CN1234147C - Discharge plasma method for preparing nano composite rare-earth tungsten electron emitting material - Google Patents
Discharge plasma method for preparing nano composite rare-earth tungsten electron emitting material Download PDFInfo
- Publication number
- CN1234147C CN1234147C CN 200410050130 CN200410050130A CN1234147C CN 1234147 C CN1234147 C CN 1234147C CN 200410050130 CN200410050130 CN 200410050130 CN 200410050130 A CN200410050130 A CN 200410050130A CN 1234147 C CN1234147 C CN 1234147C
- Authority
- CN
- China
- Prior art keywords
- sintering
- nano composite
- sintered body
- electron emitting
- emitting material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 55
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 35
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 26
- 239000010937 tungsten Substances 0.000 title claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 36
- 239000010439 graphite Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 238000007599 discharging Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003870 refractory metal Substances 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 22
- 239000011159 matrix material Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 239000002784 hot electron Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Abstract
The present invention relates to a discharge plasma method for preparing nano composite rare-earth tungsten electron emitting material, which belongs to the technical field of rare-earth refractory metal electron emitting material. Aiming at the problems of the prior art, a preparing method with uniform distribution of rare earth elements and good diffusibility is provided. Raw material is loaded in a graphite mold, and then is put into a discharge plasma system to be sintered, wherein the raw material is 99.5% to 70.0% of public known tungsten powder of which the particle is 20 nm to 30 nm and 0.5% to 30.0% of rare earth oxide CeO2, La2 O3 or Y2 O3 of which the particle is below 10 nm; when the raw material is pumped into vacuum of 1Pa to 10Pa, the raw material preserves 3 min to 10 min heat at the temperature rise rate of 50 to 300 DGE C /min to 1200 DGE C to 1800 DGE C; in the sintering process, sintering pressure is from 10MPa to 70MPa; when temperature is cooled below 600 DEG C, the graphite mold is taken out to be continuously cooled at room temperature; after being demolded, a sintered body is obtained; a surface layer of 0.5 to 1mm of the sintered body is cut, and then the material of the present invention is obtained. As a figure showed, the zero field emission current density of the nano composite rare-earth tungsten electron emitting material is large, work function is small, and the nano composite rare-earth tungsten electron emitting material has good thermal electron emission performance.
Description
Technical field
A kind of plasma discharging preparation method of nano composite rare earth tungsten electronic emission material belongs to rare earth refractory metal electronic emission material technical field.
Background technology
Electronic emission material is applied to all kinds of vacuum electronics source, ion source, thermic cathode electrode etc., it is the research direction that fields such as metallurgy, welding, surface treatment, vacuum electronic are very paid close attention to both at home and abroad always, rare earth tungsten thermionic emission materials, it is the forward position of current thermionic emitter research, on military and civilian, have broad application prospects, and can replace the radiothorium tungsten electronic emission material of continuing to use for many years, have very valuable harmonious development and be worth, realize the green production and the green consumption in this field.
From finding the Th-W electronic emission material so far, though improving the research of (expecting processing method from former), material constantly carries out, but basic change does not take place in the main step of preparation process of electronic emission material, and the uniformity of oxide and basis material is the key of electronic emission material manufacturing process.And no matter oxide adds in which way in the traditional handicraft, all is to be generated through thermal decomposition by its esters.This oxide size that obtains near poised state can not reach ultra-fine or nano level metastable state particle.As seen traditional handicraft exists obviously not enough: the rare earth element skewness after 1, adding, thus cause the appearance of the inhomogeneous and unusual Schottky effect of emission.2, the diffusion of rare earth element and oxide thereof is bad, makes to replenish difficulty, influences the raising in thermionic emission materials life-span.
The existence of these problems has limited the development and the application of this electron-like emitter, thereby in the research field of world's electron emitter, becomes one of focus of research.
Summary of the invention
Above problem at prior art exists the invention provides a kind of rare earth element and is evenly distributed, the plasma discharging preparation method of the nano composite rare earth tungsten electronic emission material that diffusion is good.
The plasma discharging preparation method of nano composite rare earth tungsten electronic emission material of the present invention, it is characterized in that: it may further comprise the steps:
(1) put into the plasma discharging system after earlier raw material being packed in the graphite jig and carry out sintering, wherein raw material is that known particle is that the percentage by weight of 20nm～30nm is that 99.5%～70.0% tungsten powder and particle are that the following percentage by weight of 10nm is 0.5%～30.0% rare earth oxide CeO
2Or La
2O
3Or Y
2O
3
When (2) being evacuated down to 1Pa～10Pa, with programming rate is insulation 3min～10min of 50～300 ℃/min to 1200 ℃～1800 ℃, sintering pressure in sintering process is: 10Mpa～70Mpa, be cooled to the taking-up of back below 600 ℃ graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding;
(3) top layer of the above-mentioned sintered body 0.5～1mm of excision, remaining material is material of the present invention.
The electron emission material of rare earth tungsten that the present invention prepares, its microscopic structure are the nano Ce O of particle diameter less than 10nm
2Or La
2O
3Or Y
2O
3Disperse is distributed on the tungsten basal body, and this institutional framework is different fully with the emissive material of same composition traditional handicraft preparation.Because the nano-oxide particles even dispersion in this rare earth tungsten emissive material is distributed on the W matrix, therefore this microscopic structure is from solid-state reaction speed, tripartite surface strengthenings such as diffusion length and crystal boundary diffusion the diffusion of dopant, thereby improved the hot-electron emission property of material.Nanometer tungsten emissive material has excellent hot-electron emission property (seeing accompanying drawing 1-6), and the null field emission that nanometer tungsten emissive material is 1500 ℃ is respectively: nanometer La-W, nano Ce-W, nanometer Y-W emissive material 2.52Acm
-2, 1.94Acm
-2, 1.48Acm
-2, the emissive material of corresponding existing technology is 1.78Acm
-2, 1.18Acm
-2, 1.14Acm
-2The work function of nanometer La-W, Ce-W, Y-W emissive material is respectively: 2.788eV, 2.916eV, 2.926eV, the emissive material of corresponding existing technology are 2.84eV, 3.023eV, 2.981eV.
The particle that can know the nano rare earth tungsten powder body that is adopted from Fig. 1 is 20nm～30nm; Can know that from Fig. 2 adopting the prepared rare earth tungsten emissive material of the present invention is nano composite material; Can know the null field emission of the nano composite rare earth tungsten emissive material that the present invention prepares from Fig. 3; Can know the null field emission of the rare earth tungsten emissive material of existing prepared from Fig. 4; Comparison diagram 3 and Fig. 4 can know that the null field emission of the nano composite rare earth tungsten emissive material that the present invention prepares is bigger, and its work function is littler, and promptly nanometer tungsten emissive material has excellent hot-electron emission property.
Description of drawings
Fig. 1: the TEM picture of the nanometer La-W powder of preparation method's example 10 of the present invention
Fig. 2: the fracture SEM picture of the nano combined Y-W emissive material of preparation method's example 10 of the present invention
Fig. 3: the emission properties of the nano combined Y-W emissive material of preparation method's example 10 of the present invention
Fig. 4: Comparative Examples, the emission properties of the Y-W emissive material of existing prepared
Embodiment
Comparative Examples (adopting prior art to make): adopt the rare earth tungsten powder (La-W or Ce-W or Y-W powder) about 3 μ m, be pressed into the thin slice sample of Φ 3.5 * lmm on hydraulic press, pressing pressure is 350Mpa/cm
2Obtain rare earth tungsten emissive material after in the tungsten silk screen stove, under hydrogen atmosphere, 1750 ℃, carrying out sintering processes.
Example 1: with weight ratio is 0.5%La
2O
3, the nanometer La-W powder of 99.5%W is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 1Pa, when beginning is warmed up to 1300 ℃ with the programming rate of 150 ℃/min, begin insulation, the heat preservation sintering time is 8min, the sintering pressure in sintering process is 50Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the La-W emissive material that promptly obtains is nanometer La
2O
3In even distribution of particle and the W matrix.
Example 2: with weight ratio is 10.0%La
2O
3, the nanometer La-W powder of 90.0%W is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 5Pa, when beginning is warmed up to 1400 ℃ with the programming rate of 50 ℃/min, begin insulation, the heat preservation sintering time is 5min, the sintering pressure in sintering process is 10Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the La-W emissive material that promptly obtains is nanometer La
2O
3In even distribution of particle and the W matrix.
Example 3: with weight ratio is 20.0%La
2O
3, the nanometer La-W powder of 80.0%W is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 10Pa, when beginning is warmed up to 1800 ℃ with the programming rate of 300 ℃/min, begin insulation, the heat preservation sintering time is 3min, the sintering pressure in sintering process is 70Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the La-W emissive material that promptly obtains is nanometer La
2O
3In even distribution of particle and the W matrix.
Example 4: with weight ratio is 30.0%La
2O
3, the nanometer La-W powder of 70.0%W is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 8Pa, when beginning is warmed up to 1200 ℃ with the programming rate of 200 ℃/min, begin insulation, the heat preservation sintering time is 10min, the sintering pressure in sintering process is 30Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the La-W emissive material that promptly obtains is nanometer La
2O
3In even distribution of particle and the W matrix.
Example 5: with weight ratio is 0.05%CeO
2, the nano Ce of 99.5%W-W powder is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 5Pa, when beginning is warmed up to 1200 ℃ with the programming rate of 50 ℃/min, begin insulation, the heat preservation sintering time is 3min, the sintering pressure in sintering process is 10Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the Ce-W emissive material that promptly obtains is nano Ce O
2In even distribution of particle and the W matrix.
Example 6: with weight ratio is 30.0%CeO
2, the nano Ce of 70.0%W-W powder is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 1Pa, when beginning is warmed up to 1800 ℃ with the programming rate of 200 ℃/min, begin insulation, the heat preservation sintering time is 5min, the sintering pressure in sintering process is 70Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the Ce-W emissive material that promptly obtains is nano Ce O
2In even distribution of particle and the W matrix.
Example 7: with weight ratio is 25.0%CeO
2, the nano Ce of 75.0%W-W powder is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 10Pa, when beginning is warmed up to 1400 ℃ with the programming rate of 300 ℃/min, begin insulation, the heat preservation sintering time is 10min, the sintering pressure in sintering process is 50Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the Ce-W emissive material that promptly obtains is nano Ce O
2In even distribution of particle and the W matrix.
Example 8: be 30.0% Y with weight ratio
2O
3, the nanometer Y-W powder of 70.0% W is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 1Pa, when beginning is warmed up to 1600 ℃ with the programming rate of 300 ℃/min, begin insulation, the heat preservation sintering time is 10min, the sintering pressure in sintering process is 10Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the Y-W emissive material that promptly obtains is nanometer Y
2O
3In even distribution of particle and the W matrix.
Example 9: be 20.0% Y with weight ratio
2O
3, the nanometer Y-W powder of 80.0% W is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 8Pa, when beginning is warmed up to 1200 ℃ with the programming rate of 250 ℃/min, begin insulation, the heat preservation sintering time is 8min, the sintering pressure in sintering process is 30Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the Y-W emissive material that promptly obtains is nanometer Y
2O
3In even distribution of particle and the W matrix.
Example 10: be 0.5% Y with weight ratio
2O
3, the nanometer Y-W powder of 99.5% W is packed in the graphite jig, graphite jig is put into carried out discharge plasma sintering in the plasma discharging system then, guarantee that point for measuring temperature is aimed in the center of powder.Behind the plasma discharging system sealing, vacuumize, when vacuum degree reaches 10Pa, when beginning is warmed up to 1800 ℃ with the programming rate of 50 ℃/min, begin insulation, the heat preservation sintering time is 3min, the sintering pressure in sintering process is 70Mpa.After reaching temperature retention time, be cooled to below 600 ℃, promptly can take out graphite jig and at room temperature continue cooling, obtain nano composite rare earth tungsten sintered body after the demoulding with sintering furnace.Adopt the top layer of conventional line cutting excision sintered body 0.5mm again, the Y-W emissive material that promptly obtains is nanometer Y
2O
3In even distribution of particle and the W matrix.
Claims (1)
1, a kind of plasma discharging preparation method of nano composite rare earth tungsten electronic emission material, it is characterized in that: it may further comprise the steps:
(1) put into the plasma discharging system after earlier raw material being packed in the graphite jig and carry out sintering, wherein raw material is that known particle is that the percentage by weight of 20nm～30nm is that 99.5%～70.0% tungsten powder and particle are that the following percentage by weight of 10nm is 0.5%～30.0% rare earth oxide CeO
2Or La
2O
3Or Y
2O
3
When (2) being evacuated down to 1Pa～10Pa, with heating rate is insulation 3min～10min of 50～300 ℃/min to 1200 ℃～1800 ℃, sintering pressure in sintering process is: 10MPa～70MPa, be cooled to the taking-up of back below 600 ℃ graphite jig and at room temperature continue cooling, obtain sintered body after the demoulding;
(3) top layer of the above-mentioned sintered body 0.5～1mm of excision, remaining material is material of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410050130 CN1234147C (en) | 2004-06-28 | 2004-06-28 | Discharge plasma method for preparing nano composite rare-earth tungsten electron emitting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410050130 CN1234147C (en) | 2004-06-28 | 2004-06-28 | Discharge plasma method for preparing nano composite rare-earth tungsten electron emitting material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1586768A CN1586768A (en) | 2005-03-02 |
| CN1234147C true CN1234147C (en) | 2005-12-28 |
Family
ID=34602167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410050130 Expired - Fee Related CN1234147C (en) | 2004-06-28 | 2004-06-28 | Discharge plasma method for preparing nano composite rare-earth tungsten electron emitting material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1234147C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446898C (en) * | 2007-05-11 | 2008-12-31 | 北京工业大学 | Method for sintering multielement composite electron emission material of rare earth tungsten |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063068A (en) * | 2005-08-31 | 2007-03-15 | Toshiba Ceramics Co Ltd | Yttria ceramic sintered compact |
| JP4942140B2 (en) * | 2005-10-27 | 2012-05-30 | コバレントマテリアル株式会社 | Plasma resistant spraying material |
| CN100478103C (en) * | 2006-06-22 | 2009-04-15 | 中国科学院电子学研究所 | Method for producing spongy body of tungsten |
| CN101880808B (en) * | 2010-08-11 | 2012-09-26 | 北京科技大学 | Method for preparing nano oxide dispersion reinforced superfine crystal tungsten-based composite material |
| CN105108131A (en) * | 2015-09-30 | 2015-12-02 | 东北大学 | Preparation method for metal-tungsten-based yttria ceramic nozzles |
| CN107988539A (en) * | 2017-11-28 | 2018-05-04 | 北京工业大学 | A kind of quick method for preparing high-compactness fine grained texture xenon flash lamp electrode |
| CN112030026B (en) * | 2020-08-31 | 2021-10-15 | 合肥工业大学 | Preparation method of high-hardness and high-density composite rare earth oxide doped tungsten-based composite material |
| CN113106279A (en) * | 2021-03-01 | 2021-07-13 | 北京工业大学 | Multi-element doped oxide dispersion strengthening tungsten-based alloy and preparation method and application thereof |
-
2004
- 2004-06-28 CN CN 200410050130 patent/CN1234147C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446898C (en) * | 2007-05-11 | 2008-12-31 | 北京工业大学 | Method for sintering multielement composite electron emission material of rare earth tungsten |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1586768A (en) | 2005-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7754185B2 (en) | Method of making MoO2 powders, products made from MoO2 powders, deposition of MoO2 thin films, and methods of using such materials | |
| JP4797712B2 (en) | ZnO-Al2O3-based sintered body, sputtering target, and method for producing transparent conductive film | |
| JP2014005538A (en) | Zinc oxide-based sputtering target, method of manufacturing the same, and thin film transistor having shield film evaporated through the same | |
| CN1234147C (en) | Discharge plasma method for preparing nano composite rare-earth tungsten electron emitting material | |
| JPWO2007066490A1 (en) | Gallium oxide-zinc oxide sputtering target, method for forming transparent conductive film, and transparent conductive film | |
| CN101372339A (en) | Preparation of high purity high dense polycrystal CeB6 block cathode material | |
| CN112981159B (en) | Preparation method of graphene reinforced copper-based composite material | |
| JP2014172783A (en) | Zinc oxide powder and method for producing the same | |
| Late et al. | Field emission studies on well adhered pulsed laser deposited LaB6 on W tip | |
| JP2013173658A (en) | Tin oxide-based sintered body and method for manufacturing the same | |
| AU2004284043A1 (en) | Method of making high-purity (>99%) MoO2 powders, products made from MoO2 powders, deposition of MoO2 thin films, and methods of using such materials | |
| Yuntao et al. | Effect of scandia on tungsten oxide powder reduction process | |
| WO2007010702A1 (en) | In Sm OXIDE SPUTTERING TARGET | |
| CN112813397A (en) | Preparation method of molybdenum-sodium alloy plate-shaped target material | |
| JP2009235541A (en) | Method for producing zinc oxide based sintered target | |
| JP3780932B2 (en) | Sintered target for producing transparent conductive thin film and method for producing the same | |
| CN102586741B (en) | Preparation method of doped zinc oxide film | |
| CN1651590A (en) | Preparation technology of tungsten copper or tungsten silver composite material | |
| CN100431748C (en) | Rare-earth element gadolinium nano particle and nano crystal block material preparing method | |
| JP4917725B2 (en) | Transparent conductive film, method for producing the same, and use thereof | |
| JP5952031B2 (en) | Oxide sintered body manufacturing method and target manufacturing method | |
| CN114436641A (en) | Magnetron sputtering ceramic target material and preparation method thereof | |
| TW201404909A (en) | Zinc oxide-based sputtering target, method of manufacturing the same, thin-film transistor having barrier layer deposited using the same, and method of manufacturing the thin-film transistor | |
| JP2012197216A (en) | Oxide sintered compact, method for manufacturing the same and target using the same | |
| JP2013177260A (en) | Zinc oxide-tin oxide sintered body and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20051228 Termination date: 20140628 |
|
| EXPY | Termination of patent right or utility model |