CN1013813B - 高tc超导薄膜材料低温合成方法 - Google Patents
高tc超导薄膜材料低温合成方法Info
- Publication number
- CN1013813B CN1013813B CN88100403A CN88100403A CN1013813B CN 1013813 B CN1013813 B CN 1013813B CN 88100403 A CN88100403 A CN 88100403A CN 88100403 A CN88100403 A CN 88100403A CN 1013813 B CN1013813 B CN 1013813B
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- CN
- China
- Prior art keywords
- dpm
- metal organic
- mocvd
- film material
- present
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 title claims description 7
- 230000002631 hypothermal effect Effects 0.000 title claims description 3
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000005594 diketone group Chemical group 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001947 vapour-phase growth Methods 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract 1
- 229910002480 Cu-O Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- -1 diketone metalloid Chemical class 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 210000004055 fourth ventricle Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Vapour Deposition (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
本发明涉及超导薄膜材料的制造方法。本发明用金属有机化学气相淀积法(MOCVD)。以挥发性金属有机化合物为源，采用射频或微波等离子体为激发源，形成金属有机化学气相淀积(MOCVD)过程。在低于400℃温度下，于衬底材料表面形成高TC超导氧化物薄膜材料。
本发明方法可以在低温下直接合成高TC超导薄膜，不须经高温热处理。用本发明方法制造高TC超导薄膜材料，易于精确控制，淀积速率快，衬底材料广泛。制成的薄膜光亮平整，与衬底附着牢固而无明显的相互作用。
Description
本发明涉及超导薄膜材料的制造方法。
目前，制造高Tc超导薄膜材料的方法有：电子束蒸发，磁控溅射或高频溅射等物理气相淀积法（PVD），丝网印刷厚膜工艺，化学喷雾热解和等离子体喷涂等。这些工艺方法具有一个共同的问题：即是制备的薄膜材料必须经过后续高温（700℃-950℃）热处理才能获得高Tc超导电性。通过这样高温热处理发生高温固相反应不仅使得其材料膜表面十分粗糙，而且引起严重的衬底材料对薄膜的扩散污染，使得可用衬底材料稀少，且价格贵。尤其是高温热处理工艺难以与微电子学工艺相容，从而严重限制了高Tc超导材料膜在大规模集成电路中使用，更难于用于超导线材、带材的研制。
本发明的目的在于提供一种低温合成高Tc超导薄膜的方法，可以低温直接成膜，从而避免由高温热处理带来的不足之处。
本发明是这样实现的，用金属有机化学气相淀积法（MOCVD）：以挥发性金属有机化合物为源。这里挥发性金属有机化合物可以是钡、锶、铜的β二酮类螯合物Ba（DPM）2，Sr（DPM）2，Cu（AA）2，和Cu（DPM）2及钇和镧系元素（除Sm）的螯合物Ln（DPM）3，Ln（PTA）3和Ln（FOD）3。其中，DPM代表二特戊酰基甲烷，AA代表乙酰丙酮，PTA代表特戊酰基三氟丙酮，FOD是1，1，1，2，2，3，3，e氟7，7二甲基3，5庚二酮。在化学气相淀积反应器中，加温使其挥发。以适当流量的氧气或惰性气体和氧气的混合物为载气和反应介质，将挥发的源蒸汽载送到淀积区。采用射频或微波等离子体为激发源，形成低温等离子体辅助的化学气相淀积（MOCVD）过程。在等离子体环境中，金属有机源汽被分解、激活。这些具有相当高能量的激发态物种在400℃以下的衬底材料表面上发生淀积反应，直接形成高Tc超导氧化合物薄膜材料。
实施方案，做一个金属有机化合物气相淀积反应器，具有四个反应室，各室温度在80°-400℃之间不等。将钡、钇、铜的挥发性β二酮类固态螯合物分别放置在其中三个室，使其挥发。衬底材料放在第四室（淀积区）。以适当流量的氩气和氧气（Ar+O2）的混合物为载气和反应介质（氧气分压为10-80%），将挥发的源蒸汽载送到淀积区。在淀积区采用射频发生器（或微波发生器）为等离子体激发源，射频发生器频率为10.5MHz（或13.5MHz），功率为200W（微波发生器频率为2450MHz，功率为0-1.2KW可调）。体系总压力在射频等离子体情况下为0.1-1乇（在微波等离子情况下为1-20乇）在等离子体环境下，源汽在衬底材料表面上发生淀积反应，形成高Tc超导薄膜材料。
实施例1：
以Ba（DPM）2，Y（DPM）3，Cu（AA）2为挥发性源化合物，采用射频（13.56MHz）等离子体MOCVD工艺，三源区温度分别为250℃，150℃，150℃，载气（Ar+O2）流量范围10-20SCCM，O2/Ar之比为0.5-2.0，淀积区压力为3乇，衬底温度低于400℃，在YSZ（氧化钇稳定的氧化锆）单晶衬底上直接得到以YBa2Cu3O7-x超导化合物为主相的淀积薄膜。在玻璃衬底上得到非晶态薄膜，经就地等离子体退火得到以正交YBa2Cu3O7-x为主的薄膜。直流四端子法电阻测量表明，100K左右发生电阻急剧下降转变至78K，降低了90%以上。
实施例2：
采用电容耦合的射频等离子体（f＝13.56MHg）CVO装置，以β二酮类金属螯合物Ba（DPM）2，Y（DPM）3，及Cu（DPM）2为源，源温分别为250、140、140℃反应室总压力为2乇，Ar为载气，O2为反应气，YSZ单晶片为衬底，衬底温度400℃左右，淀积完成后就地热处理。四端子测量Tonset＝92K，零电阻温度为78.5K。
本发明方法可以在低温下直接合成高Tc超导薄膜，不须经高温热处理。用本发明方法制造高Tc超导薄膜材料，材料组成和物相易于精确控制，淀积速率快，所用衬底材料广泛，包括单晶，多晶SrTiO3，ZrO2，α-Al2O3，MgAl2O4，MgO，石英，BaF2，Si，玻璃等。用本发明方法制成的高Tc超导薄膜，平整光亮，与衬底附着牢固而无明显的相互作用。可与微电子学工艺相容，在大规模集成电路中使用。本发明方法也可用来研制超导带材、线材，制备新近发现的各种高Tc超导氧化物薄膜，如：Sr-La-Cu-O，Sr-Y-Cu-O，Ba-Y-Cu-O，Ba-Ln-Cu-O（Ln为镧系元素）以及它们的掺杂体系，制作各种形状复杂的器件。
Claims (3)
1、一种高Tc超导薄膜材料低温合成方法，其特征在于该方法是用金属有机化学气相淀积法(MOCVD)：以挥发性金属有机化合物为源，惰性气体和氧气的混合物为载气和反应介质，采用射频或微波等离子体为激发源，形成低温等离子体辅助的金属有机化学气相淀积(MOCVD)过程，在低于400℃温度下，于衬底材料表面形成高Tc超导氧化物薄膜材料。
2、如权利要求1所述方法，其特征在于所说挥发性金属有机化合物是指钡、锶、铜的β二酮类螯合物Ba（DPM）2，Sr（DPM）2，Cu（AA）2和Cu（DPM）2及钇和Ln的螯合物Ln（DPM）3，Ln（PTA）3和Ln（FOD）3。
其中：DPM代表二特戊酰基甲烷（即2，2，6，6，四甲基3，5庚二酮）
AA代表乙酰丙酮
PTA代表特戊酰基三氟丙酮（即1，1，1，三氟2，4己二酮）
FOD是1，1，1，2，2，3，3，e氟7，7二甲基3，5庚二酮
Ln代表镧系元素（除Sm）
3、如权利要求1所述方法，其特征在于也可用氧气作为载气和反应介质。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88100403A CN1013813B (zh) | 1988-01-20 | 1988-01-20 | 高tc超导薄膜材料低温合成方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88100403A CN1013813B (zh) | 1988-01-20 | 1988-01-20 | 高tc超导薄膜材料低温合成方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034449A CN1034449A (zh) | 1989-08-02 |
| CN1013813B true CN1013813B (zh) | 1991-09-04 |
Family
ID=4831324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88100403A Expired CN1013813B (zh) | 1988-01-20 | 1988-01-20 | 高tc超导薄膜材料低温合成方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013813B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4240423B2 (ja) * | 1998-04-24 | 2009-03-18 | 中部キレスト株式会社 | 金属酸化物薄膜形成用ターゲット材およびその製造方法、並びに該ターゲット材を使用した金属酸化物薄膜の形成法 |
| EP1271666A3 (en) * | 2001-06-22 | 2006-01-25 | Fujikura Ltd. | Oxide superconductor layer and its production method |
| CN115863567A (zh) * | 2022-11-24 | 2023-03-28 | 广东邦普循环科技有限公司 | 高倍率小粒径单晶正极材料的制备方法及其应用 |
-
1988
- 1988-01-20 CN CN88100403A patent/CN1013813B/zh not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1034449A (zh) | 1989-08-02 |
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