CN101172656A - Method of producing low pressure gas-phase of ferromagnetism chromium oxide compound nano-grain film - Google Patents
Method of producing low pressure gas-phase of ferromagnetism chromium oxide compound nano-grain film Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910000423 chromium oxide Inorganic materials 0.000 title claims abstract description 11
- -1 chromium oxide compound Chemical class 0.000 title claims description 10
- 230000005307 ferromagnetism Effects 0.000 title claims description 9
- 230000005291 magnetic effect Effects 0.000 claims abstract description 24
- 239000011651 chromium Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 23
- 238000009833 condensation Methods 0.000 claims description 20
- 230000005494 condensation Effects 0.000 claims description 19
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000012808 vapor phase Substances 0.000 abstract 4
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005019 vapor deposition process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a low temperature and low pressure vapor phase preparation method for ferromagnetic chromium oxide nanometer grain membrane. The invention is characterized in that metallic Cr is used as precursor; the Cr oxide nanometer grain is generated under the vapor phase environment by utilizing the particular nucleation growth and reaction environment during the vapor phase collection process through a method of plasma vapor phase collection and real time oxidation; the nanometer grain is settled on a substrate through a difference vacuum system; the chromium oxide nanometer grain membrane is obtained under room temperature and low pressure; and the main component of the oxide is ferromagnetic chormium dioxide. The invention can be used in the preparation flow of the high density storing device and the nanometer magnetic electronic device. The invention has the advantages of simple technology, stability, high efficiency and easy management of scale.
Description
Technical field:
The present invention relates to a kind of ferromagnetic nano material, specifically relate to a kind of method of producing low pressure gas-phase of ferromagnetism chromium oxide compound nano-grain film.
Background technology:
CrO
2It is a kind of technical very important transition metal binary oxide ferromagnetic material.Since phase late 1960s, needle-like CrO
2The micron magnetic is widely used in magnetic recording material.Discovered in recent years CrO
2Have the semi-metal characteristic,, become the little metal of residual resistivity, and present significant giant magnetoresistance effect to 5 μ Ω cm at the complete spin polarization(SP) state that spins up certainly; And, then become semi-conductor in the downward energy state of spin.And, CrO
2Curie temperature up to 390K, far above other the Curie temperature of ferromagnetic half-metal, therefore, CrO
2In magnetoelectronic devices, has important potential using value.
The development of high-density storage and magnetic electron device, for the compatible mutually condition of device preparation technology under the intensive film of preparation high quality magnetic nanoparticle very big demand has been proposed.CrO
2Nano particle is because the exchange bias effect of its half-metallic ferromagnet, the folk prescription that can cause its magnetic hysteresis loop is to mobile, and coercitive raising, thereby can handle and control its magnetic property at nanoscale, overcome the super paramagnetic limit, this specific character is at exploitation Tbit/in
2The ultrahigh density storage aspect have good application prospects.
But because CrO
2Belong to the metastable phase of chromated oxide, change other oxidation state easily into, as CrO in the temperature more than 288 ℃ and atmospheric oxygen atmosphere
2Can be decomposed into anti-ferromagnetic Cr
2O
3, cause under conventional gas phase condition to prepare CrO
2Nano structure membrane is restricted.CrO
2Traditional preparation process need under high pressure carry out usually.Industrial, by in hyperbaric oxygen atmosphere, decomposing chromic anhydride, or in 50-200 normal atmosphere water vapor hydrothermal decomposition CrO
3Prepare CrO
2Powder can obtain the pin type powder of micron diameter, but can't prepare the spheroidal particle of nanometer diameter.K.-Y.Wang etc. attempt to prepare CrO by body material ball milling
2Nano-powder (J.Appl.Phys., 91,8204 (2002)), but CrO takes place in mechanical milling process
2Be transformed into Cr
2O
3What at present, be seen in reported in literature can prepare high quality CrO preferably
2The unique method of continuous film is with CrO
3Or CrO
2Cl
2Deng the chemical vapor deposition (CVD) that is precursor, but do not see to have and obtain monodispersed CrO by this method
2The report of nanometer particle film.For with main flow preparation technology's compatibility of high-density memory device and magnetic electron device, the normal temperature low pressure synthetic method of development ferromagnetism chromium oxide compound nano-grain film is significant.But for a long time, the physical vapor deposition by routine can't obtain high-quality CrO
2Film prepares high-quality CrO
2Nano-particular film also is considered to a masty problem for many years.
Summary of the invention:
The object of the present invention is to provide a kind of method of producing low pressure gas-phase of ferromagnetism chromium oxide compound nano-grain film.
The nano structure membrane of magnetic nanoparticle and composition thereof, when the size of nano particle reaches several nanometers to the tens nanometer magnitude, often present the not available unusual magnetic properties of large size body material, in the research and development of sub-material of magnetoelectricity and device etc., have significant values.With CrO
2For the chromated oxide nanometer particle film of main component is the ferro-magnetic with semi-metal characteristic, because the exchange bias effect of half-metallic ferromagnet, the folk prescription that can cause its magnetic hysteresis loop is to moving, and coercitive raising, thereby can handle and control its magnetic property at nanoscale, overcome the super paramagnetic limit, be in the CrO of complete spin polarization(SP) state simultaneously
2Also present significant giant magnetoresistance effect, these characteristics make it at Tbit/in
2The ultrahigh density storage device and the exploitation of nano magnetic electron device on have good application prospects.
The present invention proposes a kind of method for preparing the ferromagnetic nanostructures film of spherical chromated oxide nano particle dense arrangement formation by vapor deposition processes.This method is precursor with the Metal Cr, method by gathering of plasma body gas phase and oxidation in real time, utilize nucleating growth and reaction environment unique in the gas phase accumulation process, in gaseous environment, form the Cr oxide nano particles, and by the difference vacuum system, make formed nano particle in the high vacuum deposit on substrate, at room temperature form nano particle solid matter film.This method is based on physical vapor deposition, and all processes are finished under normal temperature low pressure, has good compatibility with the main flow preparation technology of high-density memory device and magnetic electron device.
The objective of the invention is to realize by following technical scheme:
The present invention proposes the method that a kind of way that adopts physical vapor deposition prepares the high-quality chromated oxide nanometer particle film with semi-metal ferromagnetic characteristic.This method can be applicable in preparation technology's flow process of high-density memory device and nano magnetic electron device, has that technology is simple, stable, efficient is high, is easy to characteristics such as mass-producing.
The principle of work of present method is: based on the plasma gas accumulation process, obtain high-density Cr atom gas by magnetron sputtering in the inert buffer gas of the proper pressure of cooled with liquid nitrogen, the Cr atom is assembled growth in buffer gas, and with the reaction of the high purity oxygen gas of the suitable proportion of mixing, because the nucleating growth and the reaction environment of uniqueness cause with CrO in condensing zone gas phase accumulation process
2Be the formation of master's chromated oxide nano particle, and be incorporated in the high vacuum, be deposited at normal temperatures on the substrate, form nanometer particle film through the difference air-bleed system.
The method of producing low pressure gas-phase of ferromagnetism chromium oxide compound nano-grain film is characterized in that the preparation process of this method is as follows:
A. in condensation chamber (1), carry out the magnetic controlled plasma sputter, from being fixed in the Cr atom gas of Metal Cr target (3) the surface generation high density on the magnetic control target stand (2); Magnetron sputtering target stand in this step can obtain by commercial sources, belongs to the universal component of Pvd equipment;
B. in magnetron sputtering, to condensation chamber (1), feed highly purified rare gas element as buffer gas from gas-filled valve (9), its air pressure is controlled at 100Pa to a stationary value between the 500Pa, buffer gas is filled liquid nitrogen (4) cooling in the condensation chamber wall interlayer, in the buffer gas of the Cr atom that sputters out condensing zone (5) in condensation chamber nucleating growth taking place, forms nano particle; Because pouring of buffer gas, air pressure is than the high 1-2 of an operating air pressure order of magnitude of conventional magnetron sputtering in the condensation chamber;
C. when feeding buffer gas, mix high purity oxygen gas,, form the chromated oxide nano particle so that chromium atom is carried out oxidation;
D. offering aperture (6) on the wall of condensation chamber (a 1) end relative with Cr target (3), is sediment chamber (7) at the opposite side of aperture (6), bleeds (11) by the vacuum pump difference, makes sediment chamber (7) remain on high vacuum 10
-4～10
-5Pa, the nano particle that forms in the condensation chamber (1) is ejected into sediment chamber (7) from aperture (6) under the carrying of buffer gas, form nanometer particle beam (10), and be deposited on the substrate (8), the control depositing time can obtain the chromated oxide nanometer particle film on substrate (8) surface.
Above-mentioned magnetic controlled plasma sputter, the power source of its magnetron sputtering adopts the medium-frequency pulse power supply, and voltage control is at 400-600V, and pulse-repetition is 20-40KHz, and dutycycle is 0.6-0.8;
The rare gas element that feeds among the above-mentioned steps B is helium or argon gas, and its purity is 〉=99.99%;
The oxygen purity that feeds among the above-mentioned steps C is 〉=99.99%, and the molecular ratio of oxygen and argon gas is controlled at 0.5%-5%;
Its bore dia of aperture described in the above-mentioned steps D (6) is 1-2mm, and the distance between Cr target (3) surface and the aperture (6) is controlled at 100-200mm;
The nanometer particle beam (10) that forms in sediment chamber (7) among the above-mentioned steps D is deposited on the substrate (8), and its depositing time can be selected according to concrete processing requirement, is controlled at 1-20 minute;
Substrate among the above-mentioned steps D (8) can be according to concrete processing requirement, adopts a kind of in glass, silicon chip, the high molecular polymer film.
Beneficial effect:
The present invention is prepared into the chromated oxide nanometer particle film by the vapor deposition processes under the normal temperature low pressure.The chromated oxide nano particle that is obtained is spherical in shape, has the diameter of 5-30 nanometer, and can form the dot matrix of dense arrangement at the substrate surface uniform distribution.This chromated oxide nanometer particle film is good ferromegnetism, and coercive force is hundreds of Oe, and coercive force has reached 186 Oe (Fig. 2 (a)) under the temperature of 5K, and coercive force is 132 Oe (Fig. 2 (b)) under the temperature of 150K.Industrial preparation CrO
2The normally used high temperature and high pressure preparation process of micro mist, the present invention carries out under normal temperature low pressure, can access the nano particle with uniform-dimension, and can be by control of operating parameters being realized the control to nano-particles size and particle density.Making processes can be monitored in real time by various rigorous analysis technology, has excellent controllability.This method is fully based on vapor deposition processes, and the main flow preparation technology with high-density memory device and magnetic electron device has good compatibility technically, may be used in preparation technology's flow process of nano-device.
Description of drawings:
Fig. 1: the synoptic diagram 1-condensation chamber of stripped gas accumulation source such as magnetic control and nanometer particle beam depositing system, 2-magnetron sputtering target stand, 3-chromium metal target, 4-liquid nitrogen, 5-condensing zone, 6-separate aperture, 7-high vacuum sediment chamber, 8-substrate, 9-gas-filled valve, 10-nanometer particle beam, the 11-difference bleeding point of condensation chamber and high vacuum sediment chamber
The magnetzation curve of chromated oxide nanometer particle film under Fig. 2 (a) 5K temperature; (b) magnetzation curve of chromated oxide nanometer particle film under the 150K temperature
Embodiment:
Below be a typical step and a working parameter that adopts present method to prepare ferromagnetism chromium oxide compound nano-grain film:
(1) shown in figure l, in the condensation chamber (1) of cooled with liquid nitrogen, carry out the magnetic controlled plasma sputter, sputtering target (3)---diameter 50mm, the high-purity metal chromium sheet of thickness 3mm is fixed on the magnetron sputtering target stand (2), by sputtering at the Cr atom gas that Metal Cr target (3) surface produces high density;
(2) from gas-filled valve (9), in condensation chamber (1), charge into purity be 99.99% argon gas as buffer gas, its air pressure remains on the stationary value of 200Pa;
(3) in sputter procedure, when charging into buffer gas, in condensation chamber (1), charge into 99.99% pure oxygen, so that the Cr atom is carried out oxidation, the molecular ratio of oxygen and argon gas is controlled at 2%;
(4) power source of magnetron sputtering adopts the medium-frequency pulse power supply, and its voltage control is at 500V, and pulse-repetition is 30kHz, and dutycycle is 0.8, and electric current is 0.3A, under this power, can obtain
The nanometer particle beam intensity of equivalence deposition;
(5) separation condensation chamber (1) is 2mm with the diameter of the aperture (6) of high vacuum sediment chamber (7), and the length of the condensing zone between aperture (6) and the chromium target (3) is l00mm, adopts turbomolecular pump to carry out difference at high vacuum chamber and bleeds, keep 10
-4The dynamic vacuum of Pa;
(6) the chromated oxide nano particle that forms at condensing chamber (1) enters high vacuum sediment chamber (7) through the difference air-bleed system, forms nanometer particle beam (10), is deposited on the quartz glass substrate (8) that places high vacuum chamber:
(7) quartz glass substrate (8) is deposited 10 minutes, obtain the chromated oxide nanometer particle film on substrate (8) surface.Stop to deposit the back and prepared chromated oxide nanometer particle film is advanced the shape pattern with atomic force microscope characterize, show that this film is is the dot matrix that the spheroidal particle dense arrangement of 20nm constitutes by mean diameter.(SQUID) carries out Magnetic Measurement to film by superconducting quantum interference device (SQUID), and the widely different line of magnetic hysteresis that records in 5K and 150K temperature provides in Fig. 2, shows that this film is all presenting good ferromegnetism under near the temperature of room temperature.In chromium and its each valency oxide compound, has only CrO
2For ferromagnetic, therefore as can be known, CrO
2Main component for prepared nanometer particle film.
Claims (7)
1. the method for producing low pressure gas-phase of a ferromagnetism chromium oxide compound nano-grain film is characterized in that the preparation process of this method is as follows:
A. in condensation chamber (1), carry out the magnetic controlled plasma sputter, from being fixed in the Cr atom gas of Metal Cr target (3) the surface generation high density on the magnetic control target stand (2);
B. in magnetron sputtering, to condensation chamber (1), feed highly purified rare gas element as buffer gas from gas-filled valve (9), its air pressure is controlled at 100Pa to a stationary value between the 500Pa, buffer gas is filled liquid nitrogen (4) cooling in the condensation chamber wall interlayer, nucleating growth takes place in the buffer gas of the Cr atom that sputters out condensing zone (5) in condensation chamber, form nano particle, because charging into of buffer gas, the air pressure in the condensation chamber is than the high 1-2 of an operating air pressure order of magnitude of conventional magnetron sputtering;
C. when feeding buffer gas, mix high purity oxygen gas,, generate the chromated oxide nano particle so that chromium atom is carried out oxidation;
D. offering aperture (6) on the wall of condensation chamber (a 1) end relative with Cr target (3), is sediment chamber (7) at the opposite side of aperture (6), bleeds (11) by the vacuum pump difference, makes sediment chamber (7) remain on high vacuum 10
-4～10
-5Pa, the nano particle that forms in the condensation chamber (1) is ejected into sediment chamber (7) from aperture (6) under the carrying of buffer gas, form nanometer particle beam (10), and be deposited on the substrate (8), the control depositing time can obtain ferromagnetism chromium oxide compound nano-grain film on substrate (8) surface.
2. preparation method according to claim 1, it is characterized in that in the magnetic controlled plasma sputter described in the steps A power source of its magnetron sputtering adopts the medium-frequency pulse power supply, voltage control is at 400-600V, pulse-repetition is 20-40KHz, and dutycycle is 0.6-0.8.
3. preparation method according to claim 1 is characterized in that the rare gas element that feeds is helium or argon gas in step B, its purity is 〉=99.99%.
4. preparation method according to claim 1 is characterized in that the oxygen purity that feeds is 〉=99.99% in step C, the molecular ratio of oxygen and rare gas element is controlled at 0.5%-5%.
5. preparation method according to claim 1 is characterized in that at its bore dia of aperture (6) described in the step D be 1-2mm, and the distance between Cr target (3) surface and the aperture (6) is controlled at 100-200mm.
6. preparation method according to claim 1 is characterized in that the nanometer particle beam (10) that forms is deposited on the substrate (8) in sediment chamber (7) in step D, its depositing time was controlled at 1-20 minute.
7. preparation method according to claim 1 is characterized in that substrate in step D (8) can adopt a kind of in glass, silicon chip or the high molecular polymer film.
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|---|---|---|---|
| CNB2007101344571A CN100564266C (en) | 2007-10-23 | 2007-10-23 | The method of producing low pressure gas-phase of ferromagnetism chromium oxide compound nano-grain film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101344571A CN100564266C (en) | 2007-10-23 | 2007-10-23 | The method of producing low pressure gas-phase of ferromagnetism chromium oxide compound nano-grain film |
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| CN100564266C CN100564266C (en) | 2009-12-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329528A (en) * | 2010-06-30 | 2012-01-25 | Jds尤尼弗思公司 | Magnetic multi-layer pigments sheet and coating composition |
| CN106698515A (en) * | 2017-01-11 | 2017-05-24 | 吉林大学 | Preparation method of controllable-size CrO2 nanoparticles |
| CN110124599A (en) * | 2018-02-09 | 2019-08-16 | 松下知识产权经营株式会社 | Fine-grain manufacturing apparatus and particle manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613385B2 (en) * | 2001-04-23 | 2003-09-02 | The United States Of America As Represented By The Secretary Of The Navy | Highly spin-polarized chromium dioxide thin films prepared by CVD using chromyl chloride precursor |
| CN1208498C (en) * | 2002-12-06 | 2005-06-29 | 中国科学院金属研究所 | Chromium oxide coating preparing process |
| CN100434353C (en) * | 2006-01-24 | 2008-11-19 | 南京大学 | Gas phase synthesis process of nanometer particle array with one-dimensional diameter and number density gradient |
-
2007
- 2007-10-23 CN CNB2007101344571A patent/CN100564266C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329528A (en) * | 2010-06-30 | 2012-01-25 | Jds尤尼弗思公司 | Magnetic multi-layer pigments sheet and coating composition |
| CN102329528B (en) * | 2010-06-30 | 2015-01-07 | Jds尤尼弗思公司 | Magnetic multilayer pigment flake and coating composition |
| CN106698515A (en) * | 2017-01-11 | 2017-05-24 | 吉林大学 | Preparation method of controllable-size CrO2 nanoparticles |
| CN110124599A (en) * | 2018-02-09 | 2019-08-16 | 松下知识产权经营株式会社 | Fine-grain manufacturing apparatus and particle manufacturing method |
| CN110124599B (en) * | 2018-02-09 | 2021-11-12 | 松下知识产权经营株式会社 | Fine particle production apparatus and fine particle production method |
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| CN100564266C (en) | 2009-12-02 |
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