Atomic distribution in phosphors for neutron detection has not been fully elucidated, although their ionization efficiency is strongly dependent on the state of the rare earth in the matrix. In this work, we examine optical properties of Eu-doped 80LiF-20CaF 2 eutectics for neutron detector applications based on the Eu distribution. At low concentrations, aggregation of Eu cations is observed, whereas homogeneous atomic dispersion in the CaF 2 layer, to substitute Ca 2+ ions, is observed in the eutectics at high concentrations. Eu L III edge X-ray absorption fine structure (XAFS) analysis suggests that neutron responses do not depend on the amount of Eu 2+ ions. However, transparency, which depends on an ordered lamellar structure, is found to be important for a high light yield in neutron detection. The results confirm the effectiveness of the basic idea concerning the separation of radiation absorbers and activators in particle radiation scintillation and present potential for further improvement of novel bulk detectors.Scintillators, which convert ionizing radiation to thousands of photons, have played a major role in a variety of fields that involve radiation detection including medical imaging, security, astrophysics, particle physics, and searching for natural resources [1][2][3][4][5][6][7] . Among the several types of scintillators, the thermal neutron scintillation detector is one of the most fascinating. The conventional thermal neutron detector is a gas proportional counter filled with 3 He gas because of high thermal neutron cross-section and the low background γ -ray sensitivity. However, 3 He gas, which is a product of the decay of 3 H in nuclear reactors, is no longer available owing to its high demand and declining supply. Therefore, the enhancement of production was impossible [8][9] . Meanwhile, there is a demand for sensitive thermal neutron detectors for both scientific and industrial purposes. To resolve this situation, the effort toward the fabrication of novel thermal neutron scintillators to replace the present 3 He-based systems has been heightened. To this end, we propose a candidate:6 Li-containing solid state materials. Because 6 Li has a high interaction probability with thermal neutrons based on the 6 Li(n, α ) 3 H reaction with a high Q-value of 4.8 MeV, there are several reports on Li-containing solid state matter exhibiting good scintillation properties of a 252 Cf neutron source [10][11][12][13][14][15] . Recently, lithium-containing fluorides have attracted attention regarding the high conversion efficiency attained by low phonon energy. Among these Li-containing fluorides, the activator-doped LiF/CaF 2 eutectic prepared by a simple solidification method 16 is reported as a candidate for neutron scintillator applications 17,18 . The concept of the scintillation mechanism of rare-earth-doped LiF/CaF 2 eutectic is based on the separation of the neutron absorber and the conversion of photons by