The disclosure relates to multi-showerhead metal organic chemical vapor deposition (MOCVD) reactors having multiple shower heads, particularly useful for manufacture of high temperature superconductor (HTS) tapes or wires, and to processes for manufacturing HTS tapes or wires, and to HTS tapes or wires producible using the disclosed reactor and/or method.
Second generation high temperature superconductor (HTS) tapes or wires consist of a rare-earth-barium-copper oxide (REBCO) layer deposited on a textured metal tape (typically Hastelloy or stainless steel). These have been deposited by physical vapor deposition techniques such as pulsed laser deposition (PLD) and reactive co-evaporation (RCE), by a solution technique such as metal organic deposition (MOD) and by metal organic chemical vapor deposition (MOCVD). For successful commercial use, kilometer-scale lengths of HTS tapes with uniform properties—and at costs comparable to copper cables of similar current carrying capacity—are needed. To date, no manufacturing equipment or process has been sufficiently successful to meet this need.
Use of photoexcited MOCVD has been proposed to improve the crystal quality of the REBCO layer and hence improve performance of the HTS tape. In addition, it has been suggested that photoexcitation may enable increasing the growth rate while maintaining good performance. However, there has been no process or reactor design in which photoexcitation can be used to produce kilometer lengths of HTS tape. In addition, or in the alternative, no reactor with photoexcitation has been demonstrated where high growth rates, uniform deposition and high reactor efficiency can be obtained over a large deposition zone—such as a 10 cm×100 cm deposition zone, for example. It would thus be desirable to establish a process and/or a reactor in which photoexcitation can be used to produce kilometer lengths of HTS tape and/or in which uniform deposition and high reactor efficiency can be obtained over a large deposition zone. Particularly if these properties can be achieved together in a process and/or reactor, it is believed that successful commercial production of HTS tapes can be achieved in that kilometer-length HTS tapes or wires can be produced with good quality and at reasonable cost.
According to some aspects of the present disclosure, a multiple showerhead chemical vapor deposition reactor is provided. The reactor comprises a reactor chamber enclosed by a chamber wall, the chamber having a length and a width, the length being greater than the width. The chamber wall has entry and exit seal ports at opposite ends of the chamber in the length direction for receiving and delivering a tape during deposition on said tape. The chamber contains a support plate for supporting said tape. The support plate has a length and a width, the length being greater than the width.
A precursor showerhead is positioned within the chamber, and has a length and a width, the length being greater than the width. The precursor showerhead positioned over the support plate with the length dimension of the precursor showerhead parallel to the length dimension of the support plate. First and second gas curtain shower heads are positioned within the chamber on either side of the precursor showerhead. The first and second gas curtain shower heads each have a length and a width with the length being longer than the width. The gas curtain showerheads are positioned with the length dimensions of the gas curtain showerheads aligned parallel to the length dimension of the precursor showerhead.
The reactor further comprises one or more first illumination sources positioned on a first side of the width of the chamber and one or more second illumination sources positioned on a second side of the width of the chamber. The illumination sources are so positioned and aligned as to be capable to illuminating an upper surface of said tape during deposition, by shining a beam of illumination under the respective gas curtain shower head and under the precursor showerhead to said upper surface.
According to other aspects of the present disclosure, a method of forming a kilometer(s)-length high temperature superconductor tape is provided. The method comprises feeding a textured tape from a feed roll, through a reactor chamber having a chamber wall, to a take-up roll; flowing high temperature superconductor precursors from an elongated precursor showerhead positioned in the chamber facing an upper surface of the tape, the precursor showerhead elongated in a direction along a centerline of the tape; flowing gas from first and second elongated gas curtain shower heads positioned in the chamber on either side of the precursor showerhead, the first and second elongated gas curtain shower heads elongated in a direction parallel to the centerline of the tape; and illuminating the upper surface of the tape with illumination from one or more first and one or more second illumination sources on opposing sides of the reactor, the illumination sources positioned so as to allow illumination to pass under a respective one of the curtain shower heads, and under the precursor showerhead, to the upper surface of the tape.
Additional features and advantages will be set forth in the detailed description which follows, and will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.
It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understanding the nature and character of the disclosure and the appended claims.
The accompanying drawings are included to provide a further understanding of principles of the disclosure, and are incorporated in, and constitute a part of, this specification. The drawings illustrate one or more embodiment(s) and, together with the description, serve to explain, by way of example, principles and operation of the disclosure. It is to be understood that various features of the disclosure disclosed in this specification and in the drawings can be used in any and all combinations. By way of non-limiting examples, the various features of the disclosure may be combined with one another according to the following embodiments.
The following is a brief description of the figures in the accompanying drawings. The figures are not necessarily to scale, and certain features and certain views of the figures may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.
In the drawings:
Additional features and advantages will be set forth in the detailed description which follows and will be apparent to those skilled in the art from the description, or recognized by practicing the embodiments as described in the following description, together with the claims and appended drawings.
As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
In this document, relational terms, such as first and second, top and bottom, and the like, are used solely to distinguish one entity or action from another entity or action, without necessarily requiring or implying any actual such relationship or order between such entities or actions.
Modifications of the disclosure will occur to those skilled in the art and to those who make or use the disclosure. Therefore, it is understood that the embodiments shown in the drawings and described above are merely for illustrative purposes and not intended to limit the scope of the disclosure, which is defined by the following claims, as interpreted according to the principles of patent law, including the doctrine of equivalents.
For purposes of this disclosure, the term “coupled” (in all of its forms: couple, coupling, coupled, etc.) generally means the joining of two components directly or indirectly to one another. Such joining may be stationary in nature or movable in nature. Such joining may be achieved with the two components and any additional intermediate members being integrally formed as a single unitary body with one another or with the two components. Such joining may be permanent in nature, or may be removable or releasable in nature, unless otherwise stated.
As used herein, the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. When the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. Whether or not a numerical value or end-point of a range in the specification recites “about,” the numerical value or end-point of a range is intended to include two embodiments: one modified by “about,” and one not modified by “about.” It will be further understood that the end-points of each of the ranges are significant both in relation to the other end-point, and independently of the other end-point.
The terms “substantial,” “substantially,” and variations thereof as used herein are intended to note that a described feature is equal or approximately equal to a value or description. For example, a “substantially planar” surface is intended to denote a surface that is planar or approximately planar. Moreover, “substantially” is intended to denote that two values are equal or approximately equal. In some embodiments, “substantially” may denote values within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.
Directional terms as used herein—for example up, down, right, left, front, back, top, bottom—are made only with reference to the figures as drawn and are not intended to imply absolute orientation.
As used herein the terms “the,” “a,” or “an,” mean “at least one,” and should not be limited to “only one” unless explicitly indicated to the contrary. Thus, for example, reference to “a component” includes embodiments having two or more such components unless the context clearly indicates otherwise.
A number of deposition methods for depositing YBCO layers on metal tapes exist.
These include pulsed laser deposition (PLD), reactive co-evaporation (RCE), metal organic deposition (MOD) and metal organic chemical vapor deposition (MOCVD). MOCVD has been used to deposit YBCO on metal tapes in a reel-to-reel process. The tapes are 12 mm wide and are passed multiple times to obtain a sufficiently thick layer in a reasonable time. Multiple passes are used because the deposition rate is low. At higher deposition rates the crystalline quality deteriorates and the desired performance (critical current, critical temperature, magnetic field performance, etc.) cannot be obtained. Photo-excitation assisted deposition has been used to achieve good quality layers at higher deposition rates, but poor utilization of the metal organic precursors and a poor uniformity of YBCO thickness have been encountered.
In general, the disclosure is directed to a metal organic chemical vapor deposition (MOCVD) reactor having multiple shower heads which is particularly suited for manufacture of high temperature superconductor (HTS) tapes or wires, and to processes for manufacturing HTS tapes or wires.
Disclosed is a reactor that enables the reel-to-reel deposition of high temperature superconductor layers, such as YBCO, on a kilometer-length textured metal tape, by photo-excited metal organic chemical vapor deposition with consistent high quality. The reactor can operate over long periods of time without appreciable attenuation of the photo-excitation, enabling kilometer(s)-scale tapes or wires to be produced.
Referring to
According to one embodiment, a first set 72 of light emitting diodes shines light on one half of the tape 20 and a second set 82 onto the other half, as indicated in
A heating mechanism such as channels (not shown) is provided to the reactor walls and other parts of the reactor to allow heating of the reactor parts and walls, such as by a flow of a heat transfer fluid, so as to maintain all reactor walls and internal part surfaces (except the LEDs or windows) at a high enough temperature to prevent condensation of precursors or reaction byproducts but not so high as to decompose them (for example, in the range of from 300 to 400° C., or about 350° C.).
With reference to
With reference again to
Precursors in a carrier gas are fed at multiple points 42 along a deposition zone having a length in the range of from 25 to 1000 cm, or from 50 to 500 cm, or from 60 to 300, or from 70 to 250 cm, or from 80 to 150 cm or about 100 cm, by the close-spaced (and central) precursor showerhead 40. The precursor showerhead 40 is positioned close (1-2 cm) to the textured tape 20. The precursor showerhead 40 has two porous plates (placed serially in the gas flow, functioning as a mixing plate and a showerhead) so as to provide enough pressure differential and even distribution of the precursors over the upper surface of the tape 20. Two additional showerheads 50, 60 create an inert gas curtain that prevent precursors or reaction byproducts from reaching the LEDs or the window through which the LED light is brought into the reactor 10. In addition, the LEDs or the window is placed in a purged recess 80 to further inhibit any precursor or reaction byproducts from reaching the light source. An exhaust manifold on the two sides (shown in
The precursor showerhead 40 produces a stagnant point flow to obtain uniform YBCO layers on a 10 cm wide metal (Hastelloy, stainless steel, etc) tape 20 while at the same time achieving high precursor utilization. The tape 20 could be narrower or wider, in which case a narrower or wider precursor showerhead 40 is needed. The length of the precursor showerhead 40 is desirably 100 cm long in this design but can be shorter or longer depending on the desired length of the deposition zone. Photo-excitation is desirably provided by light emitting diodes (LEDs) emitting at 385-405 nm (e.g. where the wavelength can be tailored to be shorter or longer) The beam of light from the LEDs on one side of the reactor is directed on to on half of the tape. Tape heating can be done bypassing a current through the tape or by tungsten-halogen lamps placed below the tape. A schematic of a reactor 10, where the tape 20 is heated by passing a current through it, is shown in
As can be seen in
The tape temperature is monitored by an emissivity corrected pyrometer or by one or more such pyrometers P as indicated in
The tape 20 is desirably brought into the reactor through differentially pumped chamber/outer enclosure 31 (
The tape 20 can alternatively or additionally be heated using tungsten-halogen lamps 120 placed under the tape 20 as also shown in
A group of the lamps 120 are desirably controlled by one PID controller that gets feedback from an emissivity corrected pyrometer P which monitors the top or bottom surface of the tape 20. Emissivity corrected optical pyrometers are placed along the length of the deposition zone to provide feedback to the particular group of lamps that are below them. Multi-zone heating zones enables the temperature profile along the tape to be adjusted. The pyrometers P can be positioned so as to monitor the temperature of the top surface of the tape or the bottom surface. If the pyrometers monitor the top surface, narrow diameter purged ports that are sealed at one end with a fused quartz window are fabricated within the showerhead as shown in
The tape can also be heated by an electrically heated susceptor (heater) placed in contact with the tape. The susceptor and the tape path will need to be curved to maintain good contact between the susceptor and the tape. In some embodiments, the radius of the curve is between about 20 to 50 m, preferably 25 m. In some embodiments, in order to maintain a constant height between the tape and the showerhead, the shower heads are also be curved
The tape may be heated using a combination of methods, such as Tungsten halogen lamps heating the tape from underneath and also heated by passage of electric current, as shown in
Using either a linear array of transmissive glass cylindrical lenses or a linear reflective collimator, such as available from Chromasens (Konstanz Germany). Light from the linear array of LEDs can thus be collimated in one dimension to illuminate the entire length and width of the tape, such as seen in the illustration of the beams 73, 83 in
One embodiment of a cylindrical lens that can work is a K&S Optics (Greene N.Y. USA) 100-200 cylindrical plano-convex lens made of N-BK7 with a focal distance of 10 mm and a diameter of 12.5 mm. The lens can be placed approximately 10 mm away from the LED to capture more than half the light from the LED and collimate it into a linear beam approximately 10 mm wide.
An alternative lens is one available from Thorlabs (Newton N.J. USA), the LJ1878L2-A, with similar focusing characteristics. The Thorlabs lens has one advantage, namely an antireflective coating for the 350 to 700 nm wavelength range that encompasses the wavelengths most of interest for the deposition chamber.
The linear reflective embodiment can use a reflector similar to the reflectors Type C or Type D from Chromasens, for example. Details of the specific form of the reflector can be tailored to the final form of the deposition chamber so the proper trade-off can be made between the uniformity and the efficiency of the light illumination.
The choice of metallic coating is important for the reflective elements. For wavelengths shorter than 500 nm, Aluminum is generally the low loss choice. At longer wavelengths, Silver and Gold are favored. If one material needs to be used across a wide range of wavelengths including wavelengths both above and below 500 nm, aluminum is generally preferred for its uniformly low loss.
The choice of LEDs wavelengths: It is possible to construct the arrays of LEDs with a diversity of wavelengths that are chosen to optimize the reaction and deposition processes. For this YCBO reactor, a series of wavelengths can be used from the UV into the visible. One embodiment has groups of 3 wavelength LEDs repeated along the length of the LED array with 365, 385 and 405 nm LEDs in the group to provide complete spectral coverage in the near UV and the shortest blue wavelength range. The same kind of wavelength diversity schemes can be made with other kinds of optical sources like lasers.
While exemplary embodiments and examples have been set forth for the purpose of illustration, the foregoing description is not intended in any way to limit the scope of disclosure and appended claims. Accordingly, variations and modifications may be made to the above-described embodiments and examples without departing substantially from the spirit and various principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.
This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application No. 62/809,986, filed Feb. 25, 2019, the content of which is incorporated herein by reference in its entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/US2020/019632 | 2/25/2020 | WO | 00 |
Number | Date | Country | |
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62809986 | Feb 2019 | US |