US3226183A - Preparation of monocrystals of rare earth manganites - Google Patents
Preparation of monocrystals of rare earth manganites Download PDFInfo
- Publication number
- US3226183A US3226183A US200918A US20091862A US3226183A US 3226183 A US3226183 A US 3226183A US 200918 A US200918 A US 200918A US 20091862 A US20091862 A US 20091862A US 3226183 A US3226183 A US 3226183A
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- United States
- Prior art keywords
- monocrystals
- rare earth
- solution
- oxide
- manganites
- 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 - Lifetime
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 13
- 150000002910 rare earth metals Chemical class 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 23
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 13
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910018663 Mn O Inorganic materials 0.000 description 5
- 239000008240 homogeneous mixture Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- -1 rare earth cation Chemical group 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 2
- PLSGTZIVCBJMPS-UHFFFAOYSA-N [Mn](=O)([O-])[O-].[Er+3].[Mn](=O)([O-])[O-].[Mn](=O)([O-])[O-].[Er+3] Chemical compound [Mn](=O)([O-])[O-].[Er+3].[Mn](=O)([O-])[O-].[Mn](=O)([O-])[O-].[Er+3] PLSGTZIVCBJMPS-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- OSCSMOVPJCIXGI-UHFFFAOYSA-N dioxido(oxo)manganese yttrium(3+) Chemical compound [Y+3].[Y+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O OSCSMOVPJCIXGI-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241000120020 Tela Species 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- ZFDNLYKUOBZKEY-UHFFFAOYSA-N dioxido(oxo)manganese thulium(3+) Chemical compound [Mn](=O)([O-])[O-].[Tm+3].[Mn](=O)([O-])[O-].[Mn](=O)([O-])[O-].[Tm+3] ZFDNLYKUOBZKEY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
- H01G7/025—Electrets, i.e. having a permanently-polarised dielectric having an inorganic dielectric
Definitions
- the present invention relates to the preparation of monocrystals of rare earth manganites corresponding to the general formula TMnO in which T represents a rare earth cation, which expression as used herein includes yttrium and lanthanum, as well as the elements from cerium to lutecium.
- the manganites obtained have a crystal structure similar to the perowskites. If the number of complementary 4f electrons is greater than 9 (holmium, erbium, thulium, ytterbium and lutecium), the manganites obtained have a novel crystal structure, of a non-centrosymmetric kind on the hexagonal system, characterised by abnormal coordinances of the manganese and rare earth ions.
- the manganites prepared by the usual methods by decomposition of manganese and rare earth nitrates and high temperature combination of the oxides obtained, yield the manganese in both the Mn and Mn forms.
- These compounds are semi-conductors of low resistivity, which are not suitable for use as dielectrics.
- the non-centrosymmetric hexagonal crystals, when cut and metallised parallel to the base planes, can have interesting piezoelectric and ferroelectric properties.
- the present invention has the object of providing a method of preparation of monocrystals of rare earth manganites grown parallel to the base planes, having a very high resistivity and interesting piezoelectric and ferroelectric properties and also articles of manufacture comprising monocrystals made by such method.
- a method of preparing a rare earth manganite monoerystal comprises dissolving a mixture of rare earth and manganese oxides in molten bismuth oxide, supersaturating the solution by slow evaporation and then separating the rare earth manganite monocrystals formed therein.
- Molten bismuth oxide used as the solvent has the advantages of readily dissolving other oxides and also of yielding monocrystals in which all the manganese is present in the form of manganites and, thus, in the Mn form.
- One advantage of the method is the production of tabular monocrystals grown parallel to the base planes.
- the monocrystals obtained by this method have very interesting ferroelectric properties which are only slightly modified by the particular rare earth cation chosen:
- a first embodiment of the method consists in melting a mixture of bismuth oxide, manganese oxide and a rare earth oxide, at a temperature above 1000 C., and then supersaturating the solution so obtained, by slow evaporation until the first crystals appear. At this point, in order to cause the crystals to grow, slow cooling to the ambient temperature is effected, so as to avoid internal mechanical stresses.
- a second embodiment of the method consists in melting a mixture of bismuth oxide, manganese oxide and a rare earth oxide, at a temperature above 1000 C., and then supersaturating the solution so obtained, by slow evaporation until the bismuth oxide completely disappears. The mixture is then uniformly cooled to the ambient temperature.
- Example 1 A homogeneous mixture constituted by 30 gram moles of Bi O 6 gram moles of Mn O and 3 gram moles of Y O was melted in a platinum crucible at 1350 C. The solution was supersaturated by slow evaporation at 1410 C. until the Bi O was completely eliminated, according to the second embodiment of the method. The solution was then slowly cooled to room temperature at a rate of 10 C./h., to produce a crop of yttrium manganite crystals.
- Example 3 A homogeneous mixture constituted by 20 gram moles of Bi O 4 gram moles of Mn O and 3 gram moles of Er O was melted in a platinum crucible at 1350 C. The solution was supersaturated by slow evaporation at 1450 C. until the Bi O was completely eliminated, according to the second embodiment of the method. The solution was then slowly cooled to room temperature at a rate of 10 C./h., to produce a crop of erbium manganite crystals.
- a method of preparing rare earth manganite monocrystals which comprises dissolving a mixture of a rare earth oxide and manganese oxide in molten bismuth oxide, supersaturating the solution by slow evaporation of the bismuth oxide and then separating the rate earth manganite monocrystals formed therein.
- a method of preparing thulium manganite monocrystals comprising the steps of melting a homogeneous mixture comprising 15 gram moles of B-i O 3 gram moles of Mn O and 3 gram moles of Tm O at 1350 C., supersaturating the solution by slow evaporation of bismuth oxide at 1400 C. until the first crystals appear andthen slowly cooling to room temperature.
- a method of preparing yttrium manganite monocrystals comprising the steps of melting .a homogeneous mixture comprising 30 gram moles of Bi O 6 gram moles of Mn O and 3 gram moles of Y O at 1350 C., supersaturating the solution by slow evaporation at 1450 C. until the Bi O is completely eliminated and slowly cooling the mass to room temperature.
- a method of preparing erbium manganite monocrystals comprising the steps of melting a homogeneous mixture comprising 20 gram moles of Bi O 4 gram moles of Mn O and 3 gram moles of Er O at 1350 C., supersaturating the solution by slow evaporation at 1450 C. until the Bi O is completely eliminated and slowly cooling the mass to room temperature.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
United States Patent 3,226,183 PREPARATION OF MONOCRYSTALS OF RARE EARTH MANGANITES Erwin Flix Bertaut, 29 Rue Andre Rivoire, Grenoble, France, and Francis Forrat, 2 Rue Eugene Pllsson, Marcoussis, France No Drawing. Filed June 8, 1962, Ser. No. 200,918 Claims priority, application France, June 12, 1961, 864,585 12 Claims. (Cl. 23-58) The present invention relates to the preparation of monocrystals of rare earth manganites corresponding to the general formula TMnO in which T represents a rare earth cation, which expression as used herein includes yttrium and lanthanum, as well as the elements from cerium to lutecium.
It is known that, depending upon the number of electrons contained in the N shell of the elements of the rare earth group, the manganites of such elements form two isomorphic series.
If the number of complementary 4f electrons of these elements is less than or equal to 9 (lanthanum, cerium, praseodymium, neodymium, illinium, samarium, gadolinium, terbium and dysoprosium), the manganites obtained have a crystal structure similar to the perowskites. If the number of complementary 4f electrons is greater than 9 (holmium, erbium, thulium, ytterbium and lutecium), the manganites obtained have a novel crystal structure, of a non-centrosymmetric kind on the hexagonal system, characterised by abnormal coordinances of the manganese and rare earth ions.
It is also known that the manganites prepared by the usual methods, by decomposition of manganese and rare earth nitrates and high temperature combination of the oxides obtained, yield the manganese in both the Mn and Mn forms. These compounds are semi-conductors of low resistivity, which are not suitable for use as dielectrics. It is also known that the non-centrosymmetric hexagonal crystals, when cut and metallised parallel to the base planes, can have interesting piezoelectric and ferroelectric properties.
The present invention has the object of providing a method of preparation of monocrystals of rare earth manganites grown parallel to the base planes, having a very high resistivity and interesting piezoelectric and ferroelectric properties and also articles of manufacture comprising monocrystals made by such method.
According to the invention, a method of preparing a rare earth manganite monoerystal comprises dissolving a mixture of rare earth and manganese oxides in molten bismuth oxide, supersaturating the solution by slow evaporation and then separating the rare earth manganite monocrystals formed therein.
Molten bismuth oxide used as the solvent has the advantages of readily dissolving other oxides and also of yielding monocrystals in which all the manganese is present in the form of manganites and, thus, in the Mn form.
One advantage of the method is the production of tabular monocrystals grown parallel to the base planes. The monocrystals obtained by this method have very interesting ferroelectric properties which are only slightly modified by the particular rare earth cation chosen:
( 1) The ferroelectricity only appears in the direction perpendicular to the plane of the tabular monocrystal;
(2) It is satisfactorily stable between 173 and 373 K.,
which allows use at the ambient temperature;
(3) The saturation polarisation of this temperature is about 3ac./sq. cm., the coercive field strength being about 20 kv./cm. (measurements made on samples several centimetres thick).
3,226,183 Patented Dec. 28, 1965 ice A first embodiment of the method consists in melting a mixture of bismuth oxide, manganese oxide and a rare earth oxide, at a temperature above 1000 C., and then supersaturating the solution so obtained, by slow evaporation until the first crystals appear. At this point, in order to cause the crystals to grow, slow cooling to the ambient temperature is effected, so as to avoid internal mechanical stresses.
A second embodiment of the method consists in melting a mixture of bismuth oxide, manganese oxide and a rare earth oxide, at a temperature above 1000 C., and then supersaturating the solution so obtained, by slow evaporation until the bismuth oxide completely disappears. The mixture is then uniformly cooled to the ambient temperature.
Various examples, given by way of illustration, are described below. The details described in these examples should be considered as comprising part of the invention, though all equivalent means can also be used without exceeding its scope.
Example 1 A homogeneous mixture constituted by 30 gram moles of Bi O 6 gram moles of Mn O and 3 gram moles of Y O was melted in a platinum crucible at 1350 C. The solution was supersaturated by slow evaporation at 1410 C. until the Bi O was completely eliminated, according to the second embodiment of the method. The solution was then slowly cooled to room temperature at a rate of 10 C./h., to produce a crop of yttrium manganite crystals.
Example 3 A homogeneous mixture constituted by 20 gram moles of Bi O 4 gram moles of Mn O and 3 gram moles of Er O was melted in a platinum crucible at 1350 C. The solution was supersaturated by slow evaporation at 1450 C. until the Bi O was completely eliminated, according to the second embodiment of the method. The solution was then slowly cooled to room temperature at a rate of 10 C./h., to produce a crop of erbium manganite crystals.
We claim:
1. A method of preparing rare earth manganite monocrystals, which comprises dissolving a mixture of a rare earth oxide and manganese oxide in molten bismuth oxide, supersaturating the solution by slow evaporation of the bismuth oxide and then separating the rate earth manganite monocrystals formed therein.
2. A method as claimed in claim 1, in which the monocrystals are separated by slowly evaporating the bismuth oxide until the first rare earth manganite crystals appear and then slowly cooling the solution to room temperature at a rate of from 4 C. to 10 C. per hour.
3. A method as claimed in claim 1, in which the monocrystals are separated by the complete evaporation of the bismuth oxide.
4. A method of preparing thulium manganite monocrystals comprising the steps of melting a homogeneous mixture comprising 15 gram moles of B-i O 3 gram moles of Mn O and 3 gram moles of Tm O at 1350 C., supersaturating the solution by slow evaporation of bismuth oxide at 1400 C. until the first crystals appear andthen slowly cooling to room temperature.
5. A method as claimed in claim 4, in which the solution is cooled to 1200 C. at a rate of 4 C./h. and from 1200" C. to room temperature at a rate of 10 C./h.
6. A method of preparing yttrium manganite monocrystals comprising the steps of melting .a homogeneous mixture comprising 30 gram moles of Bi O 6 gram moles of Mn O and 3 gram moles of Y O at 1350 C., supersaturating the solution by slow evaporation at 1450 C. until the Bi O is completely eliminated and slowly cooling the mass to room temperature.
7. A method of preparing erbium manganite monocrystals comprising the steps of melting a homogeneous mixture comprising 20 gram moles of Bi O 4 gram moles of Mn O and 3 gram moles of Er O at 1350 C., supersaturating the solution by slow evaporation at 1450 C. until the Bi O is completely eliminated and slowly cooling the mass to room temperature.
8. A method as claimed in claim 6, in which the mass is cooled at a rate of 10 C./h.
9. A method as claimed in claim 1 in which the dissolution of the oxides is effected at a temperature greater than 1000 C.
4 10. A method as claimed in claim 9 in which the temperature is about 1350 C.
11. A method as claimed in claim 1 in which the molar ratio of bismuth oxide to manganese oxide is about 5 to 1. 12. A method according to claim 7 in which the mass is slowly cooled at a rate of about 10 C./h.
References Cited by the Examiner UNITED STATES PATENTS 2/1963 Remeika 252 62.5 8/1963 Stuijts 252-62.5
OTHER REFERENCES Jonker et al.: Phillips Technical Reviewf vol, 18, No. 6, November 1956, pages 145-180.
Mones et al.: J. Phys. Chem. Solids," Pergamon Press, 1958, vol. 4, pages 217-222.
Sitova: Soviet Physics, Solid State, 1960, pages 1714- 15. Translated from Fizika Querdogo Tela, vol. 1, No. 12.
BENJAMIN HENKIN, Primary Examiner.
Claims (1)
1. A METHOD OF PREPARING RARE EARTH MANGANITE MONOCRYSTALS, WHICH COMPRISES DISSOLVING A MIXTURE OF A RARE EARTH OXIDE AND MANGANESE OXIDE IN MOLTEN BISMUTH OXIDE, SUPERSATURATING THE SOLUTION BY SLOW EVAPORATION OF THE BISMUTH OXIDE AND THEN SEPARATING THE RATE EARTH MANGANITE MONOCRYSTALS FORMED THEREIN.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR864585A FR1302468A (en) | 1961-06-12 | 1961-06-12 | Process for manufacturing single crystals of piezoelectric and ferroelectric rare earth manganites |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3226183A true US3226183A (en) | 1965-12-28 |
Family
ID=8757011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US200918A Expired - Lifetime US3226183A (en) | 1961-06-12 | 1962-06-08 | Preparation of monocrystals of rare earth manganites |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3226183A (en) |
| BE (1) | BE618554A (en) |
| DE (1) | DE1195284B (en) |
| FR (1) | FR1302468A (en) |
| LU (1) | LU41847A1 (en) |
| NL (1) | NL143824B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070085470A1 (en) * | 2003-10-30 | 2007-04-19 | Japan Science and Technology Agency, Kawaguchi-shi | Electroluminescent material and electroluminescent element using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3079240A (en) * | 1960-05-13 | 1963-02-26 | Bell Telephone Labor Inc | Process of growing single crystals |
| US3102099A (en) * | 1957-06-22 | 1963-08-27 | Philips Corp | Method of manufacturing monocrystalline bodies |
-
1961
- 1961-06-12 FR FR864585A patent/FR1302468A/en not_active Expired
-
1962
- 1962-06-05 BE BE618554A patent/BE618554A/en unknown
- 1962-06-07 LU LU41847D patent/LU41847A1/xx unknown
- 1962-06-08 US US200918A patent/US3226183A/en not_active Expired - Lifetime
- 1962-06-08 DE DEC27198A patent/DE1195284B/en active Pending
- 1962-06-12 NL NL62279607A patent/NL143824B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3102099A (en) * | 1957-06-22 | 1963-08-27 | Philips Corp | Method of manufacturing monocrystalline bodies |
| US3079240A (en) * | 1960-05-13 | 1963-02-26 | Bell Telephone Labor Inc | Process of growing single crystals |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070085470A1 (en) * | 2003-10-30 | 2007-04-19 | Japan Science and Technology Agency, Kawaguchi-shi | Electroluminescent material and electroluminescent element using the same |
| US7674399B2 (en) * | 2003-10-30 | 2010-03-09 | Japan Science And Technology Agency | Electroluminescent material and electroluminescent element using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1302468A (en) | 1962-08-31 |
| BE618554A (en) | 1962-10-01 |
| NL143824B (en) | 1974-11-15 |
| DE1195284B (en) | 1965-06-24 |
| LU41847A1 (en) | 1962-08-07 |
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