Effect of Ce concentration on optical properties of Li6Gd(BO3)3 single crystals

A.K. Singh, S.G. Singh, D.G. Desai, S. Sen and S.C. Gadkari * *email: gadkari@barc.gov.in Crystal Technology Section, Technical Physics Division, BARC, Mumbai-400085.

Introduction
Single crystals of cerium doped Li6Gd(BO3)3 (LGBO) are promising scintillators for neutron detection. They have a short decay time (~30 ns) and high light output which is about six fold of Li-glass scintillators. The scintillation takes place through energy transfer from Gd3+ centers to Ce3+ centers in this matrix. The energy transfer mechanism is strongly dependent upon temperature and the cerium concentration.
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Growth of Single crystals

High temperature solid state reaction at 750 C was used for the preparation of initial charge using the 4N pure (99.99%) constituent oxides (Li2O3, Gd2O3, CeO2, B2O3). Undoped and Cerium doped LGBO single crystals of 20 mm diameter and 30 mm length were grown in Platinum crucibles using the Czochralski technique. A pull rate of 0.5 mm/h and rotation rate of 10-15 rpm were employed for the growth. The crystals were grown along <010> direction using the Czochralski technique.

Fig. As-grown LGBO Single crystal.

Fig. Comparison of transmission spectra of undoped LGBO, 0.1% Ce doped LGBO and 1% Ce doped LGBO single crystals
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The transmission curve shows approximately 85% transmission with sharp absorption lines in the region from 200 to 350 nm for the undoped and 0.1% Ce doped samples. The absorption lines corresponds to the transitions from the ground state (8S7/2) to the excited states (6PJ 6I and 6D ) in Gd3+ centers. J J The broad absorption band in the region 300 to 400 nm for the 1% Ce doped sample is due to the charge transfer band of Ce4+ + O2- Ce3+ + O- .
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Fig. Emission at 400nm at excitation 274 nm, 312 nm and 345 nm. (Inset shows the Gd3+ emission at 313 nm for 1% Ce doped LGBO)
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 The room temperature emission spectra of Ce doped LGBO single crystals shows three emission bands peaking at 313 nm. 400 nm and 490 nm. The emission band at 313 nm corresponds to the transition of electrons from the first excited state (6PJ ) to the ground state (8S7/2) in the Gd3+ centers. The broad emission band at 400 nm is due to the transition from 5d4f energy levels in the Ce3+ centers which consist of two peaks originating from the splitting of ground level of Ce3+ into 2F5/2 and 2F7/2 due to a spin-orbit coupling. The emission band at 490 nm corresponds to the transitions in the Gd3+ levels.

For an excitation at 345 nm the emission consists of only 400 nm component. However when the sample is excited at either 310 or 274 nm the emission consists of two emission bands at peaking at 400 and 490 nm. For an excitation of 310 or 274 nm, the LGBO matrix (Gd3+ centers) also absorbs a part of the energy along with the Ce3+ centers which results in the 490 nm band along with the 400 nm band.

Excitation spectrum corresponding to Ce3+ and Gd3+ centers

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Fig. Decay profile of 400 nm emission at an excitation of 312 nm in case of 1% Ce concentration.

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The decay profile fits into a double exponential decay with a life time of approximately 250s for the primary component. The decay of the Ce3+ emission has a slow component which is not present when the excitation is centered at 345 nm that directly transfers energy to the Ce3+ centers. The life time gets reduced for higher Ce concentrations, but the presence of Gd3+ emission still affects the decay profile of the Ce3+ centers.

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Conclusion
This clearly indicates that the Gadolinium in LGBO affects the decay profile of Ce3+ centers even at higher Ce doping is not suitable for the detector response. One of the possible solutions for this could be replacement of Gd3+ ions with some other trivalent ions such as yttrium or lutetium which would not affect the decay profile like gadolinium.

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