CN101887910A - 一种适合于半导体闪存器件的栅叠层结构及制备方法 - Google Patents
一种适合于半导体闪存器件的栅叠层结构及制备方法 Download PDFInfo
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Abstract
本发明属于半导体集成电路制造技术领域，具体为一种适合于闪存器件的栅叠层结构及其制备方法。该栅叠层结构以P型(100)晶向的硅片为衬底，自下而上依次为：Al2O3薄膜，作为电荷隧穿层；钌基纳米晶，作为第一种电荷俘获层；HfxAlyOz薄膜，作为第二种电荷俘获层；Al2O3薄膜，充当电荷阻挡层；上电极层。本发明中，钌基纳米晶具有很好的热稳定性，在高温下不容易扩散；HfxAlyOz薄膜具有较高的电荷陷阱密度；上电极采用金属钯，拥有较大的功函数。因此该栅叠层结构在纳米晶存储电容器中有广阔的应用前景。
Description
技术领域
本发明属于半导体集成电路制造技术领域，具体涉及一种快闪存储器的电容结构和制备方法，尤其涉及基于金属纳米晶和高介电常数介质的新型异质电荷俘获层及制备方法。
背景技术
随着半导体工艺技术的不断发展，非挥发性快闪存储器集成密度越来越高、操作电压越来越低，这就驱使器件特征尺寸持续减小，在65nm技术节点之后传统的多晶硅浮栅结构出现了一系列的问题，极大地影响了器件存储的性能，诸如擦写速度慢，工作电压高等[1]。基于非连续电荷俘获机理(如纳米晶、SONOS存储器等)的新一代非挥发性存储器最近引起了广泛关注，它们采用分离的电荷陷阱代替连续的多晶硅浮栅存储电荷，使得隧穿层中存在的局部缺陷不会引起电荷俘获层中大量的电荷流失，从而有效地提高了存储器的数据保存能力，并且可以获得更低的操作电压，实现更快的擦写速度等[2，3]。与半导体纳米晶相比，金属纳米晶在费米能级附近有更高的态密度，功函数的选择范围更广，与衬底沟道有较强的耦合等[2]，故其能够实现较低的操作电压、较高密度的电荷存储和较长时间的电荷保留。研究表明，通过选择具有较大功函数的金属纳米晶，可以形成较深的势阱，从而有效地俘获电荷并能提供更好的数据保存特性。另一方面，随着SONOS存储器的发展，采用高介电常数材料(High-k)代替SONOS中的氮化硅电荷俘获层[4]，能够相应地增加降落在隧穿层上的电场强度，从而提高编程和擦除速度。但是这种结构存储器的缺点是其操作电压较高，并且操作速度较慢[5]。因此，为了充分结合上述两种结构的优点，本发明提出了以金属纳米晶和高介电常数介质结合在一起的异质电荷俘获层的存储器电容结构。
这种新型异质电荷俘获层中由于引入了高介电常数介质，所以可以增加降落在隧穿层上的电场强度，达到降低电荷注入的势垒，从而提高存储器的编程和擦除速度，同时实现器件在较低的电压下操作。同时，拥有较大功函数的金属纳米晶可以形成较深的势阱，从而在俘获电荷后有较好的数据保存特性。因此，这种新型异质电荷俘获层结构存储器能更好地满足下一代非挥发性快闪存储器的要求，有更大的应用前景。
本发明中的纳米晶为钌和氧化钌的复合物(记为RuOx)，它具有很好的热稳定性，既使被氧化，也是一种良好的导体。此外，它在高温下不容易扩散，易于干法刻蚀。本发明中高介电常数介质为HfxAlyOz(y＝0或＞0)，它的介电常数在10～25之间，具有较高的电荷陷阱密度，这就使得HfxAlyOz材料可以作为理想的电荷俘获层代替氮化硅。本发明中的电极采用金属钯(Pd)材料，它拥有较大的功函数(5.22eV)，能与电荷阻挡层介质形成有利于电荷擦写的垫垒高度，且钯具有良好的化学稳定性和热稳定性，因此其在纳米晶存储电容器中有很大的应用前景。
参考文献
[1]J.D.Blauwe，IEEE Trans.Nanotechnology 1，1(2002).
[2]J.J.Lee，and D.L.Kwong，IEEE Trans.Electron Devices 52，507(2005).
[3]H.L.Hanafi，S.Tiwari，and I.Khan，IEEE Trans.Electron Devices 43，1553(1996).
[4]P.-H.Tsai，K.-S.Chang-Liao，C.-Y.Liu，T.-K.Wang，P.J.Tzeng，C.H.Lin，L.S.Lee，and M.-J.Tsai.IEEE Electron Device Letters，29，265(2008).
[5]B.Govoreanu，D.P.Brunco，and J.Van Houdt，Solid-State Electronics，49，1841-1848(2005).
发明内容
本发明的目的是提供一种存储电荷密度高、操作电压低、擦写速度快且电荷保持特性好的适合于半导体闪存器件的栅叠层结构。
本发明的再一目的是提供上述栅叠层结构的制备方法。
本发明提出的栅叠层结构存储电容器，采用钌基纳米晶和高介电常数HfxAlyOz薄膜组成异质电荷俘获层，该栅叠层结构以P型(100)晶向的硅片为衬底，自下而上依次为：
1)原子层淀积的Al2O3薄膜，作为电荷隧穿层，厚度为5～15纳米；
2)钌基纳米晶RuOx，作为第一种电荷俘获层；
3)原子层淀积的高介电常数HfxAlyOz薄膜，作为第二种电荷俘获层，厚度为5～10纳米；
4)原子层淀积的15～40纳米厚的Al2O3薄膜，充当电荷阻挡层；
5)上电极层。
本发明提出的栅叠层结构存储电容器制备方法的步骤为：
以P型单晶硅片为衬底层，用原子层淀积的方法生长的Al2O3薄膜作为电荷隧穿层，厚度为5～15纳米。
在形成隧穿层之后，接着磁控溅射一层2～4纳米厚的钌膜，然后在N2气氛中，于700～900℃下快速热退火10～30秒，形成钌基纳米晶，其中含有金属钌和氧化钌(记为RuOx)，作为第一种电荷俘获层。
接着，原子层淀积5～10纳米厚的高介电常数HfxAlyOz薄膜，作为第二种电荷俘获层，HfxAlyOz薄膜中x＞0，z＞0，同时y＝0或y＞0。其中Hf与Al的组成通过原子层淀积HfO2和Al2O3的循环数来确定。
随后，原子层淀积15～40纳米厚的Al2O3薄膜作为电荷阻挡层，同时进行淀积后快速热退火处理，条件为温度500～800℃，时间10～30秒。
最后，经过标准的光刻工艺，利用lift-off方法形成栅电极，栅电极厚度为50～200纳米。本发明中适用于快闪存储器的栅叠层结构的剖面示意图如图1所示。
本发明中，原子层淀积Al2O3的条件为：衬底温度控制在250-350℃范围内，反应前驱体为三甲基铝Al(CH3)3(TMA)和水蒸汽。原子层淀积HfO2的条件为：衬底温度控制在250-350℃范围内，反应前驱体为四(乙基甲胺基)铪(TEMAH)和水蒸汽。
所述栅电极材料为金属钯(Pd)。
本发明具有以下优点：
1、采用磁控溅射淀积形成超薄金属钌膜，通过调节淀积功率、时间、衬底温度等，能够在高真空度下比较精确地控制薄膜的厚度和淀积速率，以形成超薄且均匀的金属膜，这使得退火后更易形成直径小、分布均匀且密度高的纳米晶颗粒。
2、电荷俘获层之一采用RuOx纳米晶作为电荷存储中心，由于它们的功函数较高(4.7～5.2eV)，所以能提供较大的势阱深度，有利于提高电荷的存储能力。本发明中金属纳米晶的形成温度与存储器的制作工艺温度相兼容，没有超过器件制作中源、漏离子注入后的激活退火温度。
3、另一电荷俘获层采用高介电常数介质HfxAlyOz作为存储中心，由于HfxAlyOz的介电常数高(10～25)，能够有效地增加了降落在隧穿层上的电场强度，从而提高了存储器的编程和擦除速度，并且降低了操作电压。同时，HfxAlyOz材料能提供足够多的电荷陷阱，用来存储电荷。
4、由高介电常数HfxAlyOz与高密度的RuOx纳米晶组成的异质电荷俘获层，可以共同俘获来自衬底的电荷注入，大大提高了电荷的存储密度。此外，高密度RuOx纳米晶嵌入到HfxAlyOz薄膜中，有效地抑制了HfxAlyOz介质在高温退火后发生结晶，因此减小了沿着晶粒间界的电荷泄漏，提高了存储器的电荷保持特性。
5、采用原子层淀积的方法制备HfxAlyOz薄膜，不仅可以精确地控制薄膜的组成和厚度，还能有效填充间距在纳米量级的缝隙，从而使得RuOx纳米晶能被HfxAlyOz完全隔离开。
6、采用金属钯作为电极，不仅可以和阻挡层的氧化铝介质形成利于擦写的垫垒，且钯不易被氧化，具有很好的化学稳定性和热稳定性。利用电子束蒸发设备在高真空下生长钯薄膜，此方面生长的钯膜与氧化铝介质能形成很好的接触界面，从而提高了电容存储器的性能。
附图说明
图l基于RuOx纳米晶和高介电常数HfxAlyOz薄膜的异质电荷俘获层结构存储电容器剖面结构图。
图2基于RuOx纳米晶和高介电常数薄膜(分别为HfO2和HfAlO)的异质电荷俘获层存储电容器在不同电压下编程/擦除0.1毫秒后的平带电压变化图。
图3基于RuOx纳米晶和高介电常数薄膜(分别为HfO2和HfAlO)的异质电荷俘获层存储电容器在+/-9V编程/擦除不同时间后的平带电压变化图。
图4基于RuOx纳米晶和高介电常数薄膜(分别为HfO2和HfAlO)的异质电荷俘获层存储电容器在+9V编程、-9V擦除1毫秒后的电荷保持特性。
具体实施方式
本发明所提出的新型栅叠层结构快闪存储电容的制备方法如下：
(1)采用(100)晶向的P型单晶硅片作为衬底，硅片的电阻率为8-12欧姆·厘米。首先对硅片进行标准清洗，并利用稀氢氟酸去除残留的自然氧化层。
(2)隧穿层Al2O3的形成：以三甲基铝和水蒸汽为反应源，采用原子层淀积的方法生长Al2O3薄膜，衬底温度控制在250～350℃范围内。Al2O3隧穿层厚度控制在为5～10纳米范围内。
(3)异质电荷俘获层中纳米晶RuOx的形成：采用磁控溅射淀积的方法，在Al2O3隧穿层上淀积超薄金属钌层，钌层的厚度为2～4纳米，然后在氮气气氛中进行快速热退火，即可形成RuOx纳米晶。退火温度为700～900℃，退火时间为10～30秒。该纳米晶作为异质电荷俘获层中的一种。
(4)异质电荷俘获层中高介电常数介质HfxAlyOz薄膜的形成：采用原子层淀积的方法生长HfxAlyOz薄膜，其中一种薄膜的组成为HfO2和Al2O3的淀积循环数之比为1∶1，记为HfAlO。另一种薄膜不含Al2O3，即为纯HfO2。衬底温度控制在250～350℃范围内，HfO2的反应源为四(乙基甲胺基)铪(TEMAH)和水蒸汽。Al2O3的制备条件如(2)所述。HfAlO和HfO2薄膜的厚度均为5～10纳米，分别用于异质电荷俘获层中的另外一种。
(5)电荷阻挡层Al2O3薄膜的形成：采用(2)中所述的方法淀积15～40纳米厚的Al2O3薄膜。然后，将所得样品在氮气中进行快速热处理，温度为500～800℃，时间为10～30秒。目的是获得高质量的Al2O3阻挡层，抑制电荷的泄漏。
(6)栅电极的形成：采用lift-off方法形成栅电极，即首先通过光刻形成图形，接着利用电子束蒸发设备生长钯金属薄膜，膜厚为50～200纳米。最后，利用丙酮清洗剩余的光刻胶。
(7)为了方便器件性能的测量，先用氢氟酸去除衬底背面的自然氧化层，然后淀积一层金属铝层作为下电极，以形成良好的欧姆接触，从而完成栅叠层结构存储电容器的制作工艺。
图2为本实例中的异质电荷俘获层存储电容在不同电压下编程和擦除0.1毫秒后的平带电压变化图。由图可知，随着正向偏压的增大，所得平带电压均向正方向漂移，这是由于电子注入导致负电荷的俘获造成的。随着负向偏压的增大，所得的平带电压均向负方向漂移，这是由于电荷俘获层中被俘获的电荷发生释放或来自衬底的空穴注入所造成的。此外，可以观察到在相同操作电压下，RuOx/HfO2异质电荷俘获层比RuOx/HfAlO异质电荷俘获层能提供更大的存储窗口，例如，在6V的操作电压下，前者的存储窗口为2.6V，后者则为1.4V。
图3为本实例中所制作的异质电荷俘获层存储电容在+/-9V编程/擦除不同时间后的平带电压变化图。由图可知，两个电容在编程/擦除状态下的平带电压均随着脉冲时间的增加而增大，并最终趋向饱和。对于0.1毫秒的编程/擦除，基于RuOx/HfAlO电荷俘获层的器件所得到的存储窗口接近2V，基于RuOx/HfO2电荷俘获层的器件所得到的存储窗口达到3.5V。二者均表现出了低压下快速编程和擦除的功能。
图4为本实例中所制作存储电容在+9V、1毫秒编程和-9V、1毫秒擦除后的保持特性。当异质电荷俘获层中的介质为HfO2时，外推至十年后该存储电容器的存储窗口约为3.4V，显示出了优良的保持特性；当异质电荷俘获层中的介质为HfAlO时，其相应的存储窗口约为1.6V。
上述结果表明，基于RuOx和HfxAlyOz的异质电荷俘获层的存储电容均表现出了低压下快速擦写的功能，以及良好的电荷保存特性，因此，本发明中所提出的栅叠层结构将在下一代快闪存储器上具有很好的应用前景。
Claims (4)
1.一种适合于闪存器件的栅叠层结构，其特征在于采用钌基纳米晶和高介电常数HfxAlyOz薄膜组成的异质电荷俘获层，该栅叠层结构以P型(100)晶向的硅片为衬底，自下而上依次为：
1)原子层淀积的Al2O3薄膜，作为电荷隧穿层，厚度为5～15纳米；
2)钌基纳米晶，作为第一种电荷俘获层；
3)原子层淀积的高介电常数HfxAlyOz薄膜，作为第二种电荷俘获层，厚度为5～10纳米；
4)原子层淀积的15～40纳米厚的Al2O3薄膜，充当电荷阻挡层；
5)上电极层。
2.一种如权利要求1所述的适合于闪存器件的栅叠层结构的制备方法，其特征在于具体步骤如下：
以P型单晶硅片为衬底层，用原子层淀积的方法生长Al2O3薄膜，作为电荷隧穿层，薄膜厚度为5～15纳米；
在形成隧穿层之后，磁控溅射一层钌膜，厚度为2～4纳米，然后在N2气氛中，于700～900℃下快速热退火10～30秒，形成钌基纳米晶，作为第一种电荷俘获层。该钌基纳米晶中含有金属钌和氧化钌，记为RuOx纳米晶；
用原子层淀积方法淀积5～10纳米厚的高介电常数HfxAlyOz薄膜，作为第二种电荷俘获层，HfxAlyOz薄膜中x＞0，z＞0，同时y＝0或y＞0；其中Hf与Al的组成通过原子层淀积HfO2和Al2O3的循环数来确定；
用原子层淀积方法淀积15～40纳米厚的Al2O3薄膜作为电荷阻挡层，淀积后进行热退火处理，热退火为温度500～800℃，时间10～30秒；
最后，用光刻工艺，利用lift-off方法形成栅电极，栅电极厚度为50～200纳米。
3.根据权利要求1所述的适合于闪存器件的栅叠层结构的制备方法，其特征在于，所述原子层淀积方法淀积Al2O3的条件为：衬底温度控制在250-350℃范围内，反应前驱体为三甲基铝Al(CH3)3和水蒸汽；原子层淀积方法淀积HfO2的条件为：衬底温度控制在250-350℃范围内，反应前驱体为四(乙基甲胺基)铪和水蒸汽。
4.根据权利要求2所述适合于闪存器件的栅叠层结构的制备方法，其特征在于所述电极材料为金属钯。
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| CN102208442A (zh) * | 2010-06-03 | 2011-10-05 | 复旦大学 | 一种适合于半导体闪存器件的栅叠层结构及制备方法 |
| CN102623459A (zh) * | 2012-04-10 | 2012-08-01 | 复旦大学 | 一种薄膜晶体管存储器及其制备方法 |
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| CN102938404A (zh) * | 2011-08-16 | 2013-02-20 | 北京天中磊智能科技有限公司 | 一种智能电能表专用eeprom存储芯片 |
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| US9336919B2 (en) | 2012-08-17 | 2016-05-10 | The Trustees Of The University Of Pennsylvania | Methods for preparing colloidal nanocrystal-based thin films |
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| WO2011150670A1 (zh) * | 2010-06-03 | 2011-12-08 | 复旦大学 | 一种适合于半导体闪存器件的栅叠层结构及制备方法 |
| CN102646579A (zh) * | 2011-02-17 | 2012-08-22 | 中芯国际集成电路制造(上海)有限公司 | 一种sonos结构及制造方法 |
| CN102646579B (zh) * | 2011-02-17 | 2015-01-07 | 中芯国际集成电路制造(上海)有限公司 | 一种sonos结构及制造方法 |
| CN102938404A (zh) * | 2011-08-16 | 2013-02-20 | 北京天中磊智能科技有限公司 | 一种智能电能表专用eeprom存储芯片 |
| CN102623459A (zh) * | 2012-04-10 | 2012-08-01 | 复旦大学 | 一种薄膜晶体管存储器及其制备方法 |
| WO2013152458A1 (zh) * | 2012-04-10 | 2013-10-17 | 复旦大学 | 一种薄膜晶体管存储器及其制备方法 |
| CN102623459B (zh) * | 2012-04-10 | 2015-01-07 | 复旦大学 | 一种薄膜晶体管存储器及其制备方法 |
| CN112080732A (zh) * | 2020-07-29 | 2020-12-15 | 西安交通大学 | 一种硅集成的bt-bmz薄膜、电容器及其制造方法 |
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| Publication number | Publication date |
|---|---|
| EP2442364A1 (en) | 2012-04-18 |
| EP2442364A4 (en) | 2014-08-27 |
| US20130062684A1 (en) | 2013-03-14 |
| CN102208442A (zh) | 2011-10-05 |
| WO2011150670A1 (zh) | 2011-12-08 |
| CN102208442B (zh) | 2013-04-17 |
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