Mn4+掺杂K2Ge4O9单晶的生长、猝灭机制及其发光性能研究

doi:10.16553/j.cnki.issn1000-985x.2026.0037

摘要/Abstract

摘要： 针对传统Mn⁴⁺掺杂多晶氧化物荧光粉体面临的严重热猝灭瓶颈，本研究采用提拉法生长了新型Mn⁴⁺∶K₂Ge₄O₉（Mn∶KGO）单晶。结合密度泛函理论（DFT）计算，揭示了该体系中格位依赖的双重热猝灭机制：占据Ge1位点的Mn⁴⁺受宇称选律制约，触发了载流子自电离过程；而占据主发光中心Ge2位点的Mn⁴⁺与价带发生强烈共价杂化，迫使电荷迁移态能量显著下移。研究表明，相较于多晶粉体，单晶的连续晶格结构有效阻断了非辐射跃迁通道，将热猝灭温度提升了6.2 ℃，内量子效率实现了44%的大幅跃升，达到48.3%。器件应用评估显示，将该单晶集成于白光发光二极管（LED）封装后，系统的显色指数提升7.5，相关色温降低逾2 000 K，成功驱动了冷白光向暖白光的转变；同时，该系统的664 nm的深红光发射光谱与植物光敏色素的特征吸收带高度契合。本研究开发了低熔点Mn⁴⁺掺杂氧化物晶体，为大功率固态照明及植物生长照明应用提供了极具潜力的单晶红光材料。

关键词: Mn∶KGO晶体; 热猝灭; DFT; 白光LED; 植物生长照明

Abstract: Red-emitting luminescent materials constitute core components in solid-state lighting and display technologies，offering distinct advantages for high-color-rendering-index （CRI） white light-emitting diodes （wLEDs） and agricultural illumination. Commercial red phosphors currently rely heavily on rare-earth activators，such as Eu²⁺，Eu³⁺，and Sm³⁺. While these materials exhibit excellent luminescence via 4f-4f and 4f-5d transitions，inherent resource scarcity and complex extraction processes inflate costs，severely restricting their large-scale deployment. Consequently，developing efficient，rare-earth-free alternatives has emerged as a critical research frontier. In facility agriculture，specific light spectra precisely govern plant development. While blue light promotes vegetative growth，deep-red emission （~660 nm） is essential for flowering，fruiting，leaf expansion，and stem elongation，directly dictating crop maturation cycles and ultimate yields. Transition metal Mn⁴⁺ demonstrate exceptional suitability for agricultural applications，as their emission profile perfectly matches the peak absorption of plant phytochromes. Because the luminescent properties of Mn⁴⁺ depend heavily on the local crystal field，selecting an appropriate host lattice is paramount. K₂Ge₄O₉ （KGO） represents an ideal matrix. Here，Ge⁴⁺ perfectly matches Mn⁴⁺ in both ionic radius and valence state. Furthermore，its unique tetrahedral-octahedral composite framework provides the requisite ［GeO₆］ octahedral sites for Mn⁴⁺ incorporation. Despite these structural advantages，traditional Mn∶KGO polycrystalline phosphors suffer from poor photothermal stability，retaining less than 40% of their room-temperature emission intensity at 100 ℃，with underlying thermal quenching mechanisms remaining ambiguous. To address the severe thermal quenching bottleneck commonly observed in traditional Mn⁴⁺-doped polycrystalline oxide phosphors，a novel low-melting-point Mn∶KGO single crystal was successfully grown using the Czochralski method. Through density functional theory （DFT） calculations，a site-dependent dual thermal quenching mechanism within this system is elucidated. Specifically，Mn⁴⁺ occupying the Ge1 sites are restricted by parity selection rules，whereby a carrier autoionization process is triggered. Conversely，Mn⁴⁺ at the Ge2 sites，which serve as the primary luminescent centers，are subjected to strong covalent hybridization with the valence band，forcing the charge transfer state energy to be lowered significantly. Furthermore，it is demonstrated that non-radiative transition pathways are effectively suppressed by the continuous lattice structure of the single crystal. Consequently，the thermal quenching temperature of the crystal is elevated by 6.2 ℃，and the internal quantum efficiency （IQE） is substantially increased by 44%，reaching a remarkable value of 48.3%. In terms of device application evaluations，it was observed that upon the integration of this single crystal into wLED packages，the CRI is improved by 7.5，and the correlated color temperature （CCT） is reduced by over 2 000 K，successfully driving a transition from cool to warm white light. Simultaneously，the 664 nm deep-red emission spectrum of the crystal is found to be closely matched with the characteristic absorption bands of plant phytochromes. Ultimately，a low-melting-point Mn⁴⁺-doped oxide crystal is developed in this study，which provides a highly promising single-crystal red-emitting material for high-power solid-state lighting and plant growth illumination applications.

Key words: Mn:KGO crystal; thermal quenching; DFT; white LED; plant growth illumination

中图分类号:

O734

宋青松, 刘坚, 张帆, 张超逸, 王无敌, 曹笑, 钱新宇, 唐慧丽, 王庆国, 张晨波, 刘波, 徐晓东, 徐军. Mn⁴⁺掺杂K₂Ge₄O₉单晶的生长、猝灭机制及其发光性能研究[J]. 人工晶体学报, 2026, 55(6): 910-929.

SONG Qingsong, LIU Jian, ZHANG Fan, ZHANG Chaoyi, WANG Wudi, CAO Xiao, QIAN Xinyu, TANG Huili, WANG Qingguo, ZHANG Chenbo, LIU Bo, XU Xiaodong, XU Jun. Growth, Quenching Mechanism, and Luminescent Properties of Mn⁴⁺∶K₂Ge₄O₉ Single Crystals[J]. Journal of Synthetic Crystals, 2026, 55(6): 910-929.

图/表 29

图1 K2O-GeO2体系相图［26］

Fig.1 Phase diagram of the K2O-GeO2 system［26］

图2 探索阶段制备的Mn∶KGO样品实物照片及其在紫外灯下的发光图。（a）浮区炉中Mn∶KGO上下料棒熔融滴落后的样品（透明与橘黄色部分）；（b）浮区法熔滴的透明样品；（c）透明与橘黄色样品在紫外灯照射下的照片；（d）0.1%Mn∶KGO预烧结粉体；（e）图（d）中粉体在马弗炉中熔化后形成的晶体；（f）图（d）中粉体在紫外灯照射下的照片；（g）图（e）中晶体在紫外灯照射下的照片

Fig.2 Physical photo of the Mn∶KGO sample prepared during the exploration stage and its luminescence image under ultraviolet light. （a） Samples formed by the molten drops from the feed rods in the optical floating zone furnace （transparent and orange parts）；（b） transparent sample obtained from the molten drops via the floating zone method；（c） luminescence images of the transparent and orange samples under UV irradiation；（d） pre-sintered 0.1%Mn∶KGO powder；（e） crystal formed by melting the pre-sintered powder （Fig.（d）） in a muffle furnace；（f） luminescence images of the samples in Fig.（d） under UV irradiation；（g） luminescence images of the samples in Fig.（e） under UV irradiation

图3 提拉法生长的不同Mn掺杂浓度KGO晶体照片。（a）0.1%Mn∶KGO晶体，插图显示了用于光谱与ICP测试的取样区域及对应命名；（b）纯KGO晶体；（c）0.05%Mn∶KGO晶体；（d）0.05%Mn，0.5%Si∶KGO晶体。

Fig.3 Photographs of KGO crystals with varying Mn-doping concentrations grown by the Czochralski method. （a） 0.1%Mn∶KGO crystal，where the inset illustrates the sampling regions for spectroscopy and ICP measurements alongside their corresponding designations；（b） pure KGO crystal；（c） 0.05%Mn∶KGO crystal；（d） 0.05%Mn，0.5%Si∶KGO crystal

表1 KGO晶体样品的密度

Table 1 Densities of the KGO crystal samples

Sample	Average dry weight/g	Average buoyant weight/g	Density/（g·cm^-3）
KGO-as-grown crystal	33.441 7	25.650 0	4.292
KGO-crucible residue	71.448 4	54.647 7	4.253
0.1%Mn∶KGO-E2	0.767 6	0.588 7	4.287
0.1%Mn∶KGO-I1	0.357 2	0.274 5	4.315
ICSD#3169 KGO （calculated）			4.292

图4 KGO样品的XRD图谱

Fig.4 XRD patterns of the KGO samples

表2 KGO晶体样品的晶胞参数

Table 2 Lattice parameters of the KGO crystal samples

Sample	a/Å	c/Å
KGO-FZ-T	11.765 2	9.786 0
KGO-FZ-O	11.812 5	9.795 1
KGO-TGFM	11.812 5	9.798 9
ICSD#31969 KGO	11.84	9.80

图5 KGO的晶体结构（a）与超胞模型（b）~（d）

Fig.5 Crystal structure （a） and supercell models （b）~（d） of KGO

表3 KGO模型结构优化后的晶体结构参数

Table 3 Optimized crystal structure parameters of the KGO model

KGO112-K₂₄Ge₄₈O₁₀₈

Ge1 1.947 2

Ge2 1.917 6

9.837 9

9.392 7

1.565 1

2.388 9

0.005 9

图6 Mn∶KGO晶体与荧光粉的室温拉曼光谱

Fig.6 Room-temperature Raman spectra of Mn∶KGO crystal and phosphor

图7 Mn∶KGO晶体的XPS图

Fig.7 XPS of the Mn∶KGO crystal

图8 Mn∶KGO晶体的EPR波谱

Fig.8 EPR spectrum of the Mn∶KGO crystal

图9 0.1%Mn∶KGO晶体不同区域的光学性质

Fig.9 Optical properties of different regions in the 0.1%Mn∶KGO crystal

图10 Mn∶KGO晶体的光学性质

Fig.10 Optical properties of the Mn∶KGO crystal

图11 DFT计算的纯KGO及Mn掺杂KGO的电子结构与光学性质

Fig.11 DFT-calculated electronic structures and optical properties of pure and Mn-doped KGO

表4 KGO晶体样品的透过率及吸收系数

Table 4 Transmittance and absorption coefficients of the KGO crystal samples

Sample	T@650 nm/%	$α a b s$ @460 nm/cm^-1	UV cutoff edge/nm	Optical band gap/eV
0.1%Mn∶KGO-E1	85.2	0.83	233.0	4.95
0.05%Mn∶KGO	86.6	0.28	229.5	5.31
0.05%Mn，0.5%Si∶KGO	61.1	1.89	231.5	5.00

表4 KGO晶体样品的透过率及吸收系数

Table 4 Transmittance and absorption coefficients of the KGO crystal samples

Sample	T@650 nm/%	$α a b s$ @460 nm/cm^-1	UV cutoff edge/nm	Optical band gap/eV
0.1%Mn∶KGO-E1	85.2	0.83	233.0	4.95
0.05%Mn∶KGO	86.6	0.28	229.5	5.31
0.05%Mn，0.5%Si∶KGO	61.1	1.89	231.5	5.00

图12 0.1%Mn∶KGO晶体不同区域的发光光谱与荧光寿命

Fig.12 Luminescence spectra and fluorescence lifetime of different regions in the 0.1%Mn∶KGO crystal

图13 0.1%Mn∶KGO晶体不同样品的激发光谱拟合结果

Fig.13 Gaussian fitting of the excitation spectra for different samples of the 0.1%Mn∶KGO crystal

表5 Mn∶KGO晶体的光谱参数

Table 5 Spectroscopic parameters of the Mn∶KGO crystal

Sample	CTB/cm^-1	⁴A_2g→⁴T_1g，a/cm^-1	⁴A_2g→²T_2g/cm^-1	⁴A_2g→⁴T_2g/cm^-1	²E_g→⁴A_2g/cm^-1	R²
KGO-E1	34 444	28 933	24 972	21 601	15 337	0.997 4
KGO-E2	34 795	28 913	24 222	21 565	15 337	0.997 6
0.1%Mn∶KGO	34 667	29 213	24 966	21 623	15 337	0.998 1
0.05%Mn∶KGO	34 610	29 662	24 530	21 606	15 337	0.997 8
0.05%Mn，0.5%Si∶KGO	34 599	29 272	25 352	21 580	15 337	0.999 1

图14 Mn∶KGO晶体在室温与100 K下的发射光谱

Fig.14 Emission spectra of the Mn∶KGO crystal at room temperature and 100 K

图15 Mn∶KGO晶体的发光光谱与荧光寿命

Fig.15 Luminescence spectra and fluorescence lifetime of the Mn∶KGO crystals

表6 部分Mn4+掺杂锗酸盐荧光材料的晶体场参数Dq 、B、C及 β1

Table 6 Crystal field parameters Dq，B，C，and β1 of selected Mn4+-doped germanate phosphors

Sample	D_q	B	C	D_q /B	β₁
K₂SrGe₈O₁₈ phosphor^［34］	2 336.4	800.1	3 064.4	2.92	0.991
K₂BaGe₈O₁₈ phosphor^［46］	2 164.5	654.0	3 345.5	3.31	0.960
LiBaGe₄O₉ crystal^［47］	2 175.2	813.0	3 235.7	2.68	1.028
KGO-E1	2 160.1	701.0	3 347.2	3.08	0.985
KGO-E2	2 156.5	703.3	3 342.5	3.07	0.985
0.1%Mn∶KGO	2 162.3	731.4	3 280.1	2.96	0.989
0.05%Mn∶KGO	2 160.6	788.5	3 156.1	2.74	1.000
0.05%Mn，0.5%Si∶KGO	2 158.0	744.1	3 252.7	2.90	0.991

图16 Mn∶KGO晶体的能级图及相关参数依赖关系

Fig.16 Energy level diagram and related parameter dependencies of the Mn∶KGO crystals

图17 Mn∶KGO晶体的量子效率

Fig.17 Quantum efficiency of the Mn∶KGO crystal

表7 Mn4+掺杂锗酸盐材料的内、外量子效率

Table 7 Internal and external quantum efficiencies （IQE/EQE） of Mn4+-doped germanate materials

Sample	λ_ex/nm	IQE/%	AE/%	EQE/%
K₂SrGe₈O₁₈ phosphor^［34］	287	35.50	52.96	18.80
K₂BaGe₈O₁₈ phosphor^［46］	365	32.90
Ba₂GeO₄ phosphor^［53］	290	22.53		—
（Mg，Ba）₃Al₂GeO₈ phosphor^［54］ Mg₃Al₂GeO₈ phosphor^［54］	284 284	— —	— —	49.35 29.44
BaGe₄O₉ phosphor^［55］ SrGe₄O₉ phosphor^［55］	440 430	50.00 46.00
LiNaGe₄O₉ phosphor^［56］	310 450	78.00 48.00
LiNaGe₄O₉ glass-ceramic^［57］	—	37.50
Mn∶KGO phosphor^［52］	300 460 470	45.00 33.50 33.80
0.05%Mn∶KGO	460	46.10	17.70	8.16
0.05%Mn，0.5%Si∶KGO	460	27.10	25.50	4.34
0.1%Mn∶KGO-E1	460	48.30	37.00	17.87
E2	460	41.60	60.60	25.21
E3	460	38.90	60.60	23.57
I1	460	46.70	43.60	20.36
I2	460	35.10	40.70	14.29
I3	460	41.10	47.00	19.32

图18 Mn∶KGO晶体在低温下的变温发光特性。（a）低温发射光谱；（b）PL积分强度与ZPL峰值强度随温度的变化曲线；（c）变温荧光衰减曲线

Fig.18 Temperature-dependent luminescence properties of the Mn∶KGO crystal at low temperatures. （a） Low-temperature emission spectra；（b） temperature dependence of the integrated PL intensity and zero-phonon line （ZPL） peak intensity；（c） temperature-dependent fluorescence decay curves

图19 Mn∶KGO晶体与荧光粉在高温下的变温发光特性对比。晶体（a）和荧光粉（b）的变温发射光谱；晶体（c）和荧光粉（d）的变温荧光衰减曲线；（e）PL积分强度随温度的变化曲线

Fig.19 Comparison of the temperature-dependent luminescence properties between the Mn∶KGO crystal and phosphor at elevated temperatures. Temperature-dependent emission spectra of the crystal （a） and phosphor （b），respectively； temperature-dependent fluorescence decay curves of the crystal （c） and phosphor （d），respectively；（e） temperature dependence of the integrated PL intensity

表8 Mn∶KGO晶体的CIE色坐标及色纯度参数

Table 8 CIE chromaticity coordinates and color purity parameters of Mn∶KGO crystals

Sample	CIE 1931 chromaticity coordinates （X，Y）	Color purity/%
0.1%Mn∶KGO	（0.724 1，0.275 8）	98.24
0.05%Mn∶KGO	（0.724 0，0.276 0）	98.21
0.05%Mn，0.5%Si∶KGO	（0.724 2，0.275 8）	98.26

图20 基于Mn∶KGO晶体封装LED器件的光谱性能与色度坐标。植物补光LED（a）和白光LED器件（b）的电致发光光谱；（c）Mn∶KGO晶体与LED器件的CIE色度坐标图

Fig.20 Spectral performance and chromaticity coordinates of LED devices packaged with the Mn∶KGO crystal. Electroluminescence spectra of the plant-growth LED device （a） and the white LED device （b）；（c） CIE chromaticity diagram of the Mn∶KGO crystal and the LED devices

图21 日光组、暗室组和植物补光LED组下大蒜生长情况的对比

Fig.21 Comparison of garlic growth conditions under sunlight，dark field，and plant growth LED illumination

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Mn⁴⁺掺杂K₂Ge₄O₉单晶的生长、猝灭机制及其发光性能研究

Growth, Quenching Mechanism, and Luminescent Properties of Mn⁴⁺∶K₂Ge₄O₉ Single Crystals

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