1 Internal contamination of the Cs2 HfCl6 crystal

2 scintillator

3 C.Cardenasa,b,, A.Burgera,b , M.Laubensteinc , S.Nagornyc,d , S.Nisic , E.Rowea

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a Department of Life and Physical Sciences, Fisk University, Nashville, TN 37208, USA

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b Department of Physics and Astronomy, Vanderbilt University, Nashville, TN 37235, USA

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c INFN Laboratori Nazionali del Gran Sasso, I-67100 Assergi, Italy

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d GSSI Gran Sasso Science Institute, I-67100 LAquila, Italy

8 Abstract

A 3 cm3 cesium hafnium chloride (Cs2 HfCl6 ) scintillating crystal was grown by
using the vertical Bridgman technique. Characterization of the crystal was car-
ried out to determine relative light output and energy resolution for -quanta.
The intrinsic radioactivity of the CHC crystal was tested by ulta-low back-
ground HPGe spectrometry deep underground at LNGS. The results of these
studies demonstrate the potentiality of this material for a variety of scintillation
applications, including low-level counting experiments.
9 Keywords: CHC crystal, purification, radiopurity, cosmogenic activation

10 1. Introduction

11 Today there are many experiments dedicated to search for neutrinoless double
12 beta decay (02). Detection of 02 would be direct proof that the neutrino
13 is a massive Majorana particle, and that lepton number conservation law can
14 be violated. The 02 is an extremely rare process with a half-life more than
15 1025 y. In order to achieve such a high level of experimental sensitivity some
16 challenges have to be met: location of experimental set up at an underground

Corresponding author
Email address: crystal.cardenas@vanderbilt.edu (C.Cardenas)
Preprint submitted to Elsevier May 8, 2017
17 site, utilization of massive passive shielding and sophisticate active veto sys-
18 tems, detector of ton-scale mass containing large amount of isotope of interest,
19 extremely high level of radiopurity, and long-time exposure.

20 The cryogenic bolometer technique is one of the most promising experimental

21 approaches in this field because of possibility to achieve the excellent energy
22 resolution and registration efficiency close to 100% as well as due to flexibility
23 in utilization of detector material. A cryogenic bolometer consists of a crystal
24 cooled at very low temperature (about few mK) and thermometer, which is
25 able to measure the temperature variations due to energy deposit by interacting
26 particles into detector and scintillating signal to variation of light-heat ratio and
27 drastically reduce background level radiation. The general properties of CHC
28 crystals are listed in Table 1.

Table 1: Properties of Cs2 HfCl6 crystal scintillator.

Property Value Reference

Effective atomic number 58 [ref]
Density (g/cm3 ) 3.86 [ref]
Melting point 870C [ref]
Crystal structure cubic [ref]
Wavelength of emission 400 - 430 nm [ref]
Energy resolution 3.3% at 662 keV of 137
Cs [ref]
Average decay time 4 - 5 s [ref]
Light yield relative to NaI(Tl) 135% [ref]
* For -quanta, at room temperature.

29 The general requirements on chemical purity of the initial raw materials in order
30 to produce the high-quality scintillating crystals impose limitations on transition
31 metals concentration [ref] and on some other elements [ref]. Higher concentra-
32 tion of these impurities will significantly degrade the optical quality, scintillation
33 (light output, energy resolution, radiation resistance, intensity of afterglow etc.)
34 and bolometric properties of the crystal. With respect to bolometer character-
35 istics this particular requirement is caused by necessity to achieve the extremely
36 low concentration of point defects (vacations and interstitial atoms) and others

2
37 kind of defects like color centers and its associates, dislocations and blocks. The
38 specific type of defect into the crystal will determine a dominant mechanism of
39 phonon scattering and, consequently change a heat capacity that will spoil the
40 energy resolution in heat channel of bolometer. Therefore, in order to achieve
41 high performance scintillating bolometer based on CHC crystal is paramount to
42 use the low radioactivity initial materials and to adjust an efficient technique of
43 its purification.

44 CHC crystal is the first scintillating material containing a high fraction of Hf by

45 mass (26%) and could be relativity easy produced by the conventional Bridgman
46 crystal growth technique. This opens new opportunities into searches of rare
47 nuclear processes occurring in natural occurring Hf isotopes by utilizing the
48 "source = detector" approach where the detector itself contains the element of
49 interest. This allows us to reach an advanced level of experimental sensitivity.

50 2. Crystal production

51 Reported in [ref], starting materials used for crystal growth were all from com-
52 mercially available feedstock with the highest available purity: CsCl beads
53 (99.998%) and HfCl4 powder (99.9%). Starting material are not hygroscopic
54 though they are slightly moisture sensitive. In order to suppress the materialss
55 absorption of water, all material is handle in an argon atmosphere glove box
56 where the moisture and oxygen level are maintained below 1 ppm. Sublima-
57 tion of HfCl4 was carried out three times for the deep purification of material.
58 As one can see from Table 2, the major chemical impurities in HfCl4 starting
59 material measured by ICP-MS decreases significantly after subsequent sublima-
60 tion. Stoichiometric ratios of material was loaded into a quartz ampule and then
61 transfer to a two-zone vertical furnace for synthesis and grown at a rate of 0.5 -
62 1 cm/day. The cylindrical CHC crystal with a mass of 12.15 g and dimensions
63  25 x 8mm was cut from a single growth crystalline boule (60 g) and was used
64 as the detector in this study. The top and bottom surfaces of the crystal were

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65 optically polished, while the lateral side was left rough to enhance light output
66 of the crystal.

67 The chemical purity of the cesium chloride (CsCl), hafnium chloride (HfCl4 )
68 before and after sublimation, and the grown CHC crystal; have been measured
69 with the help of High Resolution Inductively Coupled Plasma-Mass Spectro-
70 metric analysis (HR-ICP-MS, Thermo Fisher Scientific ELEMENTS2) at the
71 Laboratori Nazioali del Gran Sasso of INFN (LNGS, Italy), are listed in Table
72 2.

Table 2: Chemical purity of initial materials and CHC crystal measured

by HR-ICP-MS, expressed in ppb.

Element CsCl HfCl4 (initial) HfCl4 (after*) CHC crystal

La 8.7 2627 555 132
Ce <5 <5 <5 19
Pr <5 <1 <1 5.8
Nd <10 <10 <10 <12
Sm <15 <15 <15 <15
Eu <3 33 25 130
Gd <5 <15 <5 <35
Tb 11 <2 <2 6
Dy 2.2 <1 <1 16
Ho <4 250 204 <25
Er <2 <2 <2 <2
Tm <3 <2 <2 <2
Yb <5 <100 <100 <50
Lu <10 <500 <500 <300
Ta <3 <8000 <8000 <4000
W <1 <1 <1 <0.2
Re <2 <15 <15 <10
Os <5 <20 <20 <15
Ir <2 <4000 <4000 <2000
Pt <2 <8000 <7000 <4000
Tl <5.5 <4 <4 <15
Bi <3 <2000 <2000 <1000
Th <0.5 <1 <1 <0.5
U <0.5 3200 267 <0.5
* Sublimed 3x (see text)
ppm

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73 As can be seen from the data presented in Table 2 the developed complex method
74 of refinement is very effective for the entire range of impurity elements. For most
75 elements their concentration was reduced by one-two orders of magnitude. For
76 example ... . Not listed elements have concentrations which are limited by the
77 instrumental detection limit.

78 3. Low background measurements with HP-Ge detector

79 The radiopurity (level of internal radioactive contamination) of the 3 c.c. CHC

80 crystal with respect to uranium and thorium natural decay chains, and, in
81 particular, to their daughter nuclides, was investigated by means pf gamma-
82 ray spectroscopy with an ultra-low background high purity germanium (ULB-
83 HPGe) detector. The measurements were carried out in the STELLA (SubTer-
84 ranean Low Level Assay) facility in the Gran Sasso National laboratories of the
85 INFN (Italy), which provided an average shielding of 3600 m.w.e, details can
86 be found in [].

87 The ULB-HPGe detector named "Ge-Cris", is a coaxial p-type germanium de-

88 tector with an active volume of about 400 cm3 , and has an optimized design for
89 high counting efficiency in a wide energy range. The energy resolution of the
90 spectrometer is 2.0 keV at 1332 keV line of 60
Co. In order to reduce external
91 background, the detector is shielded by 20 cm layers of low-radioactivity lead,
92 OFHC copper ( 5 cm). To prevent radon contamination the set-up is continu-
93 ously flushed by high purity nitrogen. More details on experimental set up and
94 detector performance can be found in [].

95 A sample of CHC crystal with mass 12.2 g was vacuum sealed in two separate
96 plastic? bags above the end cap of the ULB-HPGe detector. The CHC crystal
97 was measured for 494 hours. The resulting analysis concluded that the crystal is
98 free of nuclides of U/Th natural decay chains, therefore, only limits could be set
99 on their activities and found at the level of few mBq/kg. However, the crystal

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100 contains artificial 137 Cs nuclide (0.8 Bq/kg) and nuclides produced by cosmic ray
101 radiation 132,134
Cs and 181
Hf with activities on the level of tens of mBq/kg, see
102 Figure 1. A summary on activities (or limits) obtained by ULB-HPGe detector
103 is found in Table 3.

Figure 1: Energy spectrum of the 3 c.c. CHC crystal scintillator measured over 494
hours. The crystal is free of nuclides of the U/Th natural decay chain, thus, only limits
on their activities were set at the level of a few mBq/kg. There is a contamination
of artifical 137 Cs nuclide (0.8 Bq/kg) and nuclides produced by cosmic ray radiation
132,134
Cs and 181 Hf with activities at levels of tens of mBq/kg.

Table 3: Internal radioac-

tive contamination expressed
in Bq/kg measured by ULB-
HPGe detector (see text).

Chain Nuclide Activity

40
K <0.18
60
Co <19
132
Cs 258
134
Cs 526
137
Cs 83090
181
Hf 140.7
232
Th 228
Ra <12
228
Th <6.3
238
U 226
Ra <12
234
Th <8.6
234m
Pa <3.7

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104 4. Conclusion

105 5. Acknowledgements

106 We acknowledge the support provided by the National Science Foundation un-
107 der Grant number HRD-1547757 (CREST-BioSS Center). In addition, we would
108 like to acknowledge and show our appreciation to Laboratori Nazionali del Gran
109 Sasso and the Gran Sasso Science Institute that allowed for an effective investi-
110 gation into PSD with CHC.

111 6. References