CN1461356A - 用于形成栅氧化物膜的硅化铪靶材及其制备方法 - Google Patents

用于形成栅氧化物膜的硅化铪靶材及其制备方法 Download PDF

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CN1461356A
CN1461356A CN02801192A CN02801192A CN1461356A CN 1461356 A CN1461356 A CN 1461356A CN 02801192 A CN02801192 A CN 02801192A CN 02801192 A CN02801192 A CN 02801192A CN 1461356 A CN1461356 A CN 1461356A
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oxide film
gate oxide
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hafnium silicide
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入间田修一
铃木了
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JX Nippon Mining and Metals Corp
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Abstract

本发明涉及由HfSi0.05－0.37组成的用于形成栅氧化物膜的硅化铪靶材，所得到的硅化铪靶材的加工性能和耐脆化性能优良，并适合于形成可取代SiO2膜用作高介电栅绝缘膜的HfSiO膜和HfSiON膜，本发明也涉及靶材的制备方法。

Description

用于形成栅氧化物膜的硅化铪靶材及其制备方法
技术领域
本发明涉及一种加工性能和耐脆化性能优良，适合于形成可用作高介电栅绝缘膜的HfSiO膜和HfSiON膜的硅化铪靶材及其制备方法。另外，说明书中使用的单位“ppm”在所有的情况下均意指重量ppm。
背景技术
介电栅绝缘膜的膜厚很大程度上受到MOS晶体管性能的影响，与硅衬底的界面保持电学光滑并且不使载流子的移动性变差是很重要的。
通常，人们把SiO2膜用作栅绝缘膜，就界面特性来说，这种膜是最优良的膜，另外，还有一个特性就是，用作栅绝缘膜的SiO2膜越薄，载流子数(即，电子或电子空穴)就越增加，源漏电流也会由此而增加。
根据上述情况，每次由于布线小型化而降低电源电压的时候，一贯是在不损坏绝缘破坏可靠性的范围内而将栅SiO2膜制得尽可能薄，但是，当将栅SiO2膜制成厚度为3nm或更薄时，隧道漏电流会直接流动，使得该膜不能起到绝缘膜的作用。
与此同时，尽管人们业已尝试将晶体管小型化，但只要用作如上所述栅绝缘膜的SiO2膜的膜厚存在限制，晶体管的小型化就失去了意义，并使得其性能难以得到改善。
此外，为了降低LSI的电源电压和降低能量损耗，有必要将栅绝缘膜制得更薄，然而，如上所述，因为将栅SiO2膜制成厚度为3nm或更薄时，会产生栅绝缘破坏的问题，所以膜的变薄本身也存在着一定的限制。
根据上述情况，后来人们考虑用高介电的栅绝缘膜来代替SiO2膜，由此，可用作这类高介电栅绝缘膜的HfSiO膜和HfSiON膜正在日益引起人们的注意。
这种高介电栅绝缘膜以比较厚的膜厚能够获得与SiO2膜相当的容量，并且具有能够抑制隧道漏电流的特性，另外，因为可以将它看作是将Hf填充到SiO2或SiOn中的膜，所以可以预计它有与SiO2类似的界面特性。
因此，正在寻找一种能够易于并且稳定地形成高等级HfSiO和HfSiON高介电栅绝缘膜的溅射靶材。
发明的公开
为了克服以上问题，本发明旨在提供一种加工性能和抗脆化性能优良，适合于形成可代替SiO2膜用作高介电栅绝缘膜的HfSiO膜和HfSiON膜的硅化铪靶材及其制备方法。本发明提供：
1.用于形成栅氧化物膜的硅化铪靶材，其由HfSi0.05-0.37组成；
2.用于形成栅氧化物膜的硅化铪靶材，其由HfSi0.05-0.37组成，并包含以Hf2Si相和Hf相为主的兼容性相；
3.根据上述1或2的用于形成栅氧化物膜的硅化铪靶材，其中相对密度为95％或更高；
4.根据上述1-3任一项的用于形成栅氧化物膜的硅化铪靶材，其中氧含量为500-10000ppm；
5.根据上述1-4任一项的用于形成栅氧化物膜的硅化铪靶材，其中锆含量为2.5重量％或更低；
6.根据上述1-5任一项的用于形成栅氧化物膜的硅化铪靶材，其中杂质为：C：300ppm或更低；Ti：100ppm或更低；Mo：100ppm或更低；W：10ppm或更低；Nb：10ppm或更低；Fe：10ppm或更低；Ni：10ppm或更低；Cr：10ppm或更低；Na：0.1ppm或更低；K：0.1ppm或更低；U：0.01ppm或更低和Th：0.01ppm或更低；
7.根据上述1-6任一项的用于形成栅氧化物膜的硅化铪靶材，其中平均结晶粒径为5-200μm；和
8.用于形成栅氧化物膜的硅化铪靶材的制备方法，其中合成由HfSi0.05-0.37组成的组合物粉末，之后在1700-1830℃下进行热压。实施发明的方式
通过在HfSi靶材上进行氧反应性溅射而形成具有代替SiO2膜的特性的高介电栅绝缘膜。该氧化物膜被认为是由HfO2·SiO2表示的氧化物膜的混杂体，或其中部分氧被氮置换的膜，并且通常要求该靶材的组成为Si/Hf＝1.0。然而，随着HfO2·SiO2的发展，甚至要求组成中Hf更多。
因此，尝试了一种方法，其中相对于铪含量降低了硅的含量，并且进行了烧结。当降低了硅含量并进行烧结时，形成了混合晶体，如Hf5Si4(HfSi0.8)、Hf3Si2(HfSi0.67)和Hf2Si(HfSi0.5)，但其中存在一个问题就是，在烧结过程中，这些硅化铪间化合物由于熔点高而不能获得充分的密度增加，变成多孔组织的烧结体，之后变成大量产生粒子的靶材。
在不断进行密度增加的改进中，本发明终于成功地获得了适合作为用于形成栅氧化物膜的硅化铪靶材。
本发明是由HfSi0.05-0.37组成的用于形成栅氧化物膜的硅化铪靶材。该硅化铪靶材包含以Hf2Si相和Hf相为主的兼容性相，多孔组织消失，由此得到的铪靶材的相对密度为95％或更高。
当相对密度低于95％时，由于密度不足，脆性变差，加工性能也随着劣化。这也会导致由于易碎晶体的破坏和飞散而使粒子增加。因此，优选相对密度在前述范围之内。
希望用于形成栅氧化物膜的硅化铪靶材氧含量在500-10000ppm范围内。当氧含量低于500ppm时，在制造过程中靶材可能会发火，相反，当氧含量超过10000ppm时，靶材中的氧将会以氧化物的形式沉积，并使得在溅射过程中发生异常放电，由此而使粒子增加，并致使成品率降低。
另外，优选靶材中的锆含量控制在2.5重量％或更低，当锆含量超过2.5重量％时，为形成氧化膜进行反应性溅射时，电压、电流和衬底温度等操作条件会发生很大的变化，这是不优选的。
此外，优选用于形成栅氧化物膜的硅化铪靶材中杂质为：C：300ppm或更低；Ti：100ppm或更低；Mo：100ppm或更低；W：10ppm或更低；Nb：10ppm或更低；Fe：10ppm或更低；Ni：10ppm或更低；Cr：10ppm或更低；Na：0.1ppm或更低；K：0.1ppm或更低；U：0.01ppm或更低和Th：0.01ppm或更低。这是因为这些杂质将会变成栅电极及下部Si衬底的污染源。
为了制备耐脆性优良的由HfSi0.05-0.37组成的用于形成栅氧化物膜的硅化铪靶材，合成由HfSi0.05-0.37组成的组合物粉末，之后在1700-1830℃下进行热压。
在合成由HfSi0.05-0.37组成的组合物粉末时，调制并以1∶0.05-1∶0.37的摩尔比混合氢化金属铪粉末和硅粉末，之后在600-800℃下烧结。
尽管可以考虑使用Hf粉末，但因为它具有强氧化性，当粉碎时可能会出现发火问题，所以它是不优选的。
因此，氢化铪用于防止出现这种发火。在粉碎成平均粒径为20μm或更低的时候使用氢化铪粉末。使用这种细粉末可以使得在烧结过程中获得高密度。
在上述烧结过程中使用加热方法来进行脱氢和硅化物形成。大约在600℃开始发生脱氢，尽管烧结是在真空(1×10-4-1×10-2Torr(托))下进行的，但为了进行脱氢，将其变成轻微的氢气氛。
此外，在加热到800℃的温度下时脱氢完成，并且金属Hf中有发火担心的部分形成了硅化物，或被烧结到不担心发火的程度(约3μm或更大)。
如上所述，通过在热合成过程中进行低温脱氢和形成硅化物，可以抑制粒子的生长，烧结粉末的一次粒子仍保持微细，在成型时可能会形成高密度。如果烧结的粉末变成粗粒，烧结前的粉碎就会变得很困难，并使得粗粒残留下来，及密度降低。
因此，一个重要的特征是，由于在低温下进行烧结，所以可以抑制晶体颗粒生长，并且可以使用于形成栅氧化物膜的硅化铪靶材的平均粒径为5-200μm。而且，在烧结时可以获得高密度化。
当靶材的平均晶体粒径低于5μm时，难以使氧含量为10000ppm或更低，并且在制备过程中有发火的担心。此外，当平均晶体粒径超过200μm时，因为粒子将会增加，所以成品率会降低，因此，希望平均晶体粒径在如上所述的5-200μm之间。
烧结过程中的高密度化能够通过合成由前述HfSi0.05-0.37组成的粉末和在1700-1830℃进行热压实现。
前述热压温度是液相生成合成粉末的即时温度，该温度范围对于烧结来说是很重要的，它使得相对密度为95％或更高的高密度硅化铪靶材的实现成为可能。
本发明的高密度硅化铪靶材具有防止溅射过程中由孔所引起的粒子形成的效果。
实施例
下面将说明实施例，另外，这些实施例仅仅在于阐述，本发明将决不局限于此，换句话说，本发明将包括除这些实施例外属于本发明技术思想范围内的所有其他的方式或变化。
实施例1
通过将HfH2粉末和Si粉末混合，并在真空、800℃下加热，之后立即进行脱氢反应和硅化物合成反应，而得到合成的HfSi0.32粉末。将该硅化铪粉末粉碎以得到-200目的硅化铪粉末。通过XRD证实，该硅化铪粉末由以Hf2Si相和Hf相为主的兼容性相组成。
通过在1800℃下，300kg/cm2×2小时条件下热压该硅化物粉末而得到密度为99.7％的烧结体。另外对其进行机械加工以制作φ300mm×6.35mmt的靶材，由此得到几乎没有任何孔的组织。
对如上所述制作的靶材进行溅射，在6英寸的晶片上测定粒子时，总共发现有24个粒子具有0.2μm或更大的粒径，粒子的生成明显得以降低。
基于以上方法得到了具有优良加工性能和耐脆化性能的硅化铪靶材。另外，因为该靶材可以在湿法加工中使用，所以不再担心会在加工的过程中出现发火。实施例2
通过将HfH2粉末和Si粉末混合，并在真空、800℃下加热，之后立即进行脱氢反应和硅化物合成反应，而得到合成的HfSi0.25粉末。将该硅化铪粉末粉碎以得到-200目的硅化铪粉末。通过XRD证实，该硅化铪粉末由以Hf2Si相和Hf相为主的兼容性相组成。
通过在1800℃下，300kg/cm2×2小时条件下热压该硅化物粉末而得到密度为99.8％的烧结体。另外对其进行机械加工以制作φ300mm×6.35mmt的靶材。对如上所述制作的靶材进行溅射，在6英寸的晶片上测定粒子时，总共发现有30个粒子具有0.2μm或更大的粒径，粒子的生成明显得以降低。
基于以上方法得到了具有优良加工性能和耐脆化性能的硅化铪靶材，另外，不再担心会在加工的过程中出现发火。比较例1
通过将HfH2粉末和Si粉末混合，并在真空、800℃下加热，之后立即进行脱氢反应和硅化物合成反应，而得到合成的HfSi0.42粉末。将该硅化铪粉末粉碎以得到-200目的硅化铪粉末。通过XRD证实，该硅化铪粉末由以Hf2Si相和Hf相为主的兼容性相组成。
通过在1800℃下，300kg/cm2×2小时条件下热压该硅化物粉末而得到烧结体。尽管该热压条件与实施例1相同，但烧结体的密度低，为87.0％。对其进行进一步的机械加工以制作φ300mm×6.35mmt的靶材。
对如上所述制作的靶材进行溅射，在6英寸的晶片上测定粒子时，总共发现有310个粒子具有0.2μm或更大的粒径。另外，在靶材的外周表面上生成了被称为“瘤”的许多突起。
此外，当采用湿法加工时，因加工液引起污染，并且，因为这种污染在随后的过程中不能去除，所以存在的问题是不能获得具有适合于实际应用的纯度的靶材。比较例2
通过将HfH2粉末和Si粉末混合，并在真空、800℃下加热，之后立即进行脱氢反应和硅化物合成反应，而得到合成的HfSi0.42粉末。将该硅化铪粉末粉碎以得到-200目的硅化铪粉末。通过XRD证实，该硅化铪粉末由以Hf2Si3相和一定量的Hf5Si3相为主的兼容性相组成。
通过在1800℃下，300kg/cm2×2小时条件下热压该硅化物粉末而得到烧结体。尽管该热压条件与实施例1相同，但烧结体的密度低，为80.0％。对其进行进一步的机械加工以制作φ300mm×6.35mmt的靶材。
对如上所述制作的靶材进行溅射，在6英寸的晶片上测定粒子时，总共发现有510个粒子具有0.2μm或更大的粒径。另外，生成了许多“瘤”。
此外，与比较例1同样，当采用湿法加工时，因加工液引起污染，并且，因为这种污染在随后的过程中不能去除，所以存在的问题是不能获得具有适合于实际应用的纯度的靶材。
实施例1和2中靶材的相对密度为95％或更高。另外，粒子数为35或更低。在1700-1830℃的热压条件下，同样可获得相对密度的改进。尽管没有必要弄清原因，但如实施例中所示，通过将Hf∶Si比例降低到如上所述的1∶0.37或更低，已证实可以稳定地提高烧结体的密度。
相反，比较例1中的相对密度低，为87.0％。结果是，粒子数为310、并由此而引起“瘤”的差结果。
此外，比较例2中的相对密度低，为80.0％。结果是，粒子数为510、并由此而引起“瘤”的差结果。
因此，本发明实施例的优越之处是非常明显的，并且也使本发明所具有的优良的特性更进一步清淅。
发明效果
本发明的特征在于它可以获得加工性能和耐脆化性能优良，适合于形成可取代SiO2膜用作高介电栅绝缘膜的HfSiO膜和HfSiON膜的硅化铪靶材。
本发明的硅化铪靶材的相对密度为95％或更高，并具有优良的强度。
此外，本发明的高密度化的硅化物靶材能够防止在溅射过程中因孔而引起的粒子生成以及由于易碎组织的破坏和飞散而引起的粒子生成，并具有在靶材加工或制造过程中不发火的明显的优点。

Claims (8)

1.用于形成栅氧化物膜的硅化铪靶材，其由HfSi0.05-0.37组成。
2.用于形成栅氧化物膜的硅化铪靶材，其由HfSi0.05-0.37组成，并包含以Hf2Si相和Hf相为主的兼容性相。
3.根据权利要求1或2的用于形成栅氧化物膜的硅化铪靶材，其中相对密度为95％或更高。
4.根据权利要求1-3任一项的用于形成栅氧化物膜的硅化铪靶材，其中氧含量为500-10000ppm。
5.根据权利要求1-4任一项的用于形成栅氧化物膜的硅化铪靶材，其中锆含量为2.5重量％或更低。
6.根据权利要求1-5任一项的用于形成栅氧化物膜的硅化铪靶材，其中杂质为：C：300ppm或更低；Ti：100ppm或更低；Mo：100ppm或更低；W：10ppm或更低；Nb：10ppm或更低；Fe：10ppm或更低；Ni：10ppm或更低；Cr：10ppm或更低；Na：0.1ppm或更低；K：0.1ppm或更低；U：0.01ppm或更低和Th：0.01ppm或更低。
7.根据权利要求1-6任一项的用于形成栅氧化物膜的硅化铪靶材，其中平均结晶粒径为5-200μm。
8.用于形成栅氧化物膜的硅化铪靶材的制备方法，其中合成由HfSi0.05-0.37组成的组合物粉末，之后在1700-1830℃下进行热压。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101115861B (zh) * 2005-02-08 2012-06-27 法国圣戈班玻璃厂 采用热喷涂生产基于硅与锆的靶的方法
CN103231185A (zh) * 2013-04-03 2013-08-07 株洲宏大高分子材料有限公司 一种HFSi焊销及其制备方法

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3995082B2 (ja) * 2001-07-18 2007-10-24 日鉱金属株式会社 ゲート酸化膜形成用ハフニウムシリサイドターゲット及びその製造方法
EP1528120B1 (en) * 2002-08-06 2011-04-13 Nippon Mining & Metals Co., Ltd. Hafnium silicide target and method for preparation thereof
JP4388263B2 (ja) * 2002-09-11 2009-12-24 日鉱金属株式会社 珪化鉄スパッタリングターゲット及びその製造方法
JP4526758B2 (ja) * 2002-09-11 2010-08-18 日鉱金属株式会社 珪化鉄粉末及びその製造方法
JP4203070B2 (ja) * 2003-03-07 2008-12-24 日鉱金属株式会社 ハフニウム合金ターゲット及びその製造方法
US7476916B2 (en) * 2003-05-29 2009-01-13 Nec Corporation Semiconductor device having a mis-type fet, and methods for manufacturing the same and forming a metal oxide film
CN100376696C (zh) * 2003-07-25 2008-03-26 日矿金属株式会社 高纯度铪材料、由同种材料构成的靶和薄膜以及高纯度铪的制造方法
JP3956225B2 (ja) * 2003-08-26 2007-08-08 株式会社トリケミカル研究所 膜形成方法
DE10344039B4 (de) * 2003-09-23 2011-06-01 Qimonda Ag Elektrisch programmierbarer nichtflüchtiger Speicher auf Basis eines Schwellwert veränderbaren MOSFET und ein Verfahren zu dessen Herstellung
US20060266158A1 (en) * 2003-11-19 2006-11-30 Nikko Materials Co., Ltd. High purity hafnium, target and thin film comprising said high purity hafnium, and method for producing high purity hafnium
JP2005251801A (ja) * 2004-03-01 2005-09-15 Nec Electronics Corp 半導体装置
JP5032316B2 (ja) * 2005-07-07 2012-09-26 Ｊｘ日鉱日石金属株式会社 高純度ハフニウム、高純度ハフニウムからなるターゲット及び薄膜並びに高純度ハフニウムの製造方法
JP2009167530A (ja) * 2009-02-10 2009-07-30 Nippon Mining & Metals Co Ltd ニッケル合金スパッタリングターゲット及びニッケルシリサイド膜
WO2011141266A1 (de) 2010-04-15 2011-11-17 Basf Se Verfahren zur herstellung von flammgeschützten polyurethan-schaumstoffen
CN102453866A (zh) * 2010-10-21 2012-05-16 中国科学院微电子研究所 一种高介电常数栅介质材料及其制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619697A (en) * 1984-08-30 1986-10-28 Mitsubishi Kinzoku Kabushiki Kaisha Sputtering target material and process for producing the same
KR940008936B1 (ko) * 1990-02-15 1994-09-28 가부시끼가이샤 도시바 고순도 금속재와 그 성질을 이용한 반도체 장치 및 그 제조방법
JP2921799B2 (ja) 1990-02-15 1999-07-19 株式会社 東芝 半導体素子形成用高純度スパッタターゲットの製造方法
DE69117868T2 (de) * 1990-05-15 1996-07-25 Toshiba Kawasaki Kk Zerstäubungstarget und dessen herstellung
JPH05214523A (ja) 1992-02-05 1993-08-24 Toshiba Corp スパッタリングターゲットおよびその製造方法
US5464520A (en) * 1993-03-19 1995-11-07 Japan Energy Corporation Silicide targets for sputtering and method of manufacturing the same
JPH0820863A (ja) 1995-06-12 1996-01-23 Toshiba Corp シリサイド膜およびその膜を使用した半導体装置
JP3792007B2 (ja) * 1997-06-12 2006-06-28 株式会社日鉱マテリアルズ スパッタリングターゲットの製造方法
DE69808664T2 (de) * 1997-07-15 2003-07-24 Tosoh Smd, Inc. Feuerfeste metall-silizid-legierung sputter-targets, dessen verwendung und herstellung
KR19990014155A (ko) * 1997-07-24 1999-02-25 윌리엄 비. 켐플러 고 유전율 실리케이트 게이트 유전체
JP4501250B2 (ja) * 2000-06-19 2010-07-14 日鉱金属株式会社 耐脆化性に優れたゲート酸化膜形成用シリサイドターゲット

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101115861B (zh) * 2005-02-08 2012-06-27 法国圣戈班玻璃厂 采用热喷涂生产基于硅与锆的靶的方法
CN103231185A (zh) * 2013-04-03 2013-08-07 株洲宏大高分子材料有限公司 一种HFSi焊销及其制备方法

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EP1405932A4 (en) 2007-07-18
EP1405932B1 (en) 2008-07-09
WO2003006702A1 (fr) 2003-01-23
TW574403B (en) 2004-02-01
CN1260389C (zh) 2006-06-21
US7241368B2 (en) 2007-07-10
KR20030033049A (ko) 2003-04-26
JP4596379B2 (ja) 2010-12-08
KR100528934B1 (ko) 2005-11-15
DE60227523D1 (de) 2008-08-21
EP1405932A1 (en) 2004-04-07

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