可见光波段稀土激光晶体的研究进展

doi:10.15541/jim20180403

摘要/Abstract

摘要：

可见光激光在数据存储、光通讯、激光显示、激光医疗、激光打印以及科学研究等领域具有非常重要的应用价值。随着蓝光LD泵浦源的商用化, 直接泵浦稀土离子掺杂激光晶体实现可见光激光输出吸引了人们极大的研究兴趣。目前, 可见光稀土离子主要集中在Pr ³⁺、Dy ³⁺、Tb ³⁺和Sm ³⁺等。其中, Pr ³⁺的研究较多, 发光波长涵盖面较广, 发射波段覆盖蓝光、绿光、红光、橙光; Dy ³⁺和Tb ³⁺因为能够发射黄光以填补Pr ³⁺的不足也吸引了广泛的研究; 此外, Sm ³⁺和Eu ³⁺也是典型的可见波段稀土发光离子。本文综述了近几年可见波段稀土离子掺杂激光晶体的研究现状, 主要以Pr ³⁺、Dy ³⁺、Tb ³⁺和Sm ³⁺掺杂YAlO₃(YAP)、Mg : SrAl₁₂O₁₉(SRA)等晶体为研究对象, 总结了一套适合Pr ³⁺掺杂材料的判据, 对晶体生长、结构、热学性能、偏振光谱性能和激光性能进行了系统的研究。

关键词: 激光晶体, 可见光, 铝酸钇, 铝酸锶, 综述

Abstract:

Visible laser has been widely used in data storage, optical communication, laser display, laser medical treatment, laser printing, and scientific research. With the development of commercial blue light LD, the direct pumping of rare-earth ions doped laser crystals have attracted a lot of interests. Currently, visible ions mainly concentrat on Pr ³⁺, Dy ³⁺, Tb ³⁺, and Sm ³⁺. Trivalent praseodymium (Pr ³⁺) is a famous rare-earth ion with extensive laser transitions in visible region such as blue, green, red and orange light. However, there is still a region in yellow emission which is not covered by Pr ³⁺. Dy ³⁺ and Tb ³⁺ have attracted much attention because of their yellow laser transitions. In addition, Sm ³⁺ and Eu ³⁺ are also typical visible rare-earth ions. In this paper, we mainly reviewed properties of rare-earth ions doped laser crystals for visible lasers, especially Pr ³⁺, Dy ³⁺, Tb ³⁺ and Sm ³⁺-doped YAlO₃(YAP), SrAl₁₂O₁₉(SRA) crystals. A design criterion for Pr ³⁺ doped oxide materials was summarized. The crystal growth, structure, thermal properties, polarization spectroscopic and laser characteristics were analyzed in detail.

Key words: laser crystal, visible laser, YAlO₃(YAP), SrAl₁₂O₁₉(SRA), review

中图分类号:

TQ174

李纳, 刘斌, 施佼佼, 薛艳艳, 赵衡煜, 施张丽, 侯文涛, 徐晓东, 徐军. 可见光波段稀土激光晶体的研究进展[J]. 无机材料学报, 2019, 34(6): 573-589.

Na LI, Bin LIU, Jiao-Jiao SHI, Yan-Yan XUE, Heng-Yu ZHAO, Zhang-Li SHI, Wen-Tao HOU, Xiao-Dong XU, Jun Xu. Research Progress of Rare-earth Doped Laser Crystals in Visible Region[J]. Journal of Inorganic Materials, 2019, 34(6): 573-589.

图/表 22

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Transitions	Parameters	LLF	YLF	GLF		LaF₃	BYF	LMA	ASL	YAP	SRA
	Absorption
³H₄→³P₂	l_abs/nm σ_abs/(×10^-20, cm²) FWHM_abs/nm	444 10.3 1.70	444 9.0 1.80	444 7.8 1.9		442 1.6 5	445 3.7 -	444 1.2 7.1	444 1.3 -	449 5.64 5.6	445 1.14 9.59
	Emission
³P₁→³H₅	l_em/nm σ_em/(×10^-20, cm²) FWHM_em /nm σ_emτ_f/(×10^-20, cm²·μs)	522 3 ~2 113.7	522 3 ~2 107.1	522 3 1 130.8		537 0.7 ~3 35.7	522 0.4 ~4 17.9	530 0.25 4 8.6	542 2 - 76	533 8.8 1.9 168.6	525 1.35 9.8 41.5
³P₀→³H₆	l_em/nm σ_em/(×10^-20, cm²) FWHM_em /nm σ_emτ_f/(×10^-20, cm²·μs)	607 12 ~3 454.8	607 14 ~3 499.8	607 13 - 566.8		610 2.9 ~6.9 147.9	607 24.7 1.2 1062.1	625 3.7 11 127.7	620 2.9 - 110.2	621 25.01 1.56 479.2	622 3.52 6.53 108.3
³P₀→³F₂	l_em/nm σ_em/(×10^-20, cm²) FWHM_em /nm σ_emτ_f/(×10^-20, cm²·μs)	640 21 ~0.7 795.9	640 22 ~0.7 785.4	640 23 - 1003		635 1.2 ~1 61.2	639 12.1 0.6 520.3	647 2.3 6.6 79.4	643 8.5 - 323	662 4.71 1.28 90.2	644 10.37 5.07 319.0
³P₀→³F₄	l_em/nm σ_em/(×10^-20, cm²) FWHM_em /nm σ_emτ_f/(×10^-20, cm²·μs)	720 7 ~1 265.3	720 9 ~1 321.3	720 16 - 697.6		720 6.6 ~3 336.6	721 7.3 1.3 309.6	728 3.3 8.5 113.9	725 11 - 418	747 10.37 1.54 198.7	725 5.75 4.35 176.9
	τ_f/μs	37.90	35.70	43.6		51	43	34.5	38	19.16	30.76
	Ref.	[23]	[23]		[23]	[24]	[25-26]	[27]	[28]	This work

Transitions	Parameters	LLF	YLF	GLF		LaF₃	BYF	LMA	ASL	YAP	SRA
	Absorption
³H₄→³P₂	l_abs/nm σ_abs/(×10^-20, cm²) FWHM_abs/nm	444 10.3 1.70	444 9.0 1.80	444 7.8 1.9		442 1.6 5	445 3.7 -	444 1.2 7.1	444 1.3 -	449 5.64 5.6	445 1.14 9.59
	Emission
³P₁→³H₅	l_em/nm σ_em/(×10^-20, cm²) FWHM_em /nm σ_emτ_f/(×10^-20, cm²·μs)	522 3 ~2 113.7	522 3 ~2 107.1	522 3 1 130.8		537 0.7 ~3 35.7	522 0.4 ~4 17.9	530 0.25 4 8.6	542 2 - 76	533 8.8 1.9 168.6	525 1.35 9.8 41.5
³P₀→³H₆	l_em/nm σ_em/(×10^-20, cm²) FWHM_em /nm σ_emτ_f/(×10^-20, cm²·μs)	607 12 ~3 454.8	607 14 ~3 499.8	607 13 - 566.8		610 2.9 ~6.9 147.9	607 24.7 1.2 1062.1	625 3.7 11 127.7	620 2.9 - 110.2	621 25.01 1.56 479.2	622 3.52 6.53 108.3
³P₀→³F₂	l_em/nm σ_em/(×10^-20, cm²) FWHM_em /nm σ_emτ_f/(×10^-20, cm²·μs)	640 21 ~0.7 795.9	640 22 ~0.7 785.4	640 23 - 1003		635 1.2 ~1 61.2	639 12.1 0.6 520.3	647 2.3 6.6 79.4	643 8.5 - 323	662 4.71 1.28 90.2	644 10.37 5.07 319.0
³P₀→³F₄	l_em/nm σ_em/(×10^-20, cm²) FWHM_em /nm σ_emτ_f/(×10^-20, cm²·μs)	720 7 ~1 265.3	720 9 ~1 321.3	720 16 - 697.6		720 6.6 ~3 336.6	721 7.3 1.3 309.6	728 3.3 8.5 113.9	725 11 - 418	747 10.37 1.54 198.7	725 5.75 4.35 176.9
	τ_f/μs	37.90	35.70	43.6		51	43	34.5	38	19.16	30.76
	Ref.	[23]	[23]		[23]	[24]	[25-26]	[27]	[28]	This work

Hosts	λ_em/nm	Polarizations	Laser transitions	η_slope/%	P_out/mW	P_thr/mW	Pump source	Year
YLF	491	σ	³P_J→³H₄	6	70	285	2w-OPSL	2014^[44]
	523	π	³P_J→³H₅	45	~4200	>500	2×2w-OPSL	2016^[17]
	546	π	³P_J→³H₅	60	2000	120	2w-OPSL	2014^[45]
	605	σ	³P_J→³H₆	25	2100	~1500	Blue-LD	2017^[46] 2017^[46]
	640	σ	³P_J→³F₂	50	4800	~500	Blue-LD	2017^[46] 2017^[46]
	698	σ	³P_J→³F₃	36	1300	78	InGaN-LD	2016^[47]
	721	π	³P_J→³F₄	53	1000	16	2w-OPSL	2014^[47]
LLF	523	E//c	³P₀→³H₅	56	52.7	10	2-OPSL	2007^[48]
	607	E//c	³P₀→³H₆	31	34.5	26	2-OPSL	2007^[48]
	640	E//c	³P₀→³F₂	56	52.7	39	2-OPSL	2007^[48]
	722	E//c	³P₀→³F₄	46	50	31	2-OPSL	2007^[48]
BYF	495	E//X	³P_J→³H₄	27	201	163	2w-OPSL	2014^[44]
	607	E//Y	³P_J→³H₆	12.6	99	264	Blue-LD	2014^[49]
	639	E//Y	³P_J→³F₂	6.4	60	146	Blue-LD	2014^[49]
KYF	554	-	³P_J→³H₅	27	121	166	InGaN-LD	2013^[50]
	610	-	³P_J→³H₆	18	97	162	InGaN-LD	2013^[50]
	645	-	³P_J→³F₂	38	268	30	InGaN-LD	2013^[50]
YGF	523	E//a	³P_J→³H₅	11	63	148	InGaN-LD	2015^[21]
	538	E//b	³P_J→³H₅	24	140	135	InGaN-LD	2015^[21]
	604	E//a	³P_J→³H₆	13	105	72	InGaN-LD	2015^[21]
	638	E//a	³P_J→³F₂	16	128	188	InGaN-LD	2015^[21]
	700	E//a	³P_J→³F₄	18	78	47	InGaN-LD	2015^[21]
	724	E//b	³P_J→³F₄	20	117	48	InGaN-LD	2015^[21]
CaF₂	642	-	³P_J→³F₂	7.5	22	305	InGaN-LD	2017^[51]
LaF₃	537	π	³P_J→³H₅	16	15	159	InGaN-LD	2012^[24]
	612	π	³P_J→³H₆	15	20	98	InGaN-LD	2012^[24]
	635	c	³P_J→³F₂	16	23	95	InGaN-LD	2012^[24]
	720	π	³P_J→³F₄	37	80	10	InGaN-LD	2012^[24]
ASL	620	π	³P_J→³H₆	11	50	~510	2w-OPSL	2018^[52] 2018^[52] 2018^[52]
	643	π	³P_J→³F₂	27	160	~200	2w-OPSL
	725	π	³P_J→³F₄	37	318	~280	2w-OPSL
LMA	620	σ	³P_J→³H₆	2	2.9	~100	2w-OPSL	2012^[27]
	648	σ	³P_J→³F₂	4	10.1	~90	2w-OPSL	2012^[27]
	729	σ	³P_J→³F₄	12	63.7	~25	2w-OPSL	2012^[27]
YAP	547	E//c	³P_J→³H₅	6.1	37	320	InGaN-LD	2013^[53]
	662	E//c	³P_J→³F₂	9	27.4	680	GaN-LD	2011^[54]
	747	E//b	³P_J→³F₄	45	490	300	2×InGaN-LD	2014^[55]
SRA	525	-	³P_J→³H₅	-	36	~1000	2w-OPSL	2013^[56]
	623	σ	³P_J→³H₆	11	114	~200	4×InGaN-LD	2014^[15]
	644	-	³P_J→³F₂	37	1065	~500	2w-OPSL	2013^[56]
	724	σ	³P_J→³F₄	50	564	15.5	4×InGaN-LD	2014^[15]

Hosts	λ_em/nm	Polarizations	Laser transitions	η_slope/%	P_out/mW	P_thr/mW	Pump source	Year
YLF	491	σ	³P_J→³H₄	6	70	285	2w-OPSL	2014^[44]
	523	π	³P_J→³H₅	45	~4200	>500	2×2w-OPSL	2016^[17]
	546	π	³P_J→³H₅	60	2000	120	2w-OPSL	2014^[45]
	605	σ	³P_J→³H₆	25	2100	~1500	Blue-LD	2017^[46] 2017^[46]
	640	σ	³P_J→³F₂	50	4800	~500	Blue-LD	2017^[46] 2017^[46]
	698	σ	³P_J→³F₃	36	1300	78	InGaN-LD	2016^[47]
	721	π	³P_J→³F₄	53	1000	16	2w-OPSL	2014^[47]
LLF	523	E//c	³P₀→³H₅	56	52.7	10	2-OPSL	2007^[48]
	607	E//c	³P₀→³H₆	31	34.5	26	2-OPSL	2007^[48]
	640	E//c	³P₀→³F₂	56	52.7	39	2-OPSL	2007^[48]
	722	E//c	³P₀→³F₄	46	50	31	2-OPSL	2007^[48]
BYF	495	E//X	³P_J→³H₄	27	201	163	2w-OPSL	2014^[44]
	607	E//Y	³P_J→³H₆	12.6	99	264	Blue-LD	2014^[49]
	639	E//Y	³P_J→³F₂	6.4	60	146	Blue-LD	2014^[49]
KYF	554	-	³P_J→³H₅	27	121	166	InGaN-LD	2013^[50]
	610	-	³P_J→³H₆	18	97	162	InGaN-LD	2013^[50]
	645	-	³P_J→³F₂	38	268	30	InGaN-LD	2013^[50]
YGF	523	E//a	³P_J→³H₅	11	63	148	InGaN-LD	2015^[21]
	538	E//b	³P_J→³H₅	24	140	135	InGaN-LD	2015^[21]
	604	E//a	³P_J→³H₆	13	105	72	InGaN-LD	2015^[21]
	638	E//a	³P_J→³F₂	16	128	188	InGaN-LD	2015^[21]
	700	E//a	³P_J→³F₄	18	78	47	InGaN-LD	2015^[21]
	724	E//b	³P_J→³F₄	20	117	48	InGaN-LD	2015^[21]
CaF₂	642	-	³P_J→³F₂	7.5	22	305	InGaN-LD	2017^[51]
LaF₃	537	π	³P_J→³H₅	16	15	159	InGaN-LD	2012^[24]
	612	π	³P_J→³H₆	15	20	98	InGaN-LD	2012^[24]
	635	c	³P_J→³F₂	16	23	95	InGaN-LD	2012^[24]
	720	π	³P_J→³F₄	37	80	10	InGaN-LD	2012^[24]
ASL	620	π	³P_J→³H₆	11	50	~510	2w-OPSL	2018^[52] 2018^[52] 2018^[52]
	643	π	³P_J→³F₂	27	160	~200	2w-OPSL
	725	π	³P_J→³F₄	37	318	~280	2w-OPSL
LMA	620	σ	³P_J→³H₆	2	2.9	~100	2w-OPSL	2012^[27]
	648	σ	³P_J→³F₂	4	10.1	~90	2w-OPSL	2012^[27]
	729	σ	³P_J→³F₄	12	63.7	~25	2w-OPSL	2012^[27]
YAP	547	E//c	³P_J→³H₅	6.1	37	320	InGaN-LD	2013^[53]
	662	E//c	³P_J→³F₂	9	27.4	680	GaN-LD	2011^[54]
	747	E//b	³P_J→³F₄	45	490	300	2×InGaN-LD	2014^[55]
SRA	525	-	³P_J→³H₅	-	36	~1000	2w-OPSL	2013^[56]
	623	σ	³P_J→³H₆	11	114	~200	4×InGaN-LD	2014^[15]
	644	-	³P_J→³F₂	37	1065	~500	2w-OPSL	2013^[56]
	724	σ	³P_J→³F₄	50	564	15.5	4×InGaN-LD	2014^[15]

Hosts	σ_abs/(×10^-21, cm²)	β/%	σ_em/(×10^-20, cm²)	τ_f/μs	Ref.
YAG	1.6	50.96	1.50	376	[64]
YAl(BO₃)₄	-	65.90	1.90	520	[65]
LiLuF₄	-	65.40	1.02	582	[66]
Lu₂SiO₄	-	61.0	0.74	509	[67]
KY₃F₁₀	-	59.8	0.83	440	[66]
Li₂Gd₄(MoO₄)₇	σ: 2.5 π: 4.4	σ:72.0 π: 71.9	σ: 1.45 π: 1.34	139	[68]
YAP	a:0.743 b:0.690 c:0.870	a:88.5 b:88.7 c:87.8	a:0.298 b:0.450 c:0.452	185	This work