EP0610175A1 - Films supraconducteurs a haute temperature sur substrats d'oxyde d'aluminium - Google Patents
Films supraconducteurs a haute temperature sur substrats d'oxyde d'aluminiumInfo
- Publication number
- EP0610175A1 EP0610175A1 EP91907776A EP91907776A EP0610175A1 EP 0610175 A1 EP0610175 A1 EP 0610175A1 EP 91907776 A EP91907776 A EP 91907776A EP 91907776 A EP91907776 A EP 91907776A EP 0610175 A1 EP0610175 A1 EP 0610175A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- substrate
- buffer layer
- films
- structure according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 42
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title description 3
- 239000000872 buffer Substances 0.000 claims abstract description 53
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 31
- 239000010980 sapphire Substances 0.000 claims abstract description 31
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 29
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000608 laser ablation Methods 0.000 claims abstract description 11
- 239000002887 superconductor Substances 0.000 claims abstract 8
- 239000010408 film Substances 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 12
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 13
- 230000007704 transition Effects 0.000 abstract description 7
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 abstract description 5
- 238000005137 deposition process Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 41
- 239000010949 copper Substances 0.000 description 27
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- 239000000395 magnesium oxide Substances 0.000 description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000004544 sputter deposition Methods 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000000407 epitaxy Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000000313 electron-beam-induced deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000000333 X-ray scattering Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011222 crystalline ceramic Substances 0.000 description 1
- 229910002106 crystalline ceramic Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/225—Complex oxides based on rare earth copper oxides, e.g. high T-superconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0576—Processes for depositing or forming copper oxide superconductor layers characterised by the substrate
- H10N60/0632—Intermediate layers, e.g. for growth control
Definitions
- This invention relates to high critical temperature superconducting (HTSC) films and, more particularly, this invention relates to the preparation of HTSC films on sap ⁇ phire (aluminum oxide) substrates by the use of stable, epitaxial buffer layers.
- HTSC high critical temperature superconducting
- HTSC metal cuprate materials cannot readily be produced in bulk with geometries and properties suitable for microwave devices.
- devices based on the HTSC materials are fabri ⁇ cated by formation of thin films on substrates by tech ⁇ niques similar to those used to fabricate semiconductor devices.
- the HTSC film must be grown on a substrate having low dielectric losses at high frequencies.
- Sapphire Al 2 0 3
- Sapphire would appear to be an excellent substrate since it has a very low dielectric loss and is a strong, low cost, highly crystalline material available commercially in large sizes. Sapphire would be a good substrate for bolometer
- substrate materials that provide epi ⁇ taxial growth of thin HTSC films with high superconducting transition temperatures and low rf surface resistance, such as strontium titanate (SrTi0 3 ) , calcium titanate (CaTi0 3 ) , lanthanum alu inate (LaAlO-) , magnesium oxide (MgO) and yttria stabilized zirconia (YSZ) .
- strontium titanate SrTi0 3
- CaTi0 3 calcium titanate
- LaAlO- lanthanum alu inate
- MgO magnesium oxide
- YSZ yttria stabilized zirconia
- thick substrat ⁇ es of some of these materials e.g. strontium or calcium titanate, exhibit too high an rf loss or do not have high enough strength to act as a substrate for large area micro ⁇ wave devices.
- Some of these materials are only available in small sizes and/or at very high cost.
- thin epitaxial films of these materials ex- hibit a low dielectric loss and would be useful as a buffer layer between the HTSC film and the sapphire substrate if they provided an epitaxial surface for the HTSC film and were stable and non-reactive with the HTSC film and the substrate.
- the HTSC film did not have sufficient orientation and there were too many random grains.
- Morris et al. [3] formed an MgO buffer layer by sputter deposition at 5.5 to 7 Pa (about 40-50 m Torr) a fairly low pressure.
- the resulting YBCO film grown on the epitaxial MgO has high normal state resistance and a broad superconducting transition.
- the invention provides a HTSC buffer layered structure on sapphire that is stable and suitable for microwave en ⁇ vironments or for use in the fabrication of bolometers.
- the layered structure with a thin SrTi0 3 or CaTi0 3 buffer layer has a sharp transition and good thermal response, making it suitable for bolometer applications.
- the HTSC film can be grown over a wide temperature range without the HTSC reacting with the sapphire substrate or the buffer reacting with the substrate or the HTSC film.
- the layered structures of the invention provides the highest microwave performance of any sapphire supported HTSC film reported to date. Others have reported surface resistance measuring on a par with copper.
- the layered sapphire supported HTSC structure of the invention exhibits rf surface resistance 2 to 3 times better than copper at 10 GHz and 77 K and much better than copper at lower temperatures.
- the YBCO films grown on the buffer layer exhibit low normal state resist- ance and a narrow superconducting transition.
- the buffer layer in the HTSC structure of the inven ⁇ tion is grown in a high pressure process such as laser ab ⁇ lation, sputtering or metallo-organic compound vapor depo- sition (MOCVD) .
- MOCVD metallo-organic compound vapor depo- sition
- Talvacchio et al. [2] used electron beam deposition of the MgO film.
- Electron beam epitaxial depo ⁇ sition is conducted at relatively high vacuum, about 10 "5 Torr.
- the low partial pressure of oxygen is believed to result in an oxygen deficient buffer layer film. These films are chemically active and react with water which de ⁇ grades the quality of the overlying HTSC film.
- the buffer layer in the process of the invention is deposited at high ⁇ er pressure which results in inert buffer layers with good epitaxial qualities.
- the SrTi0 3 and CaTi0 3 buffer layers are excellent intermediate substrates for forming high per ⁇ formance, stable HTSC
- Figure 1 is a schematic drawing of a layered HTSC-Buf- fer-Sapphire structure produced according to the process of this invention
- Figure 2 is a series of curves showing Surface Resis ⁇ tance, R s of epitaxial YBa 2 Cu 3 0 7 films as a function of tem ⁇ perature at 10 GHz;
- Figure 3 is a series of plots of Surface Resistance, R s vs. frequency with Cu data at 77 K and Nb data at 7.7 K;
- Figure 4(a) is a c-axis scan of the YBa 2 Cu 3 0 7 film
- Figure 4(b) is a ⁇ -axis scan of the [103] peak of the YBa 2 Cu 3 0 7 film
- Figure 5(a) is the mutual inductance response of the YBa 2 Cu 3 0 7 film at 1 A;
- Figure 5(b) is the mutual inductance response of the YBa 2 Cu 3 0 7 film at 100 mA.
- Figure 6 is a graph of surface resistivity, R s versus temperature.
- the layered structure 10 is composed of a sapphire base or substrate 12, a thin buffer layer 14 and a HTSC layer 16.
- the buffer layer 14 and the HTSC layer 16 may be laid down in a pattern to form a de- vice by use of a mask formed by conventional lithographic techniques or by use of shutters or shields.
- Sapphire substrates are commercially available in high purity and in a variety of thicknesses and shapes.
- the support need only have sufficient thickness such as 0.1 millimeters to provide a mechanically strong substrate.
- Substrates having thicknesses above 1.0 millimeters would usually not be utilized since they add cost and weight to the device without providing any other benefit.
- the buffer layer is an epitaxial layer having suffi- cient thickness such that the growth of HTSC film is influ ⁇ enced solely by the buffer layer and not by the sapphire substrate.
- the buffer layer can have a minimum thickness of a monolayer or less. However, it is preferred that the buffer layer cover the sapphire surface and any anomalies on the surface and suitably has a thickness of at least 50 Angstroms. Thicknesses above about 3000 Angstroms are un ⁇ necessary and may interfere with the microwave device.
- the buffer can be formed from crystalline materials having a close epitaxial match to the HTSC material such as stron- tiu .
- Stron ⁇ tium titanate and calcium titanate are preferred since it appears that they form the best HTSC films.
- the thin layer of buffer is formed by deposition in a chamber having a high percentage, usually from 10 to 100% of oxygen.
- the pres ⁇ sure in the chamber is higher than practiced in the elec- tron beam deposition process and in other deposition pro ⁇ Deposition.
- the pressure in the chamber is at least 40 m Torr and can be as high as 10 Torr, usually about 100 to 500 m Torr.
- the buffer layer may be formed by a variety of vapor deposition techniques such as on- or off-axis sputtering, metallo-organic vapor deposition (MOCVD) or laser ablation. Laser ablation is preferred since it appears to pro ⁇ vide a buffer layer that provides the highest quality HTSC films. This may be due to several factors.
- Laser ablation is conducted at a fairly high pressure.
- the deposition chamber contains from 20 to 100% oxygen at a pressure typi ⁇ cally from 100 Torr up to several Torr.
- the higher oxy ⁇ gen pressure could provide a more stable, more perfect crystalline epitaxial layer.
- Laser ablation generates its own plasma.
- the charged ionic species may assemble into a more ordered crystal form.
- the laser is pulsed during las ⁇ er ablation. During the non-pulsed period the growing crystal can relax to allow the metal and oxygen atoms to assume their positions in the crystal lattice of strontium titanate or calcium titanate.
- the HTSC film is preferably grown by off-axis sputter ⁇ ing, laser ablation or MOCVD. Any of these procedures can be used to form the buffer layer.
- a common chamber can be used to form the buffer layer and HTSC film by two consecu- tive laser-ablation depositions or two consecutive off-axis sputtering depositions.
- the sapphire substrate or the buffer layer coated sapphire substrate is placed on a heat ⁇ ed substrate holder in a sputtering chamber at an angle of at least 40°, usually 90°, from the sputtering source.
- the substrate is heated to a temperature of from about 650 K to 800 K.
- the chamber contains from 10-50% of an oxidizing gas such as oxygen or nitrous oxide.
- the vapor source is a composite ceramic in the correct stoichiometric ratio for the film such as a Y_,Ba 2 Cu 3 alloy or a SrTi0 3 crystal or pressed powder source.
- Deposition is usually conducted over several hours at a high pressure between 100 and 500 Torr.
- a post deposition treatment in oxygen at a tempera ⁇ ture from 400 K to 600 K can be conducted in case of the HTSC film.
- the films of high critical temperature (T c ) supercon- ducting materials (HTSC) prepared in the present invention are mixed metal cuprates or mixed metal bismuthates having a T c above about 30 K, usually above 70 K which belong to four families: the rare earth cuprates, the thallium-based cuprates, the bismuth-based cuprates and the alkaline earth bismuthates.
- the HTSC materials have an ordered lattice and are usually crystalline ceramics of the general formula
- M 1 is a Group IIIA metal, Group IIIB metal, Group VB or a rare earth metal
- M 2 is a Group IIA metal
- x, y, z and n are integers.
- the ratio of y:x is about 2:1 and the ratio of z:x is at least 3 usually from 3:1 to 6:1.
- the oxygen is present in an amount to satisfy valency of the metals and n is usually no more than 20, typically about 5-15.
- M 1 can be a Group IIIA metal such as Yttrium (Y) or lanthanum (La) , a Group IIIB metal such as Thallium (Tl) , or Group VB metal such as Bismuth (Bi) or a rare earth met ⁇ al such as Erbium (Er) , Cerium (Ce) , Praseodymium (Pr) , Samarium (Sm) , Europium (Eu) , Gadolinium (Gd) , Terbium (Tb) , Dysprosium (Dy) , Holmium (Ho) , Ytterbium(Yb) , Lute- tiu (Lu) or combinations of these metals.
- M 2 is a Group IIA metal such as strontium, barium, calcium or mixtures thereof.
- Both laser ablation and off-axis sputtering techniques were utilized in growing low surface resistance "123" films on A1 2 0 3 with SrTi0 3 buffer layers.
- laser ablation about 1.8 Joule/cm 2 energy density of 248 nm wave ⁇ length pulsed excimer laser beam was focused on a SrTi0 3 or an "123" pellet.
- Other deposition parameters were 200 m Torr of oxygen pressure and 750 C substrate temperature.
- two sputtering guns were mounted face to face and the substrates were glued on a heater that faces perpendicular to the both SrTi0 3 and "123" targets.
- Oxygen pressure of 40 m Torr and Argon pressure of 160 m Torr were used at the substrate temperature of 740 C.
- Figure 2 shows the temperature dependence of surface resistance R s of the "123" films grown on SrTi0 3 buffer lay ⁇ ers on Al 2 0 3 (1102) substrates.
- the circles denote the data on a pair of films made by laser ablation and the crosses represent the data on films grown by the off-axis sputter ⁇ ing technique. They have a residual resistance of about 65 ⁇ at low temperature and about 800 ⁇ at 77 K at 10 GHz.
- the actual resonance frequency (w) was about 11 GHz and the usual R hinder(w) ⁇ w 2 relation was used to scale back to 10 GHz.
- These surface resistance values are compared to those of Cu at 77 K and Nb at 7.7 K in Figure 3.
- the resistance range 65 to 200 ⁇ between 10 K and 50 K is lower than the
- Nb 7.7 K value at 10 GHz The 800 ⁇ at 77 K is also at least a factor 10 better than that of Cu at 77 K.
- x-ray diffraction data of a c-axis scan and a ⁇ scan of the (103) peak are shown in Figures. 4a and 4b.
- the c-axis scan shows that the samples are well aligned in the c-axis direction.
- the existence of (200) peaks means that there are some a-axis oriented grains in the sample.
- a SEM (Scanning Electron Microscope) image reveals that these a-axis oriented grains reside on the surface mostly as isolated grains.
- the rocking curve of the (005) peak is about 2.4 degree wide, which is not much different from the epitaxial "123" films on bare sap ⁇ phire.
- the big diff rence in microstructure between epitaxial "123" thin films with SrTi0 3 buffer layer and films without SrTi0 3 buffer layer can be found in the ⁇ -scan of (103) peak in Figure 4b.
- the sharp peaks every 90 degree means that the a-axis and b-axis are also aligned in the sapphire plane (1102).
- the full width at half maximum, ⁇ , of the peaks in the ⁇ -scan is about 3.8 degree.
- ⁇ of good epitaxial films on MgO, SrTi0 3 is about 1.5 de- gree.
- these peaks do not have the shoulders.
- the "123" films with a SrTi0 3 buffer layer have better in-plane epitaxy than those without a SrTi0 3 buffer layer. It is known that the I-V characteristics of the grain boundary of two misaligned grains have Josephson junction behavior. It was further found by a weakly coupled grain model that these grain boundaries lead to higher surface resistance as well as longer penetration depth. Improved in-plane epitaxy can be interpreted as reduction of grain boundaries, which results in lower surface resistance.
- Strontium titanate has some reactivity with the compo ⁇ nents of the growing HTSC film limiting the temperature that can be used during growth of the HTSC film to about 760°C. High quality HTSC film can be grown at higher tem ⁇ perature.
- strontium titanate has a lattice spacing of about 3.92 Angstroms which is close to the approximate 3.9 Angstroms lattice spacing of YBa 2 Cu 3 0 7 . x , it is far from the lattice spacing of sapphire (about 3.5 Angstroms). This lattice mismatch can cause some grains to grow in undesired directions.
- Strontium titanate buffers are usually deposited in a thickness of at least 100 Angstroms which increases micro- wave losses and is not conducive to the formation of the smoothest HTSC films.
- the calcium titanate can be a bulk substrate or a thin buf- fer film or a substrate of different composition such as silicon or sapphire.
- Calcium titanate has a lattice spacing of about 3.82 Angstroms which is intermediate to the lattice spacing of YBa 2 Cu 3 0 7 . ⁇ ( ⁇ 3.9 Angstroms) and sapphire ( ⁇ 3.5 Angstroms). Calcium titanate films can be grown with less strain. Thinner films have less dislocations and crystal defects. Epitaxial films of calcium titanate which are 100 Angstroms in thickness or less provide excellent substrates for grow ⁇ ing thin HTSC films. Thinner buffer films provide lower microwave losses.
- the deposition temper ⁇ ature can be substantially higher, e.g. about 800°C which contributes to the quality and performance of the HTSC film.
- Preliminary measurements indicate that the critical current density of the HTSC film are about 2 times better than comparable films grown on strontium titanate buffer films on sapphire.
- Figure 6 illustrates the data from 3 different meas ⁇ urements of the surface resistance of 500 Angstrom thick 123 YBCO films grown on 100 Angstrom thick CaTi ⁇ 3 buffer layers. The surface resistivity was scaled to 10 GHz.
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Abstract
On fabrique des structures stratifées supraconductrices à haute température destinées à être utilisées dans des applications à micro-ondes par dépôt d'une couche mince de tampon épitaxial (14) tel que du titanate de strontium ou du titanate de calcium, selon un procédé de dépôt tel que l'ablation au laser sur un substrat (12) en saphir à faible perte, suivi par le dépôt d'un film formé par croissance in-situ de supraconducteur (16) à haute température tel que Y1Ba2Cu3O7 sur la couche tampon. Le film YBCO a une faible résistance de surface et une plage de températures de transition étroite.
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
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US49473090A | 1990-03-16 | 1990-03-16 | |
US494730 | 1990-03-16 | ||
US07/495,568 US5132282A (en) | 1990-03-16 | 1990-03-16 | High temperature superconductor-strontium titanate sapphire structures |
US495568 | 1990-03-16 | ||
US565691 | 1990-08-13 | ||
US07/565,691 US5130294A (en) | 1990-08-13 | 1990-08-13 | High temperature superconductor-calcium titanate structures |
PCT/US1991/001788 WO1991014028A1 (fr) | 1990-03-16 | 1991-03-18 | Films supraconducteurs a haute temperature sur substrats d'oxyde d'aluminium |
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EP0610175A4 EP0610175A4 (fr) | 1993-03-01 |
EP0610175A1 true EP0610175A1 (fr) | 1994-08-17 |
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EP91907776A Withdrawn EP0610175A1 (fr) | 1990-03-16 | 1991-03-18 | Films supraconducteurs a haute temperature sur substrats d'oxyde d'aluminium |
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EP (1) | EP0610175A1 (fr) |
AU (1) | AU7653391A (fr) |
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EP0512679A3 (en) * | 1991-05-02 | 1993-01-27 | General Electric Company | Method of making laser ablated oriented films on metal substrates and articles formed thereby |
US6986955B2 (en) * | 2000-08-03 | 2006-01-17 | Ngimat Co. | Electronic and optical materials |
Citations (1)
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DE3834402C1 (fr) * | 1988-10-10 | 1989-05-03 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe, De |
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JPS63241823A (ja) * | 1987-03-27 | 1988-10-07 | Nissin Electric Co Ltd | 超電導薄膜の製造方法 |
KR910007382B1 (ko) * | 1987-08-07 | 1991-09-25 | 가부시기가이샤 히다찌세이사꾸쇼 | 초전도 재료 및 초전도 박막의 제조방법 |
DE3744145A1 (de) * | 1987-12-24 | 1989-07-06 | Asea Brown Boveri | Supraleiter und verfahren zu seiner herstellung |
US4874741A (en) * | 1988-04-14 | 1989-10-17 | The Research Foundation Of State University Of New York | Non-enhanced laser evaporation of oxide superconductors |
US4943558A (en) * | 1988-04-15 | 1990-07-24 | Ford Motor Company | Preparation of superconducting oxide films using a pre-oxygen nitrogen anneal |
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1991
- 1991-03-18 EP EP91907776A patent/EP0610175A1/fr not_active Withdrawn
- 1991-03-18 WO PCT/US1991/001788 patent/WO1991014028A1/fr not_active Application Discontinuation
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Non-Patent Citations (3)
Title |
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JOURNAL OF CRYSTAL GROWTH. vol. 109, no. 1/4, February 1991, AMSTERDAM NL pages 401 - 417 SCHIEBER ET AL 'deposition of high temperature superconducting films' * |
Section Ch, Week 8528, 30 May 1985 Derwent Publications Ltd., London, GB; Class CH, AN 85-167860 & JP-A-60 096 599 (NIPPON TELEGR & TELEPH.) 30 May 1985 * |
See also references of WO9114028A1 * |
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EP0610175A4 (fr) | 1993-03-01 |
WO1991014028A1 (fr) | 1991-09-19 |
AU7653391A (en) | 1991-10-10 |
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