
人工晶体学报 ›› 2026, Vol. 55 ›› Issue (9): 1460-1471.DOI: 10.16553/j.cnki.issn1000-985x.2026.0061
孟晓燕(
), 郑书怡, 罗朝铭, 汤文杰, 吴丽丹, 杨流赛
收稿日期:2026-04-16
出版日期:2026-09-20
发布日期:2026-09-29
作者简介:孟晓燕(1978—),女,安徽省人,副教授。E-mail:mengxiaoyan_bin@163.com
基金资助:
MENG Xiaoyan(
), ZHENG Shuyi, LUO Chaoming, TANG Wenjie, WU Lidan, YANG Liusai
Received:2026-04-16
Online:2026-09-20
Published:2026-09-29
摘要: 本文采用高温固相法制备了Na2Ca1-x SiO4∶xTb3+(x=0~0.08)和Na2Ca0.95SiO4∶0.05Tb3+/yK+(y=0.03~0.07)系列绿色荧光粉,系统研究了Tb3+单掺、Tb3+/K+共掺杂对样品物相结构、微观形貌、光学吸收、发光性能、色坐标与热稳定性的影响。结果表明,掺杂均未改变Na2CaSiO4基质的立方晶相结构,相结晶度高,且Tb3+有效取代了Ca2+的晶格位置并降低基质带隙。样品的微观形貌不规则且存在明显团聚,在376 nm激发下,Na2Ca1-x SiO4∶xTb3+荧光粉在544 nm处出现Tb3+的5D4→7F5最强特征发射,最佳掺杂物质的量浓度x=0.05;在Na2Ca0.95SiO4∶0.05Tb3+/yK+(y=0.03~0.07)荧光粉中,K+的最佳掺杂物质的量浓度y=0.05。最优组分Na2Ca0.95SiO4∶0.05Tb3+/0.05K+的荧光发光强度约为Na2Ca0.95SiO4∶0.05Tb3+的2.3倍,荧光寿命为3.006 ms,带隙为5.03 eV,CIE色坐标为(0.255, 0.551),473 K时发光强度仍保留室温(298 K)的92.4%,热稳定性优异。该荧光粉是一种在白光发光二极管中有着潜在应用价值的绿色荧光粉。
中图分类号:
孟晓燕, 郑书怡, 罗朝铭, 汤文杰, 吴丽丹, 杨流赛. K+掺杂对Na2CaSiO4∶Tb3+荧光粉发光性能的增强效应研究[J]. 人工晶体学报, 2026, 55(9): 1460-1471.
MENG Xiaoyan, ZHENG Shuyi, LUO Chaoming, TANG Wenjie, WU Lidan, YANG Liusai. Enhancement Effect of K+ Doping on Luminescence Properties of Na2CaSiO4∶Tb3+ Phosphor[J]. Journal of Synthetic Crystals, 2026, 55(9): 1460-1471.
图1 NCSO∶xTb3+(x=0~0.08)(a),NCSO∶0.05Tb3+/yK+(y=0.03~0.07)(b)的XRD图谱,Na2CaSiO4的晶体结构图(c),以及Na2Ca0.95SiO4∶0.05Tb3+的XRD精修图谱(d)
Fig.1 XRD patterns of NCSO∶xTb3+(x=0~0.08) (a) and NCSO∶0.05Tb3+/yK+(y=0.03~0.07) (b), the crystal structure of Na2CaSiO4 (c), and XRD refinement pattern of Na2Ca0.95SiO4∶0.05Tb3+ (d)
| Sample | a=b=c/nm | V/nm3 | D/nm | Rwp/% | χ2 | Eg | CIE (X, Y) | τ/ms |
|---|---|---|---|---|---|---|---|---|
x=0 x=0.01 | 0.748 95 0.748 70 | 0.420 11 0.419 69 | 37.9 37.5 | 14.895 13.962 | 1.753 1.419 | 5.84 | — | — |
| 5.01 | (0.213, 0.362) | 3.109 | ||||||
| x=0.03 | 0.748 49 | 0.419 33 | 36.6 | 14.028 | 1.445 | 5.02 | (0.232, 0.452) | 3.047 |
| x=0.04 | 0.748 36 | 0.419 11 | 36.8 | 14.282 | 1.621 | 5.01 | (0.238, 0.479) | 2.972 |
| x=0.05 | 0.748 30 | 0.419 01 | 34.8 | 12.893 | 1.239 | 5.01 | (0.238, 0.487) | 2.954 |
| x=0.06 | 0.747 72 | 0.418 04 | 37.1 | 14.138 | 1.482 | 5.01 | (0.239, 0.486) | 2.872 |
| x=0.07 | 0.748 13 | 0.418 73 | 37.0 | 13.433 | 1.387 | 5.00 | (0.241, 0.494) | 2.831 |
| x=0.08 | 0.748 50 | 0.419 35 | 37.2 | 13.090 | 1.255 | 5.02 | (0.241, 0.488) | 2.811 |
| y=0.03 | 0.749 25 | 0.420 61 | 36.4 | 13.051 | 1.297 | 5.02 | (0.245, 0.504) | 2.931 |
| y=0.04 | 0.748 86 | 0.419 95 | 37.0 | 13.531 | 1.444 | 5.02 | (0.253, 0.541) | 2.993 |
| y=0.05 | 0.748 59 | 0.419 50 | 38.2 | 13.602 | 1.374 | 5.03 | (0.255, 0.551) | 3.006 |
| y=0.06 | 0.748 98 | 0.420 16 | 38.7 | 13.088 | 1.329 | 5.00 | (0.255, 0.547) | 2.990 |
| y=0.07 | 0.749 18 | 0.420 49 | 39.5 | 13.307 | 1.387 | 5.02 | (0.254, 0.545) | 3.010 |
表1 Na2Ca1-x SiO4∶xTb3+和Na2Ca0.95Tb0.05SiO4∶0.05Tb3+/yK+的晶格常数、粒径(D)、带隙(Eg)、CIE坐标和寿命( τ )
Table 1 Lattice parameters, crystallite sizes (D), band gap(Eg), CIE coordinates and lifetime ( τ ) of Na2Ca1-x SiO4∶xTb3+ and Na2Ca0.95Tb0.05SiO4∶0.05Tb3+/yK+
| Sample | a=b=c/nm | V/nm3 | D/nm | Rwp/% | χ2 | Eg | CIE (X, Y) | τ/ms |
|---|---|---|---|---|---|---|---|---|
x=0 x=0.01 | 0.748 95 0.748 70 | 0.420 11 0.419 69 | 37.9 37.5 | 14.895 13.962 | 1.753 1.419 | 5.84 | — | — |
| 5.01 | (0.213, 0.362) | 3.109 | ||||||
| x=0.03 | 0.748 49 | 0.419 33 | 36.6 | 14.028 | 1.445 | 5.02 | (0.232, 0.452) | 3.047 |
| x=0.04 | 0.748 36 | 0.419 11 | 36.8 | 14.282 | 1.621 | 5.01 | (0.238, 0.479) | 2.972 |
| x=0.05 | 0.748 30 | 0.419 01 | 34.8 | 12.893 | 1.239 | 5.01 | (0.238, 0.487) | 2.954 |
| x=0.06 | 0.747 72 | 0.418 04 | 37.1 | 14.138 | 1.482 | 5.01 | (0.239, 0.486) | 2.872 |
| x=0.07 | 0.748 13 | 0.418 73 | 37.0 | 13.433 | 1.387 | 5.00 | (0.241, 0.494) | 2.831 |
| x=0.08 | 0.748 50 | 0.419 35 | 37.2 | 13.090 | 1.255 | 5.02 | (0.241, 0.488) | 2.811 |
| y=0.03 | 0.749 25 | 0.420 61 | 36.4 | 13.051 | 1.297 | 5.02 | (0.245, 0.504) | 2.931 |
| y=0.04 | 0.748 86 | 0.419 95 | 37.0 | 13.531 | 1.444 | 5.02 | (0.253, 0.541) | 2.993 |
| y=0.05 | 0.748 59 | 0.419 50 | 38.2 | 13.602 | 1.374 | 5.03 | (0.255, 0.551) | 3.006 |
| y=0.06 | 0.748 98 | 0.420 16 | 38.7 | 13.088 | 1.329 | 5.00 | (0.255, 0.547) | 2.990 |
| y=0.07 | 0.749 18 | 0.420 49 | 39.5 | 13.307 | 1.387 | 5.02 | (0.254, 0.545) | 3.010 |
图2 Na2Ca0.95SiO4∶0.05Tb3+的SEM照片(a)和EDS(b),及Na2Ca0.95SiO4∶0.05Tb3+/0.05K+的SEM照片(c)和EDS(d)
Fig.2 SEM image (a) and EDS (b) of Na2Ca0.95SiO4∶0.05Tb3+, and SEM image (c) and EDS (d) of Na2Ca0.95SiO4∶0.05Tb3+/0.05K+
图3 Na2CaSiO4(a)、Na2Ca0.95SiO4∶0.05Tb3+(b)和Na2Ca0.95SiO4∶0.05Tb3+/0.05K+(c)的红外光谱
Fig.3 FT-IR spectra of Na2CaSiO4 (a), Na2Ca0.95SiO4∶0.05Tb3+ (b) and Na2Ca0.95SiO4∶0.05Tb3+/0.05K+ (c)
图4 NCSO、NCSO∶0.05Tb3+和NCSO∶0.05Tb3+/0.05K+的紫外-可见漫反射光谱(a),以及(αhν)2与能量关系曲线(b)
Fig.4 UV-Vis diffuse reflectance spectra (a) and the energy dependence of (αhν)2 (b) of NCSO, NCSO∶0.05Tb3+, and NCSO∶0.05Tb3+/0.05K+
图6 Na2Ca1-x SiO4∶xTb3+的发射光谱(插图:荧光发射积分强度随Tb3+浓度的变化)
Fig.6 Emission spectra of Na2Ca1-x SiO4∶xTb3+ (inset: variation of integrated emission intensity with Tb3+ concentration)
图7 Na2Ca1-x SiO4∶xTb3+在λem=488 nm and λem=544 nm处lg(I/x)与lg x关系曲线
Fig.7 Curves of lg(I/x) versus lg x for Na2Ca1-x SiO4∶xTb3+ at λem=488 nm and λem=544 nm
图8 NCSO∶0.05Tb3+/yK+(y=0,0.03~0.07)的发射光谱(a)和荧光发射积分强度随K+浓度的变化关系(b)
Fig.8 Emission spectra of NCSO∶0.05Tb3+/yK+(y= 0,0.03~0.07) (a), and variation of integrated emission intensity with K+ concentration (b)
图11 Na2Ca0.95SiO4∶0.05Tb3+/0.05K+的相对发射强度随温度的变化曲线(a)和ln(I0/I-1)与1/(kBT)的关系图(b)
Fig.11 Variations of the relative emission intensity as a function of temperature (a) and plot of ln(I0/I-1) versus 1/(kBT) (b) for Na2Ca0.95SiO4∶0.05Tb3+/0.05K+
图12 所制备白光LED器件在200 mA电流下的电致发光光谱和照片(a),EL光谱(b),在各种电流下参数LE、CRI和CCT(c),及CIE色度图(d)
Fig.12 Electroluminescence spectrum and photographs of the fabricated white LED device at a current of 200 mA (a), EL spectra (b), the parameters LE, CRI, and CCT (c), and CIE chromaticity diagram (d) at various currents
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