CN1755963B - 磁电阻效应元件及其制造方法 - Google Patents

磁电阻效应元件及其制造方法 Download PDF

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CN1755963B
CN1755963B CN2005100987654A CN200510098765A CN1755963B CN 1755963 B CN1755963 B CN 1755963B CN 2005100987654 A CN2005100987654 A CN 2005100987654A CN 200510098765 A CN200510098765 A CN 200510098765A CN 1755963 B CN1755963 B CN 1755963B
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大卫·D.贾亚普拉维拉
恒川孝二
长井基将
前原大树
山形伸二
渡边直树
汤浅新治
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Abstract

本发明涉及磁电阻效应元件及其制造方法，特别是涉及利用简单的溅射成膜法制作的具有极高磁电阻比的磁电阻效应元件及其制造方法。该磁电阻效应元件包含由一对强磁性层和位于其中间的势垒层组成的积层结构，至少一个强磁性层的至少与势垒层接触的部分为非晶态，势垒层是具有单晶结构的MgO层。

Description

磁电阻效应元件及其制造方法
技术领域
本发明涉及磁电阻效应元件及其制造方法，特别是涉及利用简单的溅射成膜法制作的具有极高磁电阻比的磁电阻效应元件及其制造方法。
背景技术
近年来，作为不挥发性储存器的被称为MRAM(Magnetoresistive Random Aceess Memory)的磁存储器装置受到瞩目，并逐渐进入实用化阶段。MRAM结构简单，容易达到千兆比特级的超高集成化，由于利用磁性动量的旋转而产生储存作用，从而具有可擦写的次数极大、并且能够使动作速度达到纳秒量级的特性。
图4所示的是MRAM的结构。在MRAM101中，102是存储器元件，103是字线，104是位线。多个储存器元件102分别配置在多个字线103和多个位线104的各交点位置，配置成网格状的位置关系。多个储存器元件102分别储存1比特的信息。
如图5所示，MRAM101的存储器元件102由在字线103和位线104的交点位置储存1比特信息的磁电阻效应元件即TMR元件110和具有开关功能的晶体管106组成。该存储器元件102中主要的特点是使用了TMR(Tunneling Magneto resistance)元件110。如图6所示，TMR元件的基本结构是强磁性金属电极(强磁性层)107/隧穿势垒层108/强磁性金属电极(强磁性层)109所组成的3层积层的结构。TMR元件110由一对强磁性层107、109和位于其中间的隧穿势垒层108构成。
如图6所示，TMR元件110具有以下特性：在隧穿势垒层108两侧的强磁性层107、109之间施加所需要的电压而流过恒定电流的状态下，施加外加磁场，强磁性层107、109的磁化方向同向平行时(所谓‘平行状态’)，TMR元件的电阻为最小((A)的状态：电阻值RP)，强磁性层的磁化方向反向平行时(所谓‘反平行状态’)，TMR元件的电阻为最大((B)的状态：电阻值RA)。因此，TMR元件110能够通过利用外加磁场得到平行状态和反平行状态，利用电阻值变化来进行信息的储存。
对于以上的TMR元件，为了实现具有实用性的千兆比特级的MRAM，需要使‘平行状态’的电阻值RP和‘反平行状态’的电阻值RA之差大。作为其指标使用的是磁电阻比(MR比)。MR比定义为[(RA-RP)÷RP]。
为了提高MR，原来所进行的是使强磁性金属电极(强磁性层)的电极材料最佳化，或在隧穿势垒层的制造方法上下功夫。例如，在特开2003-304010号公报和特开2004-63592号公报中提出了对强磁性金属电极(强磁性层)的材料使用FexCoyBz等几个最佳实施例的方案。
上述特开2003-304010号公报和特开2004-63592号公报中所公布的TMR元件的MR比低于70％，需要进一步提高MR比。
此外，最近，有关使用了MgO势垒层的单晶TMR薄膜，有报道使用MBE和超高真空蒸发装置制作Fe/MgO/Fe的单晶TMR薄膜，得到了MR比88％(汤浅新治、及另外4人，“High Tunnel Megnetoresistance at room temperature in Fully Epitaxial Fe/MgO/Tunnel Junctions due to Coherent Spin-Polarized Tunneling”，纳米电子学研究所，应用物理的日本期刊，2004年4月2日出版，第43卷、第4B号，p.L588-L590)。该TMR薄膜具有完全外延单晶的结构。
为了制作使用了上述文献中的单晶MgO势垒层的单晶TMR薄膜，需要使用昂贵的MgO单晶基片。此外，还有以下缺点：需要昂贵的MBE装置制备Fe膜的外延生长或超高真空电子束蒸发制备MgO薄膜等先进的成膜技术，成膜时间变长等不适合于批量生产的问题。
发明内容
本发明的目的是提供具有高MR比，提高量产性、提高实用性的磁电阻效应元件及其制造方法。
本发明的磁电阻效应元件及其制造方法为了达成上述目的，而采用以下结构。
该磁电阻效应元件的特征在于：包含由一对强磁性层和位于其中间的势垒层组成的积层结构，至少一个强磁性层的至少与势垒层接触的部分为非晶态，势垒层是具有单晶结构的MgO层。
采用上述磁电阻效应元件，通过势垒层具有单晶结构，使得强磁性层间的电流的流动可以直线前进，使其MR比为极高的值成为可能。
磁电阻效应元件较好是MgO层为利用溅射法成膜的单晶层。采用该结构，能够以简单的方法制作作为中间层的势垒层，最适合于量产。
磁电阻效应元件较好是MgO层为用MgO靶并且利用溅射法成膜的单晶层。
磁电阻效应元件较好是强磁性层为CoFeB层。
磁电阻效应元件的制造方法是包含由一对强磁性层和位于其中间的势垒层组成的积层结构的磁电阻效应元件的制造方法，做成至少与势垒层接触的部分为非晶态的强磁性层，使用溅射法制作具有单晶结构的势垒层。并且磁电阻效应元件的制造方法较好是在制作MgO层的溅射法中使用MgO靶，并且实施RF(射频)磁控溅射。
采用本发明，由于作为TMR元件等磁电阻效应元件的中间层的隧道势垒层是具有单晶结构的MgO层，从而能够使MR比极高，在将其用作MRAM的存储器元件时能够实现千兆比特级的超高集成度的MRAM。再有，通过利用溅射法制备上述单晶MgO层，能够制作适合于批量生产，实用性高的磁电阻效应元件。
本发明的所述目的以及特征，从与下面附图相关的优选实施例的技术可以明白。
附图说明
图1是展示本发明的磁电阻效应元件(TMR元件)的结构的图。
图2是展示制作本发明的磁电阻效应元件(TMR元件)的装置的俯视图。
图3是展示本发明的磁电阻效应元件(TMR元件)的磁特性的压力依赖关系的曲线图。
图4是展示MRAM的主要部分结构的立体图。
图5是展示MRAM的存储器元件的结构的图。
图6是说明TMR元件的特性的图。
具体实施方式
以下，基于附图来说明本发明的最佳实施例。
图1所示的是本发明的磁电阻效应元件的积层结构的一个例子，所示的是TMR元件的积层结构。根据该TMR元件10，在基片11上形成有构成TMR元件10的例如9层的多层膜。该9层的多层膜从最下层的第1层朝向最上层的第9层按‘Ta’、‘PtMn’、‘70CoFe’、‘Ru’、‘CoFeB’、‘MgO’、‘CoFeB’、‘Ta’、‘Ru’的顺序积层磁性膜。第1层(Ta：钽)为接地层，第2层(PtMn)为反铁磁性层，第3层到第5层(70CoFe、Ru、CoFeB)组成的层形成强磁性层。实际上的磁化固定层为第5层‘CoFeB’组成的强磁性层。第6层(MgO：氧化镁)为作为绝缘层的隧穿势垒层。第7层(CoFeB)为强磁性层，是磁化自由层。第6层(MgO)为在位于其上下的一对强磁性层(CoFeB)之间的中间层。第8层(Ta：钽)和第9层(Ru：铷)形成为硬屏蔽层。利用上述磁化固定层(第5层‘CoFeB’)和隧穿势垒层(第6层‘MgO’)和磁化自由层(第7层‘CoFeB’)形成作为基本结构狭义上的TMR元件部12。作为磁化固定层的第5层‘CoFeB’和作为磁化自由层的第7层‘CoFeB’是作为非晶态的强磁性体而知道的。作为隧穿势垒层的MgO层在整个厚度方向具有单晶结构而形成。
还有，在图1中，各层中括号中记载的数值表示各层的厚度，单位是‘nm(纳米)’。该厚度是一个例子，并不限定于此。
其次，参照图2对制造具有上述积层结构的TMR元件10的装置和制造方法进行说明。图2是制造TMR元件10的装置的概略俯视图，本装置是能够制作包含多层磁性膜的多层膜的装置，是批量生产用的溅射成膜装置。
图2所示的磁性多层膜制作装置20是组群式装置，具备基于溅射法的多个成膜腔室。在本装置20中，具备未图示出的机器人搬送装置的搬送腔室22设置在中间位置。在磁性多层膜制作装置20的搬送腔室22内设有2个装料/取料腔室25、26，分别进行基片(硅基片)11的搬入/搬出。通过交替使用这些装料/取料腔室25、26，而成为能够以更高的生产效率制作多层膜的结构。
在上述磁性多层膜制作装置20中，在搬送腔室22周围，例如，设有3个成膜腔室27A、27B、27C和一个刻蚀腔室28。在刻蚀腔室28对TMR元件10的所要表面进行刻蚀处理。在各腔室之间设置隔离两个腔室并根据需要开关自如的闸板阀30。还有，在各腔室附属设置有未图示出的真空排气机构、气体导入机构、电力供给机构等。
在磁性多层膜制作装置20的成膜腔室27A、27B、27C利用溅射法在基片11上分别从下侧依次沉积上述各磁性膜。例如在成膜腔室27A、27B、27C的顶部，分别配置有4个或5个配置于适当的圆周上的靶(31、32、33、34、35)、(41、42、43、44、45)，(51、52、53、54)。并且，在位于与该圆周同轴的位置上的基片台上配置基片。
在上述中，例如，靶31的材料为‘Ta’，靶33的材料为‘CoFeB’。此外，靶41的材料为‘PtMn’，靶42的材料为‘CoFe’，靶43的材料为‘Ru’。再有，靶51的材料为‘MgO’。
上述多个靶为了更有效地沉积适当组分的磁性膜，较好的是设置成朝向各基片倾斜，以与基片面平行的状态设置亦可。此外，基于多个靶和基片相对旋转的结构来配置。在具有上述结构的装置20中，图1所示的磁性多层膜是利用各成膜腔室27A、27B、27C通过溅射法在基片11上依次成膜的。
叙述作为本发明的主要元件部的TMR元件部12的成膜条件。磁化固定层(第5层‘CoFeB’)是用CoFeB组分比为60/20/20原子百分比的靶，以Ar压力0.03Pa，利用磁控DC溅射(磁控直流溅射)以溅射率来成膜的。接着，隧穿势垒层(第6层‘MgO’)是用MgO组分比为50/50原子百分比的靶，以Ar为溅射气体，压力在0.01～0.4Pa的范围改变来成膜的。利用磁控射频溅射以溅射率来进行成膜。然后，以与磁化固定层(第5层‘CoFeB’)相同的成膜条件制备磁化自由层(第7层‘CoFeB’)。
在本实施例中，MgO的成膜速率为但在0.01～
Figure B2005100987654D00054
的范围成膜也没问题。
在成膜腔室27A、27B、27C分别进行溅射而沉积结束的TMR元件10在热处理炉中进行退火处理。此时，退火温度为例如约300℃，在例如8kOe(632kA/m)的磁场中，进行例如4小时的退火处理。这样，使TMR元件10的第2层PtMn得到所要的磁化率。
图3所示的是测量MgO的磁性质的结果。在测量的全范围得到了高的MR比。特别地，在压力为0.05Pa或其以上0.2或其以下的范围，得到高的MR比。这可能是因为在压力为0.05Pa或其以上的范围，基片上的压力增加，离子碰撞降低，结果膜的缺陷减少。在压力为0.05Pa或其以上，MR比增大，隧穿电阻值(RA)增加。这可能是因为形成了良好的单晶膜，结果，膜的漏电流减少。另一方面，在0.05Pa或其以下的范围，隧穿电阻值(RA)降低，MR比下降。这被认为是离子碰撞增大导致MgO单晶膜的缺陷增多。以截面TEM观察样品的结果，在测量的压力的所有范围，MgO膜从下侧的界面直到上侧的界面横跨整个层具有单晶结构，观察到取向为MgO单晶的(001)面平行于界面。另外，观察到CoFeB层形成非晶状态。
此次的样品在MgO层的两侧的强磁性层都以非晶的CoFeB形成，但以非晶CoFeB仅形成某一层强磁性层都观察到同样的结果。该强磁性层至少与势垒层接触的部分具有非晶物质态就足够。
另一方面，在形成具有多晶结构的CoFe作为MgO层两侧的强磁性层时，在MgO层发现许多扩散，没得到良好的单晶膜，特性较差。
此时，如前所述，使用MgO靶51作为靶，并且较好是采用RF(射频)磁控溅射法。还有，使用反应溅射法，用Ar和O2的混合气体溅射Mg靶也能够形成MgO膜。
还有，在上述中，MgO层横跨整个层都是单晶，具有(001)面平行于界面的取向单晶结构。再有，形成TMR元件部12的一对强磁性层能够代替具有非晶态的CoFeB而使用CoFeZr、CoTaZr、CoFeNbZr、CoFeZr、FeTaC、FeTaN、FeC等具有非晶态的强磁性层。
对以上的实施例说明的结构、形状、大小以及配置关系来说，本发明只是以能够理解和实施本发明的程度大致地进行了说明，或者只是例示数值以及各结构的组成(材质)。因此，本发明并不限定于说明过的实施例，只要不超脱权利要求的范围所示的技术思想的范围，能够有各种变更。
本开示涉及到2004年9月7日提出的日本专利申请第2004-259280号所包含的主题，其公布内容因明确地参照其整体而被包括。

Claims (7)

1.一种磁电阻效应元件，包含：由第一强磁性层、第二强磁性层和位于所述第一强磁性层和第二强磁性层之间的势垒层组成的积层结构；以及位于所述第一强磁性层侧的基板，其特征在于：
所述势垒层自与所述第一强磁性层的界面至与所述第二强磁性层的界面，在层厚度方向上，具有(001)面与界面平行取向的单晶结构的MgO；所述第一强磁性层的至少与所述势垒层接触的部分为非晶态。
2.根据权利要求1所述的磁电阻效应元件，其特征在于：
所述第一强磁性层是CoFeB。
3.根据权利要求1所述的磁电阻效应元件，其特征在于：在所述势垒层成膜时，所述第一强磁性层是非晶态。
4.根据权利要求1-3中任一项所述的磁电阻效应元件，其特征在于：上述势垒层是用MgO靶并以溅射法成膜的层。
5.一种磁电阻效应元件的制造方法，该磁电阻效应元件包含由强磁性层和该强磁性层上的势垒层构成的积层结构，其特征在于：使至少表面为非晶态的强磁性层成膜，用溅射法使得从与所述强磁性层的界面至与所述强磁性层相反一侧的界面，在厚度方向上，将具有(001)面与界面平行取向的单晶结构的氧化镁的势垒层成膜的工序。
6.根据权利要求5所述的磁电阻效应元件的制造方法，其特征在于，所述强磁性层是CoFeB。
7.根据权利要求5所述的磁电阻效应元件的制造方法，其特征在于：使所述势垒层成膜的工序包括：使用溅射法使MgO层成膜的工序；以及进行退火处理的工序。
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