CN106348610B - 一种Co2+:KZnF3微晶玻璃及其制备方法和应用 - Google Patents
一种Co2+:KZnF3微晶玻璃及其制备方法和应用 Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 239000000156 glass melt Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 abstract description 8
- 239000000463 material Substances 0.000 description 6
- 229910001428 transition metal ion Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
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- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
本发明公开了一种Co2+:KZnF3微晶玻璃,以Co2+掺杂的KZnF3为微晶相;所述Co2+:KZnF3微晶玻璃的组成为KF‑ZnF2‑Al2O3‑SiO2‑CoO,其中,各组分的摩尔百分比分别为20~30%KF,20~30%ZnF2,0~10%Al2O3,0.1~0.3%CoO,余量为SiO2。本发明还公开了上述Co2+:KZnF3微晶玻璃的制备方法和应用。本发明的Co2+:KZnF3微晶玻璃具有近中红外发光性能,其发光范围为1400~2400nm,发光峰位于1800~1850nm处,可作为近中红外激光增益介质。
Description
技术领域
本发明涉及微晶玻璃,特别涉及一种Co2+:KZnF3微晶玻璃及其制备方法和应用。
背景技术
研究发现,红外波段激光穿透力强,不易受天气的影响,可广泛应用于激光测距、激光通信、激光雷达等领域,因此研制红外激光器具有重要的实际应用意义。固体激光器是指以金属离子掺杂材料作为激光增益介质的激光器,具有体积小,输出峰值功率高等优点,应用较为广泛,而其核心部分即为激光增益介质。目前,红外波段激光增益介质主要包括稀土离子掺杂增益材料,过渡金属离子掺杂增益材料等。过渡金属离子的3d轨道处于最外层,d-d电子跃迁受配位环境影响大,易形成带状光谱。因此,利用过渡金属离子掺杂材料作为激光增益介质,有利于实现激光可调谐,扩大激光器的应用范围。目前,对于过渡金属离子掺杂增益材料的研究范围比较窄,大部分集中Cr3+,Cr4+,Ni2+等离子。研究发现,Co2+掺杂晶体在红外波段有超宽带的发光,但晶体制备困难,成本高。
发明内容
为了克服现有技术的上述缺点与不足,本发明的目的之一在于提供一种 Co2+:KZnF3微晶玻璃,发光范围为1400~2400nm,发光峰位于1800~1850nm处。
本发明的目的之二在于提供上述Co2+:KZnF3微晶玻璃的制备方法,制备较为简单,成本低,可大量生产。
本发明的目的之三在于提供上述Co2+:KZnF3微晶玻璃的应用。
本发明的目的通过以下技术方案实现:
一种Co2+:KZnF3微晶玻璃,以Co2+掺杂的KZnF3为微晶相;所述Co2+:KZnF3微晶玻璃的组成为KF-ZnF2-Al2O3-SiO2-CoO,其中,各组分的摩尔百分比分别为:
所述的Co2+:KZnF3微晶玻璃的制备方法,包括以下步骤:
(1)分别称量原料KF、ZnF2、SiO2、Al2O3和CoO,混合均匀后,将粉末样品于1400~1600℃熔制,得到玻璃熔体;
(2)将玻璃熔体冷却,制成玻璃块;
(3)将玻璃块于500~600℃热处理,随炉冷却至室温,得到透明的 Co2+:KZnF3微晶玻璃。
步骤(1)所述混合均匀,具体为:
置于玛瑙研钵中研磨搅拌至均匀。
步骤(2)所述熔制,具体为:
于1400~1600℃熔制20~30min。
步骤(2)所述将玻璃熔体冷却,制成玻璃块,具体为:
把玻璃熔体倒在光滑铜板上冷却成为玻璃块。
步骤(3)所述热处理,具体为:
于500~600℃热处理10~20小时。
所述Co2+:KZnF3微晶玻璃的应用,作为近中红外激光增益介质。
与现有技术相比,本发明具有以下优点和有益效果:
(1)本发明的Co2+:KZnF3微晶玻璃,发光范围为1400~2400nm,发光峰位于1800~1850nm处,可作为近中红外激光增益介质。
(2)本发明的Co2+:KZnF3微晶玻璃的制备方法,制备较为简单,成本低,可大量生产。
(3)本发明的Co2+:KZnF3微晶玻璃,泵浦激光可采用常见的532nm半导体激光,易于得到,使用方便。
附图说明
图1为实施例1制备的Co2+:KZnF3微晶玻璃的X射线衍射图谱。
图2为实施例1制备的Co2+:KZnF3微晶玻璃的吸收光谱。
图3为实施例1制备的Co2+:KZnF3微晶玻璃的荧光光谱。
具体实施方式
下面结合实施例,对本发明作进一步地详细说明,但本发明的实施方式不限于此。
实施例1
本实施例制备的Co2+:KZnF3微晶玻璃,其组成为KF-ZnF2-SiO2-CoO,各原料摩尔百分比分别为:25%KF,25%ZnF2,50%SiO2,0.1%CoO。将各原料分别称量好,置于玛瑙研钵中研磨搅拌使其混合均匀,将粉末样品转移入氧化铝坩埚中。在1450℃的高温箱式电阻炉中熔融20min,然后把玻璃熔体倒在光滑铜板上形成玻璃块。把玻璃块切割成规则的玻璃薄片,在500℃的马弗炉保温20 小时,然后随炉冷却至室温,得到透明的Co2+:KZnF3微晶玻璃。
本实施例制备的Co2+:KZnF3微晶玻璃的X射线衍射图谱如图1所示,由图可知该Co2 +:KZnF3微晶玻璃析出的晶体与KZnF3的标准PDF卡片 PDF#01-078-1962对应良好,证实了本实施例所得晶相为KZnF3。图2为本实施例所得Co2+:KZnF3透明微晶玻璃的吸收光谱,吸收峰分别为512nm,588nm和 646nm,源于四六配位Co2+离子的电子跃迁。图3为本实施例所得材料的荧光光谱,可以看到样品在1400~2400nm具有宽带发光,发光峰位于1800nm处,源于六配位Co2+离子4T2→4T1a电子跃迁。
实施例2
本实施例制备的Co2+:KZnF3微晶玻璃,其组成为KF-ZnF2-Al2O3-SiO2-CoO,各原料摩尔百分比分别为:22.5%KF,22.5%ZnF2,5%Al2O3,50%SiO2,0.1%CoO。将各原料分别称量好,置于玛瑙研钵中研磨搅拌使其混合均匀,将粉末样品转移入氧化铝坩埚中。在1500℃的高温箱式电阻炉中熔融20min,然后把玻璃熔体倒在光滑铜板上形成玻璃块。把玻璃块切割成规则的玻璃薄片,在520℃的马弗炉保温15小时,然后随炉冷却至室温,得到透明的Co2 +:KZnF3微晶玻璃,在近中红外具有宽带发光,发光峰位于1810nm处。
实施例3
本实施例制备的Co2+:KZnF3微晶玻璃,其组成为KF-ZnF2-Al2O3-SiO2-CoO,各原料摩尔百分比分别为:20%KF,20%ZnF2,5%Al2O3,55%SiO2,0.2%CoO。将各原料分别称量好,置于玛瑙研钵中研磨搅拌使其混合均匀,将粉末样品转移入氧化铝坩埚中。在1550℃的高温箱式电阻炉中熔融20min,然后把玻璃熔体倒在光滑铜板上形成玻璃块。把玻璃块切割成规则的玻璃薄片,在530℃的马弗炉保温10小时,然后随炉冷却至室温,得到透明的Co2+:KZnF3微晶玻璃,在近中红外具有宽带发光,发光峰位于1850nm处。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受所述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (7)
1.一种Co2+:KZnF3微晶玻璃,其特征在于,以Co2+掺杂的KZnF3为微晶相;所述Co2+:KZnF3微晶玻璃的组成为KF-ZnF2-Al2O3-SiO2-CoO,其中,各组分的摩尔百分比分别为:
2.根据权利要求1所述的Co2+:KZnF3微晶玻璃的制备方法,其特征在于,包括以下步骤:
(1)分别称量原料KF、ZnF2、SiO2、Al2O3和CoO,混合均匀后,将粉末样品于1400~1600℃熔制,得到玻璃熔体;
(2)将玻璃熔体冷却,制成玻璃块;
(3)将玻璃块于500~600℃热处理,随炉冷却至室温,得到透明的Co2+:KZnF3微晶玻璃。
3.根据权利要求2所述的Co2+:KZnF3微晶玻璃的制备方法,其特征在于,步骤(1)所述混合均匀,具体为:
置于玛瑙研钵中研磨搅拌至均匀。
4.根据权利要求2所述的Co2+:KZnF3微晶玻璃的制备方法,其特征在于,步骤(1)所述熔制,具体为:
于1400~1600℃熔制20~30min。
5.根据权利要求2所述的Co2+:KZnF3微晶玻璃的制备方法,其特征在于,步骤(2)所述将玻璃熔体冷却,制成玻璃块,具体为:
把玻璃熔体倒在光滑铜板上冷却成为玻璃块。
6.根据权利要求2所述的Co2+:KZnF3微晶玻璃的制备方法,其特征在于,步骤(3)所述热处理,具体为:
于500~600℃热处理10~20小时。
7.权利要求1所述Co2+:KZnF3微晶玻璃的应用,其特征在于,作为近中红外激光增益介质。
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