TREA

Preparation of superconducting Tl-Ba-Ca-Cu-O thin films by Tl.sub.2 O.sub.3

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Information

  • Patent Grant
  • 5112800
  • Patent Number
    5,112,800
  • Date Filed
    Monday, July 30, 1990
    34 years ago
  • Date Issued
    Tuesday, May 12, 1992
    32 years ago
Information
Abstract
A process of making high temperature Tl-based superconductors is disclosed. The process includes the steps of reacting solid Ba-Ca-Cu-oxides with Tl.sub.2 O.sub.3 vapor. The process allows high quality Tl-based superconductors to be easily fabricated.
Description

BACKGROUND OF THE INVENTION
The present invention relates generally to high temperature superconductors More specifically, the present invention relates to the fabrication of the high temperature Tl-Ba-Ca-Cu-O superconductors.
U.S. patent application Ser. No. 155,247 now U.S. Pat. No. 4,962,083, filed in the name of the inventors, of the present patent application discloses, in part, Tl-Ba-Ca-Cu-O superconductors that were discovered by the present inventors. These Tl-Ba-Ca-Cu-O superconductors have a transition temperature up to and above 120 K, this transition temperature, the inventors of the present patent application believe, is the highest to date among all existing high temperature superconductors
For useful operation, the transition temperature of a superconductor typically must be at least 1/3 higher than the temperature of operation. For this reason, the Tl-Ba-Ca-Cu-O system has been called the first real liquid nitrogen temperature superconducting system.
The present existing procedures of preparing Tl-based superconductors involve the mixing of all component elements followed by a final sinter. Since Tl.sub.2 O.sub.3 evaporates easily, the quality of the Tl-samples is not easily controlled. In addition, in view of its toxicity, Tl.sub.2 O.sub.3 presents an additional set of difficulties during the fabrication of these types of superconductors.
An improved method for making Tl-Ba-Ca-Cu-O superconductors would be desirable for many reasons such a process would: (1) allow Tl-based superconductors to be easily constructed .+-.n the forms of complex bulk components, wires and fibers, and thick and thin films; (2) minimize the toxicity problem caused by Tl compounds; and (3) provide low cost processing and manufacturability.
Accordingly, there is a need for a new process of making Tl-based high temperature superconductors.
SUMMARY OF THE INVENTION
The present invention provides a new process for making Tl-based superconductors The process includes the step of reacting vapor phase Tl.sub.2 O.sub.3 and solid Ba-Ca-Cu-oxides. Pursuant to the method of the present invention the Tl-based superconductors are produced in approximately two steps. The first step is the preparation of Ba-Ca-Cu-oxides; and the second step is the processing of the Ba-Ca-Cu-oxides by the use of Tl.sub.2 O.sub.3 vapor to form high quality Tl-based superconductors. Pursuant to the present invention, the method of making Tl-based superconductors is simplified and only requires the manufacture of Ba-Ca-Cu-oxides and a final Tl.sub.2 O.sub.3 vapor phase treatment.
Accordingly, an advantage of the present invention is that it provides a method which can easily produce Tl-based superconductors.
A further advantage of the present invention is to provide high quality Tl-based superconductors.
A still further advantage of the present invention is that it provides a method which can make Tl-based superconductors in the forms of bulk materials, wires or fibers, thick and thin films.
Furthermore, an advantage of the present invention is that certain elements can be added into the precursor Ba-Ca-Cu-oxides to satisfy specific needs for various applications.
An additional advantage of the present invention is that the Ba-Ca-Cu-oxides can be made in the recrystalline form of a melt.
Still another advantage of the present invention is that Tl.sub.2 O.sub.3 -vapor-processing can be carried out in closed containers.
Yet another advantage of the present invention is that it provides a method of making Tl-based superconductors which minimizes contamination by Tl compounds.
Additional advantages and features of the present invention are described in and will be apparent from, the detailed description of the presently preferred embodiments and the drawings.





BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 illustrates the relationship of electrical resistance versus temperature for a Tl.sub.2 O.sub.3 -vapor-processed Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 sample made pursuant to the method of the present invention.
FIG. 2 illustrates the relationship of electrical resistance versus temperature for a Tl.sub.2 O.sub.3 -vapor-processed BaCa.sub.3 Cu.sub.3 O.sub.7 sample made pursuant to the method of the present invention.
FIG. 3 illustrates the relationship of electrical resistance versus temperature for a Tl.sub.2 O.sub.3 -vapor-processed Ba.sub.2 CaCu.sub.2 O.sub.5 sample made pursuant to the method of the present invention.
FIG. 4 illustrates resistance-temperature dependence for a Tl.sub.2 O.sub.3 -vapor-processed Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 thick wire sample made pursuant to the method of the present invention.
FIG. 5 illustrates resistance-temperature dependence for a Tl.sub.2 O.sub.3 -vapor-processed Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 recrystallized thick film sample made pursuant to the method of the present invention.
FIG. 6 illustrates resistance as a function of temperature for a Tl.sub.2 O.sub.3 -vapor-processed In.sub.2 Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.10 sample made pursuant to the present invention.
FIG. 7 illustrates the (Tl-of electrical resistance versus temperature for a Tl.sub.2 O.sub.3 vapor processed Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 thin film (Tl-223) made pursuant to the present invention and a Tl.sub.2 O.sub.3 vapor processed Ba.sub.2 Ca.sub.3 Cu.sub.3 O.sub.8 thin film (T9-223) made pursuant to the present invention.





DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS
The present invention provides a method for making high quality Tl-Ba-Ca-Cu-O superconductors. The present invention is based on reactions between vapor phase Tl.sub.2 O.sub.3 and solid Ba-Ca-Cu-oxides. The fabrication procedure for the making Tl-Ba-Ca-Cu-O superconductors according to the present invention can be divided into two steps: (1) preparation of Ba-Ca-Cu-oxides; and (2) Tl.sub.2 O.sub.3 -vapor-processing of the Ba-Ca-Cu-oxides to form Tl-Ba-Ca-Cu-O superconductors The present invention simplifies the fabrication of Tl-Ba-Ca-Cu-oxides to the fabrication of Ba-Ca-Cu-oxides, and minimizes problems caused by the toxicity and volatility of Tl compounds. The present invention allows high quality Tl-based superconductors to be easily made in the forms of complex bulk components, wires and fibers, and thick and thin films, and provides low cost processing and manufacturability of Tl-based superconductors.
Pursuant to the method of the present invention, first Ba-Ca-Cu-oxides are produced. Preferably compounds, the Ba-Ca-Cu-oxides are produced by grinding and mixing one of the following groups of: BaCO.sub.3, CaO, CuO; BaCO.sub.3, CaCO.sub.3, CuO; BaO.sub.2, CaO.sub.2, CuO; or BaO.sub.2, CaO, CuO. In a preferred embodiment, the molar ratio is 2:2:3, respectively, of the components. In an embodiment, the molar ratio of BaCO.sub.3, CaO, CuO is 1:3:3.
Preferably, after the grinding and mixing the powder is heated. Preferably the powder is heated to approximately 925.degree. C. for approximately 24 to about 48 hours with intermediate grindings.
In an embodiment the resultant powder has the following nominal composition:
BaCa.sub.x Cu.sub.y O.sub.I+x+y
wherein:
O.ltoreq.X.ltoreq.100; and O.ltoreq.y.ltoreq.100.
In an embodiment, the powder is then pressed into a pellet.
After the powder is prepared, or pressed into a pellet, it can then be reacted with Tl.sub.2 O.sub.3 vapor. The Tl.sub.2 O.sub.3 vapor can be produced by heating Tl.sub.2 O.sub.3 with the Ba-Ca-Cu-oxides or heating any Tl-containing compound that can form Tl.sub.2 O.sub.3 vapor upon being heated in oxygen to, for example, approximately 900.degree. C.
In an embodiment, prior to being reacted with Tl.sub.2 O.sub.3 vapor, the powder is mixed with a compound chosen from the group consisting of: Tl.sub.2 O.sub.3, MgO, AgO, K.sub.2 O, Na.sub.2 O, ZrO.sub.2, In.sub.2 O.sub.3, HgO, Bi.sub.2 O.sub.3, PbO.sub.2, and KCl. The resultant mixture is then reacted with Tl.sub.2 O.sub.3 vapor.
In an embodiment of the method of the present invention, a Ba-Ca-Cu-oxide film is created and processed with Tl.sub.2 O.sub.3 to creating a superconducting thin film.
By way of example and not limitation, examples of the of the present invention process of making high quality Tl-Ca-Ba-Cu-O superconductors will now be given.
EXAMPLE 1
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. CaO,
3. BaCO.sub.3,
4 CuO.
B. The following procedure was followed:
1. A mixture of a two molar portion of BaCO.sub.3, a two molar portion of CaO, and a three molar portion of CuO was ground with an agate mortar and pestle, heated in air at 925.degree. C. for more than 24 hours (with several intermediate grindings) to obtain an uniform black Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder.
2. The resulting Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder was completely ground, and pressed into a pellet.
3. The pellet was heated at about 925.degree. C. in a tube furnace for about 10 minutes.
4. The heated pellet was then taken out of the furnace and cooled in air to room temperature.
5. A small amount (approximately 0.1 to about 0.2 gm) of Tl.sub.2 O.sub.3 was put in a platinum boat, and the platinum boat was placed in a quartz boat.
6. The cooled pellet was placed over the platinum boat.
7. The quartz boat, containing the platinum boat, was placed into a tube furnace which had been heated to about 900.degree. C., and was heated for about 3 minutes in flowing oxygen.
8. The sample was then furnace-cooled to room temperature in flowing oxygen, the sample was then taken out of the furnace.
The samples prepared by this procedure formed a layer of superconductive compounds on their bottom surface, which had an onset temperature of above 120 k and a zero resistance temperature of above 100 k. FIG. 1 illustrates the resistance as a function of temperature for a Tl.sub.2 O.sub.3 -vapor-processed Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 sample made pursuant to this example. This sample reaches zero resistance at 104 k. FIG. 4 illustrates comparable behavior for a Tl.sub.2 O.sub.3 vapor-processed Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 thick wire precursor made by a similar procedure.
EXAMPLE 2
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. CaO,
3. BaCO.sub.3,
4. CuO.
B. The following procedure was followed:
1. A mixture of a one molar portion of BaCO.sub.3, a three molar portion of CaO, and a three molar portion of CuO was ground with an agate mortar and pestle, heated in air at 925.degree. C. for more than 24 hours (with several intermediate grindings) to obtain a uniform black BaCa.sub.3 Cu.sub.3 O.sub.7 powder.
2. The resulting BaCa.sub.3 Cu.sub.3 O.sub.7 powder was completely ground, and pressed into a pellet.
The pellet was heated at approximately 925.degree. C. in a tube furnace for about 10 minutes.
4. The heated pellet was then taken out of the furnace and cooled in air to room temperature.
5. A small amount (approximately 0.1 to about 0.2 gm) of Tl.sub.2 O.sub.3 was placed in a platinum boat, and the platinum boat was then placed in a quartz boat.
6. The cooled pellet was placed over the platinum boat.
7. The quartz boat was put into the tube furnace which had been heated to about 900.degree. C., and was heated for about 3 minutes in flowing oxygen.
8. The sample was then furnace-cooled to room temperature in flowing oxygen, and the sample was then taken out of the furnace.
The samples prepared by this procedure formed a layer of superconductive compounds on their bottom surface, which had an onset temperature of above 120 K, and a zero resistance temperature of above 100 K. FIG. 2 illustrates resistance as a function of temperature for a Tl.sub.2 O.sub.3 -vapor-processed BaCa.sub.3 Cu.sub.3 O.sub.7 sample prepared pursuant to this example. This sample reaches zero resistance at 110 K. FIG. 3 illustrates comparable behavior for a Ba.sub.2 CaCu.sub.2 O.sub.5 precursor similarly prepared.
EXAMPLE 3
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. CaCO.sub.3,
3. BaCO.sub.3,
4 CuO.
B. The following procedure was followed:
1. A mixture of a two molar portion of BaCO.sub.3, a two molar portion of CaCO.sub.3, and a three molar portion of CuO was ground with an agate mortar and pestle, heated in air at approximately 925.degree. C. for more than 24 hours (with several intermediate grindings) to obtain a uniform black Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder.
2. The resulting Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder was completely ground, and pressed into a pellet.
3. The pellet was heated at approximately 925.degree. C. in a tube furnace for about 10 minutes.
4. The heated pellet was then taken out of the furnace and cooled in air to room temperature.
5. A small amount (approximately 0.1 to about 0.2 gm) of Tl.sub.2 O.sub.3 was put in a platinum boat, and the platinum boat was placed in a quartz boat.
6. The cooled pellet was placed over the platinum boat.
7. The quartz boat was put into the tube furnace which had been heated to approximately 900.degree. C., and was heated for about 3 minutes in flowing oxygen.
8. The sample was then furnace-cooled to room temperature in flowing oxygen, and was then removed from the furnace.
The samples prepared by this procedure formed a layer of superconductive compounds on their bottom surface, which have an onset temperature of above 120 K, a midpoint of about 110 K, and a zero resistance temperature of above 100 K.
EXAMPLE 4
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. CaO,
3. BaCO.sub.3,
4. CuO.
B. The following procedure was followed:
1. A mixture of a two molar portion of BaCO.sub.3, a two molar portion of CaO, and a three molar portion of CuO was ground with an agate mortar and pestle, heated in air at 925.degree. C. for more than 24 hours (with several intermediate grindings) to obtain a uniform black Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder.
2. The resulting Ba.sub.2 Ca.sub.2 Cu.sub.3 powder was placed on a platinum substrate which was put in a quartz boat, and was heated in a tube furnace at approximately 950 to about 1000.degree. C. for 3-5 minutes in flowing oxygen.
3. The quartz boat was then taken out of the furnace. The Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder had melted completely, forming a layer of recrystalline Ba-Ca-Cu-O.
4. A small amount (approximately 0.1 to about 0.2 gm) of Tl.sub.2 O.sub.3 was put in a platinum boat, and the platinum boat was placed in a quartz boat.
5. The platinum substrate was put over the platinum boat with the molten Ba-Ca-Cu-O facing downward.
6. The quartz boat was put into the tube furnace which had been heated to about 900.degree. C., and was heated for about 3 minutes in flowing oxygen.
7. The sample was then furnace-cooled to room temperature in flowing oxygen, and was then taken out of the furnace.
A Tl.sub.2 O.sub.3 -vapor-processed Ba.sub.2 Cu.sub.3 O.sub.7 thick film was produced that was superconducting. FIG. 5 illustrates resistance as a function of temperature for a Tl.sub.2 O.sub.3 -vapor-processed Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 recrystallized thick film created pursuant to this example. The film had an onset temperature of above 120 K and reached zero resistance at about 111 K.
This experiment also shows that thin film Tl-Ca-Ba-Cu-O superconductors can be made using the Tl.sub.2 O.sub.3 vapor process with appropriately deposited Ca-Ba-Cu-O precursor thin films. These thin films can be produced by depositing a thin-film of Ca-Ba-Cu-O precursor utilizing known techniques of physical or chemical deposition. These techniques include, inter alia, sputtering, evaporation, ablation, electrodeposition, electroless deposition, and chemical vapor deposition. After the thin film of Ca-Ba-Cu-O is produced, it can then be reacted with Tl.sub.2 O.sub.3 vapor, for example, by placing Tl.sub.2 O.sub.3 in a boat under or near the precursor and heating the boat.
EXAMPLE 5
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. In.sub.2 O.sub.3,
3. CaO,
4. BaCO.sub.3,
5. CuO.
B. The following procedure was followed:
1. A mixture of two molar portion of BaCO.sub.3, a two molar portion of CaO, and a three molar portion of CuO was ground with an agate mortar and pestle, heated in air at approximately 925.degree. C. for more than 24 hours (with several intermediate grindings) to obtain a uniform black Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder.
2. A one molar portion of the resulting Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder was mixed with a one molar portion of In.sub.2 O.sub.3, and was completely ground and pressed into a pellet.
3. The pellet was heated in a tube furnace at about 900.degree. C. in flowing oxygen for about 3 minutes, and was then removed from the furnace.
4. A small amount (approximately 0.1 to about 0.2 gm) of Tl.sub.2 O.sub.3 was put in a platinum boat, and the platinum boat was put in a quartz boat
5. The In.sub.2 Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 pellet was put over the platinum boat.
6. The quartz boat was then put into the tube furnace which had been heated to approximately 900.degree. C., and was heated for about 3 minutes in flowing oxygen.
7. The sample was then furnace-cooled to room temperature in flowing oxygen, and was then removed from the furnace.
The bottom surface of the Tl.sub.2 O.sub.3 -vapor-processed In.sub.2 Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 sample constructed pursuant to this method was found to be superconducting FIG. 6 illustrates resistance as a function of temperature for a Tl.sub.2 O.sub.3 -vapor-processed In.sub.2 Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 sample, made pursuant to this example, which had an onset temperature about 120 K, and reached zero resistance at 89 K.
EXAMPLE 6
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. CaO,
3. BaCO.sub.3,
4. CuO.
B. The following procedure was followed:
A mixture of a two molar portion of BaCO.sub.3, a two molar portion of CaO, and a three molar portion of CuO was ground with an mortar and pest-e, heated in air at 925.degree. C. for more than 24 hours (with several intermediate grindings) to obtain a uniform black Ba.sub.2 Ca.sub.2 Bu.sub.3 O.sub.7 powder.
2. The resulting Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder was completely ground, and pressed into a pellet.
3. The pellet was heated in a tube furnace at approximately 925.degree. C. for about 5 minutes.
4. The pellet was then taken out of the furnace and cooled in air to room temperature.
5. A small amount (approximately 0.1 to about 0.2 gm) of Tl.sub.2 O.sub.3 was put in a platinum boat, and the platinum boat and cooled pellet were put in a go-d container.
6. The gold container, was sealed so that the platinum boat and pellet were sealed in oxygen, was put into a tube furnace which had been heated to approximately 900.degree. C., and was heated for about 10 minutes.
7. The gold container was then furnace-cooled to room temperature, and was removed from the furnace.
8. The gold container was opened, and the sample taken out.
This example produced a Tl.sub.2 O.sub.3 -vapor-processed sample that formed a layer of superconducting compounds on its surface, which had an onset temperature of above 120 K and a zero resistance temperature of above 100 K.
EXAMPLE 7
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. CaO,
3. BaCO.sub.3,
4. CuO.
B. The following procedure was followed:
A mixture of a two molar portion of BaCO.sub.3, a two molar portion of CaO, and a three molar portion of CuO was ground with an agate mortar and pestle, heated in air at approximately 925.degree. C. (with several intermediate grindings) to obtain a uniform black Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder.
2. The resulting Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder was mixed with Tl.sub.2 O.sub.3 in a molar ratio of 1:1, and was completely ground and pressed into a pellet.
3 The pellet was heated at approximately 925.degree. C. in a tube furnace for approximately 4 hours. The sample could have been heated for a longer time however.
4. The heated pellet was then taken out of the furnace and cooled in air to room temperature. The resultant pellet was found to have a semiconductor behavior.
5. A small amount (approximately 0.1 to about 0.2 gm) of Tl.sub.2 O.sub.3 was put in a platinum boat, and the platinum boat was put in a quartz boat.
6. The resultant pellet was put over the platinum boat.
7. The quartz boat was then put into the tube furnace which had been heated to approximately 900.degree. C., and was heated for about 3 minutes in flowing oxygen.
8. The sample was then furnace-cooled to room temperature in flowing oxygen, and was then removed from the furnace.
The resulting Tl.sub.2 O.sub.3 -vapor-processed sample, produced by this example, had a superconducting behavior, and had an onset temperature of above 120 K, and a zero resistance temperature of above 100 K.
EXAMPLE 8
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. CaO,
3. BaCO.sub.3,
4. CuO.
B. The following procedure was followed:
1. A mixture of a two molar portion of BaCO.sub.3, a two molar portion of CaO, and a three molar portion of CuO was ground with an agate mortar and pestle, heated in air at 925.degree. C. for more than 24 hours (with several intermediate grindings) to obtain a uniform black Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 powder. A pellet was then formed in a 3/8 inch die under pressure.
2. A Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 precursor film was then deposited by laser deposition from the pellet as a target onto a Y-stabilized ZrO.sub.2 substrate using a frequency-doubled Nd-YAG laser operating at 523 nm, forming a Ba-Ca-Cu-O thin film with a thickness of approximately 2 to about 3 .mu.m.
3. The thin film precursor was then placed above a platinum boat which contained approximately 0.1 to about 0.2 gram of Tl.sub.2 O.sub.3, and the platinum boat was placed in a quartz boat.
4. The quartz boat and its contents was heated at 900 .degree. C. in a tube furnace for approximately 2 to about 3 minutes in flowing oxygen, and then furnace cooled to room temperature.
A resultant Tl.sub.2 O.sub.3 vapor processed Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7 thin film was found to be superconducting with an onset temperature above 120 K and a zero resistance temperature of 115 K. The measurements of a sample prepared pursuant to this example are illustrated in FIG. 7 as Tl-223.
EXAMPLE 9
A. The following reagents were utilized:
1. Tl.sub.2 O.sub.3,
2. CaO,
3. BaCO.sub.3,
4. CuO.
B. The following procedure was followed:
1. A mixture of a two molar portion of BaCO.sub.3, a three molar portion of CaO, and a three molar portion of CuO was ground with an agate mortar and pestle, heated in air at 925.degree. C. for more than 24 hours (with several intermediate grindings) to obtain an uniform black Ba.sub.2 Ca.sub.3 Cu.sub.3 O.sub.8 powder. A pellet was then formed in a 3/8 inch die under pressure.
2. A Ba.sub.2 Ca.sub.3 Cu.sub.3 O.sub.8 precursor was deposited by laser deposition onto a Y-stabilized ZrO.sub.2 substrate using a frequency-doubled Nd-YAG laser operating at 523 nm, forming a Ba-Ca-Cu-O thin film with a thickness of approximately 2 to about 3 .mu.m.
3. The thin film precursor was placed above a platinum boat which contained approximately 0.1 to about 0.2 gram of Tl.sub.2 O.sub.3, and the platinum boat was placed in a quartz boat.
4. The quartz boat and its contents was heated at 900 .degree. C. in a tube furnace for approximately 2 to about 3 minutes in flowing oxygen, and then furnace cooled to room temperature.
A resultant Tl.sub.2 O.sub.3 vapor processed Ba.sub.2 Ca.sub.3 Cu.sub.3 O.sub.8 thin film was found to be superconducting with an onset temperature above 120 K and a zero resistance temperature of 104 K. The measurements of a sample prepared pursuant to this method are illustrated in FIG. 7 as Tl-233.
It should be understood that various changes and modifications to the presently preferred embodiments described I be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. It is therefore intended that such changes and modifications be covered by the appended claims.
Claims
  • 1. A method for making thin-film Tl-Ca-Ba-Cu-O superconductors comprising the steps of:
  • a. depositing a thin-film of Ca-Ba-Cu-O precursor utilizing physical vapor deposition;
  • b. placing Tl.sub.2 O.sub.3 in a boat under or near the precursor thin film;
  • c. heating the boat and precursor film in flowing O.sub.2 ; and
  • d. cooling the film and boat.
  • 2. A method for making thin-film Tl-Ca-Ba-Cu-O superconductors comprising the steps of:
  • mixing and heating BaCO.sub.3, CaO, and CuO to obtain a Ca-Ba-Cu-O powder;
  • forming a Ca-Ba-Cu-O thin film from the Ca-Ba-Cu-O powder by physical or chemical deposition; and
  • heating the film in oxygen with a quantity of Tl.sub.2 O.sub.3 in oxygen to create a Tl.sub.2 O.sub.3 vapor processed film.
  • 3. The method of claim 2 wherein the powder includes the composition Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.7.
  • 4. The method of claim 2 wherein the powder includes the composition Ba.sub.2 Ca.sub.3 Cu.sub.3 O.sub.8.
  • 5. The method of claim 2 wherein two molar portions of BaCO.sub.3, two molar portions of CaO, and three molar portions of CuO are ground, mixed, and heated to create the powder.
  • 6. The method of claim 2 wherein two molar portions of BaCO.sub.3, three molar portions of CaO, and three molar portions of CuO are ground, mixed, and heated to create the powder.
  • 7. The method of claim 2 wherein the powder is created into a pellet.
  • 8. The method of claim 7 wherein a film is deposited by laser deposition from the pallet into an Y-stabilized ZrO.sub.2 substrate.
  • 9. The method of claim 8 wherein the film has a thickness of approximately 2 to about 3 .mu.m.
  • 10. The method of claim 2 wherein the Tl.sub.2 O.sub.3 is placed in a platinum boat and the film is placed above the boat prior to heating the film and Tl.sub.2 O.sub.3.
  • 11. The method of claim 2 wherein the quantity of Tl.sub.2 O.sub.3 is approximately 0.1 to about 0.2 g.
Parent Case Info

This is a continuation of application Ser. No. 308,896 filed Feb. 9, 1989, now U.S. Pat. No. 4,997,811, which is a continuation-in-part of U.S. patent application Ser. No. 236,507 filed on Aug. 25, 1988.

US Referenced Citations (2)
Number Name Date Kind
4755493 Takeuchi et al. Jul 1988
4870052 Engler et al. Sep 1989
Foreign Referenced Citations (6)
Number Date Country
0280812 Sep 1988 EPX
0284062 Sep 1988 EPX
0286289 Oct 1988 EPX
0301952 Feb 1989 EPX
0301958 Feb 1989 EPX
0316009 May 1989 EPX
Non-Patent Literature Citations (51)
Entry
Sugise et al., "Preparation of Tl.sub.2 Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.y Thick Films from Ba-Ca-Cu-O Films", Jpn. J. Appl. Phys. 27(12), Dec. 1988, L2314-2316.
Lee et al., "Superconducting Tl-Ca-Ba-Cu-O Thin Films with Zero Resistance at Temperatures of Up to 120k," Appl. Phys. Lett. 53(4) Jul. 1988, pp. 329-321.
Lin et al., "Forming Superconducting Tl-Ca-Ba-Cu-O Thin Films by the Diffusion Method," Jpn. J. Appl. Phys. 28(1) Jan. 1989 l85-87.
Johs et al., "Preparation of High Tc Tl-Ba-Ca-Cu-O Thin Films by Pulsed Laser Evaporation and Tl.sub.2 O.sub.3 Vapor Processing", Appl. Phys. Lett. 54(18) May 1989, pp. 1810-1811.
Gopalakrishnan et al., "Synthesis and Properties of a 125k Superconductor in the Tl-Ca-Ba-Cu-O System", Appl. Phys. Lett. 53(5) Aug. 1988, pp. 414-416.
Qiu et al., "Formation of Tl-Ca-Ba-Cu-O Films by Diffusion of Tl into rt-Sputtered Ca-Ba-Cu-O", Appl. Phys. Lett. 53(12) Sep. 1988, pp. 1122-1124.
Wu et al., "Low-Temperature Preparation of High Tc Superconducting Thin Films", Appl. Phys. Lett. 52(9) Feb. 1988, pp. 754-756.
Liou et al., "Highly Oriented Tl.sub.2 Ba.sub.2 Ca.sub.2 Cu.sub.3 O.sub.10 Thin Films by Pulsed Laser Evaporation", Appl. Phys. Lett. 54(8) Feb. 1989, pp. 760-762.
Hasegawa, T., et al., High T. Superconductivity of (La.sub.1-x Sr.sub.x CuO.sub.4 -Effect of Substitution . . . Superconductivity, Japan Journal of Applied Physics, vol. 26, No. 4, Apr. 20, 1987, L337-L338.
Kishio, K., et al., Effect of Lanthanide Ion Substitutions for Lanthanum Sites on Superconductivity of (La.sub.1-x Sr.sub.x).sub.2 CuO.sub.4, Japanese Journal of Applied Physics, vol. 26, No. 4, Apr. 20, 1987, L391-L393.
Ohshima, S., et al., Superconducting and Structural Properties of the New Ba.sub.1-x Ln.sub.x CuO.sub.3-y Compound System (Ln=La, Ce, Pr, Nd, Sm, Eu, . . . and Yb), Japanese Journal of Applied Physics, vol. 26, No. 5, May 1987, L815-L817.
Tsurumi, S., et al., High T. Superconductivities of A.sub.2 Ba.sub.4 Cu.sub.6 O.sub.14+y Japanese Journal of Applied Physics, vol. 26, No. 5, May 1987, L856-L857.
Superconductivity News, vol. 1, No. 2, Aug. 1987, pp. 1, 2, and 6-8.
Yang, K. N. et al., High Temperature Superconductivity in Rare-Earth (R)-Barium Copper Oxides (RBa.sub.2)Cu.sub.3 O.sub.9-.delta., Solid State Communications, vol. 63, No. 6, 1987, pp. 515-519.
Tarascon, J. M. et al., Oxygen and Rare-Earth Doping of the 90-K Superconducting Perovskite YBa.sub.2 Cu.sub.3 O.sub.7-x, Physical Review B, vol. 36, No. 1, 1987, 226-234.
Hor, P. H. et al., Superconductivity Above 90 K in the Square-Planar Compound System ABa.sub.2 Cu.sub.3 O.sub.6+x with A=Y, La, Nd, Sm, Eu, Gd, Ho, Er, and Lu, Physical Review Letters, vol. 58, No. 18, 1987, 1891-1894.
Khurana, A., Superconductivity Seen Above the Boiling Point of Nitrogen, Physics Today, Apr., 1987, 17-23.
Cava. R. J. et al., Bulk Superconductivity at 91 K in Single-Phase Oxygen-Deficient Perovskite Ba.sub.2 YCu.sub.3 O.sub.9-.delta., Physical Review Letters, vol. 58, No. 16, 1987, 1676-1679.
Nagashima, T., et al., Superconductivity in Tl.sub.1.5 SrCaCu.sub.2 O.sub.x, Japanese Journal of Applied Physics, vol. 27, No. 6, Jun., 1988, L1077-L1079.
Saito, Y., et al., High-T.sub.c Superconducting Properties in (Y.sub.1-x Tl.sub.x)Ba.sub.2 Cu.sub.3 O.sub.7-y, Y(Ba.sub.1-x K.sub.x).sub.2 Cu.sub.3 O.sub.7-y and YBa.sub.2 (Cu.sub.1-x Mg.sub.x).sub.3 O.sub.7-y, Physica 148B, 1987, 336-338.
Kondoh, S., et al., Superconductivity in Tl-Ba-Cu-O System, Solid State Communications, vol. 65, No. 11, 1988, 1329-1331.
Sera, M. et al., On the Structure of High-T.sub.c Oxide System Tl-Ba-Cu-O, Institute for Molecular Science, Myodaiji, Okazaki 444 Japan, 1988.
Ihara, H. et al., Possibility of Superconductivity at 65.degree. C. in Sr-Ba-Y-Cu-O System, Japanese Journal of Applied Physics, vol. 26, No. 8, Aug., 1987, L1413-L1415.
Ishida, T., Compositional Variation of High T.sub.c in Yb.sub.x Er.sub.1-x Ba.sub.2 Cu.sub.3 O.sub.6+y System, Japanese Journal of Applied Physics, vol. 26, No. 8, Aug., 1987, L1294-L1295.
Kijima, T., et al., Superconductivity in the Bi-Sr-La-Cu-O System, Japanese Journal of Applied Physics, vol. 27, No. 6, Jun., 1988, L1035-L1037.
Richert, B., et al., Atomic Substitution in YBa.sub.2 Cu.sub.3 O.sub.7 : Modification of the Electronic Structure, American Institute of Physics Conference Proceedings No. 165 (Thin Film Processing and Characterization of High-Temperature Superconductors), Nov. 6, 1987, 277-283.
Ferreira, J. M., et al., Long-Range Magnetic Ordering the High-T.sub.c Superconductors RBa.sub.2 Cu.sub.3 O.sub.7-.delta. (R=Nd, Sm, Gd, Dy and Er), Physical Review B, vol. 37, No. 4, Feb. 1, 1988, 2368-2371.
Shih, I., et al., Multilayer Deposition of Thallium Barium Calcium Copper Oxide Films, Applied Physics Letter 53(6), 1988, 523-525.
Ginley, D. S., et al., Sequential Electron Beam Evaporated Films of Tl.sub.2 CaBa.sub.2 Cu.sub.2 O.sub.y with Zero Resistance at 97 K, Applied Physics Letters, 53 (5), Aug. 1, 1988, 406-408.
Parkin, S. S. P., et al., Bulk Superconductivity at 125 K in Tl.sub.2 Ca.sub.2 Ba.sub.2 Cu.sub.3 O.sub.x, Physical Review, 1988, 2539-2542.
Sheng, Z. Z., et al., Superconductivity in the Rare-Earth-Free Tl-Ba-Cu-O System Above Liquid-Nitrogen Temperature, Nature, vol. 332, Mar. 3, 1988, 55-58.
Sheng, Z. Z., et al., Superconductivity at 90 K in the Tl-Ba-Cu-O System, Physical Review Letters, vol. 60, No. 10, Mar. 7, 1988, 937-940.
Sheng, Z. Z., et al., Bulk Superconductivity at 120 K in the Tl-Ca/Ba-Cu-O System, Nature, vol. 332, Mar. 10, 1988, 138-139.
Ihara, H. et al., A New High-T.sub.c TlBa.sub.2 Ca.sub.3 Cuh.sub.4 O.sub.11 Superconductor with T.sub.c >120 K, Nature, vol. 334 Aug. 11, 1988, 510-511.
Sheng, Z. Z., et al., Tl.sub.2 O.sub.3 Vapor Process of Making TI-Ba-Ca-Cu-O Superconductors, Appl. Phys. Lett. 53 (26), Dec. 26, 1988, 2686-2688.
Hazen, R. M., et al., 100-K Superconducting Phases in the Tl-Ca-Ba-Cu-O System, Physical Review Letters, vol. 60, No. 16, Apr. 18, 1988, 1657-1660.
Sheng, Z. Z., et al., New 120 K Tl-Ca-Ba-Cu-O Superconductor, Appl. Phys. Lett., vol. 52, No. 20, May 16, 1988, 1738-1740.
Hatta, S., et al., Pt-Coated Substrate Effect on Oxide Superconductive Films in Low-Temperature Processing, Appl. Phys. Lett. 53(2), Jul. 11, 1988, 148-150.
Oota, A., et al., Electrical, Magnetic and Superconducting Properties of High-T.sub.c Superconductor (Y, Sc)-(Ba, Sr)-Cu Oxide, Japanese Journal of Appl. Physics, vol. 26, No. 8, Aug., 1987, L1356-1358.
Iwazumi, T., et al., Identification of a Structure with Two Superconducting Phases in L-Ba-Cu-O System (L=La or Y), Japanese Journal of Applied Physics, vol. 26, No. 5, May, 1987, L621-L623.
Capone, II., D. W., et al., Super Critical Fields and High Superconducting Transition Temperatures of La.sub.1.85 Sr.sub.0.15 CuO.sub.4 and La.sub.1.85 Ba.sub.0.15 CuO.sub.4, Appl. Phys. Lett., 50 (9), Mar. 2, 1987, 543-544.
Johnson, D. W., et al., Fabrication of Ceramic Articles from High T.sub.c Superconducting Oxides, Materials Research Society, Symposium S Proceedings (High Temperature Superconductors), Apr. 1987, 193-195.
Garwin, L., Superconducting Conference Yields New Temperature Record, Nature, vol. 332, Mar. 10, 1988.
Suzuki, A., et al., Rare- Earth(RE)--Barium Solubility Behavior in Y(Ba.sub.z -RE.sub.x)Cu.sub.3 O.sub.7+.delta. and Sm(Ba.sub.z-x RE.sub.x)Cu.sub.3 O.sub.7+.delta., Japanese Journal of Applied Physics, vol. 27, No. 5, May, 1988, L792-L794.
Peters, P. N., et al., Observation of Enhanced Properties in Samples of Silver Oxide Doped YBa.sub.2 Cu.sub.3 O.sub.x, Appl. Phys. Lett., 52 (24), Jun. 13, 1988, 2066-2067.
S. Natarajan et al., Superconductivity Studies on (Y.sub.1-x Ln.sub.x)Ba.sub.2 Cu.sub.3 O.sub.7, Ln=La,Pr,Tb, Physica C, vol. 153-155, Feb. 1988, 926-927.
D. D. Sarma, et al., Electronic structure of High-T.sub.c Superconductors from Soft-x-Ray Absorption, Physical Review B, vol. 37, No. 16, Jun. 1988, 9784-9787.
K. Kishio, et al., Superconductivity Achieved at Over Liquid Nitrogen Temperature by (Mixed Rare Earths)--Ba--Cu Oxides, Japanese Journal of Applied Physics, vol. 26, No. 5, May 1987, L694-L696.
Waldrop, M. Mitchell, Thallium Superconductor Reaches 125K, Research News, Mar. 1988, 1243.
Qadri, S. B., et al., X-ray Identification of the Superconducting High-T.sub.c Phase in the Y--Ba--Cu--O System, Physical Review B, vol. 35, No. 13, 1987.
Murphy, D. W., et al., New Superconducting Cuprate Perovskites, Physical Review Letters, vol. 58, May 1987, 1888-1890.
Continuations (1)
Number Date Country
Parent 308896 Feb 1989
Continuation in Parts (1)
Number Date Country
Parent 236507 Aug 1988