The present invention relates to a thin film material and a method of manufacturing the thin film material. More specifically, the invention relates to a thin film material having a single-crystal thin film layer excellent in crystallinity as well as a method of manufacturing the thin film material.
There are conventional thin film materials that are known, for example, as a superconducting thin film wire having, as an example of a single-crystal thin film layer, a superconducting layer formed directly on a substrate (see for example Japanese Patent Laying-Open Nos. 6-31604 (Patent Document 1), 6-68727 (Patent Document 2) and 6-68728 (Patent Document 3)) as well as a superconducting thin film wire having an intermediate thin film layer and a superconducting layer that are formed on a substrate (see for example “Development of High-Temperature Superconducting Thin Film Tape Using the ISD Method,” Fujino and six other authors, SEI Technical Review, September 1999, Vol. 155, pp. 131-135 (Non-Patent Document 1)).
Regarding such superconducting thin film wires as mentioned above, it is proposed to grind a surface of the substrate in advance for the purpose of forming such a single-crystal thin film layer as superconducting layer that has excellent properties (for example high critical current density) (see Patent Documents 1 to 3).
Problems to be Solved by the Invention
Regarding the above-described superconducting thin film wire having the intermediate thin film layer and the superconducting layer formed on the substrate, in the case where the intermediate thin film layer is formed on a surface of the substrate that has been ground and thereafter the superconducting layer is formed on the intermediate thin film layer, it is difficult to sufficiently improve the in-plane orientation of the superconducting layer formed as an example of a single-crystal thin film layer, since the surface of the intermediate thin film layer has not particularly undergone such a process as planarization. Consequently, there remains a problem that properties of the single-crystal thin film layer thus formed (for example, if the formed single-crystal thin film layer is a superconducting layer, such a property as critical current density of the superconducting layer) are not sufficiently improved.
The present invention is made to solve such a problem as describe above. An object of the present invention is to provide a thin film material and a method of manufacturing the thin film material with which properties of a single-crystal thin film layer formed on a substrate can be improved.
Means for Solving the Problems
A thin film material according to the present invention includes a substrate, an intermediate thin film layer formed on the substrate and comprised of one layer or at least two layers, and a single-crystal thin film layer formed on the intermediate thin film layer. An upper surface that is an upper surface of at least one layer of the intermediate thin film layer and that is opposite to the single-crystal thin film layer is ground.
Thus, the upper surface of the intermediate thin film layer that is opposite to the overlying thin film layer is ground to be smoothed, and accordingly such properties as surface smoothness and in-plane orientation of the single-crystal thin film layer formed on the ground upper surface can be improved.
A superconducting thin film material according to the present invention includes a substrate, an intermediate thin film layer formed on the substrate and comprised of one layer or at least two layers, and a single-crystal thin film layer formed on the intermediate thin film layer. A surface (upper surface) that is a surface of the intermediate thin film layer and that is in contact with the single-crystal thin film layer is ground.
Thus, the surface of the intermediate thin film layer that is in contact with the single-crystal thin film layer is ground to be smoothed, and accordingly such properties as surface smoothness and in-plane orientation of the single-crystal thin film layer formed on the ground surface can be improved. In the case where a superconducting thin film layer for example is formed as the single-crystal thin film layer, the improved surface smoothness and in-plane orientation of the single-crystal thin film layer (superconducting thin film layer) can provide improvements in such properties as critical current value and critical current density of the superconducting thin film layer.
A superconducting thin film material according to the present invention includes a substrate, an intermediate thin film layer and a single-crystal thin film layer formed on the intermediate thin film layer. The intermediate thin film layer includes a lower intermediate thin film layer formed on the substrate and comprised of one layer or at least two layers, and an upper intermediate thin film layer formed on the lower intermediate thin film layer and comprised of one layer or at least two layers. A surface (upper surface) that is a surface of the lower intermediate thin film layer and that is in contact with the upper intermediate thin film layer is ground.
Thus, the upper surface of the lower intermediate thin film layer is ground to be planarized, and accordingly the planarity of the upper surface of the upper intermediate thin film layer (upper surface opposite to the single-crystal thin film layer) is also improved. Therefore, such properties as surface smoothness and in-plane orientation of the single-crystal thin film layer formed on the upper intermediate thin film layer can be improved. In the case where a superconducting thin film layer for example is formed as the single-crystal thin film layer, the improved surface smoothness and in-plane orientation of the superconducting thin film layer can provide improvements in such properties as critical current value and critical current density of the superconducting thin film layer.
A method of manufacturing a thin film material according to the present invention includes the steps of preparing a substrate, forming an intermediate thin film layer comprised of one layer or at least two layers on the substrate, processing by grinding an uppermost surface of the intermediate thin film layer, and forming a single-crystal thin film layer on the uppermost surface of the intermediate thin film layer that is ground in the processing step.
Thus, the thin film material of the present invention can easily be manufactured. Further, since the single-crystal thin film layer can be formed on the uppermost surface of the intermediate thin film layer that has been ground to exhibit excellent planarity, the surface smoothness and in-plane orientation of the single-crystal thin film layer can be improved.
A method of manufacturing a thin film material according to the present invention includes the steps of preparing a substrate, forming a lower intermediate thin film layer comprised of one layer or at least two layers on the substrate, processing by grinding an uppermost surface of the lower intermediate thin film layer, forming an upper intermediate thin film layer comprised of one layer or at least two layers on the uppermost surface of the lower intermediate thin film layer that is ground in the processing step, and forming a single-crystal thin film layer on the upper intermediate thin film layer.
Thus, the thin film material of the present invention can easily be manufactured. Further, since the uppermost surface (upper surface) of the lower intermediate thin film layer is ground to be planarized, the planarity of the upper surface of the upper intermediate thin film layer (surface opposite to the single-crystal thin film layer) is also improved. Accordingly, such properties as surface smoothness and in-plane orientation of the single-crystal thin film layer formed on the upper intermediate thin film layer can be improved.
Effects of the Invention
As discussed above, according to the present invention, a thin film material having a single-crystal thin film layer excellent in surface smoothness and in-plane orientation can be obtained.
1 superconducting wire, 2 substrate, 3, 3a-3f intermediate layer, 4 superconducting layer, 10, 20 ground surface, 30, 40 upper surface
With reference to the drawings, embodiments of the present invention are hereinafter described. In the following drawings, like or corresponding components are denoted by like reference numerals and the description thereof is not repeated.
Referring to
As shown in
Referring then to
Next, the step of forming the intermediate layer is carried out (S20). In this step of forming the intermediate layer (S20), intermediate layer 3 made of an oxide is formed on the prepared substrate 2. For this intermediate layer 3, an oxide having such a crystal structure as rock salt type, fluorite type, perovskite type or pyrochlore type structure for example may be employed. As a film deposition method to be employed in the step of forming intermediate layer 3 (S20), an arbitrary film deposition method may be employed. For example, such a physical vapor deposition method as pulsed laser deposition (PLD) may be employed.
Then, the planarization step is performed (S30). In this planarization step (S30), CMP (Chemical Mechanical Polishing) is used to remove the upper surface layer of the aforementioned intermediate layer 3 by a predetermined thickness so as to accomplish the planarization. As a method to be employed for the planarization, any arbitrary method such as wet etching or mechanical polishing may be used instead of the aforementioned CMP.
At this time, the surface roughness (Ra) of ground surface 10 (see
After this, the step of forming the superconducting layer on intermediate layer 3 with its upper surface planarized is performed (S40). As a film deposition method to be employed in the step of forming superconducting layer 4 (S40), any arbitrary film deposition method may be employed. As employed in forming intermediate layer 3, such a physical vapor deposition method as pulsed laser deposition may be employed. Further, in the step of forming superconducting layer 4, the aforementioned PLD or ISD may be employed.
In this way, the superconducting wire shown in
Referring to
A superconducting wire 1 shown in
Referring to
First, the step of preparing the substrate shown in
Second, the step of forming the upper intermediate layer is performed (S22). In this step of forming upper intermediate layer 3b (S22) as well, an arbitrary film deposition method may be employed.
Then, the planarization step for planarizing the upper surface of upper intermediate layer 3b (S30) (see
Referring to
As shown in
Referring to
According to the method of manufacturing the superconducting wire shown in
Here, ground surface 20 of substrate 2 as planarized has a surface roughness (Ra) of at most 20 nm, more preferably at most 5 nm.
After this, similarly to the method of manufacturing the superconducting wire shown in
Referring to
A superconducting wire 1 shown in
Referring to
As shown in
After this, the step of forming the lower intermediate layer on ground surface 20 of substrate 2 is performed (S21). Thus, lower intermediate layer. 3a (see
Subsequently, the planarization step (S30) is performed by using the polishing for example to partially remove the upper surface of the lower intermediate layer and thereby accomplish planarization. For this planarization step (S30), CMP for example may be employed. In this way, at the upper surface of lower intermediate layer 3a, ground surface 10 (see
Following this, the step of forming upper intermediate layer 3b on ground surface 10 of lower intermediate layer 3a is performed (S22). Here, for the step of forming the lower intermediate layer (S21) and the step of forming the upper intermediate layer (S22), an arbitrary film deposition method may be employed. For example, such a physical vapor deposition as pulsed laser deposition may be employed.
Then, the step of forming superconducting layer 4 on upper intermediate layer 3b is performed (S40). In this way, the superconducting wire shown in
It is noted that, as shown in
As shown in
Superconducting wire 1 structured in the above-described manner also provides effects similar to those of superconducting wire 1 shown in
While upper intermediate layer 3b and lower intermediate layer 3a shown in
The characteristic structures of the superconducting wire, as an example of the thin-film material, according to the invention as described above, are summarized as follows. Superconducting wire 1 shown in
Superconducting wire 1 as the thin film material according to the present invention includes, as shown for example in
Thus, the upper surface (ground surface 10) of the intermediate thin film layer (intermediate layer 3) that is opposite to superconducting layer 4 is ground to be smoothed, and accordingly such properties as surface smoothness and in-plane orientation of the single-crystal thin film layer (superconducting layer 4) formed on the ground upper surface (ground surface 10) can be improved. Accordingly, the improved surface smoothness and in-plane orientation of superconducting layer 4 can provide improvements in such properties as critical current value and critical current density of superconducting wire 1.
Superconducting wire 1 as the thin film material according to the present invention includes, as shown in
Thus, the upper surface of lower intermediate layer 3a is ground to be planarized, and accordingly the upper surface (surface opposite to superconducting layer 4) of upper intermediate layer 3b can be improved in planarity. Therefore, such properties as surface smoothness and in-plane orientation of the single-crystal thin film layer (superconducting layer 4) formed on this upper intermediate layer 3b can be improved. The improved surface smoothness and in-plane orientation of superconducting layer 4 can provide improvements in such properties as critical current value and critical current density of superconducting layer 4.
Regarding the above-described superconducting wire 1, as shown for example in
Further, when the upper surface of intermediate layer 3 or the upper surface of lower intermediate layer 3a is to be ground, as ground in the case where the surface of substrate 2 is not ground, the planarity of the upper surface of intermediate layer 3 (or upper surface of lower intermediate layer 3a) is ensured to a degree before the upper surface of the intermediate or lower intermediate layer is ground. Therefore, the planarity of the upper surface of intermediate layer 3 (or upper surface of lower intermediate layer 3a) and the orientation of intermediate layer 3 can further be improved. Accordingly, such properties as the surface smoothness and in-plane orientation of the single-crystal thin film layer (superconducting layer 4) formed on the intermediate thin film layer (intermediate layer 3) can further be improved.
Regarding the above-described thin film material (superconducting wire 1), the single-crystal thin film layer (superconducting layer 4) is a superconducting thin film layer. In this case, as the structure of superconducting wire 1 provided as a thin film material, the structure of the thin film material of the present invention may be used. Therefore, the superconducting thin film layer (superconducting layer 4) may be formed as the single-crystal thin film layer as shown in
Regarding the above-described superconducting wire 1, substrate 2 may be made of a metal. Further, substrate 2 may be in the shape of a long strip. Intermediate layer 3 may be made of an oxide having a crystal structure of one of rock salt type, fluorite type, perovskite type and pyrochlore type. For example, intermediate layer 3 may be made of YSZ (yttria-stabilized zirconia), an oxide of a rare earth element like CeO2, BZO (BaZrO3), STO (SrTiO3) or Al2O3 for example. As shown in
As a method of manufacturing a thin film material according to the present invention, a method of manufacturing superconducting wire 1 includes the steps of preparing a substrate (S10), forming an intermediate layer 3 as an intermediate thin film layer 3 comprised of one layer or at least two layers on the substrate (S20, S21, S22), processing by grinding an uppermost surface of intermediate layer 3 (planarization step S30 in
As a method of manufacturing a thin film material according to the present invention, a method of manufacturing superconducting wire 1 includes the steps of preparing a substrate (S10), forming a lower intermediate layer 3a as a lower intermediate thin film layer comprised of one layer or at least two layers on the substrate (step S21 in
The method of manufacturing superconducting wire 1 discussed above further includes the substrate processing step for grinding a surface of substrate 2 (planarization step S50 for the substrate surface shown in
In order to confirm the effects of the present invention, the following experiment was conducted. Specifically, a sample of a Comparative Example as well as samples 1, 2 of Examples were prepared and the critical current density of the superconducting layer of each sample was measured, as indicated below. Table 1 shows a part of properties and the value of the measured critical current density of each sample.
In Comparative Example and Examples 1 and 2, the substrate, the intermediate layer formed on the substrate and the superconducting layer formed on the intermediate layer form the three-layer structure as shown in
The structure of each sample was confirmed. Regarding the sample of the Comparative Example, on the Ni alloy substrate as indicated above, YSZ was directly deposited as the intermediate layer to 1 μm without such processing as surface grinding of the substrate. Then, without such processing as grinding of the upper surface of the intermediate layer of YSZ, the HoBCO superconducting layer was deposited by pulsed laser deposition to a thickness of 0.25 μm on the intermediate layer.
As for the sample of Example 1, on the Ni alloy substrate, the YSZ as the intermediate layer was deposited by pulsed laser deposition to 1 μm as done for the sample of the Comparative Example. Then, the upper surface of this intermediate layer was ground by CMP to remove the upper surface by a thickness of 0.25 μm. This grinding process may be a two-step grinding process. Specifically, the first step is CMP using a common slurry for removing the upper surface of the intermediate layer by a predetermined thickness and the subsequent second step is grinding the upper surface of the intermediate layer using an abrasive cloth together with water instead of slurry (mechanical grinding). According to this approach, the common slurry is first used to perform normal CMP so as to carry out the grinding at a certain grinding rate (the thickness removed by grinding per unit time), thereafter the mechanical grinding is performed using water instead of slurry, and thus the precision in controlling the thickness removed by grinding can be improved, while the grinding rate decreases. Accordingly, both of the shortened processing time required for grinding and the improvement in precision in controlling the removed thickness can simultaneously be implemented to a degree. Further, for this grinding, any mechanical grinding method may be employed instead of CMP or another arbitrary method (wet etching for example) may be employed. On this intermediate layer having undergone this grinding, the HoBCO superconducting layer was deposited by pulsed laser deposition to a film thickness of 0.25 μm as done in the Comparative Example.
As for the sample of Example 2, the surface of the Ni alloy substrate was ground by CMP for surface grinding of the substrate. In this grinding process for the surface of the Ni alloy substrate, any arbitrary grinding method that is applicable to the grinding process for the intermediate layer discussed above may be used. Further, in the grinding process for the substrate surface, the surface of the substrate was ground by removing the surface by a thickness of 5 μm. As a result, the substrate surface had a surface roughness (Ra) of 2.5 nm. On the substrate surface having undergone the grinding process, the YSZ as the intermediate layer was deposited by pulsed laser deposition to a thickness of 1 μm. Then, the upper surface of the YSZ as the intermediate layer was ground by CMP by removing the surface by a thickness of 0.25 μm. Further, on the YSZ as the intermediate layer having undergone the grinding process, the HoBCO superconducting layer was deposited by pulsed laser deposition to a thickness of 0.25 μm.
As seen from Table 1, the value of the surface roughness of the YSZ as the intermediate layer is smaller in Examples 1, 2 as compared with that of the Comparative Example. Further, a comparison of the surface roughness of the YSZ as the intermediate layer between Example 1 and Example 2 shows that the value in Example 2 is smaller than that of Example 1. The reason therefor seems to be that, by grinding the substrate surface, the value of the surface roughness of the substrate serving as the underlying layer in Example 2 is allowed to be smaller than that of Example 1.
It is also seen from Table 1 that the value of the full width at half-maximum of the YSZ layer serving as the intermediate layer in Examples 1 and 2 is smaller than that in the Comparative Example. In addition, the value of the half width of the YSZ layer serving as the intermediate layer is smaller in Example 2 than Example 1. In other words, it is seen that the sample in Example 2 is most excellent in crystal orientation of the YSZ layer. Here, the half width (ΔΘ) refers to a characteristic value measured by the X-ray pole figure measurement that is a characteristic value indicating the crystal orientation of the YSZ layer.
Further, the critical current density of the superconducting layer was measured for each of the Comparative Example and Examples 1 and 2. As a result, as seen from Table 1, the critical current density of the superconducting layer in the Comparative Example is 0 while that is 0.7 in Example 1 and is 2.1 in Example 2. In other words, it is seen that the critical current density is larger in Example 2 than that in Example 1.
As a preferred example of the thin film material of the present invention, a superconducting wire 1 as shown in
As shown in
The upper surface of substrate 2 is a ground surface 20 that has been ground. The upper surface of the second intermediate layer 3d (namely the upper surface of lower intermediate layer 3a) is a ground surface 10 that has been ground. As a method of grinding, CMP is used as described in connection with Example 1. Instead, another arbitrary grinding method may be employed.
As substrate 2, the Ni alloy substrate is used as an example of the metal substrate. Further, as a material for the first intermediate layer 3c, ceria (cerium oxide) is used. This first intermediate layer 3c is a so-called seed layer for providing good orientation to the second intermediate layer 3d for example, and another material may also be used for the first intermediate layer. The first intermediate layer 3c may have thickness T1 of at most 1 μm for example.
As a material for the second intermediate layer 3d, YSZ is used. The second intermediate layer 3d is formed as an anti-diffusion layer for preventing elements that are constituents of superconducting layer 4 formed above from diffusing toward substrate 2. In order to allow this anti-diffusion capability to surely be exhibited, thickness T2 of the second intermediate layer 3d is set to be relatively larger than respective thicknesses of other intermediate layers (thickness T1 of the first intermediate layer 3c and thickness T3 of upper intermediate layer 3b). For example, thickness T2 of the second intermediate layer 3d may be at most 4 μm. As a material for the second intermediate layer 3d, any arbitrary material may be used instead of YSZ.
As a material for upper intermediate layer 3b, ceria (cerium oxide) for example is used. Upper intermediate layer 3b is so-called lattice-matched layer and is provided with the purpose of forming a layer having a lattice constant relatively close to the lattice constant of superconducting layer 4 so as to form superconducting layer 4 with good orientation on the upper surface of the upper intermediate layer. Thickness T3 of upper intermediate layer 3b may be at most 1 μm for example. As a material for upper intermediate layer 3b, any arbitrary material may be used instead of ceria.
As superconducting layer 4, the HoBCO superconducting layer is used. This HoBCO superconducting layer is deposited by pulsed laser deposition as done for the sample of Example 1. The thickness of the HoBCO superconducting layer may be 0.25 μm for example.
The upper surface of substrate 2 is ground surface 20 that has been ground using for example CMP and that may have a surface roughness (Ra) of 2.5 nm for example. Thus, the upper surface of substrate 2 is ground surface 20 and accordingly the planarity of the upper surface of substrate 2 serving as an underlying layer of intermediate layer 3 (second intermediate layer 3d for example) can be ensured. As a result, the initial surface roughness of the surface to be ground of intermediate layer 3 can be reduced. Therefore, in the case where the (upper) surface of intermediate layer 3 (second intermediate layer 3d for example) is ground to achieve a predetermined surface roughness, an amount of grinding can be reduced and thus the time required for the manufacturing process of the superconducting wire can be shortened. Further, since the upper surface of substrate 2 serving as an underlying layer is ground surface 20 with good planarity, the orientation of the intermediate layer (particularly lower intermediate layer 3a) can be improved.
Furthermore, the upper surface of the second intermediate layer 3d is also ground surface 10 having undergone the grinding process using CMP for example. The surface roughness (Ra) of the second intermediate layer 3d may be for example 2.1 nm. Thus, the upper surface of the second intermediate layer 3d is ground surface 10 so that the layer formed on the second intermediate layer 3d (upper intermediate layer 3b and superconducting layer 4) can be improved in orientation.
In addition, the second intermediate layer 3d serves as an anti-diffusion layer and thus has relatively large thickness T2 as described above. In the case where film thickness T2 is thus large, the planarity of the upper surface of the second intermediate layer 3d tends to be worse as film thickness T2 is larger. In other words, under the condition that respective underlying layers of the first intermediate layer 3c, the second intermediate layer 3d and upper intermediate layer 3b are the same, the upper surface of the second intermediate layer 3d tends to have the largest surface roughness. Therefore, the upper surface of the second intermediate layer 3d that has the largest surface roughness (the worst planarity) can be ground to provide ground surface 10 so as to most effectively obtain intermediate layer 3 having excellent planarity.
Moreover, the upper surface of the second intermediate layer 3d (ground surface 10) could have strain accumulated due to the grinding process. Presence of such a defect as strain could influence orientation for example of superconducting layer 4 in the case where superconducting layer 4 is formed directly on this ground surface 10. Therefore, upper intermediate layer 3b is formed on ground surface 10 and superconducting layer 4 is formed on this upper intermediate layer 3b. Thus, even if such a defect is present in ground surface 10, film properties (such a property as orientation) of superconducting layer 4 can be prevented from being influenced.
In superconducting wire 1 shown in
In addition, upper surface 30 of the first intermediate layer 3c or upper surface 40 of upper intermediate layer 3b for example may be ground to provide a ground surface. For example, upper surface 30 of the first intermediate layer 3c may be a ground surface to further improve the orientation of the second intermediate layer 3d and upper intermediate layer 3b. Further, the planarity of the upper surface in the initial state of the second intermediate layer 3d for example formed on the first intermediate layer 3c can be improved, so that the amount of grinding can be reduced in the grinding process for grinding the upper surface of the second intermediate layer 3d with the purpose of providing a predetermined surface roughness. Moreover, when upper surface 40 of upper intermediate layer 3b is provided as a ground surface, the orientation of superconducting layer 4 can further be improved.
It should be considered that embodiments and examples disclosed here are presented in all respects by way of illustration and example, not by way of limitation. It is intended that the scope of the present invention is defined not by the embodiments but by claims and involves all modifications in the meaning and range equivalent to the claims.
The present invention is applicable to a thin film material having a single-crystal thin film layer. In particular, the invention is applicable to a thin film material having such a single-crystal thin film layer as superconducting layer required to be excellent in such properties as surface smoothness and in-plane orientation.
Number | Date | Country | Kind |
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2004-210023 | Jul 2004 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP05/10831 | 6/14/2005 | WO | 11/27/2006 |