DE19712896C2 - Large crystalline metal silicon nitrides in single crystalline form - Google Patents
Large crystalline metal silicon nitrides in single crystalline formInfo
- Publication number
- DE19712896C2 DE19712896C2 DE19712896A DE19712896A DE19712896C2 DE 19712896 C2 DE19712896 C2 DE 19712896C2 DE 19712896 A DE19712896 A DE 19712896A DE 19712896 A DE19712896 A DE 19712896A DE 19712896 C2 DE19712896 C2 DE 19712896C2
- Authority
- DE
- Germany
- Prior art keywords
- metal silicon
- nitrogen
- metals
- silicon nitrides
- silicon
- 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
- 229910052751 metal Inorganic materials 0.000 title claims description 17
- 239000002184 metal Substances 0.000 title claims description 17
- 229910052710 silicon Inorganic materials 0.000 title claims description 10
- 239000010703 silicon Substances 0.000 title claims description 10
- -1 silicon nitrides Chemical class 0.000 title claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000071 diazene Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 150000002843 nonmetals Chemical class 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 101000801643 Homo sapiens Retinal-specific phospholipid-transporting ATPase ABCA4 Proteins 0.000 description 2
- 102100033617 Retinal-specific phospholipid-transporting ATPase ABCA4 Human genes 0.000 description 2
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000012713 reactive precursor Substances 0.000 description 2
- WBPWDGRYHFQTRC-UHFFFAOYSA-N 2-ethoxycyclohexan-1-one Chemical compound CCOC1CCCCC1=O WBPWDGRYHFQTRC-UHFFFAOYSA-N 0.000 description 1
- NJDGWMLMQLGHPA-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Nb+5].[In+3] Chemical compound [O--].[O--].[O--].[O--].[Nb+5].[In+3] NJDGWMLMQLGHPA-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- VCZFPTGOQQOZGI-UHFFFAOYSA-N lithium bis(oxoboranyloxy)borinate Chemical compound [Li+].[O-]B(OB=O)OB=O VCZFPTGOQQOZGI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- WYOHGPUPVHHUGO-UHFFFAOYSA-K potassium;oxygen(2-);titanium(4+);phosphate Chemical compound [O-2].[K+].[Ti+4].[O-]P([O-])([O-])=O WYOHGPUPVHHUGO-UHFFFAOYSA-K 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- 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
- C30B29/38—Nitrides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
Die Erfindung betrifft ein Metallsiliciumnitrid (Metallnitridosilicat), bestehend aus
Stickstoff, Silicium und einem oder mehreren Metallen und Nichtmetalle, die als groß
kristallines Produkt (Kristalle größer als 0,5 mm) bei der Synthese anfallen. Die Kri
stalle zeigen nichtlineare optische Eigenschaften, die für die optische Industrie und spe
ziell für die Laserindustrie von großer Bedeutung sind. Stoffe der gattungsgemäßen Art
existieren bereits. So unterscheidet man zwischen anorganischen und organischen Mate
rialien, die nichtlineare optische (NLO)-Eigenschaften besitzen. Zu nennen wäre das
Indiumnioboxid (InNbO3) und verschiedene Materialien auf organisch-polymerer Basis.
Die bereits bekannten Substanzen zeigen hervorragende NLO-Eigenschaften in Labor
versuchen. Für technische Anwendungen besitzen o. g. Materialien sehr schlechte me
chanische und thermische Eigenschaften. Die von uns entwickelte Stoffgruppe in Form
einkristalliner Großkristalle (Kristallgröße: Kantenlänge < 0,5 mm) weisen folgende
Vorteile gegenüber dem Stand der Technik auf:
The invention relates to a metal silicon nitride (metal nitridosilicate) consisting of nitrogen, silicon and one or more metals and non-metals, which are obtained as a large crystalline product (crystals larger than 0.5 mm) in the synthesis. The crystals show nonlinear optical properties that are of great importance for the optical industry and especially for the laser industry. Substances of the generic type already exist. A distinction is made between inorganic and organic materials that have non-linear optical (NLO) properties. These include indium niobium oxide (InNbO 3 ) and various materials based on organic polymers. The already known substances show excellent NLO properties in laboratory tests. The above-mentioned materials have very poor mechanical and thermal properties for technical applications. The group of substances we developed in the form of single-crystal large crystals (crystal size: edge length <0.5 mm) have the following advantages over the prior art:
- - Sehr gute mechanische Eigenschaften- Very good mechanical properties
- - Hohe thermische Resistenz unter Schutzgasen, Luft und Vakuum- High thermal resistance under protective gases, air and vacuum
- - Einfaches Eintopf-Syntheseverfahren- Simple one-pot synthesis process
- - Effektive NLO-Eigenschaften- Effective NLO properties
Folgende Materialien werden großtechnisch bereits im Bereich NLO eingesetzt:
LBO, Lithiumtriborat
BBO, Beta Bariumborat
KTP, Kaliumtitanylphosphat
LiIO3, LithiumjodatThe following materials are already used on an industrial scale in the NLO area:
LBO, lithium triborate
BBO, beta barium borate
KTP, potassium titanyl phosphate
LiIO 3 , lithium iodate
Sämtliche o. g. Materialien sind nicht hochtemperaturstabil.All of the above Materials are not stable to high temperatures.
Die Stoffgruppe der Metallsiliciumnitride wurde bereits in der Literatur beschrieben,
jedoch wurden bei den Synthesen ausschließlich mikrokristalline Pulver dargestellt, die
keine NLO-Eigenschaften zeigen. 1995 wurden Versuche veröffentlicht, makrokristal
line Produkte herzustellen. Bei der Umsetzung von Metallen mit einem Precursor von
Siliciumnitrid in einen Hochfrequenz-Normaldruckapparatur erhielten die genannten
Forscher Kristalle mit einer maximalen Kantenlänge von 0,1 mm. Diese Produkte zeig
ten ebenfalls keine erkennbaren NLO-Eigenschaften (Lit.: Dr. Thomas Schlieper, Dis
sertation 1995, Universität Bayreuth). Als häufigste alternative Route zur Synthese ter
närer und multinärer Metallsiliciumnitride wird die Umsetzung der binären Nitride
(Metallnitrid und Siliciumnitrid) gewählt. Da die Reaktivität von Siliciumnitrid sehr
gering ist, wurden lange Reaktionszeiten und extreme Reaktionsbedingungen bei der
Synthese benötigt. Bei diesen Synthesen fielen ausschließlich mikrokristalline Pulver
ohne genannte NLO-Eigenschaften an:
The group of metal silicon nitrides has already been described in the literature, but only microcrystalline powders which do not show any NLO properties were shown in the syntheses. In 1995 attempts were made to manufacture macrocrystalline line products. When converting metals with a precursor of silicon nitride into a high-frequency normal pressure apparatus, the researchers mentioned received crystals with a maximum edge length of 0.1 mm. These products also showed no discernible NLO properties (lit .: Dr. Thomas Schlieper, Dissertation 1995, University of Bayreuth). The most common alternative route for the synthesis of binary and multinary metal silicon nitrides is the implementation of binary nitrides (metal nitride and silicon nitride). Since the reactivity of silicon nitride is very low, long reaction times and extreme reaction conditions were required for the synthesis. Only microcrystalline powders with no mentioned NLO properties were obtained in these syntheses:
- - D Bahloul, M. Peireira, P. Goursat, J. Am. Ceram. Soc. 76 (1993) 1156- D Bahloul, M. Peireira, P. Goursat, J. Am. Ceram. Soc. 76 (1993) 1156
- - N. Brodie, J. P. Majoral, J. P. Disson, Inorg. Chem. 32 (1993) 4646- N. Brodie, J.P. Majoral, J.P. Disson, Inorg. Chem. 32 (1993) 4646
- - M Jansen, S. Rings, Z. Naturforsch. 50b (1995) 180- M Jansen, S. Rings, Z. Naturforsch. 50b (1995) 180
- - M Deckwerth, C. Rüssel, J. Mater. Sci. 29 (1994) 4500- M Deckwerth, C. Rüssel, J. Mater. Sci. 29 (1994) 4500
- - J. Löffelholz, M. Jansen, Adv. Mater. 7 (1995) 289- J. Löffelholz, M. Jansen, Adv. Mater. 7 (1995) 289
- - O. Funayama, Y. Tashiro, A. Kamo, M. Okumura, T. Isoda, J. Mater. Sci. 29 (1994) 4883- O. Funayama, Y. Tashiro, A. Kamo, M. Okumura, T. Isoda, J. Mater. Sci. 29 (1994) 4883
- - M. Jansen, J. Löffelholz, Adv. Mater 4 (1992) 746- Jansen M., J. Löffelholz, Adv. Mater 4 (1992) 746
- - W. H. Baur, Nature 240 (1972) 461- W.H. Baur, Nature 240 (1972) 461
Den bekannten Verfahren liegt die Aufgabe zugrunde, neue multinäre Metallsiliciumni tritphasen zu synthetisieren und deren Struktur zu charakterisieren. The known methods are based on the task of creating new multinary metal silicon ni synthesize trit phases and characterize their structure.
Yamane et al. und H. Huppertz et al. synthetisierten in 1996/97 erstmals die beiden Bari umnitridosilicate Ba5Si2N6 (J. of Alloys and Compounds 240, 1996, S. 33-36) bzw. Ba Si7N10 (Chem. Eur. J. 31997, Heft 3, S. 249-252). Diese Verbindungen zeigen aufgrund der in ihnen enthaltenen schweren Metallatome keine effektiven NLO Eigenschaften. Schlieper et al. gelang es 1995 bereits, ein strukturell eindeutig bestimmtes Calciumni tridosilicat zu synthetisieren. Diese Verbindung fällt ausschließlich mikrokristallin an. (Z. Anorg. Allg. Chem. 621 (1995), S. 1037-1041) und kann deshalb nicht zu NLO- effektiven Kristallen weiterverarbeitet werden.Yamane et al. and H. Huppertz et al. synthesized for the first time in 1996/97 the two barium nitridosilicates Ba 5 Si 2 N 6 (J. of Alloys and Compounds 240, 1996, pp. 33-36) and Ba Si 7 N 10 (Chem. Eur. J. 31997, booklet 3, pp. 249-252). These compounds show no effective NLO properties due to the heavy metal atoms they contain. Schlieper et al. already succeeded in 1995 in synthesizing a structurally clearly determined calcium tridosilicate. This compound is obtained only microcrystalline. (Z. Anorg. Allg. Chem. 621 (1995), pp. 1037-1041) and therefore cannot be processed further to form NLO-effective crystals.
Die Zielsetzung, die zu dieser Erfindung führte, war, im Gegensatz zu den herkömmli chen Verfahren, Metallsiliciumnitride mit nutzbaren NLO-Eigenschaften und Kanten längen größer 0,5 mm herzustellen. Diese Aufgabe wird mit den Merkmalen von An spruch 1 gelöst. Zur Erläuterung der Erfindung sind nachfolgend mehrere Beispiele an geführt:The objective that led to this invention was, in contrast to the conventional one Chen process, metal silicon nitride with usable NLO properties and edges to produce lengths greater than 0.5 mm. This task is accomplished with the characteristics of An spell 1 solved. Several examples are given below to illustrate the invention guided:
Zur Synthese von Calciumsiliciumnitrid wurden Calciummetall (Firma ABCR, Karls ruhe, Ca-1030, Reinheit 99,997%) mit Siliciumdiimid als reaktive Vorstufe von Silici umnitrid unter Schutzgasatmosphäre vermischt und in den Hochfrequenz/Hochdruck reaktor überführt. Mit einer Heizrate von 25°C/min wurden die Edukte unter Stick stoffdruck von 3,5 bar auf 1100°C aufgeheizt und 1 Stunde gehalten. Anschließend wurden die Edukte mit 15°C/min auf 1560°C erhitzt, 2 Stunden bei dieser Temperatur gehalten und innerhalb von 3 Minuten auf Raumtemperatur abgekühlt. Als Produkt wurde das Metallsiliciumnitrid einphasig in Form großer Kristalle erhalten (Kantenlän ge: ca. 2-5 mm). Die Kristalle aus dem Ansatz aus Beispiel 1 zeigen nichtlineare opti sche Eigenschaften mit hoher Effizienz. Das Ca/Si-Verhältnis beträgt 1 : 2 und Si/N- Verhältnis 6 : 10. For the synthesis of calcium silicon nitride, calcium metal (ABCR, Karls rest, Ca-1030, purity 99.997%) with silicon diimide as a reactive precursor of Silici umnitrid mixed in a protective gas atmosphere and in the high frequency / high pressure reactor transferred. With a heating rate of 25 ° C / min, the starting materials were under stick Fabric pressure heated from 3.5 bar to 1100 ° C and held for 1 hour. Subsequently the starting materials were heated at 15 ° C./min to 1560 ° C. for 2 hours at this temperature held and cooled to room temperature within 3 minutes. As a product the metal silicon nitride was obtained in the single phase in the form of large crystals (edge length ge: approx. 2-5 mm). The crystals from the batch from Example 1 show nonlinear opti properties with high efficiency. The Ca / Si ratio is 1: 2 and Si / N- Ratio 6:10.
Zur Synthese von Calciumsiliciumnitrid wurden Calciummetall (Fa. ABCR, Karlsruhe, Ca-1030, Reinheit 99,997%) mit Siliciumdiimid als reaktive Vorstufe von Siliciumni trid unter Schutzgasatmosphäre vermischt und in den Hochfrequenz/Hochdruckreaktor überführt. Mit einer Heizrate von 25°C/min wurden die Edukte unter Stickstoff normaldruck auf 1100°C aufgeheizt und 1 Stunde gehalten. Anschließend wurden die Edukte mit 15°C/min auf 1560°C erhitzt, 2 Stunden bei dieser Temperatur gehalten und innerhalb von 3 Minuten auf Raumtemperatur abgekühlt. Als Produkt wurde ein teilweise röntgenamorphes Produkt, das mit einigen Mikrokristallen durchsetzt ist, ge funden. Nach Röntgenstrukuruntersuchungen (Pulverdiffraktometrie) entsprechen die Mikrokristalle der bekannten Verbindung Ca2Si5N8.To synthesize calcium silicon nitride, calcium metal (ABCR, Karlsruhe, Ca-1030, purity 99.997%) was mixed with silicon diimide as a reactive precursor of silicon nitride under a protective gas atmosphere and transferred to the high-frequency / high-pressure reactor. The starting materials were heated to 1100 ° C. under nitrogen normal pressure at a heating rate of 25 ° C./min and held for 1 hour. The starting materials were then heated to 1560 ° C. at 15 ° C./min, kept at this temperature for 2 hours and cooled to room temperature within 3 minutes. A partially X-ray amorphous product interspersed with a few microcrystals was found as the product. According to X-ray structure investigations (powder diffractometry), the microcrystals correspond to the known compound Ca 2 Si 5 N 8 .
Durch diese beiden vergleichenden Versuche wurde gezeigt, daß hoher Stickstoffdruck entscheidend für die Synthese der gewünschten Produkte ist.These two comparative experiments showed that high nitrogen pressure is crucial for the synthesis of the desired products.
Claims (1)
- a) mit effektiv nichtlinearen optischen Eigenschaften,
- b) bestehend aus Silicium, Stickstoff und einem oder mehreren Metallen, wobei ggf.
- c) neben Stickstoff weitere Nichtmetalle enthalten sind, und
- d) der Kristall eine Kantenlänge größer als 0,5 mm besitzt,
- a) with effectively non-linear optical properties,
- b) consisting of silicon, nitrogen and one or more metals, where appropriate
- c) in addition to nitrogen, other non-metals are contained, and
- d) the crystal has an edge length greater than 0.5 mm,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712896A DE19712896C2 (en) | 1997-03-27 | 1997-03-27 | Large crystalline metal silicon nitrides in single crystalline form |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712896A DE19712896C2 (en) | 1997-03-27 | 1997-03-27 | Large crystalline metal silicon nitrides in single crystalline form |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE19712896A1 DE19712896A1 (en) | 1999-12-09 |
| DE19712896C2 true DE19712896C2 (en) | 2001-11-15 |
Family
ID=7824801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19712896A Expired - Fee Related DE19712896C2 (en) | 1997-03-27 | 1997-03-27 | Large crystalline metal silicon nitrides in single crystalline form |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19712896C2 (en) |
-
1997
- 1997-03-27 DE DE19712896A patent/DE19712896C2/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| Huppertz H. et al: Edge sharing SiN¶4¶ Tetrahedra in the Highly Condensed Nitridosilicate BaSi¶7¶ N¶10¶ Chem. Eur. J. 3, H.3, 1997, S.249-252 * |
| Schlieper T. et al: Nitrido Silicate I Hochtemper-atur-Synthese und Kristallstruktur von Ca¶2¶ SI¶5¶N¶8¶ Z. anorg. allg. Chem. 621, 1995, 1037-1041 * |
| Yamane H. et al: Preparation and crystal structureof a new barium silicon nitride, Ba¶5¶-Si¶2¶N¶6¶ In: J. of Alloys and Compounds 240, 1996, S.33-36 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19712896A1 (en) | 1999-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE112008003497B4 (en) | Process for growing a silicon carbide single crystal | |
| WO2000004211A1 (en) | METHOD FOR GROWING SiC MONOCRYSTALS | |
| Wang et al. | Physicochemical behavior of nonlinear optical crystal CdHg (SCN) 4 | |
| DE3100554C2 (en) | ||
| Chen et al. | Preparation and crystal structure of Nb14S5 | |
| WO2021140065A1 (en) | High-purity tungsten(vi) oxytetrachloride and process for preparing same | |
| Liu et al. | Novel synthesis of polymorphous nanocrystalline KNbO3 by a low temperature solution method | |
| DE19712896C2 (en) | Large crystalline metal silicon nitrides in single crystalline form | |
| DE3801862A1 (en) | METHOD FOR MELTING SOLUTION SYNTHESIS OF CRYSTALS AND EPITACTIC LAYERS FROM SOLID SOLUTIONS OF KTIOPO (ARROW DOWN) 4 (ARROW DOWN) ISOTYPES | |
| Zhang et al. | Synthesis and characterization of single-crystalline TaC whiskers | |
| Basu et al. | Characterization of various commercial forms of ammonium paratungstate powder | |
| DE10344015A1 (en) | Crystalline compounds in the systems C-N, B-N and B-C-N | |
| WO2016011994A1 (en) | Crystalline metal cyanurate compounds, method for producing said compounds, and use of said compounds | |
| US5118488A (en) | Process for making whiskers, fibers and flakes of transition metal compounds | |
| DE68914838T2 (en) | METHOD FOR PRODUCING CARBIDES AND SILICIDES BY MECHANOCHEMICAL WAY. | |
| Kumta et al. | Chemical processing of rare earth chalcogenides | |
| Zhou et al. | Preparation and characterization of β-BaB2O4 nanoparticles via coprecipitation | |
| Wang et al. | Growth and properties of UV nonlinear optical crystal ZnCd (SCN) 4 | |
| DE2441298C3 (en) | Process for making soft hexagonal boron nitride crystals | |
| Ferraglio et al. | Martensitic transformation in a splat cooled Au-50 at.% Cd alloy | |
| DE3940555A1 (en) | METHOD FOR PRODUCING A KTIOPO (DOWN ARROW) 4 (DOWN ARROW) SINGLE CRYSTAL | |
| DE69709018T2 (en) | Single crystal oxide and process for its manufacture | |
| Zhang et al. | A sodium tantalum phosphate with a noncentrosymmetric structure: Na5Ta8P5O35 | |
| EP0511490B1 (en) | Process for the production of finely divided crystalline silicon nitride | |
| DE102004048454A1 (en) | Process for the preparation of Group III nitride bulk crystals or crystal layers from molten metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OP8 | Request for examination as to paragraph 44 patent law | ||
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition | ||
| 8339 | Ceased/non-payment of the annual fee |