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Cathode-luminescence diagnostics of MgO,

MgO:Si, MgO:Sc, and MgCaO

Article · January 2012

DOI: 10.1889/JSID20.1.63

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Cathode-luminescence diagnostics of MgO, MgO:Si, MgO:Sc, and MgCaO

Wen-Jian Kuang
Harm Tolner (SID Life Member)
Qing Li* (SID Senior Member)
Abstract — The cathode-luminescence (CL) emission of crystalline MgO, MgO:Si, MgO:Sc, and
MgCaO, often used as a protective-layer material in PDPs, were measured. In some of these materials,
it was found that the UV emission band is located at a shorter wavelength than published in the lit-
erature and depends upon the type of impurities or doping. MgCaO-pellet material is found to contain
a separate CaO phase. It is concluded that the recombination mechanism is thermally assisted in most
of these materials, while only in the case of MgO:Sc tunneling recombination was found.

Keywords — PDP, cathode luminescence, ultraviolet, MgO, MgCaO, exoelectron.

DOI # 10.1889/JSID20.1.63

1 Introduction 2 Experimental method

At present, 3-D technology plays an increasingly significant
role in the information-display industry. The benefit from
this is that plasma-display panels (PDPs), which have a
wide-viewing angle, good color expression, and especially
fast response time, will bring a new wave of display evolu-
tion and are most promising in the commercial marketplace.
In plasma-display devices, it has been widely accepted that
crystal-type MgO, which is deposited in the form of submi-
cron-sized crystals on top of the regular MgO film, can pro-
mote the emission of priming electrons. After being exposed
to the plasma sustaining discharge, these materials exhibit a
delayed electron emission, which is the result of the recom-
bination emission of electrons and holes. This very small
exoelectron emission is strongly amplified inside the plasma
device by the xenon-gas voltage and reduces the addressing
jitter in a PDP.
It is well known that exoelectron emission from elec-
tron traps is much stronger, if there was a positive wall
charge deposited in the previous cycle.1,2 We therefore use
cathode luminescence (CL) to simulate the joint presence
of both free electrons and holes inside the crystal-type pro-
tective layer. We measured the light emission at a wave-
length from 180 to 850 nm, and compared the shift in the
UV emission peak when using different types of MgO,
MgO:Si, MgO:Sc, and MgCaO crystals.
Undoped MgO crystals are known to be effective in
producing priming electrons, without causing too much
wall-voltage loss.3 These types of crystals are known to emit
UV-light at about 235 nm. The shift of the UV emission
peaks will be discussed and a hypothesis is proposed to
explain the different emission characteristics and the possi-
ble relationship with exo-emission and secondary electron
emission. These results will hopefully contribute to the fun-
damental know how of crystal-type protective-layer material
and help to effectively improve the emission properties of
MgO and thereby enhance the performance of PDPs or
other plasma devices.
We mainly used the FEI-SEM with a Gatan light-collecting-
mirror CL system to make CL images and an Ocean Optics
spectrometer for the spectra (see Fig. 1). The samples are
used without any conductive coating. This enables CL imag-
ing and spectroscopy without the danger of surface absorp-
tion of the emitted UV light by, e.g., a thin gold layer. To
virtually avoid charging, we use the LFD detector of the
FEI-SEM in low-vacuum mode (100 Pa of water vapor pres-
sure) or we use a negative grid bias voltage on the SED
detector to produce backscatter images. CL images of MgO
crystals are recorded by using the Gatan light collector,
equipped with a PMT detector that is sensitive from 180 to
850 nm. The benefit from this is that we can obtain the CL
signal from UV, visible, and near-infrared regions. Finally,
we collect the CL spectra by using an Ocean Maya 2000 Pro
spectrometer.
An electron-beam energy of 10–30 kV, used in CL, is
much higher than the bandgap energy. Therefore, inside the
MgO crystals, the electron beam produces both free elec-
trons and holes in the form of excitons. During their very
short lifetime, the excitons (X) diffuse through the MgO
bulk crystal; typically, the diffusion length inside MgO crys-
tals is about 200 nm.4
It is expected that excitons also play an important role
in the case of excitation by xenon plasma. As soon as free
electrons and holes are present at the same time, they form
an exciton, which can freely diffuse through the MgO crys-
tals. After traveling typically 0.2 µm inside the MgO crystal,
they recombine, for instance, at a donor center (D) in the
form of an electron trap.3 Such a DX recombination center
is well known to be a highly efficient emitter of both UV
radiation (singlet level) and of Auger electron emission
(triplet level); emitter centers close enough to the surface
enable the Auger electrons to escape, and may contribute to
the exoelectron current. In addition, it may well be possible
that exoelectrons can also be emitted by the recombination
of two triplet excitons while emitting electrons. In OLEDs

Based on a paper presented at the 2011 SID Symposium held May 17–20, 2011, in Los Angeles, California, USA.
The authors are with the Display Center, School of Electronic Science and Engineering, Southeast University, 2 Sipailou, Nanjing, Jiangsu 210096,
China; telephone +86-25-8379-2449, e-mail: liqing@seu.edu.cn. *Corresponding author: Q. Li.
© Copyright 2012 Society for Information Display 1071-0922/12/2001-0063$1.00.

Journal of the SID 20/1, 2012 63

 FIGURE 1 — Sketch of the measurement system; a SEM machine with a CL system and spectrometer is utilized for CL
spectra, SE, and CL images.

this mechanism is an undesired loss mechanism, while in a
PDP it promotes the emission of hot electrons (see Fig. 2).
MgO single crystals, used as a “crystal-emissive” layer in
PDPs that are larger than 100 nm have been found to produce
strong UV emission centered at about 235 nm,3 and submi-
cron MgO crystals are very effective UV emitters. In thin
films, on the other hand, it is thought that most of the excitons
dissociate at the surface, thereby producing mainly surface
and bulk F-type light emission around 400–500 nm, while the
UV emission is, in general, almost completely quenched.
3 Recombination emission
Figure 2 shows some of the many different possibilities of
electron–hole formation and recombination after excitation
by an electron beam. From left to right: (1) direct recombi-
nation of free electrons and free holes; (2) recombination at
a divalent recombination center such as Ca2+ doping in
MgO; (3) recombination of trapped electrons and trapped
holes, either direct (short arrows) or after thermal excitation
(long arrows); (4) direct recombination, followed by energy
transfer to an Auger electron, resulting in exo-emission; (5)
exciton recombination, with an energy just below the
bandgap value; (6) electron emission from an F-center (see
Fig. 2), thereby forming an F+ center, followed by the exci-
tation of the second electron from the F+ center (not indi-
cated); 7) Triplet–triplet exciton annihilation, resulting also
in the emission of a hot electron (exo-emission). This is yet
another possible mechanism that might explain the delayed
electron emission.

FIGURE 2 — Excitation, recombination, and emission mechanisms in wide-bandgap materials such as MgO and MgCaO.

64 Kuang et al. / CL diagnostics of MgO, MgO:Si, MgO:Sc, and MgCaO

 Most probably, delayed electron emission is directly
related to the electron trap levels indicated in Fig. 2. The
emission kinetics, however, is not understood at all at the
moment. In addition to the direct Auger electron emission
mechanism, we also included in Fig. 2 the possible electron
emission by exciton-donor association and by exciton–exci-
ton annihilation.6 In the case of triplet excitons, the latter
might explain the long duration time of the exoemission. In
pure MgO crystals, however, the singlet levels are lower
than the triplet levels. In the MgO surface, on the other
hand, triplet levels have the lowest energy, while for doped
MgO the situation is as yet unclear.
4 Experimental details
4.1 Experimental setup
Two types of MgO crystals have been made. Firstly, one type
is pure MgO single crystals which are produced by heating
MgCO3 at 1373K. The second type of samples is polycrys-
talline and has been prepared by crushing commercially
available MgO undoped, MgO:Si, and MgO:Sc pellets, as
well as MgCaO mixed oxide crystals. These samples were
FIGURE 3 — (a) Low-vacuum SEM image of undoped MgO crystals
(~200 nm) made by MgCO3 calcination at 1373K7; (b) the CL spectrum
of undoped MgO crystals.
stored in vacuum and only briefly exposed to ambient air
before being introduced into the CL chamber.
By using a high-energy electron beam, e.g., at 30 kV,
all levels in MgO can be excited at the same time. CL images
of MgO crystals are recorded by using a Gatan light collec-
tor, equipped with a PMT detector that is sensitive from 180
to 850 nm. The spectral distribution of the emitted light is
determined by using an Ocean Maya spectrometer for wave-
lengths from 180 to 1100 nm.
At an electron-beam energy of 30 kV, electron excita-
tion mainly occurs at a depth on the order of 1 µm, so that
the emission spectrum is hardly affected by degradation of
the surface
4.2 Pure undoped MgO submicron crystals
(~200-nm crystal size)
As is illustrated in Fig. 3(b), the CL spectrum shows three
major emission bands. The broadband emission at 236 nm
is probably the electron–hole UV recombination emission
that is associated with donor impurities (electron traps).5
The broad emission band around 400 nm is related to the
F-center emission, while the broadband around 700 nm is
FIGURE 4 — Large-sized (1–2 µm) undoped MgO crystals. (a) SEM image;
(b) CL spectra from different areas.
Journal of the SID 20/1, 2012 65
most probably related to trapped holes at V centers. It also
shows sharp emission features of the chromium zero-phonon
R line at 700 nm and the 2E → 4A2 line at 720 nm, both
associated with Cr3+ impurity ions, always present in MgO
in minute amounts (<20 ppm).8

4.3 Undoped MgO sintered polycrystalline

crystals (1–2-µm crystal size)
For the analysis of larger crystals, we used crushed MgO
pellets as reference, containing 1–2-µm-sized cubic MgO
crystals. In this case, the UV emission peak is much stronger
than for the 200-nm crystal powder.
As shown in Fig. 4(b), the UV-emission-peak position
is found to change from 231 nm down to as short as 219 nm,
depending on the area and position that is analyzed. This
may indicate that different types of impurities are present
that are distributed non-homogeneously. We picked the
third CL spectrum, the blue one, as reference for compari-
son with doped MgO crystals.

FIGURE 6 — Crushed large MgO-Sc doped crystals; this area is showing

a uniform CL emission, except for the small loose particles.

4.4 CL emission from MgO:Si and MgO:Sc

The SEM images and CL emission from doped polycrystal-
line MgO:Si and MgO:Sc are given in Figs. 5 and 6.
Unexpectedly, the CL spectrum of silicon-doped MgO
is similar to that of the undoped MgO crystals, both located
around 230 nm. The UV emission peak of the MgO:Sc crys-
tals, found by the spectrometer, however, is located at about
250 nm. When imaged by the PMT this material shows a
very uniform emission over its entire crystal surface (see
Fig. 6). These densely sintered MgO:Sc crystals show almost
no F-center emission; also absent is the red V-center emis-
sion. In some areas there is also a 302-nm emission peak.

4.5 MgCaO CL emission and the effect

FIGURE 5 – Large-sized Si-doped MgO crystals. (a) SEM image; (b) CL
spectrum.
of air exposure
In the case of freshly crushed MgCaO pellets, we observe a
very strong UV peak at 218 nm (5.7 eV) [Fig. 7(a)]. After
continued exposure to air, however, the 218-nm UV emis-
sion peak, however, disappears completely and is replaced
by a strong F-center-like broad emission band around
400 nm [Fig. 8(b)].

66 Kuang et al. / CL diagnostics of MgO, MgO:Si, MgO:Sc, and MgCaO

 recombination emission is shown in Fig. 9 that appears to
explain the observed spectra.
Both “pure” cubic MgO crystals and Si-doped MgO
crystals show a UV peak emission around 235 nm (5.3 eV),
similar to the crystal emissive layer particles used by Pioneer.3
Sintered MgO polycrystals, however, show a UV emission
peak typically at shorter wavelengths, varying from 219 to
230 nm. The highest UV energy emission is observed from
MgCaO mixed oxide crystals, with a peak wavelength at
218 nm (5.7 eV).
According to Kalder et al. at 80 K the UV CL emission
from ultra-pure MgO occurs at 5.8 eV (214 nm), while the
peak emission of MgO:Al is at 5.3 eV, and for MgO:Si it is at
5.0 eV.5 When comparing our results on MgO, we conclude
that the UV emission of our pure MgO most probably con-
tain Al3+ impurities, a common impurity that can hardly be
avoided when making MgO crystals, explaining the UV peak
at 5.3 eV.
In the case of the Ca2+ ion, with an ion size of 0.100 nm,
the ion size is larger than that of Mg2+. In this case of iso-
electronic replacement, Ca2+ ions merely act as very effi-
cient recombination centers, thereby enhancing the pure

FIGURE 7 — CL spectra of MgCaO crystals: (a) freshly crushed and (b)

after continued exposure to air.

Using color filters, inserted into the light beam of the

Gatan PMT, we obtain an image that shows the UV emitting
area and the F-center emitting area in two different colors.
As is shown in the Fig. 8(b), the purple color represents the
areas which emit UV light, while the blue areas emit F-cen-
ter light, at about 400 nm. The blue–white area is probably
an area that was attacked by the short exposure to air. Nev-
ertheless, more important is the dark-blue areas in the CL
images, surrounding the UV-emitting “islands.” By SEM-
EDX microanalysis we found that the black–blue phase
areas [shown in Fig. 8(a)] is almost pure CaO, with near 50%
calcium and 50% oxygen, respectively. Because CaO has a
much lower secondary electron coefficient than MgO, these
CaO-rich phases appear as dark areas in the SEM images of
Fig. 8(a), although partially covered by the oxidized debris.
These images nicely show the incomplete diffusion and
phase separation after sintering.

5 Discussion of the emission spectra

5.1 UV emission
In order to obtain a clear perspective of the UV emission FIGURE 8 — Characteristics of MgCaO. (a) SE image; (b) CL image
shift, a diagram of the different types of electron–hole CL merged UV and F+-center light-emitting areas.

Journal of the SID 20/1, 2012 67

 FIGURE 9 — Recombination mechanisms at room temperature for the different types of doped MgO.

“host lattice” emission. In addition, contrary to ions such as
Sc3+, it does not remove the F-centers during the crystal
making process (see below). According to Dolgov,12 the UV
peak emission for MgO:Ca is at 6.8 eV (at 5.6 K), corre-
sponding to 182 nm and much shorter than the 5.5-eV
broadband emission at 5.6K for pure MgO. In the case of
MgCaO mixed crystal measured in this experiment we find
a UV emission peak at 218 nm (5.7 eV) at room temperature,
i.e., much shorter than that of pure MgO, but not as short as
the value found by Dolgov for doped MgO:Ca at 5.6 K.
The Si-doped MgO should show the UV peak at 5.0
eV. But apparently the Si-doping, inside the material we
used, is not effective at all, while Al3+ impurities cause the
UV emission to occur at 5.3 eV. The reason for this behavior
could be that the Si-ion size for a sixfold coordination of the
Si4+ ion size is only 0.040 nm, compared to that of the ion
size of Mg2+ at 0.072 nm.9 Therefore, it is very difficult to
replace Mg2+ ions by Si4+ ions, and requires special sinter-
ing technology. Most of the Si ions are probably present in
most of the F-centers, as indicated by the MgO:Sc spectra
so that the 5.0-eV light is not absorbed by the MgO:Sc crys-
tals. The tunneling recombination mechanism in MgO:Sc is
confirmed by the wall-voltage loss in a PDP containing films
from this material as the protective layer, showing a 1/t type
of loss rate, typical for tunneling.13
5.2 F-center emission
In the case of extrinsic (doped) MgO, where the magnesium
vacancy concentration is determined by the aliovalent impurity
content, the concentration of oxygen vacancies is depressed
far below the intrinsic level by using the Schottky equilib-
rium.10
The magnesium vacancy concentration is fixed by the
trivalent impurity concentration [MMg ], where M is a triva-
䊉

the form of interstitial silicon or at grain boundaries. In the lent cation such as Sc3+:
latter case, silicon still is the beneficiary, though, by promot- ∑
ing the crystal size in thin-film MgO. M2O3 Æ 2[MMg ] + 3OO + VMg
¢¢ ,
Sc3+ ions, with an ion size of 0.075 nm are perfectly ∑
¢¢ = [MMg
VMg ] 2.
matched to Mg2+ ions and easily diffuses into MgO, creating
pairs of deep electron and hole traps. The trap levels, how- The concentration of oxygen vacancies, therefore, is
ever, should be almost identical to that of Al3+; therefore, it inversely proportional to the amount of doping by trivalent
is not immediately clear why the recombination emission
ions:
from MgO:Sc is at a longer wavelength than that of MgO:Al.
Apparently, the distance between donor and acceptor is -1
[V ∑∑O] = KS ◊ [VMg
¢¢ ]-1 = 2KS [MMg
∑
] ,
larger in the case of scandium, as a result of the larger ion
size (0.056 nm for Al3+ vs. 0.075 nm for Sc3+),9 effectively
where KS is the defect reaction rate for Shottky defects.
shifting the emission energy to 5.0 eV. Therefore, only in
(Note: we use here the defect chemistry notation by Kröger,
this case we observe recombination emission by direct tun-
neling between the Sc3+ electron trap and the VSc hole trap. where a dot (䊉) represents an effective single positive charge,
In all the other cases, the recombination most probably resulting from the replacement of Mg 2+ by, e.g., M = Sc3+,
occurs after thermal excitation of electrons from their respec- and the double primes (″) represent the effective negative
tive traps. At the same time, the 3+ ion doping removes charge by the Mg2+ vacancy.)

68 Kuang et al. / CL diagnostics of MgO, MgO:Si, MgO:Sc, and MgCaO


5.3 Combined UV and F-center emission
Based on the UV emission peak at 250 nm from crystalline
MgO:Sc, this material could in principle be used to improve
the exo-electron emission because the UV emission coincides
with the excitation of the F-centers in MgO.11 Because tri-
valent doping removes most of the F-centers, a perfect
match could be the use of MgO:Sc crystals on top of a thin-
film layer that does contain a large amount of F-centers.
6 Conclusions
We measured the CL emission of crystalline MgO, MgO:Si,
MgO:Sc, and MgCaO, often used as a protective-layer material
in PDPs. In most of these materials, we find that the UV
emission band is located at a shorter wavelength than pub-
lished in the literature and depends upon the type of impu-
rities or doping. This can be explained, as shown in Fig. 9,
by assuming that in most of our materials the recombination
mechanism is thermally assisted, while only in the case of
MgO:Sc we find tunneling recombination. The results also
reveal that MgO:Sc might be an excellent candidate as a
next-generation crystal-emission layer on top of an undoped
MgO thin film.
We conclude that CL UV emission from submicron-
and micron-sized MgO-type crystals is a promising tool to
optimize the doping of crystal types of protective-layer mate-
rial used for both exoemission and secondary electron
emission.
Acknowledgments
This work was sponsored by the National Natural Science
Foundation of China (60871015), 863 Program of China
(2008AA03A308), and the Innovation Project of Jiangsu
Graduate Education (CXZZ11_0143). The authors would
like to thank Liaoning Zhongda Superconducting Material
Co., Ltd., for cooperation with MgO material.
References
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8 B. Henderson and G. F. Imbusch, Optical Spectroscopy of Inorganic
Solids (Oxford Univ. Press, 1989). p. 420, Fig. 9.3b.
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sium oxide,” Phys. Rev. B 39, 309–318 (1989).
12 S. Dolgov et al., “Low-temperature (4–295 K) thermoluminescence of
pure and Ca-doped MgO single crystals,” Phys. Status Solidi C2, No.
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Digest 42, 508–509 (2011).
Wen-Jian Kuang received his B.S. degree in infor-
mation optics from Jiangnan University, China, in
2008. He is currently a Ph.D. student at Southeast
University, Nanjing, China. His research at the
Display Center of Southeast University primarily
involves the analysis of MgO material and the
protective layer and works on the improvement of
both PDPs and flat plasma lamps.
Harm Tolner has been working in the field of flat
displays since 1990 at Philips Components BV,
where he is involved in the development and
research coordination for several types of large
flat displays, such as ZEUS, based on electrons
hopping over magnesium oxide, and plasma dis-
plays. As a visiting professor, he has regularly
been teaching since 2001 at Southeast University
in Nanjing, China. The most important topic of
this research is the investigation of the fundamen-
tal properties of both secondary and delayed electron emission from
MgO, and MgCaO, used as cathode material for the dielectric barrier
discharge. In addition, he is active in co-developing ultrathin PDPs and
UV lamps. He is a consultant to several companies involved in the
development of materials and processes for plasma devices and has
chaired many sessions of the emissive display (EMD) subcommittee of
the SID, and presented several workshops on plasma technology at SID,
IMID, and IDW.
Qing Li received her B.S. and M.S. degrees from
the University of Science and Technology in Nan-
jing, China, and her Ph.D. degree from Southeast
University, China. Since 1995, she has been with
the School of Electronic Science and Engineering,
Southeast University. She worked in the Elec-
tronic Devices Institute in Nanjing, China, from
1990 to 1995. She is a senior member of the
Society for Information Display. Her study field
covers flat display technology and opto-elec-
tronic devices research. Her main research work focuses on PDPs,
Xe–Ne flat lamps with the correlative material in plasma devices, such
as the protective layer, and on LCDs as well as optical devices using
liquid crystal. Currently, she has authored or co-authored more than 40
publications and 26 patents.
Journal of the SID 20/1, 2012 69