CN1313413C - Preparation of Cr4+ A12O3 transparent laser ceramic materials - Google Patents

Preparation of Cr4+ A12O3 transparent laser ceramic materials Download PDF

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CN1313413C
CN1313413C CNB2005100301349A CN200510030134A CN1313413C CN 1313413 C CN1313413 C CN 1313413C CN B2005100301349 A CNB2005100301349 A CN B2005100301349A CN 200510030134 A CN200510030134 A CN 200510030134A CN 1313413 C CN1313413 C CN 1313413C
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hours
laser
mgo
al2o3
transparent
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CN1778758A (en
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杨秋红
徐军
曾智江
苏良碧
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Shanghai University
University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The present invention relates to a Cr<4+>: Al2O3 transparent laser ceramic material and a preparation method thereof, which belongs to the technical field of preparing special solid laser ceramic materials. The present invention adopts high-purity Al2O3, MgO and Cr2O3 as raw materials, wherein the Al2O3 is used as base material, the Cr2O3 is used as laser activating doping material, and the MgO is used as charge compensating doping material; the weight of 100% of the base material Al2O3 is used as the metewand, the doping material comprises 0.1 to 1.0 wt% of Cr2O3 and 0.05 to 0.15 wt% of Mg. The present invention comprises the steps: the raw materials prepared according to the formula are stirred, mixed and ground by mixing in distilled water for 24 hours, and then, the prepared raw materials are dried at 150 DEG C; polyvinyl alcohol as an adhesive is added into the prepared raw materials for granulation, and the granules are pressed into a flaky test sample by isostatic cool pressing under the pressure of 200MPa; the flaky test sample is sintered in a calcining furnace with a reducing atmosphere at the sintering temperature of 1650 to 1800 DEG C under normal pressure for 2 to 10 hours, and then, the flaky test sample is annealed at the temperature of 1300 DEG C in the air for 3 to 8 hours to obtain the dense transparent Cr<4+>: Al2O3 laser ceramic material.

Description

Cr 4+: Al 2O 3The preparation method of transparent laser ceramic material
Technical field
The present invention relates to a kind of Cr 4+: Al 2O 3The preparation method of transparent laser ceramic material belongs to extraordinary Solid State Laser ceramic material Technology field.
Background technology
Since nineteen sixty invention ruby (Cr 3+: Al 2O 3) since the laser apparatus, the researchist is devoted to research and development to have different qualities, can send different wavelength of laser material and laser apparatus.
The investigator finds, Cr 4+The solid laser of ion doping can produce very wide in the tunable coherent radiation of 1130nm to the 1630nm near-infrared band.Cr 4+Adulterated gain media has several good characteristics, includes: the wide absorption band of operation wavelength eclipsed of (1) and several commercialization pump laser source; What (2) the four-level structure can produce low pumping threshold involves pulse wave laser continuously; (3) Cr 4+Adulterated gain media, existence can produce the very wide amplification bandwidth of ultrashort laser pulse; (4) adopt the non-linear frequency converting system, can be used for setting up wide tunable relevant visible light source.These good characteristics make Cr 4+The doping laser apparatus has very important use as optical communication, eye-safe imaging, medical treatment and spectroscopic techniques etc. in many aspects.
The most representative Cr 4+The doping solid laser material is Cr 4+: Mg 2SiO 4(Cr 4+: forsterite) and Cr 4+: YAG (Cr 4+: yttrium aluminum garnet), they have good power-performance.Cr 4+Adulterated laserable material is also just like Cr 4+: Y 2SiO 4, Cr 4+: Ca 2GeO 4Or the like.
At Cr 4+: Mg 2SiO 4In, Cr 4+Replace [SiO 4] tetrahedral Si 4+Ion forms [CrO 4].At other Cr 4+In the doped crystal material, Cr 4+All be to be in the tetrahedron.Therefore the researchist thinks Cr always 4+Luminous behavior at infrared band is by the Cr in the tetrahedron in the matrix 4+Luminescence center produces, and can not send the light of infrared wavelength in the octahedron of hexa-coordinate.
α-Al 2O 3Belong to hexagonal system, at Al 2O 3In the structure cell, it has only the octahedral structure of three hexa-coordinates, does not have other polyhedral structure, and wherein two octahedrons are occupied by Al, other have one empty.Al 2O 3The physical strength height, thermal expansivity is little, the thermal conductivity height, chemical constitution and structure are very stable, are a kind of widely used Solid State Laser working substrates.
Cr 3+: Al 2O 3(ruby) is first kind and is found the laser crystals with Laser emission.
Because Al 2O 3The octahedral structure that has only three hexa-coordinates in the crystal.And Cr 4+The luminous Cr that is commonly referred to be at infrared band 1100nm～1600nm 4+Be in the luminous behavior in the different substrates four-coordination tetrahedron, therefore nobody finds and research Cr 4+At the octahedra Al of hexa-coordinate 2O 3In luminous behavior.
Summary of the invention
The purpose of this invention is to provide a kind of Cr 4+: Al 2O 3The preparation method of transparent laser ceramic material.
Laser ceramic material of the present invention is a kind of with Cr 4+At the lasing polycrystalline material of infrared band 1100nm～1600nm, be solid polycrystalline laserable material.This material is with Al 2O 3Be matrix, with Cr 4+Be laser active ion, Mg 2+Be Cr 4+The charge compensation ion, with Mg 2+, Cr 4+Common [the AlO that replaces 6] Al in the hexa-coordinate octahedron 3+
A kind of Cr of the present invention 4+: Al 2O 3The preparation method of transparent laser ceramic material is characterized in that having following preparation process and step:
A. adopt high-purity 99.99%Al 2O 3, 99%MgO and 99.99%Cr 2O 3Be raw material; With Al 2O 3Be body material, with Cr 2O 3Being the laser active dopant material, is the charge compensation dopant material with MgO; With Al 2O 3The weight of body material is 100 as mete-wand, and the incorporation of dopant material is: Cr 2O 30.05～1wt%, MgO0.05～0.15%wt%;
B. will be by the good Al of above-mentioned formulated 2O 3It is mixed that body material and other each dopant materials stir, compound mix grinding 24 hours in distilled water;
C. dry under 150 ℃ of temperature subsequently, add the polyvinyl alcohol adhesive that concentration is 5wt% then, add-on is 5wt%, and carries out granulation;
D. powder depresses to the sheet sample in the 200MPa isostatic cool pressing, polyvinyl alcohol adhesive is burnt in 3 hours 800 ℃ of pre-burnings subsequently;
E. the sample after the above-mentioned pre-burning is placed in the molybdenum wire furnace, carries out sintering under the normal pressure reducing atmosphere, sintering range is 1650～1800 ℃, and sintering time is 2～10 hours;
F. with the ceramics sample that sinters in air in 1300 ℃ of following anneal 3～8 hours, finally obtain fine and close transparent Al 2O 3Laser ceramic material.
The laser ceramic material of the present invention's preparation, its mechanism is described below:
Cr is by Cr 2O 3Introduce, earlier with trivalent Cr 3+Ionic species is present in Al 2O 3In the matrix, anneal under oxidizing atmosphere makes Cr subsequently 3+Be oxidized to Cr 4+, and by Mg 2+The charge compensation effect, Cr 4+With Mg 2+Common [the AlO that replaces 6] in Al 3+Cr 4+Though what occupy is the hexa-coordinate octahedral site, its absorption band peak value is positioned near a very wide scope the 900nm.At room temperature the pump light source with 970nm excites this ceramic laser material, and its fluorescent emission wavelength is from 1157nm to 1287nm, and emission peak is positioned at 1220nm, and halfwidth is 37nm, and its fluorescence Spectra as shown in Figure 1.Therefore this stupalith can be used as the tunable laser medium of infrared band, can be used as the altra-fast fs laser apparatus, the output ultrashort laser pulse, and through non-linear conversion, the laser of the visible-range about exportable 600nm, its characteristic is Cr 4+Luminous in the hexa-coordinate octahedron.So laser ceramic material of the present invention is a kind of solid-state laser material of exportable infrared band laser completely newly.
Description of drawings
Fig. 1 be the inventive method preparation and Cr 4+: Al 2O 3Transparent laser ceramic material fluorescence spectrum at room temperature.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
In the present embodiment, preparation Al 2O 3The concrete processing step of transparent laser ceramic material is as follows:
1. adopt high-purity 99.99%Al 2O 3, 99%MgO and 99.99%Cr 2O 3Be raw material; With Al 2O 3Be body material, with Cr 2O 3Being the laser active dopant material, is the charge compensation dopant material with MgO; With Al 2O 3The weight of body material is 100 as mete-wand, and the incorporation of dopant material is: Cr 2O 30.1～1wt%, MgO0.1%wt%;
2. will be by the good Al of above-mentioned formulated 2O 3It is mixed that body material and other each dopant materials stir, compound mix grinding 24 hours in distilled water;
3. dry under 150 ℃ of temperature subsequently, add the polyvinyl alcohol adhesive that concentration is 5wt% then, add-on is 5wt%, and carries out granulation;
4. powder depresses to the sheet sample in the 200MPa isostatic cool pressing, subsequently burning-off polyvinyl alcohol adhesive under 800 ℃ of temperature;
5. the sample after the above-mentioned pre-burning is placed in the molybdenum wire furnace, carries out sintering under the normal pressure reducing atmosphere, sintering range is 1750 ℃, and sintering time is 3 hours;
With the ceramics sample that sinters in air in 1300 ℃ of following anneal 8 hours, finally obtain fine and close transparent Cr 4+: Al 2O 3Laser ceramic material.
The volume density of this stupalith is 3.98g/cm 3To Cr 4+: Al 2O 3Transparent laser ceramic material is made spectrum property and is detected, and its fluorescence emission spectrum demonstrates has good laser optics performance.At room temperature the pump light source with 970nm excites this stupalith, and its fluorescent emission peak position is at 1220nm, and halfwidth is 37nm, and its fluorescence spectrum as shown in Figure 1.
Embodiment 2
The step of preparation process of present embodiment is identical with the foregoing description 1.Its concrete processing step is as follows:
1. adopt high-purity 99.99%Al 2O 3, 99%MgO and 99.99%Cr 2O 3Be raw material; With Al 2O 3Be body material, with Cr 2O 3Being the laser active dopant material, is the charge compensation dopant material with MgO; With Al 2O 3The weight of body material is 100 as mete-wand, and the incorporation of dopant material is: Cr 2O 30.2wt%, MgO0.1%wt%;
2. will be by the good Al of above-mentioned formulated 2O 3It is mixed that body material and other each dopant materials stir, compound mix grinding 24 hours in distilled water;
3. dry under 150 ℃ of temperature subsequently, add the polyvinyl alcohol adhesive that concentration is 5wt% then, add-on is 5wt%, and carries out granulation;
4. powder depresses to the sheet sample in the 200MPa isostatic cool pressing, subsequently burning-off polyvinyl alcohol adhesive under 800 ℃ of temperature;
5. the sample after the above-mentioned pre-burning is placed in the molybdenum wire furnace, carries out sintering under the normal pressure reducing atmosphere, sintering range is 1720 ℃, and sintering time is 3 hours;
With the ceramics sample that sinters in air in 1300 ℃ of following anneal 8 hours, finally obtain fine and close transparent Cr 4+: Al 2O 3Laser ceramic material.
The volume density of this stupalith is 3.98g/cm 3To Cr 4+: Al 2O 3Transparent laser ceramic material is made spectrum property and is detected, and its fluorescence emission spectrum demonstrates has good laser optics performance.At room temperature the pump light source with 970nm excites this stupalith, and its fluorescent emission peak position is at 1220nm.
Embodiment 3
The step of preparation process of present embodiment is identical with the foregoing description 1.Concrete processing step is as follows:
1. adopt high-purity 99.99%Al 2O 3, 99%MgO and 99.99%Cr 2O 3Be raw material; With Al 2O 3Be body material, with Cr 2O 3Being the laser active dopant material, is the charge compensation dopant material with MgO; With Al 2O 3The weight of body material is 100 as mete-wand, and the incorporation of dopant material is: Cr 2O 30.8wt%, MgO0.1%wt%;
2. will be by the good Al of above-mentioned formulated 2O 3It is mixed that body material and other each dopant materials stir, compound mix grinding 24 hours in distilled water;
3. dry under 150 ℃ of temperature subsequently, add the polyvinyl alcohol adhesive that concentration is 5wt% then, add-on is 5wt%, and carries out granulation;
4. powder depresses to the sheet sample in the 200MPa isostatic cool pressing, subsequently burning-off polyvinyl alcohol adhesive under 800 ℃ of temperature;
5. the sample after the above-mentioned pre-burning is placed in the molybdenum wire furnace, carries out sintering under the normal pressure reducing atmosphere, sintering range is 1650 ℃, and sintering time is 3 hours;
With the ceramics sample that sinters in air in 1300 ℃ of following anneal 8 hours, finally obtain fine and close transparent Cr 4+: Al 2O 3Laser ceramic material.
The volume density of this stupalith is 3.98g/cm 3To Cr 4+: Al 2O 3Transparent laser ceramic material is made spectrum property and is detected, and its fluorescence emission spectrum demonstrates has good laser optics performance.At room temperature the pump light source with 970nm excites this stupalith, and its fluorescent emission peak position is at 1220nm.

Claims (1)

1. Cr 4+: Al 2O 3The preparation method of transparent laser ceramic material is characterized in that having following preparation process and step:
A. adopt high-purity 99.99%Al 2O 3, 99%MgO and 99.99%Cr 2O 3Be raw material; With Al 2O 3Be body material, with Cr 2O 3Being the laser active dopant material, is the charge compensation dopant material with MgO; With Al 2O 3The weight of body material is 100 as mete-wand, and the incorporation of dopant material is: Cr 2O 30.05～1wt%, MgO 0.05～0.15%wt%;
B. will be by the good Al of above-mentioned formulated 2O 3It is mixed that body material and other each dopant materials stir, compound mix grinding 24 hours in distilled water;
C. dry under 150 ℃ of temperature subsequently, add the polyvinyl alcohol adhesive that concentration is 5wt% then, add-on is 5wt%, and carries out granulation;
D. powder depresses to the sheet sample in the 200MPa isostatic cool pressing, polyvinyl alcohol adhesive is burnt in 3 hours 800 ℃ of pre-burnings subsequently;
E. the sample after the above-mentioned pre-burning is placed in the molybdenum wire furnace, carries out sintering under the normal pressure reducing atmosphere, sintering range is 1650～1800 ℃, and sintering time is 2～10 hours;
F. with the ceramics sample that sinters in air in 1300 ℃ of following anneal 3～8 hours, finally obtain fine and close transparent Cr 4+: Al 2O 3Laser ceramic material.
CNB2005100301349A 2005-09-29 2005-09-29 Preparation of Cr4+ A12O3 transparent laser ceramic materials Expired - Fee Related CN1313413C (en)

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CN101468915A (en) * 2007-12-26 2009-07-01 中国科学院上海硅酸盐研究所 Polycrystal alumina transparent ceramic with preferred orientation and preparation thereof
CN102942201A (en) * 2012-11-05 2013-02-27 上海大学 High purity alumina polycrystal block for growing sapphire crystals and preparation method thereof
CN105239161B (en) * 2015-10-19 2018-06-26 中国科学院青海盐湖研究所 The preparation method of ruby crystal

Citations (1)

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Publication number Priority date Publication date Assignee Title
JPH05301770A (en) * 1992-04-27 1993-11-16 Kurosaki Refract Co Ltd Polycrystalline transparent ceramic for laser

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05301770A (en) * 1992-04-27 1993-11-16 Kurosaki Refract Co Ltd Polycrystalline transparent ceramic for laser

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
氧化铝透明陶瓷中Cr3+的发光性能 曾智江等，激光与光电子学进展，第42卷第7期 2005 *

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