From Ancient Blue Pigment to Unconventional NIR Phosphor: A Thermal-Stable Near-Infrared I/II Broadband Emission from Ca1-xSrxCuSi4O10 Solid Solution.

Abstract

Phosphors used in NIR spectroscopy require broadband emission, high external quantum yield, good ability, as well as a tunable spectral range to meet the detection criteria. Two-dimensional copper silicates MCuSi4O10 (M = Ca, Sr, Ba) play an important part in ancient art and technology as synthetic blue pigments. In the recent years, these compounds were reported to show a broad near-infrared emission when excited in the visible region. Inspired by the tunable structure of MCuSi4O10, a series of broadband phosphors Ca1-xSrxCuSi4O10 were designed for realizing continuously tunable NIR emission by a modulated Cu2+ crystal field environment. The emission maximum exhibits a red shift from 915 to 950 nm and the integral intensity enhances as the Sr2+ content varies in the range of 0-0.50, which is led by the lattice expansion and the following weakened crystal field splitting on tetrahedral-coordinated Cu2+. Compared to CaCuSi4O10, the optimized sample Ca0.5Sr0.5CuSi4O10 shows enhanced NIR emission by about 2.0-fold. It exhibits quite a high external quantum efficiency covering the NIR-I and -II regions (λmax = 950 nm, fwhm = 135 nm, EQE = 26.3%) with a strong absorption efficiency (74.7%) and a long excited-state lifetime (134 μs). These solid-solution phosphors (x = 0.0-0.5) show excellent thermal stability and maintain over 50% of the RT intensity at 200 °C. The optimized phosphor was encapsulated with red-light chips to fabricate NIR pc-LED and put into night-vision application. These good properties make these Cu2+-activated NIR phosphors appealing for multiple applications such as nondestructive testing, night version, lasers, and luminescent solar concentrators.