Kinetics of Nd³⁺ luminescent complexes in CCl₄–GaCl₃ solutions

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In order to create a low-toxic and cheap liquid laser medium, carbon tetrachloride solutions activated by Nd³⁺ were prepared. The concentration of Nd³⁺ in CCl₄–GaCl₃–Nd³⁺ solutions reaches 1 mol/l, whereas the lifetime of the excited state of Nd³⁺ does not exceed 80 μs and the quantum yield of Nd³⁺ luminescence is less than 0.3. The spectral-luminescent properties of CCl₄–GaCl₃–Nd³⁺ solutions, the kinetics of formation and quenching of luminescent Nd³⁺ complexes are considered. The rate of Nd³⁺ complexation increases with increasing [GaCl₃] : [Nd³⁺] ratio. The limitation of the lifetime of the excited state of Nd³⁺ is due to the overlap of the absorption band of the CCl₄–GaCl₃–Nd³⁺ solution with the luminescent band 4F3/2 → 4I15/2 in the wavelength range of 1840 – 1870 nm.

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作者简介

G. Tikhonov

State Scientific Centre of the Russian Federation – Leypunsky Institute for Physics and Power Engineering

编辑信件的主要联系方式.
Email: gvtikhonov@ippe.ru
俄罗斯联邦, Obninsk

E. Seregina

State Scientific Centre of the Russian Federation – Leypunsky Institute for Physics and Power Engineering

Email: gvtikhonov@ippe.ru
俄罗斯联邦, Obninsk

A. Podkopaev

State Scientific Centre of the Russian Federation – Leypunsky Institute for Physics and Power Engineering

Email: gvtikhonov@ippe.ru
俄罗斯联邦, Obninsk

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2. Fig. 1. Absorption spectra of CCl₄ (1), CCl₄–GaCl₃ (2) and CCl₄–GaCl₃–Nd³⁺ (3, 4) solutions prepared from neodymium perchlorate (3) and TFA (4).

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3. Fig. 2. Absorption spectra of CCl₄–GaCl₃–Nd³⁺ solutions prepared from neodymium perchlorate (1, 2) and TFA (3–5); ([GaCl₃] : [Nd]) ᵢₙ = 8.1 (1, 2), 8.4 (3), and 2.5 (4, 5).

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4. Fig. 3. Absorption of CCl₄–GaCl₃ (1) and CCl₄–GaCl₃–Nd³⁺ solutions prepared from TFA (2–6); [GaCl₃] : [Nd³⁺] = 8.4; [Nd³⁺] = 0.25 mol/L; complexation time: 2 (2), 5 (3), 9 (4), 15 (5), and 130 (6).

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5. Fig. 4. Absorption bands of Nd³⁺ in CCl₄–GaCl₃–Nd³⁺ solutions prepared from TFA (1–5) and neodymium perchlorate (6); [GaCl₃] : [Nd³⁺] = 3.8 (1), 6.2 (2), 8.9 (3), 13 (4), 17 (5), and 8.1 (6); [Nd³⁺] = (0.092 ± 0.004) mol/L.

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6. Fig. 5. Absorption bands of Nd³⁺ in CCl₄–GaCl₃–Nd³⁺ solution; [GaCl₃] : [Nd³⁺] = 3.8; [Nd³⁺] = 0.095 mol/l; complexation time: 1 (1), 7 (2), 51 (3), 80 (4) and 93 (5).

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7. Fig. 6. Kinetic dependences of Nd³⁺ complexation in CCl₄–GaCl₃–Nd³⁺ solutions; [GaCl₃] : [Nd³⁺] = 2.5 (1), 4.0 (2), 4.8 (3), 5.9 (4), 6.7 (5), 8.4 (6), 10.4 (7), 10.5 (8), 13 (9); the ratio ([GaCl₃] : [Nd³⁺])in is the initial one.

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8. Fig. 7. Kinetic dependences of Nd³⁺ luminescence quenching in CCl₄–GaCl₃–Nd³⁺ solutions (curve numbers correspond to sample numbers from Table 2).

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9. Fig. 8. Kinetic dependences of Nd³⁺ luminescence quenching in CCl₄–GaCl₃–Nd³⁺ solutions prepared from neodymium TFA; [GaCl₃] : [Nd³⁺] = 4.8 (1), 5.3 (2, 3), 5.9 (4) and 8.4 (5, 6); [Nd³⁺] ≈ (0.27 ± 0.03) mol/L.

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10. Fig. 9. Structure of levels and transitions between them for Nd³⁺ in CCl₄–GaCl₃–Nd³⁺: solid arrows are radiative transitions, dashed arrows are nonradiative transitions.

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11. Fig. 10. Luminescence spectrum of Nd³⁺ in CCl₄–GaCl₃–Nd³⁺ solution.

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12. Fig. 11. Absorption spectra of CCl₄–GaCl₃–Nd³⁺ solutions prepared from TFA (1) and neodymium perchlorate (2), τ = 0.07 ms, SOCl₂–GaCl₃–Nd³⁺, τ = 0.3 ms (3), and the wavelength of the luminescent transition ⁴F₃/₂ → ⁴I₁₅/₂ of neodymium(III) (4).

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