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Nuclear Instruments and Methods in Physics Research A 554 (2005) 195–200

www.elsevier.com/locate/nima

Growth of pure and doped TeO2 crystals for

scintillating bolometers
I. Dafineia,, M. Diemoza, E. Longoa, Á. Péterb, I. Földvárib
a
INFN, Sezione di Roma e Dipartimento di Fisica, Università ‘‘La Sapienza’’; P-le Aldo Moro 2, 00185-Roma, Italy
b
Research Institute for Solid State Physics and Optics, Budapest, Hungary
Received 3 June 2005; received in revised form 14 July 2005; accepted 2 August 2005
Available online 22 August 2005

Abstract

Double-beta decay hybrid detectors (scintillating bolometers) are prospective sensitive tools for nuclear and particle
physics investigations. For this goal, the bolometric capability of crystals should be combined with extrinsic
scintillation. Tellurium dioxide (TeO2) crystals have well established, suitable properties to be conveniently used as
bolometers. A first attempt to grow doped TeO2 crystals to increase their scintillation was performed. Preliminary room
temperature transmission and luminescence measurements showed the incorporation of different dopants in TeO2 host
lattice.
r 2005 Elsevier B.V. All rights reserved.

PACS: 07.57.Kp; 29.40.Wk; 29.40.
n; 23.40.
s

Keywords: Tellurium dioxide; TeO2; Scintillating bolometers; Double-beta decay

1. Introduction tors or scintillators [1]. Bolometers are character-

High-precision measuring of small energy quan-
tities generated by gamma particles, electrons or
recoiling nuclei is of high interest both in nuclear
and particle physics. The key element in such
measurements is often the use of a bolometer
instead of conventional detectors like semiconduc-
Corresponding author. Tel.: +39 06 30483146;
fax: +39 06 30486119.
E-mail address: ioan.dafinei@roma1.infn.it (I. Dafinei).
ized by very low-energy threshold, high-energy
resolution, sensitivity for non-ionizing events and
possibility to distinguish the types of interaction
(alpha particle/electron, nuclear recoil/electron,
etc.) when used in conjunction with conventional
techniques.
Specific nuclei exhibit characteristic double-beta
decay (DBD), as 130Te, with the spectrum end
point at 2.5288 MeV. The detection of a sharp
energy peak at 2.5288 MeV would be a clear
signature of a neutrinoless DBD, where all the

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196 I. Dafinei et al. / Nuclear Instruments and Methods in Physics Research A 554 (2005) 195–200
energy is taken by the two decay electrons. The
discovery of the neutrinoless DBD would be the
signature of the Majorana nature of neutrinos.
Tellurium dioxide (TeO2) provides a unique
combination of a bolometric detector with a
DBD source since the natural abundance of
130
Te is rather high (33.87%). Thus the
expensive enrichment procedure typical for other
elements can be avoided. The growth of scintillat-
ing TeO2 crystals may open the possibility to
realize a hybrid detector (scintillating bolometer)
able to separate events due to radioactivity
background, thus enhancing substantially the
sensitivity to a neutrinoless double-beta decay
measurement.
Although luminescence measurements on TeO2
crystals are not reported in the literature, a
scintillation signal in a TeO2 bolometer operated
at 20 mK was put in evidence [2]. The measured
light yield was quite low (0.67% that of BGO),
rather marginal to separate between alpha parti-
cles and gamma photons at energies close to the
expected Qbb(130Te) level (2.5 MeV). There is no
indication on the spectrum or on the decay
characteristics of this scintillation. The emission
should be situated in the transparency range of the
crystal (350–1600 nm), and the decay time in the
order of a few milliseconds. The spectral limits
given above are defined by the TeO2 absorption
edge and the nature of the optical detector (Ge
photo-detector). The luminescence may be of
excitonic nature or produced by a defect, for
example V5
O (oxygen vacancy with one trapped
electron). Whatever the nature of this scintillation,
a larger light output would be welcome for an
improved discrimination power on particles. This
can be done only by doping the TeO2 crystal with
an activator. The present work gives the results of
the first attempt to grow doped TeO2 crystals as
potential scintillating material to be used in DBD
experiments.
2. TeO2 general properties and guidelines for the
synthesis of a TeO2 extrinsic scintillator
Paratellurite (a-TeO2) crystal belongs to the
tetragonal space group D44 (P41212) having a
distorted rutile structure with asymmetric covalent
Te–O bonds [3]. Crystals grown from TeO2
99.99% purity powder (melting point at 733 1C)
are colorless and highly transparent in the range of
350 nm–5 mm. The density of grown crystals is
6.04 g/cm3, in accordance with the density calcu-
lated from measured lattice constants: a ¼
4:8088 A( and c ¼ 7:6038 A.(
The main applications of TeO2 are related to its
excellent acousto-optical properties. Studies on
dopants and impurities in TeO2 lattice were made
in order to understand their influence on acousto-
optic properties of TeO2 crystals [4–7]. No studies
on luminescence or scintillation properties of TeO2
were found in the literature.
As a general rule for selecting the activator for
an extrinsic scintillator, two criteria should be
taken into consideration: luminescence properties
of the free ion and its incorporation to the host
lattice. In the particular case of possible DBD
application supplementary constraints are im-
posed by the fact that only dopants having stable
isotopes are acceptable because of the request of
extremely low–radioactivity background condi-
tions of such experiments. Moreover, the incor-
poration of uneven ions in the TeO2 lattice is to be
avoided because of the possible problems encoun-
tered when cooling paramagnetic materials at very
low temperatures (the working temperature of
DBD bolometers is of the order of 10 mK). On the
other hand, TeO2 scintillation-bolometer synthesis
for DBD application is somehow simplified by the
fact that practically no restriction is to be imposed
on the emission spectrum and/or on the decay time
of the activator ion. The limitation of the
scintillation spectrum comes only from the host
lattice transmission spectrum and the relatively
high values of TeO2 refractive indices (no: 2.4–2.2;
ne: 2.6–2.4 in the 400–1000 nm spectral region) [8].
Possible activators for a TeO2 scintillator will
therefore be ions having emission peaks in the
l4400 nm spectral region for a best possible light
collection.
For the selection of Te4+–substituting dopant,
ionic radius, oxidation number, coordination
number, type of outer atomic shell, electro-
negativity and chemical hardness of II–VI ions of
all elements should be taken into account. Table 1
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I. Dafinei et al. / Nuclear Instruments and Methods in Physics Research A 554 (2005) 195–200 197

Table 1
Search for Te substituent in TeO2 lattice

Atom Atom Electron config. Oxi. no. Coord. no. IonicR (Å) Free ion emission Stable Dev. ionR
no. of element range (nm) isot. (%) (%)

Fe 26 [Ar] 3d6 4s2 2 4 0.64 100.000
3.0

Pb 82 [Xe] 4f14 5d10 6s2 6p2 2 4 0.64 98.600
3.0
Pd 46 [Kr] 4d9 5s1 2 4 0.64 100.000
3.0
V 23 [Ar] 3d3 4s2 3 6 0.64 99.750
3.0
Nb 41 [Kr] 4d4 5s1 5 6 0.64 100.000
3.0
Ta 73 [Xe] 4f14 5d3 6s2 5 6 0.64 99.988
3.0
Fe 26 [Ar] 3d6 4s2 3 6 0.645 100.000
2.3
Mn 25 [Ar] 3d5 4s2 3 6 0.645 202–627 100.000
2.3
Co 27 [Ar] 3d7 4s2 2 6 0.65 100.000
1.5
Pb 82 [Xe] 4f14 5d10 6s2 6p2 4 4 0.65 98.600
1.5
Mo 42 [Kr] 4d5 5s1 4 6 0.65 75.530
1.5
Mo 42 [Kr] 4d5 5s1 5 4 0.65 75.530
1.5
Mg 12 [Ne] 3s2 2 5 0.66 200–9900 100.000 0.0
Mn 25 [Ar] 3d5 4s2 2 6 0.66 204–350 100.000 0.0
Te 52 [Kr] 4d10 5s2 5p4 4 4 0.66 33.606 0.0
Zr 40 [Kr] 4d10 5s1 4 5 0.66 479–634 97.200 0.0
W 74 [Xe] 4f14 5d4 6s2 4 6 0.66 55.440 0.0
Rh 45 [Kr] 4d8 5s1 3 6 0.665 100.000 0.8
Mn 25 [Ar] 3d5 4s2 2 4 0.67 204–350 100.000 1.5
Co 27 [Ar] 3d7 4s2 2 5 0.67 100.000 1.5
Ag 47 [Kr] 4d10 5s1 3 4 0.67 100.000 1.5
Ti 22 [Ar] 3d2 4s2 3 6 0.67 100.000 1.5
Au 79 [Xe] 4f14 5d10 6s1 3 4 0.68 100.000 3.0
Ir 77 [Xe] 4f14 5d7 6s2 3 6 0.68 100.000 3.0
Ru 44 [Kr] 4d7 5s1 3 6 0.68 100.000 3.0
Ru 44 [Kr] 4d7 5s1 3 6 0.68 100.000 3.0
Nb 41 [Kr] 4d4 5s1 4 6 0.68 203–225 100.000 3.0
Ta 73 [Xe] 4f14 5d3 6s2 4 6 0.68 99.988 3.0

Free ion emission range is given only in the rows corresponding to the four selected elements (bold characters).

gives the list of possible Te4+ substitutes in TeO2
lattice within 3% ionic radius compatibility. The
isotopes stability and free ion emission spectrum
criteria reduce further the list to four possible
elements (Mg, Mn, Nb, Zr), evidenced in Table 1
with bold characters. Zirconium was chosen in
spite of its potential radioactivity given by 96Zr
isotope, which is double-beta active with a half-life
of 3.9  1019 years. Taking into account the low
doping concentration (10
3 in the melt), the
segregation coefficient (o10
1) and the 2.8%
abundance of 96Zr isotope, the presence of Zr in
TeO2 crystals may give beta events approximately
10
4 times less than Te, which may be considered a
marginal effect in this phase of the study.
3. Experimental results and discussion
3.1. Crystal growth and samples preparation
Paratellurite crystals were grown by the balance
controlled Czochralski method. The description of
the growth apparatus is given in Ref. [9]. A
resistance heating, open-air furnace was employed.
For the growth, 6N purity TeO2 was used.
Tellurium oxide raw material was synthesized by
a conventional chemical method starting from 5N
purity Te metal (Asarco Company) in the Re-
search Institute for Solid State Physics and Optics
(Budapest, Hungary). Crystals were grown from a
Pt crucible of 46 mm diameter, using 180–220 g
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charge of TeO2. Mg, Mn, Nb and Zr dopant were
added to the raw material powder in oxide form
and 10
4–10
3 mol/mol concentrations. Crystals
were pulled along the /1 1 0S direction, in sizes of
22 mm diameter and about 55–65 mm length. For
the measurements, samples were cut with a
diamond saw and X-ray oriented with a precision
better than 0.51. Polished surfaces were prepared
by a standard method using SiC for grinding and
AB Alpha Alumina (Buehler Linde A 0.3 m) for
polishing. Special care was taken to avoid nuclea-
tion of cracks at sample edges along (1 0 0) and
(0 1 0) TeO2 cleavage planes.
Paratellurite (TeO2) structure, especially the
asymmetric covalent Te–O bonds, limits the
substitutional incorporation of the dopants to
extremely low, and results in very low segregation
coefficients (k10
2). In order to avoid constitu-
tional supercooling, doped crystals have to be
grown under high thermal gradient with growth
conditions similar to that of the high-temperature
solutions growth. Otherwise the rejected solute
decreases the freezing point of the melt and the
instable growth conditions disintegrate the growth
interface. Tellurium dioxide has rather high vapor
pressure above the melting point. The high
temperature gradient at the solid–liquid interface
inevitably means high temperature gradient across
the gaseous–liquid interface and can cause large
gaseous convection. To avoid the incorporation of
the gas bubbles to the crystals the control of the
liquid convection is important. Previous studies
[10] have shown that for the growth of bubble free
TeO2 crystals, a near flat, shallow concave shape
of the solid–liquid interface is optimal.
In our experimental set-up the crystals were
grown under 15–20 1C/cm axial gradient with
0.65–0.70 mm/h pulling rate. At the constant
22 mm diameter part of the crystal with seed
rotation adjusted in the range of 26–28 rpm, a near
flat growth interface could be maintained. Starting
from 180 g charge of TeO2, crack and bubble free
crystal could be grown for all of the dopants, used
with a yield of 50–67 wt% (length of 35–40 mm).
All the pure and doped crystals were colorless.
Pulling out more than 60–65 wt%, in the bottom
part of the crystals the full sequence of transition
from smooth interface to a cellular form can be
Fig. 1. 10
4 mol/mol ZrO2 doped TeO2 crystal: (a) as grown
boule, (b) (1 1 0) slice cut from the bottom with spiral
morphology of the dopant rich solute entrapment.
observed (Fig. 1a). The breakdown of the interface
stability appeared nearly at the same length of the
pulled out boules both for 10
4 and 10
3 mol/mol
dopant concentration. The occurrence of the
constitutional supercooling at a critical melt level
in the crucible indicates the appearance of
convective instability rather than the dopant
concentration in the melt exceeds the solid
solubility limit in the matrix. The spiral morphol-
ogy of the dopant rich solute entrapment corre-
lates with a forced upward hydrodynamic flow in
the melt towards the crystal interface (Fig. 1b).
High temperature gradients at the solid–liquid
interface are sources of stress. During the growth,
as the crystal is cooled down, the heat transfer
mechanism changes from predominantly radiative
to conductive. With the alteration of isotherms
from planar to non-planar, hoop stresses are
created in the crystal, especially at the top of the
cylindrical area. Above 400 1C [11], in the elasticity
range these stresses promote the formation of
dislocations, below it to brittle fracture.
Due to the very low segregation coefficients, the
built-in concentration of any dopant in TeO2 is
often below the limit for chemical analysis [12,13].
Till the present, only a few ions like Fe or Cr were
apt to incorporate to the TeO2 crystal with
concentration high enough for direct spectroscopic
investigations [4,5]. The main purpose of the
present work was to find the way of growing
doped TeO2 crystals to be further studied as
potential scintillating bolometers for double-beta
decay experiments.
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3.2. Optical transmission measurements
Optical absorption spectra were measured on
2–10 mm thick slices by a JASCO V550 spectro-
meter with a resolution of 1 nm. All spectra were
recorded at 300 K, with incident light propagating
parallel to the /0 0 1S optical axis of the crystal.
Even if the given impurity shows no distinct
absorption bands in the transparency range of the
crystal, optical absorption gives information on
the incorporation since the slope of the short
wavelength absorption edge of the oxide crystals is
very sensitive to impurities. This is mainly related
1.5
with the perturbation of the lowest energy host
excitons by dopants. Fig. 2a shows the absorption
spectra of the undoped and Mg, Mn, Nb and Zr
doped TeO2 crystals. A slight shift of the cut-off
edge position and a well-observable increase of
absorption were recorded in the lower part of the
spectra. The most dominant change was detected
for niobium doping where, as shown in Fig. 2b the
concentration dependence could also be followed
on the spectra. The impact of Zr doping on the
absorption even at concentrations of 10
3 mol in
1
λemiss=420nm

TeO2:Mg
Nb10-3 TeO2:Nb
Intensity (a.u.) 0.21
TeO2:Mn
Mn10-4 TeO2
Abs.coeff. (cm-1)

1.0 TeO2:Zr

Zr10-3 0.5
0.16

undoped 0.11

Mg3x10-4 320 340 360 380

0.50

0
0.0 250 300 350 400
340 360 380 400 420 (a) wavelength (nm)
(a) wavelength (nm) 1
1.5 λexcit=330nm

Nb 10-3
Intensity (a.u.)
Abs.coeff. (cm-1)

1.0
Nb 10-4
0.5
undoped

0.50

0
0.0 350 400 450 500 550
340 360 380 400 420 (b) wavelength (nm)
(b) wavelength (nm)
Fig. 3. Room temperature photoluminescence spectra of pure
Fig. 2. (a) Absorption spectra of undoped, Mg, Mn, Nb and Zr and doped TeO2 samples. (a) Excitation spectra for 420 nm
doped TeO2 cystals. (b) Absorption spectra of undoped, 10
4 emission (320–380 nm wavelength region enlarged in the inset)
and 10
3 mol/mol Nb doped TeO2 cystals. and (b) emission spectra for 330 nm excitation.
 ARTICLE IN PRESS
200 I. Dafinei et al. / Nuclear Instruments and Methods in Physics Research A 554 (2005) 195–200
the melt was low and the role of Mg was within the
measuring error.
3.3. Photoluminescence measurements
Photoluminescence spectra were measured at
room temperature using a Perkin Elmer LS55
Luminance Spectrometer on 10  10  1 mm3
slices having the major faces (1 1 0) oriented and
optically polished. Samples were positioned with
one of the major faces at grazing geometry with
respect to the excitation beam.
Excitation and emission spectra are given in Fig.
3. No distinct emission spectra corresponding to
doping ions are present over the whole 300–2000 nm
measured emission range. The absence of dopant-
related emission may be due to the presence of
nonradiative processes with a quenching effect upon
luminescence noticed at room temperature also for
other oxide crystals. The measured spectra with
emission peaked around 420 nm are most probably
of excitonic nature. The emission spectrum given by
undoped samples is perturbed by dopant ion
presence, the strongest effect being noticed for Mg
doped samples while Zr doped samples give
practically the same spectra as undoped ones. Low-
temperature photoluminescence measurements fore-
seen for these samples will clarify the exact nature of
photoluminescence in TeO2 crystals and possibly
reveal the presence of dopants characteristic emis-
sion spectra in doped TeO2.
4. Conclusion
The growth of scintillating TeO2 crystals opens the
possibility of substantially enhancing the measure-
ment sensitivity in neutrinoless DBD experiments.
Dealing with extremely rare processes, such experi-
ments are performed in underground laboratories
with appropriate shielding and selection of very low-
activity materials aimed at reducing the radioactivity
background dominated by alpha and beta emission
from the detector and surrounding materials.
Simultaneous measurement of scintillation light
and phonons can be used to discriminate between
electrons and alphas, thus suppressing this part of
the background.
In spite of the generally accepted difficulties,
doped TeO2 crystals were successfully grown at the
Research Institute for Solid State Physics and
Optics (Budapest, Hungary). The incorporation of
Mg, Mn, Nb and Zr dopants is demonstrated
through optical absorption and photolumines-
cence measurements performed at room tempera-
ture. The successful doping of TeO2 crystals with
potential scintillation activators is a guarantee for
the improvement of light yield at low temperatures
where the thermal quenching of the light yield
disappears. X-ray excited luminescence measure-
ments are on the way for a precise evaluation of
low-temperature light yield improvement in doped
TeO2 crystals.
Acknowledgements
Dr. Etiennette Auffray (CERN, Genève Swit-
zerland) is deeply acknowledged for kindly offer-
ing the possibility to make the photoluminescence
measurements presented in this work.
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