TWI509850B - 超導膜元件及超導膜元件之製備方法 - Google Patents
超導膜元件及超導膜元件之製備方法 Download PDFInfo
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- TWI509850B TWI509850B TW104111340A TW104111340A TWI509850B TW I509850 B TWI509850 B TW I509850B TW 104111340 A TW104111340 A TW 104111340A TW 104111340 A TW104111340 A TW 104111340A TW I509850 B TWI509850 B TW I509850B
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- superconducting film
- bacuo
- yba
- superconducting
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- 238000000034 method Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000758 substrate Substances 0.000 claims description 120
- 238000004544 sputter deposition Methods 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 12
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- -1 Lanthanum Aluminate Chemical class 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 2
- 238000010309 melting process Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 description 88
- 239000010408 film Substances 0.000 description 88
- 239000000843 powder Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 238000001816 cooling Methods 0.000 description 16
- 230000004907 flux Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000002887 superconductor Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 229910002113 barium titanate Inorganic materials 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Description
本提案係關於一種超導膜元件及超導膜元件之製備方法,特別是一種含有Y2
BaCuO5
奈米顆粒作為釘札中心之YBa2
Cu3
O7
之超導膜元件及超導膜元件之製備方法。
超導發電機由於具有體積小、重量輕以及效率高等優點,因此是能源領域中重要的研究課題。
目前高溫超導線材成本仍高。詳細來說,依照目前製程所製備的超導線材的臨界電流密度仍有改善的空間。因此,如何提高超導線材的臨界電流密度就成為高溫超導應用普及的關鍵。
一般而言,超導線材是處於高磁場的環境下應用。磁場所發出的磁力線係以量子磁通的形式穿過超導線材。由於超導線材上的電流與量子磁通之間存在有羅倫茲力,量子磁通會因為羅倫茲力而移動,而降低了超導線材的效能。也就是說,如何降低量子磁通因為羅倫茲力而移動的情形就成為目前的研究方向。
為了降低、避免量子磁通因羅倫茲力移動而降低超導線材的效能,目前發展出在超導線材的超導體內產生晶格缺陷或非超導相的方法。詳細來說,是藉由晶格缺陷或者非超導相作為釘札中心,以限制量子磁通在超導體
的移動。如此一來,透過在超導體內所形成的釘札中心,可改善所製備的超導線材的效能。
為了在超導線材的超導體內形成釘札中心,可透過離子照射的
方法,以在超導體內形成缺陷。然而,離子照射的方法較為昂貴。因此,在超導體內形成非超導相奈米顆粒作為釘札中心,對於超導線材的商用化是比較可行的作法。而如何改善目前在超導體內形成非超導相奈米顆粒的製程,以提升所製備的超導線材的效能,就成為研究人員需要解決的問題。
本提案是關於一種超導膜元件及超導膜元件之製備方法,藉以改善超導膜的設計,以提升超導膜的效能。
本提案一實施例所揭露之超導膜元件,包含一基板以及一超導膜。基板之晶格常數介於5.0Å(埃)至5.5Å之間。超導膜設置於基板上。超導膜包含YBa2
Cu3
O7
及Y2
BaCuO5
。其中Y2
BaCuO5
分散於YBa2
Cu3
O7
中。
本提案一實施例所揭露之超導膜元件的製備方法,包含以下步驟。提供一基板,基板之晶格常數介於5.0Å(埃)至5.5Å之間。提供一靶材,靶材包含YBa2
Cu3
O7
及Y2
BaCuO5
。執行一鍍膜程序,使靶材於基板上同時形成YBa2
Cu3
O7
及Y2
BaCuO5
。其中Y2
BaCuO5
分散於YBa2
Cu3
O7
中。
根據本提案實施例所揭露之超導膜元件及超導膜元件之製備方法,由於基板之晶格常數介於5.0Å至5.5Å之間,而超導體YBa2
Cu3
O7
之晶格常數a
=3.821Å,b
=3.885Å,因而基板與超導體之晶格常數具有相當之差異。另一方面,由於YBa2
Cu3
O7
與Y2
BaCuO5
是鍍膜時同時成長生成,Y2
BaCuO5
將形成奈米顆粒並均勻分布於YBa2
Cu3
O7
內,亦即達到了釘札中心微小化及分散化
的效果。如此一來,超導體YBa2
Cu3
O7
內有均勻分布的非超導相Y2
BaCuO5
奈米顆粒,可做為超導膜之釘札中心,並進而改善了超導膜之臨界電流密度。
9‧‧‧超導線材
10‧‧‧超導膜元件
20‧‧‧載體
100‧‧‧基板
200‧‧‧超導膜
第1圖為本提案一實施例所揭露之超導膜元件的製備方法之示意圖。
第2A圖為本提案一實施例所揭露之超導膜元件之示意圖。
第2B圖為本提案一實施例所揭露之超導線材之示意圖。
第3圖為本提案實施例一之超導膜的穿透式電子顯微鏡之分析結果。
第4圖為本提案比較例一之超導膜的穿透式電子顯微鏡之分析結果。
第5圖為本提案比較例三之超導膜的穿透式電子顯微鏡之分析結果。
第6圖為實施例一、二以及比較例一、二之超導膜於絕對溫度77度,不同磁場下的臨界電流密度。
以下在實施方式中詳細敘述本提案之詳細特徵以及優點,其內容足以使任何熟習相關技藝者了解本提案之技術內容並據以實施,且根據本說明書所揭露之內容、申請專利範圍及圖式,任何熟習相關技藝者可輕易地理解本提案相關之目的及優點。以下之實施例係進一步詳細說明本提案之觀點,但非以任何觀點限制本提案之範疇。
首先,請參閱第1圖。第1圖為本提案一實施例所揭露之超導膜元件的製備方法之示意圖。
首先,提供一基板(S101)。基板之晶格常數介於5.0Å(埃)至5.5Å之間。基板之材質例如為釔安定氧化鋯(Yttria-stabilized zirconia,YSZ)(晶格
常數a=5.139Å)、鋁酸鑭(Lanthanum Aluminate,LaAlO3
,LAO)(晶格常數a=5.364Å)、Y3
NbO7
(晶格常數a=5.250Å)、Gd2
Zr2
O7
(晶格常數a=5.264Å)、二氧化鈰(CeO2
)(晶格常數a=5.411Å)或NdGaO3
(晶格常數a=5.431Å),但並不以此為限。
接著,提供一靶材(S102)。靶材包含釔、鋇以及銅。靶材之組成元素是對應於所欲製備之超導膜。在另一實施例中,靶材例如包含有YBa2
Cu3
O7
及Y2
BaCuO5
,其中Y2
BaCuO5
佔靶材之總重之百分之5至百分之15重量百分比(wt%)。在部分實施例中,Y2
BaCuO5
佔靶材之總重之百分之8重量百分比。在本實施例中,所欲製備之超導膜之材質包含YBa2
Cu3
O7
(超導相)以及顆粒狀之Y2
BaCuO5
(非超導相),其中Y2
BaCuO5
佔超導膜之總重之百分之5至百分之15重量百分比(wt%)。在部分實施例中,Y2
BaCuO5
佔超導膜之總重之百分之8重量百分比。在本實施例中,靶材例如是透過一頂端接種熔融製程(Top Seeded Melt Textured Growth Process)或一燒結程序而形成,因而靶材較為緻密而具有較佳之品質,而可提升所製成之超導膜的臨界電流密度(Jc)。
須注意的是,上述提供一基板(S101)以及提供一靶材(S102)之順序並非用以限定本提案。在其他實施例中,也可以先提供一靶材,再提供一基板。
最後,執行一鍍膜程序(S103)。藉此,使靶材於基板上同時形成YBa2
Cu3
O7
及Y2
BaCuO5
。在本實施例中,雷射的中心波長為248奈米。在本實施例及部分其他實施例中,雷射的聚焦能量密度介於1.5焦耳/平方公分(J/cm2
)至2.0焦耳/平方公分之間。在本實施例及部分其他實施例中,鍍膜程序之基板溫度係介於780℃至850℃之間。
在鍍膜的過程中,靶材會分別形成YBa2
Cu3
O7
及Y2
BaCuO5
。詳細來說,由於YBa2
Cu3
O7
與Y2
BaCuO5
會接觸基板,並且因為本實施例之基板的晶格常數(5.0Å至5.5Å)與超導相YBa2
Cu3
O7
之晶格常數(a
=3.821Å,b
=3.885Å)差異較大,因而YBa2
Cu3
O7
與Y2
BaCuO5
會在鍍膜程序中同時成長生成於基板上,並且Y2
BaCuO5
是形成奈米顆粒並均勻分布於YBa2
Cu3
O7
內,亦即達到了釘札中心微小化及分散化的效果。
當釘札中心小而分散時,可有效增加釘札中心數量,並且使量子磁通更平均地分佈於超導相內,因而降低量子磁通間的互斥力,故能有效提升釘札效果,亦即臨界電流密度可得到提升。
以下介紹本提案之超導膜元件。請參閱第2A圖,第2A圖為本提案一實施例所揭露之超導膜元件之示意圖。本提案之超導膜元件10包含一基板100以及一超導膜200。本提案所指基板100例如是指超導線材中的緩衝層,特別是超導線材中超導膜所接觸、設置的緩衝層。基板100之晶格常數介於5.0Å至5.5Å之間。超導膜200設置於基板100上。超導膜200之材質包含YBa2
Cu3
O7
(超導相)以及Y2
BaCuO5
(非超導相)。Y2
BaCuO5
分散於YBa2
Cu3
O7
中,並且YBa2
Cu3
O7
及Y2
BaCuO5
接觸基板100。
在本提案部分實施例中,Y2
BaCuO5
是呈奈米顆粒狀。
在本提案部分實施例中,Y2
BaCuO5
之顆粒粒徑介於15奈米至30奈米之間。
在本提案部分實施例中,Y2
BaCuO5
佔超導膜200之總重之百分之5至百分之15重量百分比(wt%)。在部分實施例中,Y2
BaCuO5
佔超導膜200之總重之百分之8重量百分比(wt%)。
在本提案部分實施例中,基板100之材質為釔安定氧化鋯(Yttria-stabilized zirconia,YSZ)(晶格常數a=5.139Å)、鋁酸鑭(Lanthanum Aluminate,LaAlO3
,LAO)(晶格常數a=5.364Å)、Y3
NbO7
(晶格常數a=5.250Å)、Gd2
Zr2
O7
(晶格常數a=5.264Å)、二氧化鈰(CeO2
)(晶格常數a=5.411Å)或NdGaO3
(晶格常數a=5.431Å),但並不以此為限。
在本提案部分實施例中,超導膜200之厚度介於150奈米(nm)至350奈米之間。
本提案實施例之超導膜元件10可應用至超導線材中。請參閱第2B圖,第2B圖為本提案一實施例所揭露之超導線材之示意圖。如圖所示,超導線材9包含有超導膜元件10以及載體20。超導膜元件10設置於載體20。由於超導線材9包含有本提案之超導膜元件10,因而具有較佳的工作表現。
以下透過數個實施例以及比較例來說明本提案之超導膜元件的製備方法。
實施例一(LAO基板)
首先製備YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu分別為1:2:3及2:1:1等比率量秤,各自混合均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末。接著將YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末以重量百分比92:8之比例均勻混合,以25~35Mpa之壓力壓成塊,並於其表面中心放置SmBa2
Cu3
O7
晶種,於908℃持溫4小時,升溫至1045℃持溫1小時。最後以4℃/hr的降溫速率降溫至992℃,接著以0.2℃/hr的降溫速率降溫至982℃,最後自然降溫至室溫,便完成靶材製作。將內含
8wt%(重量百分比)Y2
BaCuO5
之YBa2
Cu3
O7
靶材以及LAO基板(LaAlO3
)置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提升至850℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之範圍內時,但厚度不以此為限,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基板溫度自然下降至室溫,即完成了實施例一之超導膜的製備。請參閱第3圖,第3圖為本提案實施例一之超導膜的穿透式電子顯微鏡之分析結果。如第3圖所示,Y2
BaCuO5
以顆粒狀之形式均勻分布於YBa2
Cu3
O7
之內,且Y2
BaCuO5
的粒徑約介於15奈米至30奈米之間。
實施例二(YSZ基板)
首先製備YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu分別為1:2:3及2:1:1等比率量秤,各自混合均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末。接著將YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末以重量百分比92:8之比例均勻混合,以25~35Mpa之壓力壓成塊,並於其表面中心放置SmBa2
Cu3
O7
晶種,於908℃持溫4小時,升溫至1045℃持溫1小時。最後以4℃/hr的降溫速率降溫至992℃,接著以0.2℃/hr的降溫速率降溫至982℃,最後自然降溫至室溫,便完成靶材製作。將內含8wt%(重量百分比)Y2
BaCuO5
之YBa2
Cu3
O7
靶材以及YSZ基板(釔安定氧化鋯)
置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提升至850℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之範圍內時,但厚度不以此為限,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基板溫度自然下降至室溫,即完成了實施例二之超導膜的製備。
實施例三(Y3
NbO7
基板)
首先製備YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu分別為1:2:3及2:1:1等比率量秤,各自混合均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末。接著將YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末以重量百分比92:8之比例均勻混合,以25~35Mpa之壓力壓成塊,並於其表面中心放置SmBa2
Cu3
O7
晶種,於908℃持溫4小時,升溫至1045℃持溫1小時。最後以4℃/hr的降溫速率降溫至992℃,接著以0.2℃/hr的降溫速率降溫至982℃,最後自然降溫至室溫,便完成靶材製作。將內含8wt%(重量百分比)Y2
BaCuO5
之YBa2
Cu3
O7
靶材以及Y3
NbO7
基板置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提升至850℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而
在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之範圍內時,但厚度不以此為限,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基板溫度自然下降至室溫,即完成了實施例三之超導膜的製備。
實施例四(Gd2
Zr2
O7
基板)
首先製備YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu分別為1:2:3及2:1:1等比率量秤,各自混合均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末。接著將YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末以重量百分比92:8之比例均勻混合,以25~35Mpa之壓力壓成塊,並於其表面中心放置SmBa2
Cu3
O7
晶種,於908℃持溫4小時,升溫至1045℃持溫1小時。最後以4℃/hr的降溫速率降溫至992℃,接著以0.2℃/hr的降溫速率降溫至982℃,最後自然降溫至室溫,便完成靶材製作。將內含8wt%(重量百分比)Y2
BaCuO5
之YBa2
Cu3
O7
靶材以及Gd2
Zr2
O7
基板置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提升至850℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之範圍內時,但厚度不以此為限,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基
板溫度自然下降至室溫,即完成了實施例四之超導膜的製備。
實施例五(二氧化鈰基板)
首先製備YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu分別為1:2:3及2:1:1等比率量秤,各自混合均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末。接著將YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末以重量百分比92:8之比例均勻混合,以25~35Mpa之壓力壓成塊,並於其表面中心放置SmBa2
Cu3
O7
晶種,於908℃持溫4小時,升溫至1045℃持溫1小時。最後以4℃/hr的降溫速率降溫至992℃,接著以0.2℃/hr的降溫速率降溫至982℃,最後自然降溫至室溫,便完成靶材製作。將內含8wt%(重量百分比)Y2
BaCuO5
之YBa2
Cu3
O7
靶材以及二氧化鈰基板(CeO2
)置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提升至850℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之範圍內時,但厚度不以此為限,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基板溫度自然下降至室溫,即完成了實施例五之超導膜的製備。
實施例六(NdGaO3
基板)
首先製備YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu分別為1:2:3及2:1:1等比率量秤,各自混合
均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末。接著將YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末以重量百分比92:8之比例均勻混合,以25~35Mpa之壓力壓成塊,並於其表面中心放置SmBa2
Cu3
O7
晶種,於908℃持溫4小時,升溫至1045℃持溫1小時。最後以4℃/hr的降溫速率降溫至992℃,接著以0.2℃/hr的降溫速率降溫至982℃,最後自然降溫至室溫,便完成靶材製作。將內含8wt%(重量百分比)Y2
BaCuO5
之YBa2
Cu3
O7
靶材以及NdGaO3
基板置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提升至850℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之範圍內時,但厚度不以此為限,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基板溫度自然下降至室溫,即完成了實施例六之超導膜的製備。
比較例一(鈦酸鍶基板,STO基板)
首先製備YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu分別為1:2:3及2:1:1等比率量秤,各自混合均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末。接著將YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末以重量百分比92:8之比例均勻混合,以25~35Mpa之壓力壓成塊,並於其表面中心放置SmBa2
Cu3
O7
晶種,於908℃持溫4小時,升溫至
1045℃持溫1小時。最後以4℃/hr的降溫速率降溫至992℃,接著以0.2℃/hr的降溫速率降溫至982℃,最後自然降溫至室溫,便完成靶材製作。將內含8wt%(重量百分比)Y2
BaCuO5
之YBa2
Cu3
O7
靶材以及STO基板(SrTiO3
)置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提升至850℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之範圍內時,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基板溫度自然下降至室溫,即完成了比較例一之超導膜的製備。請參閱第4圖,第4圖為本提案比較例一之超導膜的穿透式電子顯微鏡之分析結果。如圖所示,黑色部分代表YBa2
Cu3
O7
,白色部分則為Y2
BaCuO5
,比較例一之超導膜內的Y2
BaCuO5
聚集成層狀。
比較例二(STO基板)
首先製備YBa2
Cu3
O7
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu為1:2:3之比率量秤,混合均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
起始粉末。接著將YBa2
Cu3
O7
起始粉末以25~35Mpa之壓力壓成塊,於900℃持溫8小時進行燒結,最後自然降溫至室溫,便完成YBa2
Cu3
O7
靶材製作。將YBa2
Cu3
O7
靶材以及STO基板(SrTiO3
)置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提
升至780℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之範圍內時,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基板溫度自然下降至室溫,即完成了比較例二之超導膜的製備。
比較例三(MgO基板)
首先製備YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末,將Y2
O3
、BaCO3
及CuO等粉末以莫耳比率Y:Ba:Cu分別為1:2:3及2:1:1等比率量秤,各自混合均勻後,以900℃持溫8小時煆燒後,研磨均勻並再度煆燒2次,亦即共進行煆燒3次,即可得到YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末。接著將YBa2
Cu3
O7
及Y2
BaCuO5
起始粉末以重量百分比92:8之比例均勻混合,以25~35Mpa之壓力壓成塊,並於其表面中心放置SmBa2
Cu3
O7
晶種,於908℃持溫4小時,升溫至1045℃持溫1小時。最後以4℃/hr的降溫速率降溫至992℃,接著以0.2℃/hr的降溫速率降溫至982℃,最後自然降溫至室溫,便完成靶材製作。將內含8wt%(重量百分比)Y2
BaCuO5
之YBa2
Cu3
O7
靶材以及MgO基板置入濺鍍設備之腔室內。然後,透過抽氣幫浦以將腔室內之壓力降低至約10-6
毫巴(mbar)。將腔室內之基板溫度提升至850℃。通入300毫托耳(mTorr)的氧氣於腔室內。接著,使用中心波長為248奈米之雷射光源進行濺鍍,將靶材濺鍍至基板,而在基板上形成薄膜。其中,雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。待基板上之薄膜(即,超導膜)之厚度介於150-350奈米之
範圍內時,將腔室內之基板溫度降低至500℃。然後,通入0.8-1大氣壓(atm)的氧氣於腔室內,並維持0.5-1小時。最後,使腔室內之基板溫度自然下降至室溫,即完成了比較例三之超導膜的製備。請參閱第5圖,第5圖為本提案比較例三之超導膜的穿透式電子顯微鏡之分析結果。如圖所示,比較例三之基板的鎂原子擴散至超導膜。
請參閱下表一及表二,表一為實施例一及實施例二之基板、晶格常數、靶材以及超導膜之臨界電流密度之比較結果。表二為比較例一至比較例三之基板、晶格常數、靶材以及超導膜之臨界電流密度之比較結果。其中,實施例一及實施例二、比較例一以及比較例三係使用相同靶材(YBa2
Cu3
O7
及Y2
BaCuO5
)但不同之基板,而比較例二所使用之靶材為YBa2
Cu3
O7
。
由於實施例一及實施例二之基板的晶格常數與超導膜YBa2
Cu3
O7
之晶格常數(a
=3.821Å,b
=3.885Å)差異較大,因而在鍍膜的過程中,YBa2
Cu3
O7
與Y2
BaCuO5
是同時成長生成並且Y2
BaCuO5
會形成奈米顆粒並均勻分布於YBa2
Cu3
O7
內,亦即達到了釘札中心微小化及分散化的效果,如第3圖穿透式電子顯微鏡照片所示。在比較例一中,比較例一與實施例一及實施例二之差別在於比較例一使用的基板為鈦酸鍶基板。鈦酸鍶基板的晶格常數為3.905Å,與超導膜YBa2
Cu3
O7
之晶格常數相近。在第4圖之穿透式電子顯微鏡之分析結果中,黑色部分代表YBa2
Cu3
O7
,白色部分則為Y2
BaCuO5
。相較於第3圖,在第4圖中,由於比較例一所用之鈦酸鍶基板的晶格常數與超導膜YBa2
Cu3
O7
之晶格常數相近,而使得Y2
BaCuO5
呈層狀聚集在一起,而非如第3圖呈奈米顆粒狀分散分布。也就是說,當釘札中心小而分散時,可有效增加釘札中心數量,並且使量子磁通更平均地分佈於超導相內,而降低量子磁通間的互斥力,故能有效提升釘札效果。亦即,臨界電流密度可得到提升。如表一所示,實施例一之臨界電流密度(3.26MA/cm2
)以及實施例二之臨界電流密度(2.06MA/cm2
)均明顯高於比較例一之電流密度(0.99MA/cm2
)。
在比較例二中,由於所使用的靶材未含有Y2
BaCuO5
,因而比較例二具有更低之臨界電流密度(0.11MA/cm2
)。
就比較例三而言,由於濺鍍程序需要780℃-850℃之溫度,而比
較例三之基板(MgO)中的鎂元素會在此溫度範圍內擴散至超導膜,如第5圖的鎂元素擴散,而破壞了超導膜中超導相的超導性質。請一併參閱第6圖,第6圖為實施例一、二以及比較例一、二之超導膜於溫度77K,不同磁場下的臨界電流密度。如圖所示,在77K、1T之環境下,實施例一之超導膜的臨界電流密度(Jc)達3.26MA/cm2
,實施例二之超導膜的臨界電流密度(Jc)達2.06MA/cm2
。
比較例一、二之超導膜的臨界電流密度則僅分別為0.99以及0.11MA/cm2
。
根據本提案實施例所揭露之超導膜元件及超導膜元件之製備方法,本提案是使用單一之靶材在基板上濺鍍超導膜,使生成超導相YBa2
Cu3
O7
及非超導相Y2
BaCuO5
,且基板之晶格常數介於5.0Å至5.5Å之間,因而基板與超導膜之晶格常數具有相當之差異,使得本提案所製備之超導膜內之Y2
BaCuO5
係顆粒狀均勻分布於YBa2
Cu3
O7
內,而達到微小化、分散化釘札中心的效果。如此一來,可有效增加釘札中心數量,並且使量子磁通更平均地分佈於超導體內,因而降低量子磁通間的互斥力,故能有效提升釘札效果,亦即臨界電流密度可得到提升。
此外,在本提案部分實施例中,由於靶材是透過頂端接種熔融製程或燒結程序製備,因而靶材質地較緻密,對於製作之超導膜的品質,亦有幫助。
雖然本提案已以實施例揭露如上,然其並非用以限定本提案,任何所屬技術領域中具有通常知識者,在不脫離本提案之精神和範圍內,當可作些許之更動與潤飾,故本提案之保護範圍當視後附之申請專利範圍所界定者為準。
10‧‧‧超導膜元件
100‧‧‧基板
200‧‧‧超導膜
Claims (16)
- 一種超導膜元件,包含:一基板,該基板之晶格常數介於5.0Å(埃)至5.5Å之間;以及一超導膜,設置於該基板上,該超導膜包含YBa2 Cu3 O7 及Y2 BaCuO5 ;其中該Y2 BaCuO5 分散於該YBa2 Cu3 O7 中,該Y2 BaCuO5 佔該超導膜之總重之百分之5至百分之15重量百分比,該Y2 BaCuO5 之顆粒粒徑介於15奈米至30奈米之間。
- 如請求項1所述之超導膜元件,其中該Y2 BaCuO5 及該YBa2 Cu3 O7 接觸該基板。
- 如請求項1所述之超導膜元件,其中該基板為釔安定氧化鋯(Yttria-stabilized zirconia,YSZ)、鋁酸鑭(Lanthanum Aluminate,LAO)、Y3 NbO7 、Gd2 Zr2 O7 、二氧化鈰(CeO2 )或NdGaO3 。
- 如請求項1所述之超導膜元件,其中該Y2 BaCuO5 係以顆粒狀之形式形成於該YBa2 Cu3 O7 中。
- 如請求項1所述之超導膜元件,其中該超導膜之厚度介於150奈米至350奈米之間。
- 如請求項1至請求項5中任一項所述之超導膜元件,可應用至超導線材。
- 一種超導膜元件的製備方法,其包含下列步驟:提供一基板,該基板之晶格常數介於5.0Å(埃)至5.5Å之間;提供一靶材,該靶材包含有YBa2 Cu3 O7 及Y2 BaCuO5 ;以及執行一鍍膜程序,使該靶材於該基板上同時形成YBa2 Cu3 O7 及Y2 BaCuO5 ,其中該Y2 BaCuO5 分散於該YBa2 Cu3 O7 中。
- 如請求項7所述之超導膜元件的製備方法,其中,該鍍膜程序之基板溫度介於780℃至850℃之間。
- 如請求項7所述之超導膜元件的製備方法,其中,該鍍膜程序係為一雷射濺鍍程序。
- 如請求項9所述之超導膜元件的製備方法,其中,該雷射濺鍍程序之雷射的聚焦能量密度介於1.5焦耳/平方公分至2.0焦耳/平方公分之間。
- 如請求項9所述之超導膜元件的製備方法,其中,該雷射濺鍍程序之雷射的中心波長為248奈米。
- 如請求項7所述之超導膜元件的製備方法,其中,於該鍍膜程序前另包含:執行一頂端接種熔融製程或一燒結程序。
- 如請求項7所述之超導膜元件的製備方法,其中該Y2 BaCuO5 佔該靶材之總重之百分之5至百分之15重量百分比。
- 如請求項7所述之超導膜元件的製備方法,其中,於該鍍膜程序中,該Y2 BaCuO5 係以顆粒狀之形式形成於該YBa2 Cu3 O7 內。
- 如請求項7所述之超導膜元件的製備方法,其中該基板為釔安定氧化鋯(Yttria-stabilized zirconia,YSZ)、鋁酸鑭(Lanthanum Aluminate,LAO)、Y3 NbO7 、Gd2 Zr2 O7 、二氧化鈰(CeO2 )或NdGaO3 。
- 如請求項7所述之超導膜元件的製備方法,其中該Y2 BaCuO5 及該YBa2 Cu3 O7 接觸該基板。
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US20070032384A1 (en) * | 2005-07-26 | 2007-02-08 | The Regents Of The University Of California | Structure for improved high critical current densities in YBCO coatings |
US7687436B2 (en) * | 2005-12-02 | 2010-03-30 | University Of Dayton | Flux pinning enhancements in superconductive REBa2CU3O7-x (REBCO) films and method of forming thereof |
JP5327932B2 (ja) * | 2007-02-08 | 2013-10-30 | 独立行政法人産業技術総合研究所 | 超電導コーティング材料の製造方法 |
CN101319387B (zh) * | 2008-06-16 | 2011-09-14 | 北京师范大学 | 一种高温超导体纳米结构阵列的制备方法 |
CN102142300B (zh) * | 2010-12-12 | 2012-06-20 | 西北有色金属研究院 | 一种第二相纳米粒子掺杂ybco薄膜的制备方法 |
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2015
- 2015-04-08 TW TW104111340A patent/TWI509850B/zh active
- 2015-05-11 CN CN201510233812.5A patent/CN105097126A/zh active Pending
- 2015-05-13 DE DE102015107614.4A patent/DE102015107614A1/de not_active Withdrawn
- 2015-05-13 JP JP2015098529A patent/JP2015220231A/ja not_active Withdrawn
- 2015-05-15 US US14/713,850 patent/US20150332813A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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TW369727B (en) * | 1994-12-19 | 1999-09-11 | Johnson Matthey Plc | Improved thick film superconductors and preparation thereof |
EP0971422A1 (en) * | 1998-07-03 | 2000-01-12 | International Superconductivity Technology Center | Oxide superconducting element and material |
Also Published As
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CN105097126A (zh) | 2015-11-25 |
JP2015220231A (ja) | 2015-12-07 |
DE102015107614A1 (de) | 2015-11-19 |
US20150332813A1 (en) | 2015-11-19 |
TW201545386A (zh) | 2015-12-01 |
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