CA1311164C - Europium, barium, copper oxide film superconductors - Google Patents

Abstract

EUROPIUM, BARIUM, COPPER OXIDE:
FILM SUPERCONDUCTORS
Abstract of the Disclosure Superconducting thin films of RE1Ba2Cu4Oz, where RE is a rare earth metal chosen from the group consisting of yttrium, ytterbium, and europium are produced in a non-vacuum environment using Metallo-Organic Deposition techniques. An ink comprising the neodecanoates of the rare earth metal, barium, and copper is formed and spun on a single crystal substrate of strontium titanate. The ink is dried in an air environment, heated in an air environment at a temperature sufficient to decompose the neodecanoates, about 500°C, and then annealed to promote recrystallization and grain growth of the remaining metal oxides. The annealing step is preferably accomplished using rapid thermal annealing techniques wherein the material is uniformly and rapidly heated to an appropriate temperature for an amount of of time ranging between about instantaneous to about 2 minutes. The resulting films of material exhibit superconductive characteristics at elevated temperatures.

Description

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EUROPIUM, BARIUM, COPPER OXIDE
FILM SUPERCONDUCTORS
This application is related to the copending Canadian patent applications entitled, "Ytterbium, ~arium, Copper Oxide Film Superconductors," Canadian Serial Mo. 578,643, filed on 28 September 1988, and "Formation of Film Superconductors by Metallo-Organic Deposition," Canadian Serial No. 578,543 filed on 27 September 1988.
This invention relates to superconductors and methods of making films of superconductor materials.
Back~round of the Invention Since the first report of a superconductor material having a superconducting transition temperature of about 40K, there has been extensive activity in the field to develop materials havin~ an even higher range of superconducting transition t~mperatures. A wide variety of superconductor materials having high transition temperatures have been reported, including superconducting materials comprising yttrium, barium, and copper which have transition temperatures greater than about 80K. Thin film superconductors based upon these yttrium, barium, and copper compounds have been prepared by sputtering, E-beam and laser evaporation, all techniques requiring vacuum processing. As new materials with ever increasing transition temperatures are sought and developed, it is desirable to have a means for preparing thin films of these superconducting materials .. ~
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which uses non-vacuum t~chniques, permits easy alteration of chemical components, and is compatible with other film processing technique~.
Metallo-Vrganic Deposition ~MOD~ is an entirely nonvacuum method of film deposition~
Typically, a liquid 601ution of organic compounds is prepared by dissolution of the organic compounds in a suitable solvent. This solution is then applied much in the same manner as photo-re~ist, ~s by 6pin coating the organic solution onto a selected ~ub6trate material. The soft metallo-organic film is then heated in air or oxygen to burn out the organic components and produce a thin film. By utilizlng non-vacuum processing techniquest the Metallo-Organic Depo6ition method provides an economical means for film preparation o~ semiconductor materials. In addition, the ease in which compounds of a variety of elements can be made allows a wide range of multi-metal compounds to be prepared.
Summary of the Invention Xt is an object of the present invention to provide superconductor films, particularly to provide a superconducting film comprising the rare earth metal europium.
It is a further object of this invention to provide a method for forming ilms of superconductor materials.
It is still a further object of this invention that these superconductor films be formed in a non-vacuum, oxygen-containlng environment.
In accordance with a preferred embodiment of this invention, these and other objects and advantages are accomplished as follows.
We have prepared for the first time thin film ~ 3 ~

superconductors in a non-vacuum, oxygen-containing environment using metallo-organic deposition techniques. Superconducting thin films, comprising barium, copper, and a rare earth (RE) metal, were formed on single crystal strontium titanate substrates by the thermal decomposition of an ink forming ~olution of the neodecanoates of the barium, copper, and rare earth metal. The preferred rare earth metals include yttrium, ytterbium, and europium.
As an illustrative example, europium comprising superconducting films, having the approximate empirical formula Eu1sa2cu4oz, are formed in the following manner. ~n ink forming solution contains the neodecanoate~ of the europium, barium, and copper and is combined with an appropriate solvent.
Preferably, about 1 gram of the combined metal neodecanoates is added to about 1 milliliter of solvent. An ink of the preferred composition was spun onto the strontium titanate substrate at about 2000 revolutions per minute. The spun on ink was dried in air at about 110C for about fi~e minutes, then immediately placed into a urnace preheated to a~out 500C and baked in air at this temperature for about five minutes so as to decompo6e the metal neodecanoates leaving only a metal oxide film on the substrate surfaee. It is preferred that the prepared metallo-organic inks not set at ambient conditions too long. The amounts of metal remaining on the substrate surface after baking reliably correspond to the amount of metals within the original metallo-organic ink. The ilm was then rapid thermal annealed at about 930C in an oxygen-containing atmosphere for an amount of time ranging between instantaneously up to about 2 minutes, and subsequently rapidly quenched to room temperature.

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Rutherford Backscattering Spectrometry was used to determine that the resulting ilm's empirical composition prepared in accordance with this method was Eu1Ba2Cu4Oz. It i8 believed that z range~ between about 6-8, as this is the relative compo~ition in which superconducting characteris~ics are observed. Thi~
method may be employed to produce superconducting films of the rare earth (RE) metals havlng a general empirical composition of approximately RE1Ba2Cu4Oz, wherein the rare earth metal is chosen from the group consisting of yttrium, ytterbium, europium, or a yttrium/europium combination.
A superconducting film prepared in aceordance with this method, comprising europium and having an approximate empirical composition EulBa2Cu4Oz, exhibited a zero state resistance temperature of about 20K and a superconducting transition temperature of about 70K. Electrical measurements show a zero state resistance temperature of about 70K for a superconducting ilm of YlBa~Cu4Oæ, prepared in accordance with this method and a superconductin~
transition temperature of about 90K. A superconducting film prepared in accordance with this method, c~mprising ytterbium and having an approximate empirical eomposition YblBa2Cu4Oz, i~ characterized by a zero state resistance temperature of about 84~ and a superconducting transition temperature of about 90R.
Suitable superconducting results have also been obtained by baking the thin films for about six hours at about 850C, and slow cooling the materials to room temperature, rather than the short duration rapid thermal annealing and quenching steps. The inventors are the first to employ non-vacuum techniques and achieve thin film superconductors.

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Other objects and advantages of this invention will be better appreciated from a detailed description thereof, which follows.
Detailed Description of the Invention The inventors are the first to achiev2 thin film superconductors using an entirely non-vacuum method. In the present invention~ metallo-oryanic inks are prepared using carboxylates of a rare earth ~RE) metal, barium, and copper. The preferred carboxylate~
are the neodecanoates of the various metals. The preferred rare earth metals are yttrium, ytterbi~m, and europium. Rutherford sackscattering Spectrometry analysis was used to determine film GOmpoSitiOn a~d thickness. Using this techni~ue, the composition of the inks may be adjusted to obtain desired superconducting compositions.
The Rutherford Backscattering Spectrometry analysis revealed that the relative metal compo8itions of the preferred thin films were approximately R~1Ba2Cu40z, and the rare earth (RE) metal compri~ing yttrium, ytterbium, europium, or a ytterbium/europium combination. U6ing Rutherford ~ackscattering Spectrometry, the relative compositions for the ytterbium comprising film~ and the europium comprising films could were not determined precisely, 6ince the relatively heavy atomic weight of ytterbium and europium prevented the accurate detection of these metals, as the heavy metals were not entirely di~tinguishable from the barium in the composition. In addition, the concentration of oxygen in the thin films could not be determined precisely from the Rutherford sackscattering Spectrometry ~pectrum because the oxygen signal from the sapphire substrate on which the thin film coatings were formed overlapped that of the oxygen ~ 3 ~

signal from the superconducting thin films. It is believed that in the empirical formula RElBa2Cu4Og, z ranges between about 6 to about 8.
The usual solvent for the metal neodecanoates 5 is xylene, however it w~s observed that the yttriu~, ytterbium, and europium neodecanoates gel i~ xylene forming an unu~able ink. It was found th~t th~
addition of appro~imately about 5 to about lO percent pyridine by volume to the xylene forms a solvent that will not gel these neodecansates. In addition, it was observed that the addition of the pyridine in two separate steps forms superior metallo-organic inks.
First, the barium, copper, and rare earth neodecanoates are dissolved by stirring the neodecanoates in a 95%
xylene and 5% pyridine ~olvent for approximately ten hours at room temperature. An additional amount of pyridine, about 1 to about 5 percent, is ~ubsequently added to the metallo-organic ink aEter the fir~t stirring ~tep and th~ ink is further ~tirred for approximately one hour. Forming a solution of the metal neod~canoates ensures intimate mixing of the elements that will ultimately form the superconducting compound.
Inks prepared using this method are ~pun on smooth strontium titanate substrates and then fired to decompose the neodecanoates within the metallo-organic ink. The ~ethod of firing the ink onto the zubstrate i8 critical, in that thermogravimetric analysis shows that the metal neodecanoates of the rare earth metal, the copper and the barium volatilize and decompose at different temperatures. It was determined that the freshly prepared metallo-organic inks, which have been spun onto the substrates, should be rapidly placed in a furnace preheated to about 500C. It is preferred that the prepared inks do not set at ambient conditions for too long. Thi~ will result in quali~y inks fnr purposes of preparing thin films of the superconducting composition. After the firing step an oxide film of the appropriate metal oxide composition remains on the substrate, the proportion of the metal corre~ponding reliably to the amount of metal in the inks. Using this method, the composition of the metallo-organic inks may be adjusted to obtain various compositions in the oxide Eilms.
The ink is careEully poured onto the top surface of a stationary strontium titanate sub~trate, so as to flood the surface. The substrates are about one centimeter square by about 0.15 centimeter height, oriented in the <100> crystal direction. The viscous metallo-organic inks are spun onto the substrate surface at various speeds. At 20 seconds at about 2000 revolu~ions per minute (RPM~, the thickness of the ink after drying at about 85C so as to evaporate any solvent will be about 4.4 micrometer~, and the thickness of the metal oxide film after heating to about 500C so as to decompose the neodecanoates will be about 2600 ~ngstroms. ~t 20 seconds at 3000 RPM the thickness after drying at 85C will be about 3.7 micrometers and the thickness after heating at about 500C will be about 2100 Angstroms. At about 20 seconds at 4000 RPM the corresponding thicknesses after drying at 85C and heating at 500C are about 3.1 micrometers and 2090 Angstroms. At about 20 seconds at 30 7000 RPM the corresponding thicknesses a~ter drying at 85C and heating at 500C are about 2.6 micrometers and 1700 Angstroms. These measurements were determined using a step profile detector.
This two step sequence of first spinning the metallo-oryanic ink onto the substrate ollowed immediately by the firing at a temperature sufficient to decompose the metal neodecanoates, may be repeated so as to produce films having a thickness of up to about 2.0 micrometers. However, multiple depo~ition and firing sequence~ are not required though, as ~uitable results may be obtained w:ith thicknesses a~
low as about 0.1 micrometers. The~e films may be processed, by employing multiple deposition technique~
in accordance with this invention, to result in thicker or thinner films for optimal superconducting characteristics.
After repeating the spinning and firing sequence sufficiently so as tD achieve the desired metal oxide thickness on the substrate, the films are then annealed in a non-vacuum oxygen containin~
environment at a sufficient temperature for a sufficient duration to promote recrystallization and grain growth within the metal oxides. The resulting films are characterized by superconductive electrical properties. It is preferred that the metal oxide films be rapid thermal ~nnealed, i.e., exposed to the annealing temperature for a relatively ~hort duration, from an instantaneous amount of time up to about 2 minutesO It has been determined that the use of rapid thermal annealing techniques produce superconducting films characterized by higher zero state resistance temperatures than the superconducting ilms which are conventionally annealed by baking at the desired temperature for a longer duration, i.e., about 6 hours.
Rapid thermal annealing techniques raise the temperature of the substrate and deposited film uniformly and almost instantaneously to the desired annealing temperature. Two methods are generally employed for rapid thermal annealing. The first method, which is the method we prefer, compri~e~
heating the material using quartz lamps. The quartz lamps generate extremely large dosages of electromagnetic infrared radiation in the form of light. The substrates and films are heated very rapidly by exposing the substrates to the quartz lamps and electromagnetic radiation. The second method involves placing the sub~trates and films on a yraphite receptacle and exposin~ the 6ubstrates to microwaves.
The microwaves impinge the films deposited on the ~urface of the substrate and heat the film and substrate uniformly and quickly.
We are the fir~t to produce superconducking thin films using entirely non-vacuum techniquesO
Superconducting films comprising the rare earth metal, europium, and having an empirical composition of Eu1Ba2Cu40z, were also produced using this metallo-organic deposition method. A
metallo-organic ink wa~ prepared using th~
neodecanoates of europi~m, basium, and copper.
Metallo-organics of the europium and the barium neodecanoates were formed from their metal acetates by reaction with ammonium neodecanoate. The copper metall~-organic was formed by a reaction of copper (II) acetate with tetramethyl ammonium neodecanoate. The me~al neodecanoates were dissolved in a solvent solution containing approximately 5 volume percent pyridine in xylene, and stirred for approximately 10 hours. An additional 1-5 volume percent pyridine was added to the solution and stirred for about another hour. Solutions containing the europium, barium, and copper neodecanoates, of various concentrations, may be made by di6solving the three components in appropriate g amounts of xylene and pyridine.
The europium comprising solution, i.e., ink, which resulted in the superconductor film composition of approxim~tely Eulsa2cu4oz, has a ratlo of about one gram of the combined metal neodecanoates to about one milliliter of solvent. Approximately 14.65 grams of the ytterbium neodecanoate, 19.12 grams o the bariu~
neodecanoate, and 13.76 grams of the copper neodecanoate, yielding a total of about 47.53 grams of metal neodecanoate, were dissolYed in about 47.53 milliliters of ~olvent, the solvent compri~ing about 45.15 milliliters of xylene with about 2.38 milliliters of pyridine. The ink was stirred for approximately 10 hours at room temperature. Then, an additional 1 to 5 percent pyridine was added and stirring is continued for apRroximately another hour. The addition of the pyridine in a two steps followed by the stirriny step is preferred and results in superior metallo-organic inks for purposes vf forming the superconducting films.
However, suitable results are obtained when the pyridine is added in a ~ingle step also. The vi~cous solution~ having a viscosity of approximat~elyQ~14 ~) centipoi~e, were filtered, using Teflon/~brane~, to remove particles down to approximately 200 nano~eters in size.
The inks prepared from the europium, barium, and copper neodecanoates and solvents were flooded onto single crystal strontium titanate, SrTiO3, substrates of about one centimeter width by about one centimeter length by about 0.15 centimeter height, oriented in the ~100> crystal direction. The inks were spun dry on the substrates at various speeds, about 2000 revolutions per minute for about 20 seconds, being pre~erred. The spun-on inks were dried in air at about 110C for about 1~

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five minutes, then immediately placed in a furnace preheated to about 500C. The thin film inks were heated in air at that temperature, 500C, for about 5 minutes to decompose the europium, barium, and copper neodecanoate~. This two ~tep, spin-on and fire, deposition sequence was typically repea~ed multiple time~ to obtain a de~ired thicknes6 between about l.S
and 2.0 microns, however multiple deposition~ are not required.
Thermogravimetric analysis shows that complete decomposition of the combined europium, barium, and copper neodecanoates used in this invention occurs at about 450C, leaving only the europium, barium, and copper oxides remaining on the strontium titanate substrate. The amount of metal remaining on the substrate surface reliably corresponds to the amount of metal in the initial metallo-organic inks. The inventors found that if the dried inks on the substrates are immediately placed in a furnace set at 20 about 500C, after the drying step at about 110C, quality thin films of the ~uperconducting composition are made for purposes of preparing the superconducting film~. The grain size~ of the superconducting thin films prepared in accordance with this invention, using metallo-organic deposition techniques, are estimated to be about 250 nanometers in diameter.
~ fter obtaining the desired thickness of the ink and completing the subsequent firing required to decompose the organic neodecanoates and leave only the metal oxides remaining on the substrate, the europium comprising samples were annealed in a non-vacuum, oxygen containing environment at atmospheric pressure to promote recrystallization and grain growth within the material. Preferably, the films were rapid :~ 3 ~

thermal annealed using q~artz lamps at about 930C in a pure oxygen atm~sph2re for an in~tantaneous amount of time up to about 2 minutes and rapidly quenched to room temperatur~. The resulting films of Eu1sa2cu4oz, prepared in accordance with thi~ meth~d ~xhibit superconductive characteristics.
F~r a Eu1sa2C~Oæ ~a~ple~ as determined by Rutherford sackscattering Spectrometry, prepared in accordance with this metallo organic depo~ition method and rapid thermal annealed in oxygen at a temperature of about 930C for about 45 seconds and quenched in air to room temperature, a zero point resi~tance temperature of about 20K was mea~ured. The zero point resistance temperature was that temperature which corresponded to the resistivity limit set at 7.6xlO 8 ohms per centimeter. The room temperature resistivity was approximately 5.9xlO 3 ohms per c~ntimeter. This material is further characterized by a superconducting transition temperature of about 70R, wherein a rapid drop in resistancQ was obs~rved. Sil~er paint wa~ u~ed to make the four probe resi~tance measurem~nts.
It is beli~v~d that th~ empirical compo~ition for the sup~rconducting europium compri~ing fil~s is approximately Eu1sa2cu4oz, with z ranging between about 6-8. Rutherford sackscattering Analysis was e~ployed to determine the empirical composition, however due to the weight of the europium, it was difficult to distin~uish the europium from the barium during the a~alysis. This also occurred during the analysis o~
the ytterbium comprising superconducting material. It iS believed that the superconducting characteristics of the europium comprising film may be optimized upon better analysis of the material.
It is preferred that the material be annealed at a temperature ranginq between about 850C to about 1000C and for a duration of about an instantaneou~
amount of time up to about 2 minutes, with about 15 seconds to one minute being especially preferred. The duration and annealing temperature are inversely related; i.e, a shorter duration is required at a higher temperature. In addition, suitable results should be obtained using more conventional annealing techniques such as annealing at about 850C to about 1000C for a sufficient time to promote recrystallization and grain growth.
It is further believed that superconducting films comprising both europium and ytterbium having an empirical composition of Euo 5Ybo 5sa2cu4oz, with z ranging between about 6 to 8, may also be produced in accordance with this method for metallo-organic deposition and rapid thermal annealing. A
metallo-organic ink comprising the appropriate amounts of the metal neodecanoates of europium, ytterbium, barium, and copper dissolved in the appropriate a~ounts of pyridine in xylene, would be spun-on to the appropriate substrate and fired at a temperature so as to decompose the organic neodecanoates. The 6ubs~r~te and film would then be annealed, preferably usin~ rapid thermal annealing techniques, at the appropriate temperature to promote grain growth and recrystallization. It is believed that the resultiny ~ilms would exhibit superconducting properties at elevated temperatures.
In addition, it is believed that superconducting films of lanthanum could also be produced in accordance with the method described above.
The inventors are the first to achieve thin film superconductors using an entirely non-vacuum :~ 3 ~

process. With this invention, superc~nducting thin films of various compositions comprising a rare earth metal have also been formed on barium titanate and sapphire substrates. Other suitable temperature and diffusion ~esistant substrates may also be u~ed. It is also believed that superconducting thin films may be formed, in accordance with this invention, on ~ilicon or silicon oxide sub6trates if a suitable barrier layer, such as a strontium titanate layer, is provided between the sub~trate and metal neodecanoate inks.
This invention readily facilitates modification of the metal cunstituents and their ratio6 in the thin films, to obtain optimal superconducting characteristics within the thin films. This invention is also, an entirely n~nvacuum pr~cs~s which is compatible with film proce~sing techniques. While our invention ha~ been described in terms of preferred embodiments it is apparent that other forms could be adopted by one ~killed in the art without departing from the spirit o the invention, such as annealing the materials be exposing the materials to a focused laser beam or employing other appropriate materials.
Accordingly the scop~ of our invention is to be limited only by the following claims.

Claims (3)

1. A method for producing films of superconductor materials comprising the steps of:
forming a solution from the neodecanoates of europium, barium, and copper metals, said metals form an oxide mixture exhibiting superconductive properties, said solution comprises a solvent having at least approximately 10 volume percent pyridine in xylene, depositing a film of said solution onto a substrate, said substrate selected from the group consisting of strontium titanate, barium titanate, and sapphire;
pyrolyzing said film in an oxygen-containing environment at a first temperature of approximately 500°C. for up to approximately 5 minutes, so as to thermally decompose said neodecanoates of europium, barium and copper into a film containing oxides of europium, barium and copper, said pyrolyzing occurring substantially immediately after said depositing step and heating said oxide film at a second temperature ranging between about 850°C. and 1000°C.
for a duration of up to approximately 2 minutes to promote grain growth of said metal oxides within said film and induce a change therein by which said film exhibits superconducting properties at a significantly increased temperature.

2. A method for producing thin film superconductor materials comprising the steps of:
forming a solution from the neodecanoates of europium, barium, and copper metals, said metals form an oxide mixture exhibiting superconductive properties, said oxide mixture characterized by a ratio of approximately 1:2:4 for said europium, barium and copper metals respectively, said solution comprises a solvent having at least approximately 10 volume percent pyridine in xylene;
depositing a film of said solution onto a substrate, said substrate selected from the group consisting of strontium titanate, barium titanate, and sapphire;
pyrolyzing said film in an oxygen-containing environment at a first temperature of about 500°C. for about 5 minutes, so as to decompose said neodecanoates of europium, barium, and copper into a film containing oxides of europium, barium, and copper, said pyrolyzing occurring substantially immediately after said depositing step; and heating said metal oxide film at a second temperature of about 930°C, for a duration of approximately no more than 1 minute to promote grain growth of said metal oxides within said film and induce a change therein by which said film exhibits superconducting properties at a significantly increased temperature.

3. A method for producing films of superconductor materials as set forth in claim 2 wherein said resulting superconductive metal oxide film has a thickness ranging between about 0.1 microns to about 2.0 microns.