ARTICLE IN PRESS

Physica B 383 (2006) 171–182

www.elsevier.com/locate/physb

Investigation of pyroelectric electron emission from monodomain

lithium niobate single crystals
El Mostafa Bourim, Chang-Wook Moon, Seung-Woon Lee, In Kyeong Yoo
Samsung Advanced Institute of Technology, U-Team, P.O. Box 111, Suwon, Kyongki 440-600, South Korea
Received 27 September 2005; received in revised form 8 February 2006; accepted 23 February 2006

Abstract

The behaviors of thermally stimulated electron emission from pyroelectric monodomain lithium niobate single crystal (LiNbO3) were
investigated by utilizing a Si p–n junction photodiode as electron detector and a receptive electron beam resist (E-beam resist) as electron
collector. In high vacuum (10
6 Torr), the pyroelectric electron emission (PEE) was found to depend on the exposed emitting polar
crystal surface (+Z face or
Z face) and was significantly influenced by the emitter-electron receiver gap distances. Thus, the PEE from
+Z face was detected during heating and was activated, in small gaps (o2 mm), by field emission effect on which was superposed an
intense field ionization effect that primed intermittent runway ionizations (plasma breakdown into a glow discharge). In large gaps
(42 mm) the emission was simply mastered by field emission effect. Whereas, The PEE from
Z face was detected during cooling and
was solely due to the field ionization effect. Therewith, for small gaps (o2 mm) the emission was governed by intermittent runway
ionization ignitions resulting from a high ionization degree leading to dense plasma formation, and for large gaps (42 mm) PEE was
governed by field ionization generating a soft and continuous plasma ambient atmosphere.
Significant decrease of electron emission current was observed from +Z face after successive thermal cycles. A fast and fully emission
recovery was established after a brief exposure of crystal to a poor air vacuum of 10
1 Torr.
r 2006 Elsevier B.V. All rights reserved.

PACS: 77.84.Dy; 77.70.+a; 79.70.+g; 79.70.+q; 52.80.
s; 51.50.+v

Keyword: Pyroelectric; Electron emission; Lithium niobate; Plasma breakdown; Runway ionization; Field emission; Field ionization; Emission recovery

1. Introduction engendered by the field emission effect [3–5], and others

Pyroelectric materials have been known to emit energetic
electrons up to 170 keV [1] by varying temperature without
need of external high voltages or any surface preparation.
It was demonstrated that a high electric field up to 107 V/
cm [2,3] generated by electrostatic charges (r ¼ D(Ps
ssc),
which could be either uncompensated screening charges
(sSC) on the crystal surface or uncompensated polarization
charges (PS) in the crystal surface (Fig. 1), can produce an
electron beam emission source, but the origin of the
emitted electrons still has not been thoroughly understood.
Some works inferred that the electron emission was
Corresponding author. Tel.: +82 31 280 9353, fax: +82 31 280 9308.
E-mail addresses: em.bourim@samsung.com, bourim@asia.com
(E.M. Bourim).
mainly suggested field ionization effect priming plasma
medium as electron source [1,6]. Furthermore it was
admitted in several articles that the electron emission yield
was not reproducible after successive thermal cycles in
vacuum [3,4]. The decrease of emission current was
primarily due to an incomplete screening of uncompen-
sated charges. The screening could be restored from crystal
bulk and/or absorbed charges from the surrounding
medium [7], its outcome is to establish a neutral electro-
static state of surface charges needed for the electron
reemission before that the crystal is subjected again to a
temperature change. Consequently, the evolution of sur-
face electrostatic state should be governed by surface
charge dynamics (charge screening and restoring), which
could be carefully controlled by the experimental condi-
tions such as environment (gas pressure around the

0921-4526/$ - see front matter r 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2006.02.034
 ARTICLE IN PRESS
172 E.M. Bourim et al. / Physica B 383 (2006) 171–182
Screening charge, σSC
– Polarization charge, PS
σSC
+Z face
PS
PS
-Z face
(a)
Fig. 1. Schematic diagram of the electrostatic state evolution of uncompensated charges (r) with temperature on +Z face surface of a monodomain-
pyroelectric crystal (a) at equilibrium ssc ¼ Ps-r ¼ D(Ps-ssc) ¼ 0- no electric field E on crystal surface; (b) when temperature change DT40-ro0 :
uncompensated charges of sSC are the source of electric field E on +Z face crystal surface; (c) when temperature change DTo0-r40 : uncompensated
charges of PS are the source of electric field E on +Z face crystal surface. Ivac and Ibulk are screening currents from the vacuum and through the bulk,
respectively. Solid and dotted arrows indicate flow direction of current and electrons, respectively.
crystal), temperature rate, interval of change in tempera-
ture, elapsed time following the temperature change, gap
spacing distance and the material parameters such as
conductivity, pyroelectric coefficient, work function etc.
Recent experimental studies were tried to reveal surface
charge and its dynamics [8,9], but the electron emission has
not been studied.
In the present paper, the electron emission and the
related surface charge dynamics of lithium niobate (LN)
are studied. The emission mechanism was found to depend
on the polar crystal surface exposed to a detector. Thereby
the pyroelectric electron emission (PEE) and its distribu-
tion were influenced significantly by varying the gap
distance between the crystal surface and the detector.
Significant decrease of emission currents from +Z face
crystal surface during repeated consecutive thermal cycles
was observed. This was attributed to an incomplete
screening (neutralizing) of polarization charges (PS) when
the crystal came back to room temperature. Restoration of
screening charges (sSC) (compensation charges of PS),
either from the crystal bulk (finite conductivity effect) that
needed a long recovery time (Maxwell relaxation) or by an
exposure to a poor vacuum of 10
1 Torr (gas molecule
ionization) that was instantaneous, could enable a repro-
ducible electron emission.
2. Materials and experimental procedure
We used polished monodomain Z-cut plates of con-
gruent lithium niobate (CLN) single crystals 1 mm thick
(Crystal Technology Inc.) and stoichiometric lithium
niobate (SLN) single crystals 0.5 mm thick (Oxide Cor-
poration); [Li2O]:[Nb2O5] mole ratio of the former is
48.4:51.6 and that of the latter is 49.9:50.1. The lithium-
deficient ‘congruent’ composition has a much higher
∆T > 0 , ρ < 0
Ivac e- Egap
σSC
–
e- +Z face
PS Ibulk
PS
(b)
∆T < 0 , ρ > 0
Ivac Egap
e-
–
+Z face
Ibulk e-
(c) PS
coercive field, about 22 kV/mm than that of the stoichio-
metric one; less than 4 kV/mm [10,11]. The crystals, placed
in a chamber at high vacuum, was heated up to 120 1C at
a heating rate of 10 1C/min then followed by a natural
cooling until room temperature. The chamber was
equipped with a turbo-molecular pump system with a base
pressure of less than 10
6 Torr. We varied the gap distance
between the sample surfaces and the electron detectors
from 90 mm to 5 mm. After electron emission, we examined
the surface of crystals by wet etching in hydrofluoric acid
HF:H2O (1:1) for 100 min. Such an etching can reveal
domain patterns, since
Z oriented domains have a much
faster etching rate than +Z ones [12,13].
Fig. 2 shows schematic diagram of sample and electron
detector cells setups for PEE current measurements and
spatial electron current distribution collections. A Si p–n
junction photodiode (AXUV–100, International Radiation
Detectors, Inc.) was used as a detector for emission
currents and resulting currents were measured by an
electrometer (Model 6514, Keithely Instruments, Inc.).
Responsivity of the photodiode (PD) is about 0.2 A/W for
electrons with energy in the range of 1–40 keV. Electrons
produced by LN crystals during heating have a large
energy up to 100 keV, and hence the PD amplification
factor of the emission current is about 104 [14]. Receptive
electron-beam resist (ZEP-520, Nippon Zeon Co., Ltd.)
was used to study the spatial distribution of the electron
current. ZEP-520 E-beam resist is known to have
sensitivities of 1 mC/cm2 for positive tone area exposures
to 1 keV electrons [15]. It was very simple to use resist-
coated wafers as detectors and the high sensitivity enabled
us to observe current distribution of PEE.
The gap between the crystal surface and the electron
detectors was adjusted by using alumina spacers of
different heights.
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E.M. Bourim et al. / Physica B 383 (2006) 171–182
Fig. 2. Schematic diagram of experimental setups. (a) LiNbO3 crystal-photodiode holder for emission current measurement (b) LiNbO3 crystal-E-beam
resist holder for electron current distribution collection.
3. Results and discussions
Fig. 3 shows the PEE current evolutions with time and
temperature measured from +Z face crystal surface during
the first heating run of as received samples (CLN (Fig. 3a)
and SLN (Fig. 3b)). The measurements were performed at
different gaps between the crystal surface and the PD
detector. For the CLN crystals, as the gap decreased below
2 mm, the current signal fluctuated and decreased abruptly.
While, a relatively smooth PEE current curves without any
abrupt drop was observed for SLN crystals in the studied
gap range.
After PEE current measurements the crystals were
etched with HF acid solution (50%), then an optical
microscope inspection was performed on the emitting +Z
face surface areas (Fig. 4). Linear patterned striations
were revealed on the +Z surfaces after etching. Magnified
view of these striation lines shows a treeing-like pattern,
which could result probably from an electrical discharge
during PEE current measurements. In fact these striations
were not other than superficial ferroelectric domain
inversion traces as was clearly seen from the striation
and spot patterns resulted on the SLN crystal surface
(see Fig. 5) [16,17] that were manifested in a regular
hexagonal geometric shape. For CLN crystals the density
of striations decreased as the gap increased and striations
practically disappeared when the gap was over 2 mm and
up. Whereas, spots and striations resulted on the SLN
crystals did not disappear even for a gap up to 4 mm. Such
173
behavior could be due to the small coercive field of the
SLN crystal.
Fig. 6 shows the evolution with time and temperature of
PEE currents measured from
Z face of as received
crystals at different gaps (1–3.5 mm) during two successive
thermal cycles with natural cooling. During heating no
significant emission current had taken part, while during
cooling the current signal at the small gap (o2 mm)
exhibited permanent flashes reaching important emission
current values. For a large gap (42 mm) the emission
current in cooling run rose and then stabilized by showing
a rapid slight swinging pace until reaching room tempera-
ture. Optical microscopic inspection of
Z face crystal
surface after acid etching did not show any notable
information.
Fig. 7 shows an overview of the spatial electron current
distribution on the developed receptive E-beam resist
surfaces that were facing the exposed faces of the crystal
emitters during one thermal cycle run for different gap
spacing variations. The emission impact from +Z face
(Fig. 7a, 8a), for small gaps (90 mm–0.5 mm), was
manifested in regular crossed and elongated lines. The
impact density decreased as the gap spacing increased and
no more impact line was discerned on the E-beam resist
when the gap exceeded 2 mm. Furthermore, the geome-
trical configuration of these impacts was analogous to the
superficial domain inversion traces observed on the crystal
surfaces. Such correspondence elucidates that the PEE was
accompanied by a superficial polarization reversal.
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174 E.M. Bourim et al. / Physica B 383 (2006) 171–182

1.5
gap=0.5mm
125
1.0 100
gap=0.5mm
10 100
0.5 50
75
0.0 0 5 50
gap=1.5mm 25
100
0.5 0
0

Temperature (°C)

Temperature (°C)
50 gap=2mm 100

IPD (nA)
IPD (µA)

0.0 10
0 75

gap=2.5mm 50
100 5
0.5 25
50
0 0
0.0 gap=4mm
0 100
10
gap=4.5mm 75
100
0.5 50
5
50
25
0.0 0 0 0
0 5 10 15 0 3 6 9 12 15
Time (min) Time (min)
(a) (b)

Fig. 3. PEE current evolution with time and temperature from +Z face of LiNbO3 crystals at different gap variations from 0.5 to 5 mm.CLN crystals (a),
SLN crystals (b).

Fig. 4. Optical microscope images with different magnified views of etched CLN +Z face surfaces after PEE for different gaps.

From
Z face (Fig. 7b), the emission impact on E-beam- fied view of these splashes showed a treeing-like shape
resist at small gap spacing equals to 90 mm was manifested (Fig. 8b), which indicated that the E-beam resist was
in a patterning with many concentrated splashes. Magni- subjected to an electrical discharge during PEE collecting.
 ARTICLE IN PRESS
E.M. Bourim et al. / Physica B 383 (2006) 171–182 175

Fig. 5. Optical microscope images with different magnified views of etched SLN +Z face surfaces after PEE for different gaps.

125 As the gap spacing increased the patterned splash size

1st thermal cycle
2 nd
thermal cycle on the E-beam resist grew and broadened until becom-
1.5 100
ing less visible with negligible impact at a gap over
75
3.5 mm.
1.0 Both the emission current curves and the spatial electron
50 current distribution impact on the E-beam resist exhibit
that PEE is extremely dependent on the gap spacing in
0.5
25 which the electric field magnitude Egap, is expressed as the
gap=3.5mm
following [4]:
0.0 0
DPs 1
100 100 E gap ¼ :
,

0 1 þ d gap =d cr
cr
Temperature (°C)

75 75
IPD (nA)

where DPS denotes the variation in spontaneous polariza-

50 gap=2.5mm 50 tion, e0 is the permittivity of free space, ecr is the relative
dielectric permittivity of the crystal (ecr ¼ 31 for CLN [4]),
25 25 dgap is the vacuum gap spacing between the upper polar
crystal surface and the electron detector and dcr is the
0 0 thickness of crystal along the Z polar axis. An estimation
of polarization charge variation DPS in a temperature
400 100 interval of 20 1C ramped in a short time compared to the
charge relaxation results in a change of PS (DPS ¼ gDT
300
gap=1mm 75 with g is the pyroelectric coefficient approximately equal to
200 8.2 nC/cm2 K for CLN [4] around room temperature) as
50 large as 0.16 mC/cm2 [4]. Therefore, the corresponding Egap
100 in a gap of 90 mm is evaluated to be about 1.8  106 V/cm.
25 Such electric field strength is high enough to engender an
0 electron emission either by field emission effect or/and field
0 10 20 30 40 50 60 ionization effect on gas molecules that approach the crystal
Time (min) surface. This later effect could also evolve a secondary
Fig. 6. PEE current evolution with time and temperature from
Z face of electron emission (SE) if the accelerated ions acquire
CLN crystals at different gap variations from 1 to 3.5 mm. enough energy [18].
 ARTICLE IN PRESS
176 E.M. Bourim et al. / Physica B 383 (2006) 171–182

Fig. 7. Spatial electron current distribution impact on the receptive E-resist from +Z face (a) and from
Z face (b) of CLN crystals at different gap
variations from 90 mm to 3.5 mm.

Before getting into the interpretations of the different
behaviors seen in our experimental results, we visualized by
sketching, in the Fig. 9, the different possible cases of
electrical charge emission, which could take place in the
gaps from both sides of pyroelectric crystal surfaces (+Z
and
Z), independently of the consideration of the
experimental conditions (ambient pressure, gap distance,
set up geometry), material parameters (conductivity, pyro-
electric coefficient, work function) and so on.
When the pyroelectric crystal heats up from room
temperature (RT) to T3, the decrease of spontaneous
polarization PS lets appear the uncompensated charges of
screening charges (sSC) on the crystal surfaces (electrons on
+Z face and positive charges on
Z face), thus pyro-
electric fields are built up in both sides of the crystal. In
+Z face side and
Z face side both mechanisms FE and/
or FI could take place. Therefore in the gap +Z face side
the released electrons are accelerated towards the collector
and positive ions towards the crystal surface. Whereas in
the gap –Z face side, species (electrons/+ions) take to drift
in the opposite way, the ions are accelerated towards the
collector and the electrons towards the crystal surface.
From such scenarios the electron emission current could be
measured only from +Z face and during heating.
When the pyroelectric crystal cools down from T3 to
RT, the rise of the spontaneous polarization lets emerge the
 ARTICLE IN PRESS
E.M. Bourim et al. / Physica B 383 (2006) 171–182
Fig. 8. Magnified view of line and splash patterns got at a gap spacing of
90 mm on the receptive E-beam resist.
polarization charges (Ps) in the crystal surfaces; when they
are uncompensated, they induce a pyroelectric field in each
crystal side. Thereby, FE and/or FI could take place in the
gap +Z face side. But in the–Z face side only the FI and its
consequent SE could be involved because the polarization
charges (PS) are embedded in the crystal surface and do not
leave the crystal under any external field influence. There-
fore, in the gap +Z face side the electrons are accelerated
towards crystal surface and positive ions towards the
collector. Whereas in the gap
Z face side, the drift of
species (electrons/+ions) is effectuated in opposite direc-
tions. From such scenarios the electron emission could be
measured only from
Z face and during cooling
[1,6,19–21].
In referring to the different sketched scenarios above and
the settled experimental conditions, an interpretation of the
probable electron emission mechanisms could be deduced.
177
3.1. Analysis of the electron emission from +Z face
The electron emission from +Z face, during heating in
high vacuum (10
6 Torr), at large gap spacings (42 mm)
where smooth PEE current curves were observed without
any remarkable perturbation (Fig. 3a), could be attributed
to a simple field emission activated by pyroelectric field
effect. Whereas, when the gap spacing decreases (o2 mm)
the electric field strongly increases at the crystal surface.
So, if some residual gas molecules persisting in the vacuum
medium, which the most probable are the air components
such N2, O2, Ar, CO2 etc., randomly approach the exposed
surface of the crystal, or any superficial gas manifestation
on the sample due to the sample surface out-gassing (CO,
CO2, N2 and H2O are almost the common formed species
on surfaces that has been exposed to the air, they desorb
when the sample heats up in the vacuum and raise the local
pressure near the crystal surface). These neutral gas
molecules, under the strong electric field, are ionized via
electron tunneling, thereby producing ion–electron pairs
(surface plasma formation). The spontaneous precipitation
of positive ions to neutralize the uncompensated negative
charges of sSC subsisting on the crystal surface releases
their associated electrons, in the meantime, the collision of
ions on the crystal surface could generate a SE. All these
electron swarms tend to provoke an electron avalanche,
and hence the plasma breakdown takes place [22–25]. Such
behavior should manifest an intense electron emission
followed instantly by an abrupt drop in the emission
current. In keeping up the temperature increase, such as
new uncompensated charges of sSC appear on the crystal
surface, the mechanism of surface plasma ignition causing
electrical discharge which leads to a neutral electrostatic
state of the surface charges (runway ionization) takes over
again. In this way, the intermittent emission current
recorded in small gaps (o2 mm) by the CLN crystal could
be explained (see Fig. 3 gap ¼ 0.5 mm).
It is to be noted that our PD and its electronics cannot
detect the discharge current directly because the current
burst duration is very short, less than 1 ms [26], and
electrons cannot arrive into the detector within the
resolving time of the electronics. Therefore, the PD can
only bear witness of plasma breakdown signature, which is
manifested by an abrupt drop in the emission current.
Also, we notice that the used E-beam resist could show the
current distribution only for a magnitude exceeding the
sensitivity of 1mC/cm2 for positive tone area exposures to
1 keV electrons [15]. The sensitivity is much larger than the
total emitted charge density, 1 nC/cm2, of CLN [3,4,27].
Consequently, the patterned impact on the E-beam resist
should be an act of current burst caused by plasma
breakdown due to a high ionization degree (dense plasma
formation), but not a simple PEE caused by field emission
or soft ionization.
The magnified view of the striation lines, which
correspond to domain inversion, revealed by etching on
+Z face after PEE at small gaps (o2 mm), showed clear
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178 E.M. Bourim et al. / Physica B 383 (2006) 171–182

Heating run Cooling run

Collector Collector Collector Collector

P P

++

++

++

++
T3

FE FE

+++++ +

<
P + E P E
+++

+++

++
FI + + FI
SE SE T2
+ +

_
FE
++++++++

<
+++++

+++++
E P E P

+++
+ FI + + FI
T1
SE SE
++++++

++++++++

++++++++

++++++++
P P
Room
Temperature

+Z Z +Z Z

Fig. 9. Sketched scenarios of electrical charge emission sources originated from different effects (FE, FI, SE) activated by spontaneous polarization PS
change with temperature of the pyroelectric crystal. FE: Field emission, FI: field ionization and SE: secondary electron emission. Note that this depicted
description does not correspond to any definite gap distance or gas pressure in the vacuum system.

dendrite form patterns (Fig. 4 gap ¼ 0.5 mm). Such tree-
like confirms the electrical discharge strike resulting from
the engendered plasma breakdown on the crystal surface
during PEE. In addition, the patterned lines on the E-beam
resist (Figs. 7a,8a) look like a transferred image of the
domain inversion striations from the crystal surface. This
implies that the partial polarization domain inversion is
related to the plasma effect on the crystal surface. The
manifestation of the domain inversion in elongated and
crossed striations seems to follow the crystal symmetry
(hexagonal lattice structure) of the LiNbO3. Probably,
when the temperature increases the released screening
charges, which are not emitted yet, tend to move on the c-
plane of +Z face and accumulate preferentially at the
hexagonal unit cell borders where the spontaneous
polarization could be weaker than in the middle of the
unit cell, and hence establishing an hexagonal repartition
chain of electrons on the crystal surface. Since the
engendered plasma under the high electric field in a small
gap involves a high electron/+ion pair density (dense
plasma). Thus, the positive ions, at the time of their
formation, are suddenly attracted to the crystal surface and
react with those uncompensated electrons accumulated on
hexagonal locales. Therefore from these locales the
electrical discharge is primed, and thence the domain
inversion could be initiated. In so doing, two predictive
cases could probably be at the origin of domain inversion.
The first case suggests that the domain reversal could be
due to the ion bombardment on the crystal surface. Many
researches have demonstrated domain inversion by elec-
tron beam bombardment [28–32], in these works, the
penetrating electrons, on the crystal surface, is believed to
cause an electric field that acts as a local re-poling field.
Similarly, a plasma-generated ion current with high energy
can induce domain inversion by surface ion bombardment.
This is supported by our finding that the developed E-beam
resist showed that the pattern in the area, where plasma
had acted, appeared similar to that in the domain inversion
regions.
The second case predicts that, at the ionization of the
residual gas molecules near the crystal surface, the accelerated
positive ions, by the electric field Egap, in the gap, towards the
supposed locales hexagonal chain, where the electrons are
preferentially accumulated, cause a local over-depletion of
these superficial charges, and thereat, immediately a local
depolarizing field takes over to reduce the material electro-
static energy. Consequently, a local-domain inversion takes
place to establish a new internal energy balance.
This inference could not be held out for SLN crystals
that remained manifesting domain inversion in shape of
spots and lines on the almost whole crystal surface even at
large gap distances of up to 4 mm where the surface plasma
breakdown should be absent. Apparently, in the stoichio-
metric crystal, the domain inversion might be formed at
cooling as well. In fact, in high vacuum level (10
6 Torr)
and at cooling, the increased positive polarization charges
(PS) in the crystal surface could not be fully screened from
the external ambient atmosphere or the crystal bulk, and as
far as that goes, the possible screening could not be
homogeneous on the entire crystal surface. So, the locales
of polarization charges (PS) subjected to a lack of screening
were compelled to a superficial domain reversal that was
facilitated by the weak coercive field of the SLN crystals
(o4 kV/mm) [11], and thus establishing a new internal
energy balance state. Unlike the CLN crystal that had
a high coercive field (20 kV/mm) [10], this one could
 ARTICLE IN PRESS
E.M. Bourim et al. / Physica B 383 (2006) 171–182
demonstrate a resistance to such partial depolarizing field
during the rising of positive spontaneous polarization Ps in
cooling. Therefore no domain reversal was observed on
+Z face surface for large gaps over 2 mm.
In the long run, it is plausible to accept that the forced
depletion of screening charges sSC on a monodomain
crystal surface leads to a multi-domain apparition by
reducing the crystal electrostatic energy. Then for a small
gap (o2 mm) when the temperature increases, the en-
gendered plasma breakdown drops the superficial screening
charges (sSC) instantaneously and locally on crystal
surface. And since the polarization intensity diminishes
with increasing temperature, domain inversion becomes
easy to take effect and annihilates the local depolarizing
fields. On the other hand, for large gaps (42 mm) the
electron emission from uncompensated screening charges
(r ¼ D(PS-sSC) on the crystal surface is regulated by the
Egap dependence on the spontaneous polarization variation
with temperature. So, the electrostatic energy equilibrium
is maintained instantly and domain inversion is avoided.
3.2. Analysis of the electron emission from
Z face
Regarding the electron emission mechanism from
Z
face in cooling, the sketched electric charge emission
scenarios (Fig. 9) emancipate that the field ionization
should be the only dominant mechanism.
In small gap spacing (1 mm) discontinuous steep drops
of emission current signal was recorded (Fig. 6). Certainly
such emission was the signature of an intermittent electrical
discharge formation resulting from surface runway ioniza-
tion ignition (plasma breakdown from the ionized gas
molecules near the crystal surface) during cooling. In fact,
when the crystal is cooling the
Z face becomes increas-
ingly negatively charged due to the raising of spontaneous
polarization Ps in the crystal surface, the corresponding
build up of electric field, which, in small gap (o2 mm), can
exceeds the runway ionization (electrical discharge ignition
giving rise to a new neutral state with an instantaneous
drop to zero of electric field at the crystal surface) of the
existing gas molecules at the given low vacuum pressure
(10
6 Torr). Therefore, from this spontaneous dense
formed plasma and via its subsequent glow discharge,
simultaneously, electrons are accelerated towards the
collector and equivalent amount of positive ions are
accelerated towards the crystal neutralizing then the
polarization charges (PS). Consequently the PPE will drop.
This sequence repeats itself as the temperature gradually
changes.
Also the splashed patterns (Figs. 7b, 8b), whose shapes
were a kind of treeing-like, collected on the receptive E-
beam resists, testified that the PEE was resulted from a
high ionization degree causing high-intensity discharge as
temperature cools down.
In large gap spacing (2.5 mm), the PEE current showed
monotonous continuous curves on which was superposed a
fast slight vacillation (Fig. 6). While the sample cooled
179
down the emission current increased and then stabilized in
a plateau until room temperature. The corresponding
spatial electron current distribution collected on the
receptive E-beam resist at different gaps showed a broad-
ening of tree-like pattern with faint impacts when the gap
distances increased (Fig. 7b). From these observations of
PEE behavior from
Z face at large gaps (42 mm); the
electron emission could be originated from a soft and
maintained plasma formation medium near the crystal
surface. Since the plasma results from the field ionization
effect on the neutral gas molecules, therefore the residual
gas molecules surrounding the crystal is the source of
electrical charges for electron emission and screening of
uncompensated charges as the temperature of the crystal
change. Consequently, in addition to the gap spacing effect
on the electron emission mechanism discussed earlier, the
gas pressure around crystal surface also plays a major role
in the influence of electron emission mechanism by
variation of the plasma density production. Therefore, if
the gas pressure is high (1 atm), the ionized gas molecules
under the existing electric field are in excess, they neutralize
the polarization charges (PS) almost as fast as these later
appear in the surface of the crystal. On the other hand, if
the gas pressure is low (o10
6 Torr) there is a limit on the
amount of free electrical charges and gas molecules in the
vacuum medium, then there will not be enough gas that can
be ionized to provide compensating charges at a rate equal
to the rate of polarization charge (PS) production,
consequently, uncompensated negative polarization
charges (PS) will still keep increasing in cooling. Once the
temperature of crystal becomes stable, the electric field in
the gap will last for a considerable time since the
polarization charge (PS) in the crystal surface will be
neutralized at a rate determined principally by the rate at
which gas molecules come close enough to the surface of
the crystal to be ionized. This explains the maintained
emission current plateau from
Z face when the crystal
temperatures approach room temperature during natural
cooling. Also, the above analyses support that the electron
emission from
Z face, in cooling, is governed by a field
ionization (FI) mechanism producing, in large gap spacings
(42 mm), a soft plasma environment. From this weak
plasma medium, the released electrons are accelerated to
the collector and the associated positive ions are acceler-
ated towards
Z face crystal surface. The emission could
be accompanied with SE if the positive ions gain enough
energy when they bombard the
Z face crystal surface.
3.3. Electron emission recovery
It was observed that the PEE current from +Z face
decreased significantly after many successive thermal cycles
in the maintained high vacuum (10
6 Torr) (Fig. 10). At the
immediate second repeated thermal cycle the emission
current has been reduced by two orders of magnitude
and appeared to start with certain retardation in both
temperature and time scales. However, a moderate

180 E.M. Bourim et al. / Physica B 383 (2006) 171–182
CLN crystal (+Z face, emitter-detector gap=2.5mm)
st
1 heating run
0.4
2nd immediat successive heating run
3rd immediat successive heating run
0.3
IPD (µA)
0.2
0.1
2nd
3rd
0.0
20 40 60 80 100
Temperature (°C)
Fig. 10. PEE current evolution with temperature from +Z face of CLN
crystal during successive thermal cycles. (Insert shows the emission
currents in log scale).
emission current decrease was observed from
Z face after
a consecutive thermal cycle. Such different behaviors of
reemission current from each polar crystal face after
consecutive thermal cycles are attributed to the difference
of times for screening (neutralizing) the electrostatic state
(uncompensated charges r) of crystal surface before the
subsequent stage of temperature change for electron
reemission. Thus, for +Z face, a compensation of
unscreened positive polarization charges (PS) is needed
before the consecutive heating run, and for
Z face a
compensation of unscreened positive screening charges
(sSC) is needed before the consecutive cooling run.
Generally, the screening process occurs by means of
various compensation currents: through the crystal bulk,
Ibulk, and from or into the vacuum, Ivac (Fig. 1c shows
screening case of +Z face at cooling). Ibulk is determined
by the LiNbO3 crystal conductivity, s, and is streamed by
the relaxation of space charges in the crystal under the
electric field of unscreened charges r. Ivac is grouped into
field emission current, IFE, and ion current, Iion. IFE is
caused by the tunneling of electrons, which are localized to
the surface quantum wells [3,5], according to the electro-
static state of the surface, the screening by field emission
could be an electron emission from the collector plate
towards the pyroelectric crystal surface or in opposite
direction, from the crystal surface toward the collector
plate. Iion consists of ionized gas molecules persisting in the
vacuum by field ionization. After Rosenman works [4,33],
Ivac is much smaller than Ibulk which is governed with the
crystal conductivity. IFE is negligible due to the high work
function of the material from where it originates (crystal or
collector surfaces) and Iion is also small because of a large
threshold of field ionization in high vacuum, thus, its
resulting secondary electron emission current is system-
atically negligible too. Therefore, in high vacuum level,
ARTICLE IN PRESS
only the contribution of the crystal bulk current (Ibulk)
could be dominant for screening process, its characteristic
relaxation time is given by Maxwell relation time t ¼

0 =s
(where e is permittivity of the crystal). The evaluated
relaxation time, t ¼ 2:1 h, is much larger than the time
1st period of one thermal cycle which lasts, in our experiment,
about 1 h. So, for +Z face screening, after one thermal
cycle, the positive polarization charges (PS) could not be
completely screened before the immediate consecutive
heating. This shirt time screening retains the crystal surface
charged positively, i.e., r ¼ PS
sSC 40 on the +Z face,
thence the subsequent heating needs larger temperature
interval difference to build up a negative electrostatic state
on the crystal surface that produces a sufficient field able to
generate electron emission. Consequently, the emission will
manifest with a retardation and reduction of the total
120 140 emitted electrons. This explanation is consistent with our
experimental results on successive PEE tests from +Z face
in vacuum (Fig. 10). Several PEE current measurements
were recorded after different relaxation time durations in
vacuum at room temperature (see Fig. 11). A relaxation of
80 h, 40 times larger than the Maxwell relation time, was
necessary to the emission current to become similar to the
initial one.
We have seen that the PEE current from
Z face was
not remarkably affected after repetitive thermal cycles. The
emission current reappeared immediately after the elapse of
the prior thermal cycle and did not need any time interval
to be restored. In fact, such behavior is due to the fast
screening, at high temperature, of uncompensated positive
screening charges (sSC) released on
Z face surface when
the polarization PS decreases upon heating until around
120 1C. The temperature raise increases the conductivity
of the crystal and consequently the relaxation time of
electrons supplied from the crystal bulk to the polar
Z
face surface decreases. Inasmuch as the screening at high
temperature takes place in a short time, therefore, when the
CLN crystal (+Z face, emitter-detector gap=2.5mm)
0.3 120
100
Temperature (°C)
0.2 80
IPD (µA)
80 hr
. 60
0.1 20 hr
. 40
20
2 hr.
0.0 0
0 5 10 15
Time (min)
Fig. 11. PEE currents from +Z face of CLN crystal measured in high
vacuum (10
6 Torr) with different time intervals between measurements.
 ARTICLE IN PRESS
E.M. Bourim et al. / Physica B 383 (2006) 171–182
crystal cools down the uncompensated negative polariza-
tion charges (PS) could build up with a large density within
a short interval temperature change and thus the associated
Egap activates again the electron emission.
As is known that in an electric field the Iion current
generation from gas molecules ionization depends on the
vacuum level, it is plausible to restore the screening charges
(sSC) or to screen the uncompensated charges r by
choosing a suitable gas pressure to maintain a constant
ionization rate equal to the rate of polarization charges
(PS) variation, or even by raising the vacuum pressure from
low to high gas pressure for priming an electrical discharge
thus generating an instant screening. Paschen’s law [26],
which states that the air breakdown voltage is function of
the product of gas pressure and gap distance, indicates that
for a fixed gap the electrical discharge can be primed by
varying the medium gas pressure. So, to promote an
electrical discharge to stimulate screening of uncompen-
sated charges, an exposed +Z face of LN crystal was
subjected to an increase of pressure from a high vacuum of
10
6 Torr to a low vacuum of 10
1 Torr by introducing air
into the vacuum chamber after the first thermal cycle, then,
the vacuum was reinstalled to respect the usual experi-
mental conditions of PEE current measurements at a
pressure below 10
6 Torr. Furthermore, the total time
period of sample exposure to low vacuum and high vacuum
reinstalling which took only about 2 min, allowed succes-
sive PEE current measurements in a period much lower
than the estimated relaxation time (2.1 h). Fig. 12 shows
that the PEE current was successfully restored and a
reproducible emission can be obtained. The recovered
current was nearly the same for the exposure times varying
from 1 min to 2 h at 10
1 Torr. Indeed, the restoring of
screening charges (sSC) via the electrical discharge is
instantaneous and independent of time because during
varying the vacuum level from low to high pressures, these
pass through a critical pressure value which with the
established electric field in the gap ignites a sudden
electrical discharge and therewith screens instantly the
whole uncompensated charges in the crystal surface.
Fig. 12. PEE current evolution from +Z face of CLN crystal measured in
high vacuum (10
6 Torr) after exposing the crystal to air at 10
1 Torr.
181
10-1 Torr during cooling
10-1 Torr at R.T. for 1 min.
IPD (arb. units)
0 5 10 15 20
Time (min.)
Fig. 13. Comparison of PEE current evolution from +Z face of CLN
crystal measured in high vacuum (10
6 Torr) after exposing the crystal
to air at a pressure of 10
1 Torr all along cooling from 120 1C and for
1 min at room temperature.
Fig. 13 shows also a comparison of PEE current between
an exposure of sample to a gas pressure of 10
1 Torr during
the whole cooling run from 120 1C until room temperature
and a short exposure time of just 1 min once the sample
reached room temperature under high vacuum, in spite of
such exposure difference, nearly similar PEE current levels
in the subsequent heating in high vacuum were observed.
These results also justified that the recovered current was a
consequence of the discharge effect whose the screening
was instantaneous, and the restoring of screening charges
by adsorption of free electrical charges from the ambient
gas pressure medium was not palpably dominant since the
measured current signal did not depend on the exposure
time.
4. Conclusion
In this work, the PEE current from both polar surfaces
(+Z face and
Z face) of LiNbO3 monodomain single
crystal was investigated. It was demonstrated that the
mechanism dominating the electron emission activation, in
high vacuum, depends on the exposed polar crystal surface.
The PEE current from +Z face was in majority due to field
emission (FE) effect, while the one from
Z face was due
to field ionization (FI) effect.
Also, it was seen that gap spacing distances between the
crystal surface and the electron collector seriously influ-
enced the electron emission behavior. Thus, for small gaps
(o2 mm), the PEE current from both polar face surfaces
(+Z face,
Z face) was a consequence of a high ionization
degree by the high electric field in the gap causing
intermittent runway ionizations (surface discharge) by
plasma breakdown process. Such plasma breakdown was
 ARTICLE IN PRESS
182 E.M. Bourim et al. / Physica B 383 (2006) 171–182
at the origin of domain wall inversion on +Z face surface.
Whilst for large gaps (42 mm), from +Z face; the PEE
current under the field emission was continuous and
manifested in a peak shape, and from
Z face; the field
ionization maintained a soft and continuous plasma
formation that ensured a monotonous continuous emission
current lasting in a plateau evolution until room tempera-
ture.
Regarding the electron emission current reproducibility
in high vacuum. It was found to have a link to the
relaxation time of screening of uncompensated charges (r).
Such screening was in the majority by electrons supplied
from crystal bulk. Thus, for the exposed +Z face surface,
after electron emission during heating, the screening of
positive polarization charges (PS) took place all along
cooling until room temperature and since the conductivity
decreased, a long time for a complete restoring of screening
charges (sSC) on the crystal surface was needed. On the
other hand, for the exposed
Z face, the screening of the
released positive charges (sSC) on the crystal surface took
place during heating and needed then just a short time since
the crystal conductivity increased with temperature.
Also, it was found that priming electrical discharge by
exposing the crystal to a change of vacuum level by varying
continually the pressure from a low (10
6 Torr) to high gas
pressure (10
1 Torr) generated a reproducible emission
current without any consideration of time exposure.
Indeed, the discharge mediating screening was instanta-
neous.
Finally, this study let envisage that a judicious selection
of the pyroelectric crystal physical properties (conductivity,
pyroelectric coefficient, work function etc.) and a judicious
adjustment of the experimental conditions (gap spacing,
temperature rate and gas pressure) can optimize the field
emission and/or field ionization effects for ensuring a high
electron emission current intensity that could last for a
longtime once the temperature of crystal becomes stable.
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