JPH01500348A - Coincidentally molten complex oxide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Coincidentally molten complex oxide Background of the invention The present invention relates to complex oxides such as gadolinium scandium gallium garnet. Ru.

Garnet materials have many different technological applications.These garnet materials For example, it can be used as a substrate for a magnetic bubble domain device and as a host for an active light-emitting solid-state laser. It is used as a strike.

C-D-Brandle et al. [Journal of ・Journal of Crystal Growt h), Vol. 20, p. 1, 1973] using the Chickralski method. The produced gadolinium scandium gallium garnet (GSGG) is Cr Doped wavelength tunable laser (P,F, Morlton laser) Laser Focus, page 30, May 1983 and Nd:Cr-doped high-power solid-state laser [E, V, Zharikov et al., Soviet Journal of Phantom Electro Nix (Soviei Journal of Quantum Electron ics), vol. 14, p. 1056, 1984]. There is. However, when used in lasers, it is important that the crystal be uniform. . In order to obtain uniform crystals, it is necessary to have a consistent melt composition, i.e. the growing crystal is Accurate knowledge of the composition having the same composition as the melt is required.

The garnet structure has three dodecahedral sites, two octahedral sites and It is a complex oxide network structure containing three tetrahedral sites. The distribution of natural parts is large m: Gadolinium [ion radius ri - 0,1053 nanometers (1 , 053 angstroms)] are distributed, and scan Dium Crt - 0,0745 nanometers (0,745 angstroms)] Gallium (rl = 0.047 nanometers) is distributed in small tetrahedral regions. (0.47 angstroms)] is distributed. However, other garnet As is clear from the above, these ions may be distributed in unspecified locations, although in small numbers. There is also. That is, fil gallium is one of the twelve rare earth gallium garnets. (2) Gadolinium is easily incorporated into the facepiece; It is incorporated into the net (GGG) in a tetrahedral shape (C.D. Brundle). et al., Journal of Crystal Growth, vol. 26, p. 169, 1974. ); and (3) scandium is gadolinium scandium aluminum gane It is incorporated in a dodecahedral shape within the kit (C.D. Brundle, etc. mentioned above, etc.). (1973), some or all of these mechanisms may be present in the harmonic composition of 03CG. affect. The total distribution coefficients of all three components above produce crystals of uniform composition. Must be equal to 1 to make it long.

Previous studies have used measurements of lattice constants to measure the composition uniformity of 03CG. was. Brundle et al. (1973) mentioned above used their own lattice constant data as their calculation method. Comparing the values, there must be dodecahedral gadolinium in these crystals. I concluded that no. Kei Chow (L, Chow) et al. (Journal of Chris Tal Growth, vol. 23, p. 58, 1974) is from sintered (ceramic) materials. Using the lattice constant data of Gd, the matched melt composition is Gd, .

S C+, hGa3. a01! It was concluded that Its value based on one variable Such measurements are useful for ternary systems, especially complex systems in which two or more ions are distributed in unspecified locations. is not sufficient for resolving ternary systems, therefore, we have proposed Kou et al. The consistent melt composition of GSG grown by their method is inaccurate and It was revealed that the G crystal lacks considerable uniformity.

Summary of the invention The device of the invention comprises a substance containing complex oxides, the composition of which is harmonious and low ( Both correspond to the stoichiometric amount by at least 0.1 atomic percent for one constituent element. According to one aspect of the invention, the coincident melt composition of the GSGG single crystal is Gas, **Chapter e, *5SCt, *st*. *5Gas, +at*, *sO1* (It consists of 11.

A preferred composition as measured by XvA fluorescence is Gd□,,S.

It consists of SC1,9゜5cas, +□o18, or when expressed as a site sequence (Gdt , *5ySce, eai) (Sc+, ****Gas, +ss) (Gas, * **) Consists of O+t (2), where the place represents the dodecahedral part, and the bracket Sc of a dodecahedral part, where t represents an octahedral part and barcine represents a tetrahedral part. The existence of the 0.043 substituent scale is surprising, and this component is the lattice constant of the GSGG single crystal. It plays an important role in reducing the

Good quality and as active medium of solid-state laser or substrate of bubble domain device Single crystals with high uniformity could be produced. The laser material is Nd″3 and The Nd″3 active form is grown at a desired concentration of Cr″3 and Cr″3, and the Nd:Cr-doped GSCs grown using the composition of the present invention with stimulated release; G-crystals exhibit improved optical quality and hence better laser performance , Furthermore, the material of the present invention has uniform optical quality, making it suitable for large slab lasers. (For example, production of 10×20×1 (J) is possible.

Another advantage of the present invention is that the utilization of the melt (i.e. the fraction of the crystallized liquid melt) is The value has increased significantly from 30 to 50 percent of the previous technology to 80 to 90 percent. It is to add. This increase in yield means a reduction in unit price.

According to another aspect of the invention, the conformal melt composition of GSGG is Produced by the long method, this Chicksilski growth method has an elevated temperature lower than the melting point. Pre-press the compressed oxide powder of the 03CG component at a temperature (e.g. about 1173-1973°K). The gallium oxide is heated to chemically combine with the low vapor positive phase, thereby forming this garnet material. to the relatively high temperatures (e.g. about 2148-2173°K) required to melt the material. This is a method to reduce evaporation of gallium oxide.

Brief description of the drawing The present invention will be described with reference to the accompanying drawings. In these drawings: FIG. Fig. 2 is a schematic diagram of a solid-state laser according to Mr. B; FIG. 2 is a cross-sectional view of the face plate of the trochanter/optical isolator, ie, the negative Bi-ray tube.

detailed description In FIG. 1, an exemplary solid-state laser IO is shown comprising a solid-state active medium 12. The solid active medium 12 is guided by a pair of separate concave reflectors 14 and 16. Typically, the reflector 14 is arranged along the axis of the resonator formed by approximately 10 0% reflection, but the reflector 16 is partially transmissive and the output emitted beam 18 is 0% reflective. Transmit. Bumping energy is supplied to the active medium 12 and this technical field A population inversion is induced in the active medium 12 by a well-known bombing means 20. cause. In many cases, the above energy is a TM wave in the optical part of the frequency spectrum. Powered by 19. Therefore, the pumping means 2o is absorbed into the active medium. optical radiation having wavelengths that are present and of sufficient brightness to cause population inversion It is a flash lamp or laser that generates. Hula 7che bomb means is usually Laser bombing means are typically used for high power or pulsed operation, while laser bombing means are usually low power or instantaneous. It is used for continuous wave (CW) operation. For pulsed mode, the active medium is usually circular It has the shape of a cylindrical rod, but in the case of CW, its shape is slab-like, that is, rhombohedral. This rhombohedron has two main parallel surfaces 22 that absorb the pumping radiation and one that activates the laser beam. It has parallel end faces 24 for introducing into and ejecting active medium 12 from.

The end face 24 is oriented at a Brewster angle with respect to the major face 22. medium 1 2, the laser radiation undergoes radiation caused by total internal reflection at the major surface 22. It propagates along a ragged path.

According to one embodiment of the invention, the active medium 12 is GS doped with a suitable activator. It consists of a GG single crystal host, which has a coincident melting composition expressed by the following equation: Has the following configurations: Gdx, **t*, aiSCt, **t*, Ga3. +a:o , *so+i (31 In a preferred embodiment, the host consists of the following formula: Gdx , *st S C+, **** Ga, 1.13a Or* (41 desired activity There are many agents available, but depending on the desired operational wavelength, e.g. Cr'' When 3 is used as the activator, the laser emits at about 745-820 nm.

However, when Nd″3 and Cr″ are used, the laser It emits at 1.06 μ-. The above Cr” enhances the absorption effect of bombing radiation. and to move the pumping energy Nd” upward to the laser level. It is something that works.

The conformal melt composition of the present invention grows an optically uniform single crystal boule. A relatively large material with optically uniform properties throughout. (For example, if a 10X20X1(s) slab is cut from the above pool and It can be used as an active medium for solid-state lasers.

It will be appreciated that the above arrangement is subject to modification to utilize the principles of the present invention. The above arrangement is merely illustrative of the many possible embodiments that can be implemented. Numerous modifications can be made by those skilled in the art without departing from the spirit and scope of the invention. It can be devised according to the theory. In particular, the GSGG one-time melt composition of the present invention is A magnetic domain arrangement as described by Brundle et al. (1973) supra. or C,P,K]ages and Double Tor Tolksdorf (W), Journal op Crystal Glo 64j8, pp. 275-284, 1983. It can be used as a substrate for a magneto-optical device. Simply put, magnetic garnet A suitable electrode pattern is grown on the substrate. formed on the magnetic layer to control the propagation of magnetic bubble domains within the magnetic bubble device. control or reverse the direction of magnetization in the magnetic domains of the magneto-optical device.

As mentioned above, the matched composition of GSGG is not a stoichiometric composition. Understood. Furthermore, “Growth of 3-inch Diameter Qd, Gas O□・Crystals (Growth of 3 inch Diameter G d @Ga SOHCrystals) J, Journal of Applied Journal of Applied Physics, 4 91! , No. 3, pp. 1855-1858, May 1978. As stated by Brandl Jr. As shown, the matched composition of gadolinium gallium garnet (GGG) is non-stoichiometric. It turned out to be a theoretical substance. Furthermore, on September 27, 1985, C.D. ・Brandle Jr., P.K. Gallange r) and H.M. Bryan J. As set forth in U.S. Patent Application No. 781,408 filed by It was also found that the coincident composition of lithium niobate differs from the stoichiometric composition. Ta. These three (seemingly unrelated) discoveries are based on GSCG, GGG and niobium phosphate. Thirium has the same composition as the liquid only at certain non-stoichiometric harmonic compositions. structure in the solid. They are related in that they are complex oxides. (of this disclosure) Therefore, it oxides contain only oxygen anions and two or more different cations. It is a compound. Furthermore, the number of atoms of each element in the crystal unit cell is When the ratio for similar integers is approximately Differences from 1 by less than approximately 0.0O1 within a correspondence accuracy range of 0.1 atomic percent If so, the n-oxide has a stoichiometric composition. ) These three discoveries are at least It is important to some extent. This is because these discoveries are based on solid complex oxides (this are stable at that melting temperature), the melt composition of the corresponding stoichiometric composition This is because it contradicts the conventional, globally supported idea that it is a physical object. deer However, these findings may be perceived as strange exceptions to the above idea. However, the above conventional thinking still holds true for all other complex oxides. For example, lasers and/or fluorescent host materials Complex oxides proposed to be used as lanthanum aluminates The harmonic composition of Si (LMA) is still believed to be stoichiometric. . (For example, D, Vivien, etc., Nocrystalline Laser Machilia J ShikuA newmonocrystal line 1aser materia+): I, N AJ, Interna Shiranal Revue of High Tempurachi - Refractories (Ent er national Review of lighTe@peratu r@R@fractories), vol. 23, pp. 51-56, 1986. ) The above idea is completely wrong, and solid complex oxides (this substance can be used in a stable atmosphere if necessary) The harmonic composition of (which is stable at its melting temperature in the presence of air) is slightly It has always been found that the important thing ζ is stoichiometry. Maybe this harmonious composition will exhibit a continuous mono-chemical phase between its melting temperature and 3001; therefore, When the harmonic composition is cooled between its melt temperature and 3001, two or more chemical phases Harmonic compositions exhibiting less than 0.1 atomic percent of theoretical Harmonic compositions of complex oxides that differ in quantity are difficult to distinguish from stoichiometric compositions. , and therefore cannot be included in the present invention; furthermore, such complex oxides ( (Non-stoichiometric) harmonic compositions can be easily determined using novel iterative methods. It turns out that it is possible to do this. In the first step of the method, a given complex oxide (preferably or a single chemical phase) is addressed by the traditional Chickelsky method. grown from a melt with a corresponding stoichiometry; The composition is determined to be 0.1 atomic percent using conventional chemical analysis techniques, such as conventional XL fluorescence technology. Measured in cents. ! To obtain an essentially homogeneous composition close to the J1 sum state This pool must be relatively small, i.e. it must contain liquid solution. It has a mass of no more than about 10%, preferably no more than about 5% of the mass of the melt. this During the second step of the method, a second liquid melt is produced, the second liquid melt comprising at least having a mass of 100 g and the composition of the previously grown (first) pool. a new (second) having a mass equal to at least 80% of the mass of the zero-order melt; A pool is grown from this melt. Importantly, this new pool refractive index or multiple refractive indexes (two or more types, e.g. normal and extraordinary) refractive index (if present) is sensitive to changes in pool composition.

As a result, the refractive index or refractive indexes can be determined, e.g. Bete Boules For Inchgraty Nod Obtakes Ablique Testing Ljthium N1obateRoutes F or Integrated 0ptics Applications)J , Electronics Letters, 22, No. 12, pp. 674-675, June 5, 1986, G.E. Biederlin (G, [!, Peterson) and Niss R. Lund (S , R., Lunt) using the prism connection technique described by Measured along the length of the outer surface. A new (second) pool along the length of the outside surface of the pool. The change in each refractive index of the pool (from the top to the bottom of the pool) is approximately ±0.01% or less, Preferably, if it is about ±0.001% or less, the body is of substantially uniform composition, and the compositions of both the pool and the melt are in a matching set. Becomes. If the upper refractive index criterion is not satisfied, a new pool (new pool 10% (by weight) immediately above the first 10% extracted (by weight), preferably immediately above the pool. Repeat the second step of the above method according to the upper 5% composition measurements. That is, this 0th order producing a melt having the composition and having a mass of at least 100 g, A pool having a mass of at least 80% of the mass of the newly formed melt is Measure the refractive index along the length of the outside surface of the pool to meet the above refractive index criteria. Check to see if you are satisfied. (The second step of the above method must be repeated two or more times. However, the composition of the continuous melt and pool tends toward a harmonic composition. The preferred method described above involves the preparation of >ti oxides (preferably in a single chemical phase). Not only is it useful for finding Japanese compositions, but also for the purpose of the present invention, a given composition is It is used to measure the harmonic composition of complex oxides. That is, a predetermined producing a liquid melt having a composition of and a mass equal to at least 100 g A pool of zero order having a mass equal to at least 80% of the mass of the melt grow from The refractive index change along the length of the outer surface of this pool meets the above refractive index criterion. If satisfied, the resulting composition is a matched composition. (However, the coincident composition If the amount differs from the theoretical amount by less than 0.1 atomic percent for each constituent element, corresponding complex oxides are not included in the present invention) According to the above explanation, for example, LMA has the following non-stoichiometric harmonic composition Las, wst, *+ MgA 1++, ost, sa 019 +51 The preferred composition is L a 1986 M g A 12 ++, oseO+9 +61 unit -It was found to exhibit a chemical phase.

The discovery that the harmonic composition of all complex oxides is non-stoichiometric has great industrial significance. For example, current industrial methods of growing pools of n-oxides from liquid melts The technology still uses melts with corresponding stoichiometric compositions.

Although this fundamental problem was previously unrecognized, pool manufacturers are In order to obtain a pool with a uniform composition, the pool (relative to the mass of the i'8 melt) is We have known for a long time that it is necessary to limit the mass of That is, Pool manufacturers typically convert approximately 30-50% of the mass of the liquid melt into a solid pool. The remaining 50-70% of the melt was then discarded. However, (as defined above) The quality of the liquid melt can be improved by adopting a melt having a harmonic composition (such as More than 30-50%, usually even 90%, of the amount (as defined above) is essentially We found that it is easily converted into a solid pool with a uniform composition.

The above discovery (that complex oxides have a non-stoichiometric harmonic composition) also It has great significance for modern equipment. That is, it grows from a stoichiometric melt. Many deficiencies in devices using complex oxide materials derived from pools are due to the composition of the melt. For example, in the above case, this is due to the fact that is anharmonic. As mentioned above, single crystal LMA has been proposed as a laser host. Especially L MA single crystal hosts neodymium ions (which can be used as a laser) It has been proposed that it is useful as a Because neodymium is yttrium on LMA than on other hosts such as Luminium Garnet (YMC;). This is because it has a much higher distribution coefficient. As a result, neodymium-doped YAG - The possibility of obtaining much higher power densities than, for example, neodymium-doped YAG lasers There is. However, stoichiometric compositions (i.e., previously believed to be harmonic compositions) LaMgA &...

Growing an LMA boule from a melt with 01e) can be useful for laser applications. An undesirable pool results. This is because these pools are exposed to air bubbles during traditional treatment. (pores) and cracks.0 Importantly, these bubbles and Cracks have always been thought to be caused by growth rather than compositional problems.

LMA blocks grown from melts having harmonic compositions of chemical formulas (5) and (6) above. The roll is essentially bubble-free and essentially crack-free during the processing process. Understood. As a result, according to the present invention, the solid-state laser 10 ( 1) activates reflectors 14 and 16 and pumping energy source 20. It can be easily obtained by combining with the sexual medium 12. Note that the active medium 12 is neo contains an LMA host doped with Jim, and the host composition in the above case (doped (in the absence of punt) is shown by chemical formula (5).

The above discovery also shows that single-crystal complex oxides, such as garnet substrates 28, are coated with Important for many devices involving relatively thin films 26 (see section 2v!J) That's true. Some of these devices include a variety of well-known polarization rotators and optical The rotating body and isolator are epitaxially mounted on the garnet substrate 28. A taxially grown iron-containing film 26 (which is magnetized during use), e.g. Rare earth-bismuth iron grown on a converted gadolinium gallium garnet substrate Contains a garnet film (see, for example, the above-mentioned C.B. Furthermore, many cathode ray tubes are epitaxially mounted on a garnet substrate 28. A taxially grown relatively thin phosphor-doped film 26, e.g. on a YAG substrate. having a faceplate containing a cerium-doped YAG film epitaxially grown on it. (For such cathode ray tubes, see, for example, J.M. Robertson ( J., M. Robertson) and M. Double Vantor (M.J., v. anTol), Thin 5olid Film s), p. 1141221, 1984).

For all these devices, the garnet substrate has a stoichiometric It was derived from a pool grown from a theoretical melt.

The above fallacy is that the stoichiometric melt produces a substrate of nearly uniform composition. , this composition eliminates the lattice mismatch between the substrate and the film and The idea is to eliminate distortion. However, all these thin films Thin films riddled with defects often exhibit undesirable birefringence. This often results in, for example, optical isolators exhibiting relatively small extinction coefficients.

On the other hand, the thin film used as a surface for cathode ray tubes has a large number of undesirable scattering sites. These scattering sites often limit the contrast of cathode ray tubes. It is something that

``The defects associated with the thin film device described above are due to the fact that the garnet substrate has a stoichiometric This is mostly due to the fact that it is derived from a pool grown from the melt. That is, each Since the stoichiometric composition of the melt is not harmonic, the pool that grows from this melt , therefore the garnet substrate derived from it does not have an essentially uniform composition. stomach.

Therefore, the lattice constants of the film are often different from those of the substrate. , this causes distortion in the film and further induces defects in the film. , according to the present invention, an improved thin film device of the above configuration has a (non-stoichiometric) Forming a film on a garnet substrate derived from a pool grown from a coincident melt. It can be obtained by

Additionally, other devices were also found to exhibit defects. Because these devices are also This is because it contains a complex oxide component derived from a stoichiometric melt. A wave number multiplier is a device for doubling the frequency of incident light. Such a device Typically non-centrosymmetric complex oxide materials, such as strontium barium niobate tungsten bronze (e.g., J.C. Barfoot (J.C.)). , Burfoot) and G. W. Taylor, Pola Guie Electrics and There Applications (Pola r　Dielectrics　and　Their　Applicatiori s>, University of California, pp. 373-377, 1979), complex oxides To double the frequency uniformly over the body, single or multiple refractive indexes (two types) are required. (when using a grade or higher) must be constant, as the refractive index is sensitive to the composition. Previously, complex oxide materials were developed based on the idea that complex oxides with a uniform composition could be formed by stoichiometry. It was derived from a theoretical melt. However, 1. As mentioned above, This idea turns out to be wrong and produces devices that exhibit non-uniform refractive indices. . Therefore, in accordance with the present invention, the improved frequency multiplier has a non-stoichiometric harmonic composition can be obtained by using non-centrosymmetric complex oxide materials derived from .

Back side 5-1 In this example, a GSGG single cell of a predetermined composition was prepared using a modified Chick-Selsky technique. The conditions for crystal regrowth will be described below. Using X-ray fluorescence (XRF) to identify these crystal groups The uniformity of the formation was investigated and the data was used to determine the consistent melt composition of various materials and parameters. Data, devices, etc. are used for illustrative purposes only and unless otherwise noted. These factors are not intended to limit the scope of the invention.

First, stoichiometric sintering of Gds, * SCt, s Gaz, * Ott (1! Ceramic non-single crystal) was prepared and the lattice constant of stoichiometric GSGG was measured. Ta. The above lattice constants are used as XRF standards.

Next, the single material is removed from a high-frequency heated iridium crucible by the well-known Chick-Selsky technique. grew crystals. This charge material is mixed, uniformly compressed and pre-dried G dz　Os　1. It contained 35θg of SCzOs and Ga, O,. this When doping the crystal, the desired dopant (e.g. CreOs, Ndz According to one aspect of the present invention, a pre-dried oxide of Ox> is mixed into the charging material. If so, the basic tickselski technique can be modified to compress The powder was pre-combusted overnight at approximately 1373°.

The preferred range is about 1173° to 1973° for about 4 to 24 hours. The loading material is Melt at a temperature of 2148° and hold in this state for at least 1 hour before starting growth. Ta. The preferred range is about 2148-2173"K for about 1-3 hours. Crystals were grown along the <111> direction from 0300 seeds. 3.8++n/ A single crystal pool with a diameter of approximately 23 mm was grown at a linear growth rate of generated. However, the growth rate and rotation rate are not critical.

To ensure sample composition, reduce possible causes of sample weight loss. is important. These causes include: fllllll collected moisture and gases; This absorption is the main cause of compositional defects if the oxide is not pre-dried at high temperatures. Become. In particular, 5exes lost 4% of their weight after overnight baking. Approximately 137 Drying at a temperature of 3° seemed to remove all of the absorbed gas; (The evaporation of 21Gaz03 and the growth of 03GO are performed at a higher temperature than that of GGG. evaporation of gallium oxide becomes a more serious problem in GS(1;G).

Consists of 98% nitrogen and 2% oxygen to grow GGG The atmosphere is sufficiently oxidizing to suppress evaporation of QazOs. This atmosphere is GS It was used according to previous studies on the growth of GG. However, 97 capacitance - cent nitrogen and a 3 volume percent atmosphere were extracted from the GSGci melt by Gates It was found to be more effective in suppressing evaporation below the limit of detection. Unfortunate In particular, due to this relatively high oxygen concentration, some oxidation and iridium Evaporation from the crucible occurs. However, the speed of this process cannot be calibrated. and therefore can be made explicit. In addition, gallium oxide is tested as a compressed powder before melting. It can be evaporated from water. To reduce such evaporation, as mentioned above, The compressed powder is pre-combusted overnight at 1373° to convert Ga, O, into a low vapor pressure phase, e.g. d G a OsG da G at Os, G d4 G az 0ttx G tlSG as Ott and chemically bonded to Ga-3e oxide; (3 ) Sample flaking, a stubborn and irregular cause of sample weight loss, occurs during melting. This appears to result from flaking of tall compacted powder-filled materials. sample melt When flaking is high (flaking usually occurs with compacted powders of low density) , these flakes fall outside the crucible.

Therefore, the melting was done in two stages, melting half of the sample and then adding the rest). This prevented the sample from protruding beyond the top of the crucible.

Through these steps, a renewable garnet of known composition with no weight loss is produced. A functional sample was prepared. In order to increase the effect of non-unity distribution coefficients, each melt As much of the fraction as possible has grown into crystals (usually about 90%) at the top of each pool. And slices were cut out from the bottom and polished, composition of each slice GayoS c, Gas Ort was determined using XRF and well-known calculation methods. XRF de Using the data and the calculated values of X, y and 2, The GSGG melt composition (repeatedly changes until the composition of the This meant that all distribution coefficients were 1 within the measurement accuracy.

A pool grown from a melt with a stoichiometrically matched composition is sliced lengthwise. , polished, and inspected with a polarization strain meter. Birefringent photographs show distortions caused by vertical wrinkles in growth. and the facets of the growth interface in stoichiometric pools were clearly shown. Also, At the bottom of a crystal grown from a stoichiometric melt, there is a highly Dislocations and inclusion parts were observed. In contrast, the birefringence photograph shows the coincident melting of the present invention. The composition showed much less distortion in the pool grown. how much This distortion occurs near the top of the crystal where the interface is flat, and also near the top of the crystal where the interface is flat. This distortion is caused by the formation of facets on the growth surface. be.

Although the growth lines still exist, their severity is much lower and the crystalline wrinkles are still present. More than 90% of the liquid melt is clearly visible only near the edges. found in the case of stoichiometric crystals, despite the fact that they are crystallized No such interfacial failure was observed.

Typically, the technology of the present invention can crystallize 80-90 percent of the melt. However, conventional methods can only crystallize about 30-50%. Of course, this increases the yield from a given melt and thus lowers the unit cost. can be done.

Preferred harmonic compositions are based on chemical formula (4) or moiety sequence (represented by chemical formula (2)). Although closely related compositions were also found to have chemical formulas (1) and (3) ) are essentially identical compositions. Dodecahedron S The presence of 0.043 blending units of c (chemical formula (2)) was unexpected.

The dodecahedral Sc is derived from gadolinium scan by Brundle et al. (1973). was found in aluminum garnet, but so far observed in GSGG. It wasn't done. On the other hand, some gadolinium is 973), Gd content per compounding unit x > 3. G of Q Brundle et al. (1973 ) was predicted by

The lattice constant of the stoichiometric sintered sample was determined by the Exsen diffraction process. Carrier for Polycrystalline and Amorphous Materials (X -ray Diffraction Procedures for Polyc rystalline and Amorphous Materials)- 2nd edition, Siran e Willey & Sons (John Ga 11ey & 5on s), New York, 306 pages, H.B. Coorg, 1974. (B, P, I [1ug) and L.E. Alexander (L, E, Alex and). 12.583±O , OO1 angstrom is the value measured by Chou et al. mentioned above, 12. ．． 58 angstroms and Strocka et al. Journal of Research (Pbilips Journal of Re5e) Arch), Volume 33, Page 186, 12.5, calculated using the method of 1978. 87 angstroms, but according to Brundle et al. (1973) mentioned above. considerably higher than the calculated stoichiometric value of 12.554 angstroms, This explains why the conclusions of the present invention differ from the stoichiometric ones.

The lattice constant of the XRF slice is Acta Cry stallographica), 13S, 814 pages, 1960 and Acta ・Double L in Crystalographica, A311698 pages, 1975 - Measured using the method described by Bond (-1, Bond). Chemical formula The lattice constant of the coincident melt compounds of the present invention (2) and (4) is 1.2560 nanometers. (12,560 angstroms), and this bond is less than the stoichiometric value. ,0023 nanometers (0,023 angstroms) lower, this result is 0,0020 nanometers (0 , 020 angstrom), confirming the existence of dodecahedral Sc. ing.

Density at the top of one sample weighs the sample in air and in carbon tetrachloride It was measured by The data were consistent with the presence of dodecahedral Sc. 6. The measured value of 448 ± 0.006 g/d is based on the calculated composition value and lattice constant data. (6,441g/all), but the calculated stoichiometric composition is 6.419 g/-, which is clearly significantly lower.

Su JLL-Shadow The harmonic composition of LMA was determined according to the method used in Example 1.

That is, the starting materials used in the growth of LMA crystals, namely LagOs, M g　O and AlB12 at 1373° (pre-dried for 12 hours, 0-order, which removes moisture and gases contained in all materials, especially La, O, A stoichiometric mixture of pre-dried materials having a mass of 300 g is heated to The mixture was placed in a aluminum crucible and heated at 2283 to 2298° for 1 hour to melt. desired An LMA seed crystal with a C axis perpendicular to the growth direction was added to the melt, Collect at a rate of 2.5 millimeters (n) per hour while rotating at rp-. Ta. As a result, a rectangular shape with a thickness of 12 m+, a radius of 20 m, a length of 70 fi, and a mass of approximately 70 g. A prism-shaped LMA crystal was formed.

Measured on the lattice constant and along the longitudinal direction of the LMA crystal at 2951 Ta. These constants are substantially uniform, and their directivity is -21,974 people.

The density of LMA crystals was measured by immersion in CCI, and was 4.232±0. 001 g/aJ. If the crystal composition is stoichiometric, dense The degree was 4.2678/c+1. However, the formula L a e, *sM g Aj! The composition represented by ++, osOi* has a total of 4.235 g/aJ This value is close to the measured value, corresponding to the calculated density. Therefore, this composition It is considered to be a synthetic product.

FIG./ FIG.2 international search report ANNljCTo　a’HE　! NTERNATrONAL 5EARCE R EPORT ON

Claims (11)

[Claims] 1. In devices containing materials containing complex oxides, the composition of the complex oxides is harmonized. and at least 0.1 atomic percent of at least one constituent element. A device characterized by a difference from stoichiometry. 2. The above complex oxide continuously exhibits a single chemical phase between its melting temperature and 300°k. 2. The device according to claim 1, characterized in that: 3. Claim 1 or 2, wherein the device includes a solid-state laser. Apparatus described in section. 4. The above-mentioned solid-state laser is arranged in an optical resonator, and the above-mentioned material and a an active medium containing the complex oxide, and supplying pumping energy to the medium. to cause population inversion inside it, and stimulated emission of optical radiation from there. gadolinium scandium containing means, and wherein the complex oxide is doped with an activator. gallium garnet (GSGG), wherein the garnet is activated in the absence of the activator. The following composition: Gd2.9■■0.03Sc1.90■0.03Ga3.14■0.03O12 4. The device according to claim 3, characterized in that it has: 5. In the absence of the activator, the GSGG has the following composition: Gd2.937Sc1 ．． 905Ga3.138O12 as described in claim 4. equipment. 6. The above-mentioned solid-state laser is arranged in an optical resonator, and the above-mentioned material and a an active medium containing the complex oxide, and supplying pumping energy to the medium. to cause population inversion inside it, and stimulated emission of optical radiation from there. a lanthanum aluminate magnet containing means and in which the complex oxide is doped with an activator. (LMA), wherein the LMA in the absence of the activator has the following composition: La0.955■■. 01MgAl11.05■. 04O19 4. The device according to claim 3, characterized in that: 7. In the absence of the activator, the LMA has the following composition: La0.950M The device according to claim 6, characterized in that it has gAl11.050O19. Place. 8. Claim 1 or 2, wherein the device includes a polarization rotator. Apparatus described in section. 9. Claim 1 or 2, wherein the device comprises an optical isolator. The device according to paragraph 2. 10. Claim 1 or 2, wherein the device includes a cathode ray tube. Apparatus described in section. 11. Claim 1, or The device according to paragraph 2.