CN1587201A - Rare Earth Thiooxide Laser Ceramics - Google Patents
Rare Earth Thiooxide Laser Ceramics Download PDFInfo
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- CN1587201A CN1587201A CN 200410054075 CN200410054075A CN1587201A CN 1587201 A CN1587201 A CN 1587201A CN 200410054075 CN200410054075 CN 200410054075 CN 200410054075 A CN200410054075 A CN 200410054075A CN 1587201 A CN1587201 A CN 1587201A
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- sintering
- rare earth
- raw material
- oxide
- laser ceramics
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- 239000000919 ceramic Substances 0.000 title claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000005056 compaction Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000001513 hot isostatic pressing Methods 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000000280 densification Methods 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 6
- GFKJCVBFQRKZCJ-UHFFFAOYSA-N oxygen(2-);yttrium(3+);trisulfide Chemical compound [O-2].[O-2].[O-2].[S-2].[S-2].[S-2].[Y+3].[Y+3].[Y+3].[Y+3] GFKJCVBFQRKZCJ-UHFFFAOYSA-N 0.000 description 5
- 239000011222 crystalline ceramic Substances 0.000 description 2
- 229910002106 crystalline ceramic Inorganic materials 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
A rare earth thiooxide laser ceramic is characterized by comprising the following components: the base material is rare earth sulfo-oxide-Re2O2S; the doping concentration of laser activated Nd or Yb ions is 0.1-10 at%; densification agents LiF or Li2GeF60.1-10 wt%, and is prepared by high-temperature sintering. The rare earth thiooxide laser ceramic can overcome the difficulty which is difficult to avoid in the process of monocrystal growth, and has the advantages of quite low cost, optical isotropy, uniform distribution of doped ions in a matrix and excellent thermal property. The material has very high luminous efficiency, so that the material has good application prospect in fully-cured and integrated lasers.
Description
Technical field
The present invention is relevant with laserable material, and particularly a kind of rare earth thio-oxide laser ceramics is a kind of with rare earth thio-oxide (Re
2O
2S, wherein Re is La, Y or Gd) pottery is matrix, active ions are the laserable material of Nd or Yb.
Background technology
Rare earth thio-oxide (Re
2O
2S) being the Industrial materials that a class haves a great attraction, also is simultaneously very unique in scientific basic research.They are broadband semiconductors, as phosphor material, have high luminous efficiency, on the various modern engineering, used nearly 30 years (J.Electrochem.Soc., 1969,116:1047).But, because the thio-oxide fusing point is generally higher, as the LOS fusing point be 2070 ± ℃, about 2200 ℃ of yttrium oxysulfide YOS, temperature of fusion issues estranged separating with sulphur and loses, and thermal expansivity anisotropy difference is big, the crystal of growing from melt is the substantial deviation chemical dosage ratio often, is difficult to prepare high-quality single crystal, referring to J.Appl.Phys., 1971,42 (8): 3049-3053; Mater.Res.Bull., 1973,8:1421-1426.Transparent yttrium oxysulfide (YOS) the monocrystalline size that for example, can access at present only is 0.5 * 0.5 * 0.3mm
3See document Phys.Rev.B, 2002,65:094302; 2003, the report of 68:035107.
The preparation of rare-earth oxide sulfate polycrystalline ceramic but can be carried out under the temperature more much lower than fusing point, thus the problem of having avoided single crystal growing to exist well.Recently, the transparent/translucent oxysulfide pottery that adopts various sintering method preparations is successfully as high efficiency scintillation material, and performance is better than single crystal.The Pr of hot isostatic pressing preparation under the argon pressure of 1300 ℃ of temperature and about 200Mpa, the Ce:GOS scintillating ceramic has been used for the medical x-ray detector, sees J.Electrochem.Soc., and 1989,136:2713-2716.Adopt vacuum heating-press sintering, can be 1000～1250 ℃ in temperature is sintering preparation in 60～180 minutes Tb:YOS crystalline ceramics under 200～250MPa with pressure, has higher transmittance in 0.32～8 micron wave length scope, sees J.Opt.Technol., 1999,66 (5): 404-408.The Tb:GOS crystalline ceramics of similar condition preparation, density is higher than 99.9%, has quite high transmitance at visible light and near infrared region, transmitance equaled 40～65% when thickness was 1.6 millimeters, see J.Opt.Technol., 2003,70 (10): 693-698.
Summary of the invention
Main purpose of the present invention is a kind of high efficiency rare earth thio-oxide laser ceramics of exploitation, this pottery not only can overcome and is difficult to the difficulty avoided in the single crystal growth process, cost is quite low simultaneously, optical isotropy, dopant ion is evenly distributed in matrix, have excellent thermal characteristics and high luminous efficiency, to promote full curing, the miniaturization and integrated of laser apparatus.
Technical solution of the present invention is as follows:
A kind of rare earth thio-oxide laser ceramics is characterized in that the composed as follows of this laser ceramics: base-material is rare earth thio-oxide-Re
2O
2S; Laser active ion Nd or Yb ionic doping content are 0.1～10at%; Compact agent LiF or Li
2GeF
6Account for 0.1～10wt%.
The preparation method of described rare earth thio-oxide laser ceramics comprises the following steps:
1. match raw material:
Matrix adopts maximum particle diameter less than 3 microns Re
2O
2The S powder, wherein Re is La, Y or Gd; Mix laser active ion Nd or Yb, doping content is 0.1～10at%; Mix LiF or the Li of 0.1～10wt% again
2GeF
6As compact agent, to improve the relative density of pottery; Selected raw material and proportioning and each raw material of weighing;
2. the raw material thorough mixing is even;
3. adopt vaccum sintering process, normal pressure-sintered method, hot pressing sintering method and hot isostatic pressing method to carry out high temperature sintering.
Described vaccum sintering process, through cold isostatic compaction, sintering range is 1300～1500 ℃ with raw material in elder generation, the vacuum tightness in the stove is better than 10 in sintering process
-2Pa, sintering time are 1～20 hour.
Described normal pressure-sintered method, through cold isostatic compaction, sintering range is 1400～1700 ℃, charges into high-purity argon gas in the stove, is 0.5～2.5 normal atmosphere in the sintering temperature overdraft with raw material in elder generation, sintering time is 1～20 hour.
Described hot pressing sintering method is with in the material injecting mould, is better than 10 in vacuum tightness
-2Pa, condition under, be warming up to 1000～1300 ℃, keeping under the situation of vacuum tightness raw material being applied axial mechanical pressure 20～200MPa, sintering time is 1～20 hour.
Described hot isostatic pressing method is with in the material injecting mould, and vacuum condition lower seal mould is warming up to 1100～1400 ℃ then, and sintering is 1～20 hour under the argon pressure of 100～250MPa.
Can be used in integrated, miniaturization and the full solidified laser apparatus according to the rare earth thio-oxide laser ceramics of above-mentioned raw materials proportioning and sintering process preparation.
Embodiment
The invention will be further described below in conjunction with embodiment, but should not limit protection scope of the present invention with this.
Embodiment 1: vacuum sintering Nd:La
2O
2The S pottery
The doping content of Nd is 0.1at% in the raw material, adopts LiF to make compact agent, and add-on is 0.1wt%.Raw material is put into sintering oven behind cold isostatic compaction, be 1300 ℃ in temperature, and vacuum tightness is 6 * 10
-3Pa keeps powered-down after 20 hours down, and sample naturally cools to room temperature with stove.
Embodiment 2: vacuum sintering Nd:Gd
2O
2The S pottery
The doping content of Nd is 5at% in the raw material, adopts Li
2GeF
6Make compact agent, add-on is 10wt%.Raw material is put into sintering oven behind cold isostatic compaction, be 1450 ℃ in temperature, and vacuum tightness is 4 * 10
-3Pa keeps powered-down after 5 hours down, and sample naturally cools to room temperature with stove.
Embodiment 3: vacuum sintering Yb:Y
2O
2The S pottery
The doping content of Yb is 10at% in the raw material, adopts LiF to make compact agent, and add-on is 2wt%.Raw material is put into sintering oven behind cold isostatic compaction, be 1500 ℃ in temperature, and vacuum tightness is 7 * 10
-3Pa keeps powered-down after 10 hours down, and sample naturally cools to room temperature with stove.
Embodiment 4: normal pressure-sintered Nd:Y
2O
2The S pottery
The doping content of Nd is 0.2at% in the raw material, adopts Li
2GeF
6Make compact agent, add-on is 5wt%.Raw material is put into sintering oven behind cold isostatic compaction, be 1400 ℃ in temperature, and argon pressure equals to keep powered-down after 16 hours under 2 normal atmosphere, and sample naturally cools to room temperature with stove.
Embodiment 5: normal pressure-sintered Yb:La
2O
2The S pottery
The doping content of Yb is 1at% in the raw material, adopts LiF to make compact agent, and add-on is 8wt%.Raw material is put into sintering oven behind cold isostatic compaction, be 1700 ℃ in temperature, and argon pressure equals to keep powered-down after 1 hour under 0.5 normal atmosphere, and sample naturally cools to room temperature with stove.
Embodiment 6: normal pressure-sintered Yb:Gd
2O
2The S pottery
The doping content of Yb is 2at% in the raw material, adopts Li
2GeF
6Make compact agent, add-on is 0.5wt%.Raw material is put into sintering oven behind cold isostatic compaction, be 1540 ℃ in temperature, and argon pressure equals to keep powered-down after 12 hours under 1.5 normal atmosphere, and sample naturally cools to room temperature with stove.
Embodiment 7: hot pressed sintering Nd:La
2O
2The S pottery
The doping content of Nd is 3at% in the raw material, adopts LiF to make compact agent, and add-on is 6wt%.In the material injecting mould, reach 1 * 10 in vacuum tightness
-2Pa, not exerting pressure is warming up to 1000 ℃, under the situation that keeps vacuum raw material is applied axial mechanical pressure 20MPa, and sintering time is powered-down after 20 hours, and sample naturally cools to room temperature with stove.
Embodiment 8: hot pressed sintering Nd:Gd
2O
2The S pottery
The doping content of Nd is 0.7at% in the raw material, adopts Li
2GeF
6Make compact agent, add-on is 3wt%.In the material injecting mould, reach 5 * 10 in vacuum tightness
-3Pa, not exerting pressure is warming up to 1240 ℃, under the situation that keeps vacuum raw material is applied axial mechanical pressure 200MPa, and sintering time is powered-down after 2 hours, and sample naturally cools to room temperature with stove.
Embodiment 9: hot pressed sintering Yb:Y
2O
2The S pottery
The doping content of Yb is 8at% in the raw material, adopts LiF to make compact agent, and add-on is 6.5wt%.In the material injecting mould, reach 8 * 10 in vacuum tightness
-3Pa, not exerting pressure is warming up to 1300 ℃, under the situation that keeps vacuum raw material is applied axial mechanical pressure 140MPa, and sintering time is powered-down after 5 hours, and sample naturally cools to room temperature with stove.
Embodiment 10: HIP sintering Nd:Y
2O
2The S pottery
The doping content of Nd is 2.2at% in the raw material, adopts Li
2GeF
6Make compact agent, add-on is 1.8wt%.In the material injecting mould, vacuum condition lower seal mould is warming up to 1100 ℃ then, and at the powered-down after 17 hours of sintering under the argon pressure of 100MPa, sample naturally cools to room temperature with stove.
Embodiment 11: HIP sintering Yb:La
2O
2The S pottery
The doping content of Yb is 4.5at% in the raw material, adopts LiF to make compact agent, and add-on is 9wt%.In the material injecting mould, vacuum condition lower seal mould is warming up to 1260 ℃ then, and at the powered-down after 8 hours of sintering under the argon pressure of 180MPa, sample naturally cools to room temperature with stove.
Embodiment 12: HIP sintering Yb:Gd
2O
2The S pottery
The doping content of Yb is 1.2at% in the raw material, adopts Li
2GeF
6Make compact agent, add-on is 6.3wt%.In the material injecting mould, vacuum condition lower seal mould is warming up to 1380 ℃ then, and at the powered-down after 1.5 hours of sintering under the argon pressure of 250MPa, sample naturally cools to room temperature with stove.
Experimental results show that, rare earth thio-oxide laser ceramics of the present invention not only can overcome and is difficult to the difficulty avoided in the single crystal growth process, cost is quite low simultaneously, optical isotropy, dopant ion is evenly distributed in matrix, have excellent thermal characteristics and high luminous efficiency, this laser ceramics has good application prospects in full curing, miniaturization and integrated laser apparatus.
Claims (6)
1, a kind of rare earth thio-oxide laser ceramics, it is characterized in that the composed as follows of this laser ceramics: base-material is rare earth thio-oxide-Re
2O
2S; Laser active ion Nd or Yb ionic doping content are 0.1～10at%; Compact agent LiF or Li
2GeF
6Account for 0.1～10wt%.
2, the preparation method of rare earth thio-oxide laser ceramics according to claim 1 is characterized in that this method comprises:
1. match raw material:
Matrix adopts maximum particle diameter less than 3 microns Re
2O
2The S powder, wherein Re is La, Y or Gd; Mix laser active ion Nd or Yb, doping content is 0.1～10at%; Mix LiF or the Li of 0.1～10wt% again
2GeF
6As compact agent, selected raw material and proportioning and each raw material of weighing;
2. the raw material thorough mixing is even;
3. adopt vaccum sintering process, normal pressure-sintered method, hot pressing sintering method and hot isostatic pressing method to carry out high temperature sintering.
3, the preparation method of rare earth thio-oxide laser ceramics according to claim 2, it is characterized in that described vaccum sintering process, through cold isostatic compaction, sintering range is 1300～1500 ℃ with raw material in elder generation, and the vacuum tightness in the stove is better than 10 in sintering process
-2Pa, sintering time are 1～20 hour.
4, the preparation method of rare earth thio-oxide laser ceramics according to claim 2, it is characterized in that described normal pressure-sintered method, earlier with raw material through cold isostatic compaction, sintering range is 1400～1700 ℃, charge into high-purity argon gas in the stove, in the sintering temperature overdraft is 0.5～2.5 normal atmosphere, and sintering time is 1～20 hour.
5, the preparation method of rare earth thio-oxide laser ceramics according to claim 2 is characterized in that described hot pressing sintering method is with in the material injecting mould, is better than 10 in vacuum tightness
-2Pa, condition under, be warming up to 1000～1300 ℃, keeping under the situation of vacuum tightness raw material being applied axial mechanical pressure 20～200MPa, sintering time is 1～20 hour.
6, the preparation method of rare earth thio-oxide laser ceramics according to claim 2, it is characterized in that described hot isostatic pressing method is with in the material injecting mould, vacuum condition lower seal mould, be warming up to 1100～1400 ℃ then, sintering is 1～20 hour under the argon pressure of 100～250MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410054075 CN1587201A (en) | 2004-08-27 | 2004-08-27 | Rare Earth Thiooxide Laser Ceramics |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410054075 CN1587201A (en) | 2004-08-27 | 2004-08-27 | Rare Earth Thiooxide Laser Ceramics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1587201A true CN1587201A (en) | 2005-03-02 |
Family
ID=34603050
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|---|---|---|---|
| CN 200410054075 Pending CN1587201A (en) | 2004-08-27 | 2004-08-27 | Rare Earth Thiooxide Laser Ceramics |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8668844B2 (en) | 2008-07-23 | 2014-03-11 | Koninklijke Philips N.V. | Fluorescent material for use in CT applications |
-
2004
- 2004-08-27 CN CN 200410054075 patent/CN1587201A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8668844B2 (en) | 2008-07-23 | 2014-03-11 | Koninklijke Philips N.V. | Fluorescent material for use in CT applications |
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