CN1426100A - 应用于金属铁电氧化物和硅单管单元存储器的具有钛缓冲层的高－k栅氧化物 - Google Patents

应用于金属铁电氧化物和硅单管单元存储器的具有钛缓冲层的高－k栅氧化物 Download PDF

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CN1426100A
CN1426100A CN02148142A CN02148142A CN1426100A CN 1426100 A CN1426100 A CN 1426100A CN 02148142 A CN02148142 A CN 02148142A CN 02148142 A CN02148142 A CN 02148142A CN 1426100 A CN1426100 A CN 1426100A
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silicon chip
deposition
pgo
resilient coating
height
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CN1225021C (zh
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李廷凯
许胜籐
B·D·乌尔里克
L·H·斯特克
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Sharp Corp
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Abstract

一种制造存储器的方法，它包括制备硅基片；在硅基片上沉积一层高－k绝缘体；在高－k绝缘层上沉积一缓冲层；通过金属有机化学汽相沉积在缓冲层上沉积一层铁电材料；在铁电材料层上形成上部电极；并且完善由上述步骤得到的器件。

Description

应用于金属铁电氧化物和硅单管单元 存储器的具有钛缓冲层的高-k栅氧化物
                      相关申请
本申请与2001年6月5日授权的专利号为US6,242,771、名称为“Chemical Vapor Deposition of Pb5Ge3O11 Thin Film forFerroelectric Applications”的专利；2000年1月24日提交的序列号为09/489,857、名称为“A Method and System for MetalorganicChemical Vapor Deposition (MOCVD) and Annealing for LeadGerminate(PGO)Thin Films”的申请；和＿＿授权的专利US＿＿“C-axis Oriented Lead Germinate Film and Deposition Method”的专利有关。
                        技术领域
本发明涉及单管单元存储器结构(Single transistor memorystructures)和铁电非易失存储器的集成制造技术。
                        背景技术
已提出了金属铁电氧化物和硅(MFOS)单管单元(1T)存储器。在MFOS1T器件中，为了得到好的半导体性能，氧化物应不与铁电材料或硅基片反应并且不扩散至其中。沉积在氧化物上的铁电薄膜应具有低的介电常数、小的极化值(Pr)和好的铁电性能，以提供高质量的存储晶体管。基于这些需要，选择Pt/PGO/栅氧化物/Si(MFOS)作为单管单元存储器的优选结构。但是，由于界面不匹配，很难在栅氧化物上沉积具有好的铁电性能的c-轴取向的PGO(铅锗氧化物(Pb5Ge3O11))薄膜。为了解决该问题，在PGO薄膜和栅氧化物之间使用了缓冲层。
C.J.Peng等人的Oriented lead germinate thin films byexcimer laser ablation，Appl.Phys.Lett.第60卷第827-829页(1992)描述了铁电薄膜受激准分子激光器烧蚀领域的早期工作。
J.J.Lee等人的Processing of a uniaxial ferroelectricPb5Ge3O11 thin film at 450℃ with c-axis orientation，Appl.Phys.Lett.第60卷第2487-2488页(1992)描述了利用溶胶-凝胶工艺制备锗酸铅薄膜产生了无裂纹的c-轴取向薄膜。
H.Schmitt等人的Properties of undoped and dopedferroelectric lead germinate thin films，Ferroelectrics，第56卷第141-144页(1984)描述了制造锗酸铅薄膜的反应溅射技术。
S.B.Krupanidhi等人的Pulsed exeimer laser deposition offerroelectric thin films，Proceedings of 3rd InternationalSymp.on Intergated Ferroelectrics，第100-115页(1991)描述了PZT、钛酸铋和锗酸铅的脉冲UV受激准分子激光器的烧蚀。
                          发明内容
一种制造存储器的方法，包括制备硅基片；在硅基片上沉积一层高-k绝缘体；在高-k绝缘层上沉积一缓冲层；通过金属有机化学汽相沉积在缓冲层上沉积一层铁电材料；在铁电材料层上形成上部电极(topelectrode)；并且完善由上述步骤得到的器件。
本发明的一个目的是提供一种制造MFOS单管单元存储器的方法。
本发明的另一个目的是制造一种MFOS存储器，它具有夹在基片和铁电层之间的高-k层和缓冲层，以防止铁电性能的降低。
本发明的一个进一步目的是利用金属有机化学汽相沉积(MOCVD)技术、利用钛缓冲层来制造沉积在高-k材料层比如ZrO2、HfO2、和(Zrx，Hf1-x)O2上的用于PGO MFOS 1T存储器的高c-轴取向的PGO薄膜。
提供本发明的概述和目的以快速理解本发明的本质。参考下面对本发明优选实施方式的详细描述并结合附图可得到对本发明的更彻底的理解。
                         附图简述
图1绘出了利用原地氧化退火工艺沉积在钛/ZrO2上的PGO薄膜的X-射线图。
图2绘出了利用原地氧化退火工艺沉积在钛/HfO2上的PGO薄膜的X-射线图。
图3是在钛/ZrO2层上的PGO MFOS结构的存储窗(memory window)。
图4是在钛/HfO2层上的PGO MFOS结构的存储窗。
图5是等离子体蚀刻上部电极后具有钛/ZrO2的PGO MFOS存储单元的存储窗。
图6是常规蚀刻上部电极后具有钛/ZrO2的PGO布图的MFOS存储单元的存储窗。
                         具体实施方式
为了制造高质量的PGO MFOS存储单元，在具有钛或TiO2缓冲层的高-k栅氧化物、比如ZrO2和HfO2上沉积了铅锗氧化物(Pb5Ge3O11)(PGO)薄膜。利用应用于单管单元存储器的最佳化金属有机化学汽相沉积(MOCVD)和两步退火工艺实现了在具有钛或TiO2缓冲层的ZrO2、HfO2或(Zrx，Hf1-x)O2上制造该高c-轴取向的PGO薄膜。具有钛/ZrO2和钛/HfO2的PGO MFOS存储窗的测量值分别大于2.2V和3.5V，该窗足以用于1T存储器。已检查了形成于钛/ZrO2和钛/HfO2上的PGO薄膜的等离子体蚀刻引起的损伤并且使其降低至最小。
本发明的方法
本发明的方法包括制造具有PGO MFOS结构的单管铁电存储器，该PGOMFOS结构包括形成于高-k栅氧化物层比如ZrO2和HfO2层上的高c-轴取向的PGO薄膜，其中钛或TiO2缓冲层形成于高-k层和PGO薄膜之间。该绝缘/缓冲夹层阻止氧化物进入铁电或硅基片。
用P-型硅片作为MFOS单管单元存储器的基片。通过用SC1+SC2洗涤制备了硅片，其中SC1是5500ml去离子水、1100ml NH4OH和1100ml H2O2的混合物，并且SC2是6000ml去离子水、1000ml HCl和1000ml H2O2的混合物；并且用HF浸蚀除去表面氧化物。将高-k材料层、比如ZrO2、HfO2、或(Zrx，Hf1-x)O2薄膜在硅基片上溅射成约2nm-20nm的厚度，并且优选2nm-8nm的厚度。将具有高-k层的硅片在纯氧气氛中在约500℃-550℃下退火约1分钟至20分钟以实现完全氧化。将诸如钛或TiO2的缓冲层溅射沉积在高-k栅氧化物上约2nm-10nm的厚度。
利用氧化物MOCVD反应器在绝缘/缓冲夹层上生长c-轴取向的PGO薄膜，其厚度约为200nm-300nm。通过电子束蒸发在PGO薄膜上沉积厚度约100nm的Pt的上部电极。然后用常规技术将该存储器完善。
利用PGO前体通过MOCVD沉积了PGO薄膜，该前体是通过使摩尔比为5.0-5.5∶3的[Pb(thd)2](其中thd＝C11H19O2)和[Ge(ETO)4](其中ETO＝OC2H5)溶解于摩尔比为8∶2∶1的丁醚或四氢呋喃、异丙醇和四甘醇二甲醚(tetraglyme)的混合溶剂中形成的。该前体溶液的PGO浓度为0.1摩尔/升。以0.1毫升/分钟-0.2毫升/分钟的抽提速度将该溶液注入温度约150℃-250℃的蒸发器以形成前体气体。生长线的温度在约165℃-245℃之间。以约350℃-450℃的沉积温度、约5托的压力和约30％的氧分压进行MOCVD。c-轴取向的PGO薄膜的退火处理条件包括利用快速热处理(RTP)技术在氧气氛中、在约500℃-510℃之间的退火温度进行第一退火步骤约5-10分钟。在RTP室或在退火炉中、在氧气氛中以约540℃-600℃之间的退火温度进行第二退火步骤约30分钟至1小时。
用X-射线衍射来确定PGO薄膜的相。用超高分辨率X-射线光电分光计(XPS)来分析Pb5Ge3O11薄膜的组成。用Keithley 182 CV分析仪测量了PGO MFOS电容器的电容。
结果
用常规技术在ZrO2和HfO2上沉积的C-轴取向的PGO薄膜通常具有第二相和自由峰，这导致了差的铁电性能。为了在应用于MFOS 1T存储器的高-k栅氧化物上沉积高C-轴取向的PGO薄膜，根据本发明的方法，将PGO薄膜沉积在具有缓冲层比如钛或TiO2的高-k栅氧化物层上。本发明方法产生的PGO薄膜是非晶相的并且仅在高温退火后才表现出C-轴取向的峰。原地氧化的沉积在缓冲层上的PGO薄膜显示出高的C-轴取向。本发明利用具有钛缓冲层的ZrO2或HfO2产生了适用于存储器用途的PGOMFOS器件。钛层的最佳厚度为约2nm-10nm之间，并且ZrO2或HfO2的最佳厚度为约4nm-20nm。
图1和图2绘出了根据本发明的方法在不同的温度下沉积在具有钛缓冲层的ZrO2和HfO2上的PGO薄膜的X-射线图。对于PGO薄膜，c-轴PGO薄膜的成核温度约为500℃，并且晶粒生长温度高于540℃。因此，用两步退火工艺来在ZrO2或HfO2高-k层上生长高c-轴取向的PGO薄膜，在所述高-k介电层上形成有钛缓冲层。在第一步骤中，在约510℃的退火过程中发生了PGO c-轴相成核，并且在约540℃-600℃之间退火时发生了c-轴相晶粒生长。利用该技术，可在覆盖高-k ZrO2或HfO2层的钛缓冲层上形成强c-轴取向的PGO薄膜。
为了确定本发明方法对于制造PGO MFOS 1T存储器的适用性，制造了一个具有钛/ZrO2层和一个具有钛/HfO2层的PGO MFOS。图3和图4分别绘出了具有钛/ZrO2和HfO2的PGO MFOS结构的存储窗。具有钛/ZrO2和钛/HfO2的PGO MFOS存储窗分别为2.2V和3.5V，这足以用于1T存储器。
为了确定用本发明方法时等离子体蚀刻引起的损伤，利用低能的常规蚀刻工艺和等离子体蚀刻工艺蚀刻了具有Pt/PGO/钛/ZrO2/Si结构的PGO MFOS存储单元的上部电极。图5和图6分别绘出了等离子体蚀刻上部电极后和常规低能蚀刻上部电极后测量的具有钛/ZrO2存储单元的PGO MFOS的存储窗。该图表明在等离子体蚀刻Pt上部电极后，具有钛/ZrO2存储单元的PGO MFOS的存储窗从2.2V降低至1.8V，对于1T存储器这仍是充足的电压。
总之，通过利用应用于单管单元存储器的最佳化金属有机化学汽相沉积(MOCVD)和两步退火工艺实现了在具有钛或TiO2缓冲层的ZrO2和HfO2上形成高c-轴取向的PGO薄膜；具有钛/ZrO2和钛/HfO2的PGO MFOS存储窗的测量值分别大于2.2V和3.5V，这对于1T存储器是充足的；并且通过本发明的方法减小了等离子体蚀刻和剥离工艺引起的沉积在钛/ZrO2和钛/HfO2上的PGO薄膜的损伤。
由此，已公开了一种制造适用于MFOS单管单元存储器的具有钛缓冲层的高-k栅氧化物的方法。应理解为可在由所附的权利要求书所限定的本发明范围内对其进行其它的变化和修正。

Claims (12)

1.一种制造存储器的方法，它包括下面的步骤：
a)制备硅基片；
b)在硅基片上沉积一层高-k绝缘体；
c)在高-k层上沉积一缓冲层；
d)通过金属有机化学汽相沉积在缓冲层上沉积一层铁电材料；
e)在铁电材料层上形成上部电极；和
f)完善由步骤a)-e)得到的器件。
2.权利要求1的方法，其中所述制备硅基片的步骤a)包括选择P-型硅晶片；洗涤该P-型硅基片并且除去P-型硅晶片的表面氧化物。
3.权利要求1的方法，其中所述在硅基片上沉积一层高-k绝缘体的步骤b)包括由ZrO2、HfO2和(Zrx，Hf1-x)O2组成的材料组中选择出高-k材料，在硅基片上沉积厚度约2nm-20nm的高-k材料，并且优选厚度为2nm-8nm；并且使硅基片在纯氧气氛中在约500℃-550℃退火约1分钟至20分钟。
4.权利要求1的方法，其中所述沉积一缓冲金属层的步骤c)包括由钛和TiO2组成的缓冲层组中选择缓冲层，并且使缓冲层沉积约2nm-10nm的厚度。
5.权利要求1的方法，其中所述沉积一层铁电材料的步骤d)包括通过使摩尔比为5.0-5.5∶3的[Pb(thd)2]和[Ge(ETO)4]溶解于摩尔比为8∶2∶1的丁醚或四氢呋喃、异丙醇和四甘醇二甲醚的混合溶剂制备了PGO前体，导致该前体溶液的PGO浓度为0.1摩尔/升。
6.权利要求5的方法，其中所述沉积一层铁电材料的步骤d)包括以约0.1毫升/分钟-0.2毫升/分钟的抽提速度将该前体溶液注入温度约150℃-250℃的蒸馏器中以形成前体气体；并且将该前体气体以沉积温度约350℃-450℃、压力约5托并且氧分压约30％泵入CVD室。
7.权利要求6的方法，其中对其上沉积有铁电材料层的硅基片在氧气氛中、在约500℃-510℃的退火温度下、利用快速热处理工艺的第一退火步骤中退火约5-10分钟；在氧气氛中以约540℃-600℃的退火温度的第二退火步骤中退火约30分钟至1小时。
8.一种制造PGO MFOS单管单元存储器的方法，它包括：
a)制备硅基片；
b)在硅基片上沉积一层高-k绝缘体，包括
b1)由ZrO2、HfO2和(Zrx，Hf1-x)O2组成的材料组中选择出高-k材料，
b2)在硅基片上沉积厚度约2nm-20nm的高-k材料，并且优选厚度为2nm-8nm；和
b3)使硅基片在纯氧气氛中在约500℃-550℃下退火约1分钟至20分钟；
c)在高-k绝缘层上沉积一缓冲层，包括由钛和TiO2组成的缓冲层组中选择缓冲层；和使缓冲层沉积约2nm-10nm的厚度；
d)通过金属有机化学汽相沉积在缓冲层上沉积一层铁电材料；
e)在铁电材料层上部形成上电极；和
f)完善由步骤a)-e)得到的器件。
9.权利要求8的方法，其中所述沉积一层铁电材料的步骤d)包括通过使摩尔比为5.0-5.5∶3的[Pb(thd)2]和[Ge(ETO)4]溶解于摩尔比为8∶2∶1的丁醚或四氢呋喃、异丙醇和四甘醇二甲醚的混合溶剂制备了PGO前体，导致该前体溶液的PGO浓度为0.1摩尔/升；
以约0.1毫升/分钟-0.2毫升/分钟的抽提速度将该前体溶液注入温度约150℃-250℃的蒸馏器以形成前体气体；并且将该前体气体泵入沉积温度约350℃-450℃、压力约5托并且氧分压约30％的CVD室；和
使硅基片在两步退火工艺中退火，包括
第一退火步骤利用快速热处理工艺、在氧气氛中以约500℃-510℃的退火温度进行约5-10分钟；和
第二退火步骤在氧气氛中以约540℃-600℃的退火温度进行约30分钟至1小时。
10.权利要求8的方法，其中所述制备硅基片的步骤a)包括选择P-型硅晶片；洗涤该P-型硅基片和除去P-型硅晶片的表面氧化物。
11.一种制造PGO MFOS单管单元存储器的方法，它包括：
a)制备硅基片；
b)在硅基片上沉积一层高-k绝缘体，包括
b1)由ZrO2、HfO2和(Zrx，Hf1-x)O2组成的材料组中选择出高-k材料，
b2)在硅基片上沉积约2nm-20nm厚度的高-k材料，并且优选厚度为2nm-8nm；和
b3)使硅基片在纯氧气氛中在约500℃-550℃下退火约1分钟至20分钟；
c)在高-k绝缘层上沉积一缓冲层，包括由钛和TiO2组成的缓冲层组中选择出缓冲层；并且使缓冲层沉积约2nm-10nm的厚度；
d)通过金属有机化学汽相沉积在缓冲层上沉积一层铁电材料，包括
d1)通过使摩尔比为5.0-5.5∶3的[Pb(thd)2]和[Ge(ETO)4]溶解于摩尔比为8∶2∶1的丁醚或四氢呋喃、异丙醇和四甘醇二甲醚的混合溶剂中制备了PGO前体，导致该前体溶液的PGO浓度为0.1摩尔/升；
d2)以约0.1毫升/分钟-0.2毫升/分钟的抽提速度将该前体溶液注入温度约150℃-250℃的蒸馏器以形成前体气体；和将该前体气体泵入沉积温度约350℃-450℃、压力约5托并且氧分压约30％的CVD室；和
d3)使硅基片在两步退火工艺中退火，包括
第一退火步骤利用快速热处理工艺、在氧气氛中以约500℃-510℃的退火温度进行约5-10分钟；和
第二退火步骤在氧气氛中以约540℃-600℃的退火温度进行约30分钟至1小时；
e)在铁电材料层上形成上部电极；和
g)完善由步骤a)-e)得到的器件。
12.权利要求11的方法，其中所述制备硅基片的步骤a)包括选择P-型硅晶片；洗涤该P-型硅晶片并且除去P-型硅晶片的表面氧化物。
CNB021481423A 2001-10-30 2002-10-30 应用于金属铁电氧化物和硅单管单元存储器的具有钛缓冲层的高－k栅氧化物 Expired - Fee Related CN1225021C (zh)

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