CN103000805A - 具有改进的隧穿势垒的磁隧道结 - Google Patents
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Abstract
具有改进的隧穿势垒的磁隧道结。本发明涉及一种制造适合于磁随机存取存储器(MRAM)的磁隧道结的方法,该磁隧道结包括第一铁磁层,隧穿势垒层以及第二铁磁层,该方法包括:形成第一铁磁层;形成隧穿势垒层;以及形成第二铁磁层;其中所述形成隧穿势垒层包括沉积金属镁层;以及氧化沉积的金属镁层,以便将金属镁转化为MgO;形成隧穿势垒层的步骤被执行至少两次,使得隧穿势垒层包括至少两层MgO。
Description
技术领域
本发明涉及一种制造适合于磁随机存取存储器(MRAM)单元的磁隧道结的方法,所述磁随机存取存储器单元具有低缺陷率(defectivity)和较高的击穿电压。
背景技术
图1示出了传统的磁随机存取存储器(MRAM)单元1。MRAM单元1包括磁隧道结2,该磁隧道结2由第一铁磁层21、第二铁磁层23和具有结电阻-面积乘积RA的隧穿势垒层22形成。在图1的实例中,MRAM单元打算使用热辅助(TA)写操作来被写入,而且磁隧道结2进一步包括交换耦合第二铁磁层23的第二反铁磁层25。在写操作期间,加热电流32可以经由电流线4在磁隧道结2中被传递以便在高温阈值加热磁隧道结2,在所述高温阈值,存储装置的磁化可以被自由转换。第一铁磁层21可具有自由转换的磁化或者也可由第一反铁磁层24交换耦合以便具有固定磁化。
隧穿势垒层22通常由氧化镁(MgO)层制成。实际上,大的例如高达200%的隧穿磁阻(TMR)可被获得用于包括结晶的基于MgO的隧穿势垒层22的磁隧道结2。这种由MgO制成的隧穿势垒层22可以通过使用射频磁控溅射法而被获得。然而,通过射频磁控溅射的MgO形成方法可在设备制造时引起标准化的隧穿电阻值(RA)的分散和产量因子的可能的退化。
在US6841395中,MgO势垒层由包括下列步骤的方法形成:金属镁层的膜形成,形成掺杂氧的金属镁层,以及使层压的层进入氧化过程。然而,在对镁层进行氧化的步骤期间,例如针孔的缺陷可能形成在MgO层表面上。缺陷形成可能是由于MgO氧化物具有比金属镁更大的体积的事实而发生的。因此,屈服于MgO隧穿势垒22的较低的电阻和较低的击穿电压,尤其是对于低于50ohmμm2的RA值,可能出现电流泄漏。当电流在磁隧道结2中被传递用于在MRAM单元1的TA写操作期间加热磁隧道结2,或者用于在MRAM单元1的读操作期间读取结电阻时,这种电流泄漏可能出现。缺陷的存在可能由此降低MgO隧穿势垒22的电阻,且包括这种MgO隧穿势垒22的磁隧道结2的隧穿磁阻TMR也会被降低。此外,还可以观察到势垒层22的较低的击穿电压。
减小针孔效应需要具有相对厚的镁层和/或生长相对厚的氧化层。增加MgO隧穿势垒层22的厚度可能产生太大以致于用于驱动磁隧道结设备的电压变得太高的RA。而且,如果原始镁层太厚,则单步氧化不会将该镁层完全氧化。于是该镁层将是氧化不足的(under oxidized),具有较低的RA,较低的TMR和较低的击穿电压。
发明内容
本公开涉及制造适合于磁随机存取存储器(MRAM)单元的磁隧道结的方法,该磁隧道结包括第一铁磁层,隧穿势垒层,以及第二铁磁层,该方法包括:形成该第一铁磁层;形成该隧穿势垒层;以及形成该第二铁磁层;其中所述形成该隧穿势垒层包括沉积金属镁层;以及将沉积的金属镁层进行氧化以便将金属镁转化为MgO;形成隧穿势垒层的步骤被执行至少两次,使得隧穿势垒层包括至少两层MgO。
这里公开的方法允许形成具有和传统隧穿势垒相比更高的击穿电压和低缺陷率的隧穿势垒。
附图说明
借助于作为实例给出并通过图说明的实施例的描述,能够更好地理解本发明,在所述图中:
图1示出了传统的包括磁隧道结的磁随机存取存储器(MRAM)单元;
图2说明了根据实施例的包括隧穿势垒层的磁隧道结;以及
图3表示根据实施例的包括两个随后沉积的金属镁层的隧穿势垒层。
具体实施方式
图2说明了根据实施例的磁随机存取存储器(MRAM)单元的磁隧道结2。该磁隧道结2包括第一铁磁层21,隧穿势垒层22,以及第二铁磁层23。在MRAM单元将采用热辅助切换(TAS)写操作被写入的情况下,该磁隧道结2可包括交换耦合第一铁磁层21的第一反铁磁层(未示出),使得第一存储层21的磁化在第一高温阈值可以被自由地定向,以及在该温度以下被钉扎。磁隧道结2可进一步包括交换耦合第二铁磁层23的第二反铁磁层(也未示出),以便在第二低温阈值钉扎它的磁化,并在第二高温阈值释放它。该第一和第二反铁磁层可以由锰基合金制成,例如IrMn,NiMn,PtMn或者FeMn,或由任何其它合适的金属制成。
该第一和第二铁磁层21、23的铁磁材料可包括来自由钴Co、铁Fe、硼B、镍Ni构成的组的元素,例如镍铁硼NiFeB,且优选为钴铁硼CoFeB,其提供极好的磁阻(TMR)响应。优选地,该第一和第二铁磁层21、23由基于CoFeB的合金制成。隧穿势垒层22可以是例如由在除了别的以外还包括氧化铝Al2O3的组中选择的氧化物制成的绝缘层。优选地,隧穿势垒层22由基于MgO的氧化物制成。在磁隧道结中使用基于MgO的氧化物使得在室温下实现可用的磁阻信号的增加高达200%电阻变化成为可能(Parkin等人,2004,Nat.Mater.3,862)。
根据实施例,制造磁隧道结2的方法包括:
形成第一铁磁层21;
形成隧穿势垒层22;以及
形成第二铁磁层23;
其中所述形成隧穿势垒层22包括沉积金属镁层;以及氧化沉积的金属镁层以便将金属镁转化为MgO并且获得MgO层22a。形成所述隧穿势垒层22的步骤被执行至少两次,使得隧穿势垒层22包括至少两层MgO层22a。
在实施例中,通过使用溅射沉积法来执行形成所述第一和第二铁磁层21、23以及沉积金属镁层。几个沉积步骤可以在同一溅射室中被执行,或者在不同的溅射室中被执行。可替换地,通过使用任何其它的真空膜沉积技术,例如离子束沉积或者脉冲激光沉积,来执行几个沉积步骤。金属镁层优选地被沉积为所包括的厚度在0nm和1.5nm之间,且优选地在0.3nm和1.2nm之间。
氧化沉积的金属镁层以便将金属镁转化为MgO氧化物可包括通过暴露于等离子体或氧流的氧化(自然氧化)。存在可以在给定的氧化条件下被氧化的最佳厚度。例如,如果镁层比该最佳厚度更厚,那么对于那些特定的氧化条件(较低的RA和较低的TMR),其将是氧化不足的。如果其更薄,那么其将被过氧化(较高的RA和较低的TMR)。在此,包含氧离子的等离子体被施加到金属镁层。等离子体氧化可以在垂直于所暴露的金属镁层的表面的方向上、在加速氧离子的情况下或者在没有加速氧离子的情况下被执行,以将氧离子注入其中。等离子体氧化还可以被执行,无论是否伴有定向加速,用于进行注入。等离子体氧化可以在室温下或者低于室温被执行。为了更快速且更彻底地将金属镁转变为MgO氧化物,等离子体氧化还可以在升高的温度下被执行,所述升高的温度高达隧道结的完整性将允许的温度(大约300-400℃)。在等离子体氧化过程中,控制氧化的设置是离子能量(利用等离子体源施加的功率)、处理时间,和被注入室中的氧的量,通常为500sccm。该方法比下面描述的自然氧化过程更快,但是可能导致在MgO层中嵌入一些缺陷。限制MgO层中的缺陷形成的一种可能的方式可包括使用自然氧化过程。在自然氧化过程中,在存在镁金属层的情况下引入一定量的氧气,并且在该情况下,“时间”和“压强”是氧化过程的唯一设置。典型的处理时间从100s变动到500s,且典型的处理压强从0.1Torr变动到50Torr。氧原子迁移到镁层中,并且形成MgO直到达到钝化层的厚度为止。退火过程将重组该MgO层或使该MgO层结晶。可替换地,对沉积的金属镁层进行氧化可通过利用自由基氧化(ROX)氧化金属来被执行。对沉积的金属镁层进行氧化的步骤通常在不同于溅射室的室中被执行。
在实施例中,沉积金属镁层进一步包括在沉积操作期间使用惰性气体,例如N。惰性气体有利地用于使金属镁层平整或平坦化,以及在氧化步骤期间避免MgO分子的压缩。
在另一实施例中,该方法进一步包括在形成隧穿势垒层22之前和之后沉积附加的金属镁层27的步骤。该附加的金属镁层27不被氧化,使得在制造磁隧道结2之后,磁隧道结2包括在隧穿势垒层22和第一铁磁层21之间以及在隧穿势垒层22和第二铁磁层23之间的附加的金属镁层27,所述附加的金属镁层27和隧穿势垒层22相邻。附加的金属镁层27有利于防止氧从MgO隧穿势垒层22迁移到第一和/或第二铁磁层21、23中。附加的金属镁层27优选地被沉积为厚度低于大约0.5nm。
在又一实施例中,该方法进一步包括在形成第一铁磁层21之后以及在形成第二铁磁层23之前沉积CoxFe1-x层26的步骤。由此形成的磁隧道结2包括在第一铁磁层21和隧穿势垒层22之间以及在多层势垒层22和第二铁磁层23之间的CoFe层26。CoFe层26通常被沉积为厚度高达大约1nm且优选地高达大约0.5nm。薄的CoFe层26有益于防止硼从第一和第二铁磁层21、23迁移到势垒层22中。
在氧化金属镁层的步骤期间,针孔29(见图3)可在形成MgO层22a的过程中被生成。此处,术语针孔可包括在MgO层22a中产生的任何类型的缺陷,包括非穿越式空洞(non-traversing cavity)、裂缝、穿越式孔等等。由于MgO氧化物具有比金属镁更大的体积的事实,针孔29通常在氧化步骤期间被形成,引起MgO层22a的某些扩张。MgO层22a的最终厚度可能由此在针孔位置处会局部较小。实际上,MgO层22a的有效厚度e对应于没有针孔的MgO层22a的厚度减去针孔29的深度d,如在图3的实例中所示的。
由于在氧化过程期间的MgO生长机制,针孔分布有可能从一个MgO层22a变化到另一个MgO层22a。因此,在形成多层势垒层22时,在先前沉积的MgO层22a′中形成的针孔29中的非常少的针孔或者没有一个针孔与在随后沉积的镁层22a″中形成的针孔对齐。这在图3中被示意性地说明,图3示出根据上述方法的两个随后沉积和氧化的MgO层22a′,22a″。在该实例中,在首先沉积的MgO层22a′上形成的针孔29没有与在其次沉积的MgO层22a″上形成的针孔29对齐。
形成多层势垒层22的沉积的MgO层22a′、22a″的数目越大,势垒层22包括通过所有镁层22a被对齐的针孔29的概率越低,并由此势垒层22包括穿越式孔的概率越低。
这又会导致势垒层22的更低的击穿电压。减少针孔的影响需要具有相对厚的镁层和/或生长相对厚的氧化层。
势垒层22和形成这种势垒层22的方法的另一优点是由于多个镁层22a引起的平整效应。在图3中,这种平整效应通过多层势垒层22的有效厚度E被说明,该有效厚度E对应于多个镁层22a′、22a″的累积厚度减去最后沉积的镁层22a″中的针孔29的深度d。从图3中可以看到,增加沉积的镁层22a′、22a″的数目降低了针孔深度d和有效势垒层厚度E的比率d/E(该有效势垒层厚度E接近在没有针孔情况下的势垒层的厚度T)。从而,通过这里公开的方法形成势垒层22。
增加沉积的镁层22a′、22a″的数目减小了针孔的影响,并允许多层势垒层22的电阻以及包括该多层势垒层22的磁隧道结2的TMR与对于没有针孔的相同厚度的势垒层22获得的电阻和TMR基本上类似。
在实施例中,可以使用这里公开的方法形成多层势垒层22,对于相同的RA值,其具有比具有单个MgO层的传统势垒层22更高的击穿电压(大于1V)。
参考数字和符号
1MRAM单元
2磁隧道结
21第一铁磁层
22隧穿势垒层
22a镁层,MgO层
23第二铁磁层
26CoFe层
27附加的镁层
29针孔
3选择晶体管
d针孔深度
e镁层的有效厚度
E势垒层的有效厚度
T没有针孔的势垒层的厚度
Claims (12)
1.一种制造适合于磁随机存取存储器(MRAM)单元的磁隧道结的方法,该磁隧道结包括第一铁磁层,隧穿势垒层和第二铁磁层,该方法包括:
形成第一铁磁层;
形成隧穿势垒层;以及
形成第二铁磁层;
所述形成隧穿势垒层包括沉积金属镁层;以及氧化沉积的金属镁层,以便将金属镁转化为MgO;形成隧穿势垒层的步骤被执行两次以上,使得隧穿势垒层包括两个以上的MgO层,以便减小势垒层包含通过所有MgO层被对齐的针孔的概率。
2.根据权利要求1所述的方法,其中沉积金属镁层进一步包括使用惰性气体以便使沉积的金属镁层平整。
3.根据权利要求1所述的方法,其中沉积的金属镁层的厚度被包括在0nm和1.5nm之间,且优选在0.3nm和1.2nm之间。
4.根据权利要求1所述的方法,进一步包括在所述形成第一铁磁层之后以及在所述形成第二铁磁层之前,沉积CoFe层。
5.根据权利要求1所述的方法,进一步包括在形成隧穿势垒层之前和之后沉积附加的金属镁层。
6.一种包括磁隧道结的MRAM单元,该磁隧道结包括第一铁磁层,隧穿势垒层和第二铁磁层,该磁隧道结是通过包括下述的方法来被制造的:
形成第一铁磁层;
形成隧穿势垒层;以及
形成第二铁磁层;
所述形成隧穿势垒层包括沉积金属镁层,以及氧化沉积的金属镁层,以便将金属镁转化为MgO;形成隧穿势垒层的步骤被执行两次以上,使得隧穿势垒层包括两个以上的MgO层,以便减小势垒层包含通过所有MgO层被对齐的针孔的概率。
7.一种包括磁隧道结的MRAM单元,该磁隧道结包括第一铁磁层,隧穿势垒层和第二铁磁层;该隧穿势垒层包括两个以上的MgO层。
8.根据权利要求7所述的MRAM单元,其中所述磁隧道结进一步包括在隧穿势垒层和第一铁磁层之间的金属镁层;以及在隧穿势垒层和第二铁磁层之间的金属镁层。
9.根据权利要求8所述的MRAM单元,其中所述金属镁层具有低于大约0.5nm的厚度。
10.根据权利要求7所述的MRAM单元,其中所述磁隧道结进一步包括在第一铁磁层和隧穿势垒层之间的CoxFe1-x层;以及在多层势垒层和第二铁磁层之间的CoxFe1-x层。
11.根据权利要求10所述的MRAM单元,其中所述CoxFe1-x层具有高达大约1nm的厚度。
12.根据权利要求10所述的MRAM单元,其中所述CoxFe1-x层具有高达大约0.5nm的厚度。
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WO2011081203A1 (ja) * | 2009-12-28 | 2011-07-07 | キヤノンアネルバ株式会社 | 磁気抵抗素子の製造方法 |
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US20130234266A1 (en) | 2013-09-12 |
EP2568305A1 (en) | 2013-03-13 |
KR20130028684A (ko) | 2013-03-19 |
CN103000805B (zh) | 2016-03-16 |
US10002973B2 (en) | 2018-06-19 |
EP2568305B1 (en) | 2016-03-02 |
RU2012138544A (ru) | 2014-03-20 |
RU2598863C2 (ru) | 2016-09-27 |
JP2013062501A (ja) | 2013-04-04 |
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