锶含量对稀土Eu掺杂锶钙羟基磷灰石发光性能及取代位置的影响

doi:10.15541/jim20160181

摘要/Abstract

摘要：

采用化学共沉淀法制备了一系列Sr含量不同的铕掺杂锶钙羟基磷灰石粉体(Ca_10-_x-Sr_x-HAp: Eu), 通过X射线衍射(XRD)、荧光光谱以及发光能量传递等研究了锶含量对稀土掺杂锶钙羟基磷灰石结构、荧光性能和取代位置的影响。XRD分析表明, 掺杂Eu对锶钙羟基磷灰石样品的结构无明显影响, 而Sr含量增加会使得样品的结晶程度和晶面间距增大。光谱分析表明, 在394 nm波长激发下, Ca_10-_x-Sr_x-HAp: Eu样品在596 nm和618 nm处的荧光强度随着Sr含量的增加先升高再降低, 最强峰值出现在Ca₃-Sr₇-HAp: Eu样品中。同时, 样品的荧光寿命随着Sr含量增加也出现相同的变化。此外, 随着基体中Sr含量的增加, 样品的电偶极跃迁与磁偶极跃迁强度比值(I_R/I_O)先增加后减小, 而Eu荧光衰减过程中不同格点之间的能量传递参数(f)则先减小后增大, 两者的转折点都出现在Ca₃-Sr₇-HAp: Eu样品中。实验表明: Eu在基质晶格中的取代位置受Sr在基质中含量和位置的影响, 通过Sr/Ca比例的调节则可以使得Eu在基质中取代不同位点的比例变化进而获得可调节的荧光性能。

关键词: 羟基磷灰石, Sr²⁺, Eu³⁺, 发光性能, 取代位置

Abstract:

A series of Europium (Eu) and Strontium (Sr) codoped hydroxyapatite samples (Ca_10-_x-Sr_x-HAp: Eu) were designed and prepared using the chemical co-precipitation method. The crystalline structure, chemical composition and luminescent property of samples were characterized by X-ray diffraction (XRD) and photoluminescent spectrum (PL). XRD patterns showed that Eu doping had little effect on the structure of the samples, while with the increase of Sr content, crystallinity and interplanar crystal spacing were increased. PL spectra indicate that the fluorescence intensity at 596 nm and 618 nm of Ca-Sr-HAp: Eu samples increased firstly and then decreased with increase of Sr content at 394 nm excitation, and the strongest peak appeared in the Ca₃-Sr₇-HAp: Eu samples. At the same time, the fluorescence lifetime of the samples showed the same tendency with the increase of Sr content. In addition, the ratio of magnitude between electric dipole and magnetic dipole transition (I_R/I_O) also increased firstly and decreased subsequently along with the increase of Sr content in the matrix. Furthermore, the energy transfer parameters (f) calculated from luminescent dynamic of Eu³⁺ correlating to different sites and transitions present the reverse change. It is concluded that the doped sites of Eu³⁺ ions in the host lattice are affected by the content and location of Sr²⁺ ions in the matrix. Thereby a tunable luminescent property of Ca_10-_x-Sr_x-HAp: Eu samples can be obtained by changing the site of Eu ions in the matrix through adjusting the value of Sr/Ca.

Key words: hydroxyapatite, Sr²⁺, Eu³⁺, luminescent property, substitution site

中图分类号:

TB321

殷海荣, 刘晶, 乔荫颇, 李艳肖, 张攀, 周沁, 杨晨. 锶含量对稀土Eu掺杂锶钙羟基磷灰石发光性能及取代位置的影响[J]. 无机材料学报, 2016, 31(10): 1103-1109.

YIN Hai-Rong, LIU Jing, QIAO Yin-Po, LI Yan-Xiao, ZHANG Pan, ZHOU Qin, YANG Chen. Effect of Strontium on Luminescence Properties and Substitution Site of Eu Doped Sr-Ca-Hydroxyapatite[J]. Journal of Inorganic Materials, 2016, 31(10): 1103-1109.

图/表 6

图1 Ca10-x-Srx-HAp: Eu样品的XRD图谱

Fig. 1 XRD patterns of hydroxyapatite Ca10-x-Srx-HAp: Eu

图2 Ca10-x-Srx-HAp: Eu样品的荧光激发(a)和发射(b)光谱图

Fig. 2 Excitation (a) and emission (b) spectra of Ca10-x-Srx- HAp: Eu The inset shows the fluorescent intensity as a function of Sr content for 5D0→7F2 transition (λex = 394 nm, λem = 618 nm) of Ca10-x-Srx-HAp: Eu

图3 (a)Ca10-x-Srx-HAp: Eu样品的荧光发光强度的对数-时间(lnI-t)曲线和(b)Ca10-x-Srx-HAp: Eu样品的5D0→7F1磁偶极跃迁(λex=394 nm, λem=596 nm)和5D0→7F2电偶极跃迁(λex=394 nm, λem=618 nm)处荧光寿命与Sr含量的关系曲线

Fig. 3 (a) The lnI-t curves of the samples Ca10-x-Srx-HAp: Eu and (b) fluorescent lifetime as a function of Sr content for 5D0→7F1 transition (λex = 394 nm, λem = 596 nm) and 5D0→7F2 transition(λex = 394 nm, λem = 618 nm) of Ca10-x-Srx-HAp: Eu The inset shows time-dependent decay curve of 5D0→7F2 transition for Ca10-x-Srx-HAp: Eu(λex = 394 nm, λem = 618 nm)

图4 Ca10-x-Srx-HAp: Eu样品的电偶极跃迁与磁偶极跃迁强度比值(IR/IO)

Fig. 4 Ratio of luminescent intensity between electric-dipole transition emission and magnetic-dipole transition emission (IR/IO) for Ca10-x-Srx-HAp: Eu

表1 Ca10-x-Srx-HAp: Eu样品在5D0能级(λex = 394 nm, λem = 596 nm)的荧光衰减拟合参数

Table 1 Best fitting parameters of 5D0 emission decay (λex = 394 nm, λem = 596 nm) for Ca10-x-Srx-HAp: Eu

x	A₁(f_trans)	B₁(1-f_trans )	C	t₁₂/μs	t₁/μs	γ₁/s^-1/2	t₂₁/μs	R²
0	—	10.982	—	—	3967	0.5262	—	0.9954
1	35.541(0.653)	13.573(0.248)	9.97	627	4235	0.5683	277.48	0.9964
3	117.578(0.882)	15.322(0.118)	2.55	1211	3889	3.99E-12	35.43	0.9992
5	42.416(0.759)	11.716(0.241)	5.56	917	1888	3.8901	143.59	0.9986
7	105.082(0.665)	50.826(0.335)	4.18	964	3013	0.1687	8.92	0.9993
8	248.368(0.650)	128.191(0.350)	9.96	1255	3696	1.37E-12	72.81	0.9980
9	34.414(0.449)	34.472(0.551)	6.28	11544	913	3.85E-13	61.66	0.9985
10	22.097(0.315)	37.959(0.685)	4.68	7318	833	1.18E-13	4.67	0.9987

表2 Ca10-x-Srx-HAp: Eu样品在5D0能级(λex=394 nm, λem=618 nm)的荧光衰减拟合参数

Table 2 Best fitting parameters of 5D0 emission decay (λex=394 nm, λem=618 nm) for Ca10-x-Srx-HAp: Eu

x	A₂(1-f)	B₂(f)	t₁₂/μs	t₂/μs	γ₂/s^-1/2	R²
0	—	—	—	—
1	155.844(0.607)	53.804(0.393)	37.52	2477.45	1.0358	0.9978
3	466.144(0.750)	131.660(0.250)	78.85	2711.73	0.8919	0.9992
5	239.591(0.741)	58.741(0.259)	98.96	2143.47	0.7993	0.9991
7	509.235(0.715)	118.934(0.285)	101.12	2480.58	0.6962	0.9994
8	335.056(0.720)	74.884(0.280)	121.20	3846.19	0.6797	0.9994
9	259.136(0.485)	78.198(0.515)	89.03	2895.34	0.8650	0.9990
10	167.785(0.279)	49.342(0.721)	61.10	2240.63	0.9330	0.9990

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