Method for controlling gallium content in gadolinium-gallium garnet scintillators

Abstract

Disclosed herein is a method including manufacturing a powder having a composition of formula (1),
M.sup.1.sub.aM.sup.2.sub.bM.sup.3.sub.cM.sup.4.sub.dO.sub.12(1) where O represents oxygen, M.sup.1, M.sup.2, M.sup.3, and M.sup.4 represents a first, second, third, and fourth metal that are different from each other, where the sum of a+b+c+d is about 8, where a has a value of about 2 to about 3.5, b has a value of 0 to about 5, c has a value of 0 to about 5 d has a value of 0 to about 1, where b and c, b and d, or c and d cannot both be equal to zero simultaneously, where M.sup.1 is a rare earth element comprising gadolinium, yttrium, lutetium, scandium, or a combination of thereof, M.sup.2 is aluminum or boron, M.sup.3 is gallium, and M.sup.4 is a dopant; and heating the powder to a temperature of 500 to 1700 C. in an oxygen containing atmosphere to manufacture a crystalline scintillator.

Claims

1. A method comprising: blending together nanometer and/or micrometer-sized particles that comprise M.sup.1, M.sup.2, M.sup.3 and M.sup.4 to produce a powder having a composition that comprises the formula (1):
M.sup.1.sub.aM.sup.2.sub.bM.sup.3.sub.cM.sup.4.sub.dO.sub.12(1) where O represents oxygen, M.sup.1, M.sup.2, M.sup.3, and M.sup.4 represent a first, second, third, and fourth metal that are different from each other, the sum of a+b+c+d is about 8, where a has a value of about 2 to about 3.5, b has a value of 2 to about 5, c has a value of 1 to about 5, and d has a value of 0.001 to about 1, where b and c, b and d, or c and d cannot both be equal to zero simultaneously, M.sup.1 is a rare earth element comprising gadolinium, yttrium, lutetium, scandium, or a combination of thereof, M.sup.2 is aluminum or boron, M.sup.3 is gallium, and M.sup.4 is a dopant and comprises one of thallium, copper, silver, lead, bismuth, indium, tin, antimony, tantalum, tungsten, strontium, barium, boron, magnesium, calcium, yttrium, scandium, lanthanum, lutetium, praseodymium, terbium, ytterbium, samarium, europium, holmium, dysprosium, erbium, thulium or neodymium; heating the powder to a temperature of 500 to 2000 C. to melt the powder; and heating the melt to a temperature of 800 to 1700 C. in an oxygen containing atmosphere to manufacture a crystalline scintillator; where the heating of the powder to a temperature of 500 to 2000 C. to melt the powder is conducted prior to the heating of the melt to a temperature of 800 to 1700 C.

2. The method of claim 1, where for M.sup.1, a portion of the gadolinium can be substituted with one or more of yttrium, lutetium, lanthanum, terbium, praseodymium, neodymium, samarium, europium, dysprosium, holmium, erbium, ytterbium, or combinations thereof.

3. The method of claim 1, where M.sup.2 is aluminum.

4. The method of claim 1, where a has a value about 2.4 to about 3.2, b has a value of about 2 to about 3, c has a value of about 1 to about 4, and d has a value of about 0.001 to about 0.5.

5. The method of claim 4, where a has a value of about 3, b has a value of about 2.1 to about 2.5, c has a value of about 2 to about 3, and d has a value of about 0.003 to about 0.3.

6. The method of claim 1, where the blending is conducted in a ball mill or a roll mill.

7. The method of claim 1, where the powder has average particle sizes of 5 nanometers to 500 micrometers.

8. The method of claim 1, where the crystalline scintillator comprises a single crystal, a polycrystalline material or a combination thereof.

9. The method of claim 1, further comprises producing a single crystal scintillator by the Czochralski method, the Bridgman technique, the Kyropoulos technique, or the Verneuil technique from the crystalline scintillator.

10. An article manufactured by a method comprising: manufacturing a powder having a composition of formula (1),
M.sup.1.sub.aM.sup.2.sub.bM.sup.3.sub.cM.sup.4.sub.dO.sub.12(1) where O represents oxygen, M.sup.1, M.sup.2, M.sup.3, and M.sup.4 represents a first, second, third, and fourth metal that are different from each other, the sum of a+b+c+d is about 8, where a has a value of about 2 to about 3.5, b has a value of 0 to about 5, c has a value of 0 to about 5, and d has a value of 0 to about 1, where b and c, b and d, or c and d cannot both be equal to zero simultaneously, M.sup.1 is a rare earth element comprising gadolinium, yttrium, lutetium, scandium, or a combination of thereof, M.sup.2 is aluminum or boron, M.sup.3 is gallium, and M.sup.4 is a dopant and comprises one of thallium, copper, silver, lead, bismuth, indium, tin, antimony, tantalum, tungsten, strontium, barium, boron, magnesium, calcium, yttrium, scandium, lanthanum, lutetium, praseodymium, terbium, ytterbium, samarium, europium, holmium, dysprosium, erbium, thulium or neodymium; and heating the powder to a temperature of 500 to 2000 C. to melt the powder; heating the melt to a temperature of 500 to 1700 C. in an oxygen containing atmosphere to manufacture a crystalline scintillator; where the heating of the powder to a temperature of 500 to 2000 C. to melt the powder is conducted prior to the heating of the melt to a temperature of 800 to 1700 C.

11. The article of claim 10, where the article is used in an imaging device.

Description

DETAILED DESCRIPTION

(1) Disclosed herein is a method for manufacturing polycrystalline or single crystal garnet that comprises gadolinium and gallium (hereinafter garnet) and that use gallium oxide as a starting raw material. The composition contains one or more elements in addition to gadolinium and gallium in the garnet. In other words, in its simplest form the garnet comprises 3 or more elements.

(2) In an embodiment, the garnets have the formula:
M.sup.1.sub.aM.sup.2.sub.bM.sup.3.sub.cM.sup.4.sub.dO.sub.12(1)
where O represents oxygen, M.sup.1, M.sup.2, M.sup.3, and M.sup.4 represents a first, second, third, and fourth metal that are different from each other, where the sum of a+b+c+d is about 8, where about is defined as 10% deviation from the desirable value, where a has a value of about 2 to about 3.5, preferably about 2.4 to about 3.2, and more preferably about 3.0, b has a value of 0 to about 5, preferably about 2 to about 3, and more preferably about 2.1 to about 2.5, where b and c, b and d, or c and d cannot both be equal to zero simultaneously, where c has a value of 0 to about 5, preferably about 1 to about 4, preferably about 2 to about 3, and more preferably about 2.1 to about 2.5, d has a value of 0 to about 1, preferably about 0.001 to about 0.5, and more preferably 0.003 to 0.3. In one embodiment, b has a value of 2 to about 5, c has a value of 1 to about 5, and d has a value of 0.001 to about 1, where b and c, b and d, or c and d cannot both be equal to zero simultaneously.

(3) In the formula (1), M.sup.1 is a rare earth element including but not being limited to gadolinium, yttrium, lutetium, scandium, or a combination of thereof. M.sup.1 is preferably gadolinium. In an embodiment M.sup.2 is aluminum or boron, M.sup.3 is gallium, and M.sup.4 is a dopant and comprises one or more of thallium, copper, silver, lead, bismuth, indium, tin, antimony, tantalum, tungsten, strontium, barium, boron, magnesium, chromium, calcium, cerium, yttrium, scandium, lanthanum, lutetium, praseodymium, terbium, ytterbium, samarium, europium, holmium, dysprosium, erbium, thulium or neodymium.

(4) For M.sup.1, some of the gadolinium can be substituted with one or more of yttrium, lutetium, lanthanum, terbium, praseodymium, neodymium, cerium, samarium, europium, dysprosium, holmium, erbium, ytterbium, or combinations thereof. In an embodiment, some gadolinium can be substituted with yttrium. M.sup.3 is preferably aluminum.

(5) In an embodiment, the dopant M.sup.4 includes Tl+, Cu+, Ag+, Au+, Pb2+, Bi3+, In+, Sn2+, Sb3+, Ce3+, Pr3+, Eu2+, Yb2+, Nb5+, Ta5+, W6+, Sr2+, B3+, Ba2+, Mg2+, Ca2+, Cr3+, or combinations thereof.

(6) The method comprises manufacturing nanometer and micrometer sized powders of the garnet (and associated oxides and hydroxides that can be converted to the garnet upon heating) and heating these powders to a temperature that is lower than the 1850 C. used for producing single crystals in the Czochralski process. In some embodiments, the nanometer and micrometer sized powders are heated to temperatures of 500 to 1700 C. in an oxygen containing atmosphere to form polycrystalline or single crystal garnets that have the desired stoichiometry without any loss of gallium oxide due to evaporation. The powders can optionally be heated to a temperature of up to 2000 C. to melt them prior to heating them to a temperature of up to 1700 C. in an oxygen containing atmosphere to form polycrystalline or single crystal garnets. The garnet can comprise a combination of a polycrystalline and single crystal material.

(7) Without being limited to theory, it is believed that the gallium ions in each of the compositions of the formula (1) are strongly bonded to the other elements of the composition and so the energy needed to decompose such a molecule is much higher than the energy to decompose the gallium oxide.

(8) The method for manufacturing the nanometer and micrometer-sized powders of the gadolinium-gallium garnet comprises dissolving the desired metal oxides in the desired stoichiometric ratio in a strong acid. To the solution comprising the acid and the dissolved metal oxides is added an excess amount of a strong base. The addition of the base promotes the formation of a precipitate. The precipitate is then separated from the solution using a separation process to produce the garnet and associated unreacted oxides in a powdered form. A crystal boule can then be manufactured from the powders by heating them to temperatures of 500 to less than 2000 C., preferably 850 to 1900 C., and more preferably 900 to 1800 C. to melt the powder. Following the melting, the melted material can be heated to a temperature of 800 to 1700 C., preferably 900 to 110 C., and more preferably 950 to 1050 C. in an oxygen containing atmosphere, to produce in the next stage polycrystalline or single crystals that can be used as scintillators.

(9) The raw materials used for the manufacture of garnets generally comprise gallium oxide (Ga.sub.2O.sub.3) and gadolinium oxide (Gd.sub.2O.sub.3), and these materials are added to a reaction vessel in the desired stoichiometric quantities. The gallium oxide (Ga.sub.2O.sub.3) and gadolinium oxide (Gd.sub.2O.sub.3) are generally added to the reaction vessel in a molar ratio of 1:0.5 to 0.5:1, preferably 1:0.75 to 0.75:1, and most preferably 0.9:1 to 1:0.9. In an exemplary embodiment, the gallium oxide (Ga.sub.2O.sub.3) and gadolinium oxide (Gd.sub.2O.sub.3) are generally added to the reaction vessel in a molar ratio of 1:1. A preferred form of gallium oxide is -gallium (III) oxide. A preferred form of aluminum oxide is -alumina (-Al.sub.2O.sub.3).

(10) Additional metal oxides such as oxides of cerium, aluminum, scandium, yttrium, lanthanum, lutetium, praseodymium, terbium, chromium, ytterbium, neodymium, or combinations thereof can also be added to the reaction vessel in the desired stoichiometric quantities. Exemplary additional metal oxides are cerium dioxide (CeO.sub.2), aluminum oxide (Al.sub.2O.sub.3), yttrium oxide (Y.sub.2O.sub.3), lutetium (III) oxide (Lu.sub.2O.sub.3), scandium (III) oxide (Sc.sub.2O.sub.3), or a combination thereof. It is desirable for the metal oxides used in the manufacturing of the garnet to have a purity of 99.99% or greater.

(11) In some embodiments, one or more of cerium dioxide (CeO.sub.2), yttrium oxide (Y.sub.2O.sub.3), lutetium (III) oxide (Lu.sub.2O.sub.3), and scandium (III) oxide (Sc.sub.2O.sub.3) can be present in the garnet in addition to the aluminum oxide (Al.sub.2O.sub.3). The other metal oxides can be present in a mole ratio of 0.1:1 to 1:0.1, preferably 0.2:1 to 1:0.2, and more preferably 0.5:1 to 1:0.5 with respect to the gallium oxide (Ga.sub.2O.sub.3).

(12) In an exemplary embodiment, the garnet includes only aluminum oxide as the additional metal oxide component. In these embodiments, the garnet includes aluminum oxide in a molar ratio of 2:3 to 3:2 with respect to the number of moles of the gallium oxide (Ga.sub.2O.sub.3). In other embodiments, the garnet can also contain cerium oxide in a molar ratio of 1:3 to 3:1 with respect to the number of moles of the gallium oxide (Ga.sub.2O.sub.3), when the garnet also contains aluminum oxide.

(13) The raw materials (e.g., a mixture comprising gallium oxide, gadolinium oxide, aluminum oxide and/or cerium oxide) are then dissolved in a strong acid to form a solution. Examples of strong acids are hydrochloric acid, nitric acid, sulfuric acid, or a combination thereof. In an exemplary embodiment, the strong acid is hydrochloric acid present in an amount of 25 to 50 mole percent, preferably 30 to 40 mole percent in water.

(14) The solution is prepared by agitation the raw materials in the hydrochloric acid. Agitation can be accomplished by stirring, use of ultrasonic sonication, sparging, physical vibration, or combinations thereof. The solution can be manufactured at any temperature though room temperature is preferred.

(15) After the oxides have dissolved, dopants can be added to the solution. Suitable dopants are cerium, aluminum, scandium, yttrium, lanthanum, lutetium, praseodymium, terbium, ytterbium, neodymium, or a combination thereof. These dopants can be added to the solution in the form of the respective metal halides. Preferred halides are chlorides, bromides, or a combination thereof. It is to be noted that these dopants can be added to the solution even if it contains a certain amount of the dopant already previously added in the form of a metal oxide. For example, cerium can be added to the solution in the form of cerium chloride, cerium bromide, or a combination thereof, even if the solution contains cerium that was previously added in the form of cerium oxide as detailed above.

(16) The metal halide can be added as a dopant to the solution of the garnet in a mole ratio of 0.1:1 to 1:0.1, preferably 0.2:1 to 1:0.2, and more preferably 0.5:1 to 1:0.5 with respect to the number of moles of gallium oxide (Ga.sub.2O.sub.3).

(17) The solution is then treated with an excess of a strong base in a reaction vessel to facilitate a precipitation of the dissolved metal oxides. The solution is added to the base in a reaction vessel under strong agitation. Examples of strong bases are ammonium hydroxide, ammonium bicarbonate, potassium hydroxide, sodium hydroxide, or the like, or a combination thereof. The strong base is dissolved in water in an amount of 15 to 50 mole percent, preferably 20 to 40 mole percent.

(18) The molar ratio of acid present in the solution to the base is greater than 1:1.10, preferably greater than 1:1.20, and more preferably greater than 1:1.50.

(19) The addition of the solution to the base causes a precipitation of the garnet. The precipitate is subjected to a separation process to extract the garnet from the remainder to the solution. Separation processes include centrifugation, filtration, decantation, or a combination thereof. Filtration is preferred.

(20) The filtrate is subjected to additional washing steps with water to remove traces of acid, salts, and base from the precipitate. The precipitate in powdered form comprises the garnet (along with one or more additional elements) as well as oxides and hydroxides of the original metals used in the reaction vessel. The precipitate obtained after the separation of the garnet is in the form of particles that have a particle size in the nanometer range and in the micrometer range. The particles (in powder form) have an average particle size that range from 5 nanometers to 500 micrometers, preferably 10 nanometers to 50 micrometers, and more preferably 1 to 20 micrometers. The radius of gyration of the particles is measured to determine average particle size. Light scattering or electron microscopy can be used to determine the particle size. In an embodiment, the powder has average particle sizes of 5 nanometers to 500 micrometers.

(21) In another embodiment, nanometer and/or micrometer-sized particles of the aforementioned particles may be manufactured separately (or purchased separately) and blended together to form the composition of formula (1) above. For example, nanometer and/or micrometer-sized powders of the gadolinium-gallium garnet can be blended together in the desired stoichiometric quantities along with other particles (e.g., metal oxide particles, dopant particles) to form an intimate mixture. The intimate mixture is then heated to the elevated temperatures detailed below to form a single crystal. In other words, nanometer and/or micrometer-sized metal oxide powders of M.sup.1, M.sup.2 and M.sup.3 may be blended together along with halides of M.sup.4 to produce an intimate mixture that is then heated as detailed below to form the single crystal.

(22) In an embodiment, nanometer or micrometer-sized powders of gallium oxide (Ga.sub.2O.sub.3) and gadolinium oxide (Gd.sub.2O.sub.3) are added to a blender or mixer in the stoichiometric ratios detailed above. Nanometer or micrometer-sized metal oxide powders (such as those listed abovee.g., oxides of cerium, aluminum, scandium, yttrium, lanthanum, lutetium, praseodymium, terbium, chromium, ytterbium, neodymium, or combinations thereof) are added to the blender or mixer in the stoichiometric quantities listed above. Nanometer or micrometer-sized aluminum oxide may also be added to the blender or mixer. The dopant (also in nanometer or micrometer-sized particles) may be added to the blender or mixer in the form of a salt (e.g., in the form of a metal halide) or as a metal oxide. Other reactants listed above may also be added to the blender or mixer. The powders thus added to the blender or mixer are subjected to blending to form an intimate mixture.

(23) The powders obtained from solution precipitation or from the intimate mixture can be initially mixed and optionally further pulverized in a ball mill, roll mill or other pulverizing device. The pulverized powders can then be subjected to an optional sieving process if it is desirable to use particles of a particular size.

(24) The powders of the garnet are then processed at temperatures of 800 to 1700 C., preferably 900 to 1100 C., and more preferably 950 to 1050 C. in an oxygen containing atmosphere, to produce in the next stage polycrystalline or single crystals that can be used as scintillators.

(25) Single crystals can be produced by the Czochralski method, the Bridgman technique, the Kyropoulos technique, and the Verneuil technique.

(26) In the Czochralski method, the powder to be grown is melted under a controlled atmosphere in a suitable non-reacting container. By controlling the furnace temperature up to 1700C., the material is melted. A seed crystal is lowered to touch the molten charge. When the temperature of the seed is maintained very low compared to the temperature of the melt (by a suitable water cooling arrangement), the molten charge in contact with the seed will solidify on the seed. Then the seed is pulled at a controlled rate. The majority of crystals are produced by pulling from the melt. Crystals of dimensions 3 to 40 centimeters can be grown using this method.

(27) In the Bridgman (pulling method) technique, the material is melted in a vertical cylindrical container (called an ampoule), tapered conically with a point bottom. The container is lowered slowly from the hot zone of the furnace having a temperature up to 1700 C. into the cold zone. The rates of movement for such processes range from about 1-30 mm/hr. Crystallization begins at the tip and continues usually by growth from the first formed nucleus. Due to a directed and controlled cooling process of the cast, zones of aligned crystal lattices are created. In other words, a single crystal can be created.

(28) In the Kyropoulos technique, the crystal is grown in a larger diameter than in the aforementioned two methods. As in the Czochralski method, here too a seed is brought into contact with the melt and is not raised much during the growth, i.e., part of the seed is allowed to melt and a short, narrow neck is grown. After this, the vertical motion of the seed is stopped and growth proceeds by decreasing the power into the melt.

(29) In the Verneuil technique, (flame fusion) a fine dry powder of size 1 to 20 micrometers of the material to be grown is shaken through the wire mesh and allowed to fall through the oxy-hydrogen flame. The powder melts and a film of liquid is formed on the top of a seed crystal. This freezes progressively as the seed crystal is slowly lowered. The art of the method is to balance the rate of charge feed and the rate of lowering of the seed to maintain a constant growth rate and diameter. By this method ruby crystals are grown up to 90 millimeters in diameter. This technique is widely used for the growth of synthetic gems and variety of high melting oxides.

(30) Examples of polycrystalline or single crystals grown by this method have the following formulasGd.sub.3Al.sub.2Ga.sub.3O.sub.12 (GAGGgadolinium-aluminum-gallium garnet), Gd.sub.3Ga.sub.2.5Al.sub.2.5O.sub.12 (GGAGgadolinium-gallium-aluminum garnet), Gd.sub.1.5Y.sub.1.5Ga.sub.2.5Al.sub.2.5O.sub.12 (GYGAGgadolinium-yttrium-gallium-aluminum garnet), Gd.sub.3Sc.sub.2Ga.sub.3O.sub.12 (GSGGgadolinium-scandium-gallium-garnet), or Gd.sub.1.5Lu.sub.1.5Al.sub.1.5Ga.sub.1.5O.sub.12. Each of the polycrystalline or single crystals represented by the aforementioned formulas can be doped with cerium if desired.

(31) The polycrystalline or single crystals manufactured using nanometers and micrometer size powders have a more consistent stoichiometry when compared with materials manufactured using melted oxide compounds. Scintillator materials manufactured by this method can be used in imaging devices such as, for example, positron emission tomography machines.

(32) It is to be noted that all ranges detailed herein include the endpoints. Numerical values from different ranges are combinable. The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function and/or objectives of the compositions, methods, and articles. Combinations is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms a and an and the do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Or means and/or unless clearly stated otherwise. Reference throughout the specification to some embodiments, an embodiment, and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

(33) While the invention has been described with reference to some embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.