog to the 3P2 �
1S0 transi-
tion in the free Ar atom. The sharp line b is emitted by the
excited Ar* atoms desorbed from the surface of the sam-
ple to the vacuum in 3P1 state. It is due to a transition to
the ground state 3P1 �
1S0. The line corresponding to
transition 1P1 �
1S0 is too weak in this case. The intensity
distribution between transitions from the 3P1 and 1P1
states is reversed in comparison with that in the gas phase.
The population of the triplet state is preferable because of
interaction with phonons in the lattice. The W-band stems
from the desorbing excimer molecules Ar
2
�( )�
as a result
of transitions from vibrationally excited states 1 3, ( )
� u
� � to
the ground 1
� g
� state. Note that vibrational relaxation on
the surface is much slower than in the bulk. Therefore
there is a high probability for molecules to desorb from
the surface in a «hot» state.
After the irradiation of a sample was completed we
started to investigate the relaxation processes in the crys-
tal. If solid Ar contains a minor amount of nitrogen a
long-lifetime afterglow is observed after switching off the
irradiating electron beam. This effect is caused by the
presence of guest nitrogen atoms (from residual gases in
the vacuum chamber) in metastable states after excitation
with electrons. The well-known transition of the N atom
2D �
4S is followed by the emission of light with a 521 nm
wavelength. We found a similar effect in the yield of
exoelectron current — afteremission of electrons from the
sample on completion of irradiation [20]. It was shown that
afterglow is responsible for afteremission of exoelectrons.
The current decays exponentially in time. The decay curves
can be described by a second-order exponential function
with characteristic decay times 1 ~ 30 s, 2 ~ 170 s [21].
We observed a similar dependence of the M-band [22] —
afterglow in the VUV range of spectrum, stemming from
the bulk self-trapped excitons. The estimated decay time
for the afterglow of the M-band is about 19 s, which is
close to the characteristic lifetime of the radiative transi-
tion of N atom from the metastable state 2D to the 4S state
in Ar matrix [23].
During the afteremission process we switched on the
laser beam directed to the surface of the sample to register
the release of electrons from the traps by visible light.
Note that holes are self-trapped in RGS, electrons can be
trapped either by guest atoms or by such lattice defects as
vacancies or pores (in view of the negative electron affi-
nity of solid Ar). Taking into account that solid Ar pos-
sess quite a wide conduction band (several eV) one can
expect to release electrons from the traps (both deep and
wide ones) using visible light. In Fig. 2,a the yield of la-
ser-induced exoelectron emission from pre-irradiated
solid Ar recorded during afteremission is presented. The
release of electrons from the traps and the following es-
cape from the sample under the laser light is obvious.
Some fraction of free electrons reaches the surface of the
sample and goes to the vacuum due to the absence of an
energy barrier because of negative electron affinity. Other
electrons can either recombine with self-trapped holes or
positively charged guest atoms or can be retrapped.
In this study we measured the yield of afterglow on the
wavelength of the W-band emitted by desorbed Ar
2
�( )�
(Fig. 2,b). It was found that the intensity of this emission
also decayed exponentially with a characteristic decay
time ~ 2.5 s. The reason why the value of is much
smaller for the W-band in comparison with that for the
M-band lies in the origin of these bands. The M-band is
emitted by the centers in the bulk of the crystal while the
W-band is caused by excimers formed on the surface and
in its vicinity. The rate of surface centers depletion is
higher than that for the bulk ones.
It is most likely that the radiative recombination of
self-trapped holes with electrons can be considered as a
source of the hot molecule desorption from solid Ar after
preliminary irradiation of the crystal with an electron
beam. Then the recombination of electrons with
self-trapped holes should increase the number of hot
Optically-stimulated desorption of «hot» excimers from pre-irradiated Ar solids
Fizika Nizkikh Temperatur, 2008, v. 34, No. 3 311
10.8 11.0 11.2 11.4 11.6 11.8 12.0
0
200
400
600
800
1000
1200
In
te
n
si
ty
,
ar
b
.
u
n
it
s
Energy, eV
W-band
b
c
Fig. 1. Cathodoluminescence spectrum of solid Ar in the range
10.7–11.8 eV.
Ar
2
�( )�
molecules, desorbed from the sample. We detected
these particles spectroscopically by measuring the inten-
sity of W-band. Fig. 2,b demonstrates the effect of
photo-induced luminescence of solid Ar at the wave-
length corresponding to the W-band (photon energy
11.3 eV). The laser light (wavelength 632.8 nm) was fo-
cused on the surface of the sample. The yield of lumines-
cence was recorded immediately after the irradiating elec-
tron beam was switched off. The intensity of the W-band
started to decrease exponentially. Then the laser was
switched on after approximately 5 s. We observed a con-
siderable increase in W-band intensity and a following ex-
ponential decay, caused by the depopulation of electron
traps by laser light. This fact proves the suggestion that
electron-hole recombination is responsible for the
desorption of hot molecules from pre-irradiated solid Ar.
The increase in W-band intensity (number of desorbed
excimers) induced by laser light depends on the moment
when the laser was switched on. The longer the delay be-
tween switching off the electron beam and switching on
the laser, the lower the intensity of the photon-stimulated
W-band emission.
The results obtained give evidence of a possibility of
optical stimulation of post-irradiation desorption of «hot»
Ar
2
�( )�
dimers from the surface of solid Ar containing
self-trapped holes, preliminarily produced by irradiation
of the crystal with some kind of ionizing radiation.
Summary
In this study we observed for the first time the
desorption of excited molecules Ar
2
�( )�
from pre-irradi-
ated solid Ar. It was shown that desorption of vibrationally
«hot» eximers from the solid Ar after preliminary excita-
tion above the forbidden energy gap is stimulated by re-
combination of electrons with self-trapped holes. It is dem-
onstrated that the process can be triggered optically by
releasing the electrons from the traps.
The authors thank Professors P. Feulner and G. Zim-
merer for valuable discussions. Financial support from
Deutsche Forschungsgemeinschaft is gratefully acknow-
ledged.
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Time, s
Laser on a
Fig. 2. Laser-induced exoelectron emission current from pre-ir-
radiated solid Ar recorded during afteremission (a). Laser-in-
duced luminescence of solid Ar on the wavelength correspond-
ing to emission of desorbed hot molecules Ar2
*
(W-band) (b).
Sample temperature T = 9 K.
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