CN1415782A - 用于氧化锆和氧化铪薄膜沉积的前驱体 - Google Patents
用于氧化锆和氧化铪薄膜沉积的前驱体 Download PDFInfo
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- 239000002243 precursor Substances 0.000 title abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title description 4
- 238000000427 thin-film deposition Methods 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 229910003865 HfCl4 Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 18
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 13
- 239000010408 film Substances 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- -1 alkoxide hafnium chloride Chemical class 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000588731 Hafnia Species 0.000 description 2
- 150000004703 alkoxides Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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Abstract
一种用于制备通过化学气相沉积方法形成的薄膜的前驱体的方法，其包括将ZCl4同H(tmhd)3溶剂和类如苯的烃溶剂混合，形成一种溶液(其中Z为一种从包含铪和锆在内的元素组中选取的元素)；将该溶液在氩气中回流12小时；藉助真空除去溶剂，从而产生一种固体化合物；将该化合物在0.1mm Hg的近真空状态和200℃下升华；还提出一种用于化学气相沉积方法的ZOx前驱体，其包括从包含ZCI(tmhd)3和ZCl2(tmhd)2在内的化合物组中选取的一种含Z化合物。
Description
技术领域
本发明涉及在用化学气相沉积(CVD)法或原子层化学气相沉积(ALCVD)法沉积铪金属氧化物薄膜时用的醇盐氯化铪的合成。
背景技术
目前用于CVD或ALCVD的锆和铪前驱体为HfCl4，Hf(OR)4(其中R＝类如CH(CH3)2的烷基，)，Hf(tmhd)4(其中tmhd＝2，2，6，6-四甲基-3，5-庚烷聚脂(heptanedionato))，Hf(tfac)4(其中tfac＝三氟乙酰丙酮酸盐)，Hf(NO3)4以及含有锆化合物的相似前驱体。在使用金属棚氧化物时，HfCl4一直被认为是纯HfO2薄膜沉积的潜在原料。参见Ryan C.Smith等人发表在2000年Advanced Materials for Optics andElectronics(光学和电子学的高级材料)，10，105-114，111-113页上的《微电子装置中用作高K材料的钛、锆和铪氧化物的化学气相沉积。一种用于合成二氧化铪的无碳前驱体》。
至于其他前驱体，Hf(OR)4对于空气和湿气极度敏感，且难于处理；Hf(tmhd)4虽然稳定，但引发难于除去的碳污染；Hf(tfac)4为一挥发性前驱体，但其使用含有氟污染的危险。尚无关于在ALCVD中使用Hf(NO3)4的报导。
因为铪和锆的电子构型近似，故其化学性质几乎相同。正如业内人士所知，它们在化学化合物内实际上可以互相替换，而且在半导体装置上，它们表现出相似的特性。
发明内容
提出一种制备用化学气相沉积法形成薄膜的前驱体的方法，其包括将ZCl4同H(tmhd)3溶剂和类如苯的烃溶剂混合形成一种溶液(其中Z为从包含铪和锆在内的元素组中选取的元素)；在氩气中将该溶液回流12小时；藉助真空除去溶剂，从而形成一种固体化合物；在0.1mmHg的近真空状态和200℃下将该化合物升华。
提出在化学气相沉积方法中使用的一种ZOx前驱体，其包括一种从包含ZCl(tmhd)3和ZCl2(tmhd)2化合物在内的化合物组中选取的含Z化合物。
本发明的一个目的是提供可以用于通过CVD或ALCVD方法进行铪金属氧化物薄膜沉积的铪前驱体。
本发明的另一目的是在提供充分挥发的前驱体的同时，减少氯污染。
本发明还有一个目的是用醇盐配体局部取代氯，结果形成二醇盐二氯化铪或三醇盐氯化铪。
本发明的内容和目的在于使人们迅速了解本发明的性质。参看附图并阅读本发明优选实施例的详细说明，可更透彻地了解本发明。
附图说明
图1示出HfCl(tmhd)3的能量色散(EDS)谱；
图2示出HfCl2(tmhd)2的能量色散(EDS)谱；
图3示出HfCl(tmhd)3的热解重量分析谱；以及
图4示出HfCl2(tmhd)2的热解重量分析谱；
具体实施方式
业内人士咸知铪和锆的化学性质极相似，当用于半导体装置上时，其性状实际相同。本文中的一些例子使用铪，但也适用于含锆的化合物和前驱体。
由于HfCl4的氯浓度极高，新的铪前驱体应含较少的氯，并有较高的挥发性。为了达到此点，用醇盐配体部分取代氯，形成二醇盐二氯化铪或三醇盐氯化铪。HfCl(tmhd)3和HfCl2(tmhd)2化合物产生所要求的结果，即在原子层化学气相沉积(ALCVD)过程中，为了满足吸收的要求而含氯，同时在前驱体中含氯较少，因而氯污染减少，并具有较Hfcl4高的挥发性。
本发明方法的铪前驱体为HfCl(tmhd)3和HfCl2(tmhd)2，其含氯有助于晶片表面在进行ALCVD时吸收分子，同时含的氯较HfCl4少，有助于减少铪金属氧化合物薄膜中的氯污染。
合成用的化学原料为HfCl4、H(tmhd)和类如苯溶剂的烃溶剂。藉助升华使购自Aldrich Chemical公司的HfCl4纯化。购自StremChemical公司的H(tmhd)在使用前应部分蒸镏。使苯在二苯甲酮和金属钠上回流进行纯化。
为了制备HfCl(tmhd)3，在一个1000ml圆底双颈烧瓶内使HfCl4(50g，0.156mol)和H(tmhd)3(86g，0.468mol)在600ml的苯中混合。混合后，剧烈搅拌该溶液。HfCl4逐渐溶解，该溶液逐渐变成淡黄色。将该溶液在氩气中回流12小时。然后藉助真空涂去溶剂，得到白色固体化合物。将该化合物在0.1mmHg的近真空状态和200℃下升华，产生76.3g的纯HfCl(tmhd)3，产出率为64％。HfCLC33H57O6的计算成分为Hf：23.37％；C：51.90％；Cl：4.64％；H：7.52％；O：12.57％。实际的分析结果指出其百分比为Hf：24.42％；C：51.89％；Cl：4.71％；H：7.62％和O：11.36％。
同样，在合成HfCL2(tmhd)2时，应在一个1000ml圆底双颈烧瓶内使HfCl4(50g，0.156mol)和H(tmhd)3(58g，0.312mol)在600ml的苯中混合。混合后，剧烈搅拌该溶液。HfCL4逐渐溶解，该溶液逐渐变成淡黄色。将该溶液在氩气中回流12小时。然后藉助真空除去溶剂，得到白色固体化合物。将该化合物在0.1mmHg的近真空状态和200℃下升华，产生53g的纯HfCl2(tmhd)2，产出率为55％。HfCl2C22H38O4的计算成分为Hf：28.98％；C：42.90％；Cl：11.51％；：6.22％；O：10.39％。实际的分析结果指出其百分比为Hf：30.27％；C：43.13％；Cl：11.67％；H：6.24％；O：8.72％。
藉助能量色散谱对两种前驱体内的氯进一步得到确认，如图1和2所示。通过热解重量分析法(TGA)测定了两种化合物的挥发性，如图3和4所示。结果显示两种新的铪前驱体均具有挥发性，可以用作ALCVD的原料。
该前驱体可以用来形成半导体装置上的HfOx薄膜。合适基体的制备过程可能包括在基体上形成半导体结构。该半导体结构可能需要遮蔽，以防在不需要薄膜的部位上有HfOx薄膜沉积。该HfOx薄膜可以藉助CVD或ALCVD薄膜沉积，然后除去遮蔽，半导体装置于是完成。
由于铪和锆的电子构型基本相同，其化学性质亦大致相同，因此正如业内人士所知，它们在化学化合物内实际上可以互相替换，并且用在半导体装置上，将表现出相似的特性。在化学方程式中可以用“Z”代表元素，Z是从包含铪和锆在内的元素组中选取的元素。
因此本发明公开一种制备用于氧化锆和氧化铪薄膜沉积的前驱体的方法。但是，在本专利所附权利要求出界定的范围内，可以对其进行进一步的变型和更改。
Claims (5)
1.一种用于制备通过化学气相沉积方法形成的薄膜的前驱体的方法，其包括：
将ZCl4同H(tmhd)3溶剂和烃溶剂混合形成一种溶液(其中，Z为一种从包含铪和锆在内的元素组中选取的元素)；
在氩气中将该溶液回流12小时；
藉助真空除去溶剂，从而产生一种固体化合物；以及
在0.1mm Hg的近真空状态和200℃下使该化合物升华；
2.按照权利要求1所述的方法，其特征是所述混合包括将50g，0.156mol的HfCl4和86g，0.468mol的H(tmhd)3在600ml烃熔剂内混合，产生HfCl(tmhd)3。
3.按照权利要求1所述的方法，其特征是所述混合包括将50g，0.156mol的HfCl4和58g，0.312mol的H(tmhd)3在600ml烃熔剂内混合，产生HfCl2(tmhd)2。
4.一种制造在半导体装置上的ZOx薄膜的方法，其中Z为一种从包含铪和锆在内的元素组中选取的元素，该方法包括：
制备一种合适的基体，包括在其上建立起半导体结构；
使用一种从包含ZCL(tmhd)3和ZCl2(tmhd)2在内的ZOx前驱体组中选取的ZOx前驱体，藉助一种从包含化学气相沉积和原子层化学气相沉积在内的方法组中选取的方法，在该半导体结构上沉积一层ZOx；以及
完成该半导体装置。
5.一种用于化学气相沉积方法的ZOx前驱体，其中Z为一种从包含铪和锆在内的元素组中选取的元素，该前驱体包括：
一种从包含ZCl(tmhd)3和ZCl2(tmhd)2在内的化合物组中选取的含Z化合物。
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| US10/020,471 US6472337B1 (en) | 2001-10-30 | 2001-10-30 | Precursors for zirconium and hafnium oxide thin film deposition |
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| 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 |
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| US6899858B2 (en) * | 2003-01-23 | 2005-05-31 | Sharp Laboratories Of America, Inc. | Method of synthesis of hafnium nitrate for HfO2 thin film deposition via ALCVD process |
| US7037816B2 (en) * | 2004-01-23 | 2006-05-02 | Taiwan Semiconductor Manufacturing Company, Ltd. | System and method for integration of HfO2 and RTCVD poly-silicon |
| US20060062910A1 (en) * | 2004-03-01 | 2006-03-23 | Meiere Scott H | Low zirconium, hafnium-containing compositions, processes for the preparation thereof and methods of use thereof |
| US20050214458A1 (en) * | 2004-03-01 | 2005-09-29 | Meiere Scott H | Low zirconium hafnium halide compositions |
| US8119210B2 (en) | 2004-05-21 | 2012-02-21 | Applied Materials, Inc. | Formation of a silicon oxynitride layer on a high-k dielectric material |
| KR100640654B1 (ko) | 2005-07-16 | 2006-11-01 | 삼성전자주식회사 | ＺｒＯ2 박막 형성 방법 및 이를 포함하는 반도체 메모리소자의 커패시터 제조 방법 |
| JP5042548B2 (ja) * | 2005-08-04 | 2012-10-03 | 東ソー株式会社 | 金属含有化合物、その製造方法、金属含有薄膜及びその形成方法 |
| CN101238095B (zh) | 2005-08-04 | 2011-08-10 | 东曹株式会社 | 含有金属的化合物,其制备方法、含有金属的薄膜和其形成方法 |
| US7678710B2 (en) | 2006-03-09 | 2010-03-16 | Applied Materials, Inc. | Method and apparatus for fabricating a high dielectric constant transistor gate using a low energy plasma system |
| US7645710B2 (en) | 2006-03-09 | 2010-01-12 | Applied Materials, Inc. | Method and apparatus for fabricating a high dielectric constant transistor gate using a low energy plasma system |
| US7837838B2 (en) | 2006-03-09 | 2010-11-23 | Applied Materials, Inc. | Method of fabricating a high dielectric constant transistor gate using a low energy plasma apparatus |
| TWI435376B (zh) | 2006-09-26 | 2014-04-21 | Applied Materials Inc | 用於缺陷鈍化之高ｋ閘極堆疊的氟電漿處理 |
| EP2261402B1 (en) * | 2009-06-12 | 2013-10-16 | University of Limerick | Method for producing germanium semiconductor nanowires |
| JP7101051B2 (ja) * | 2018-06-07 | 2022-07-14 | 東京インキ株式会社 | ハフニアナノ粒子、その分散体、樹脂複合体および製造方法、 |
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| US4982019A (en) * | 1989-07-31 | 1991-01-01 | The United States Of America As Represented By The Secretary Of The Navy | Volatile divalent metal alkoxides |
| US5487918A (en) * | 1990-05-14 | 1996-01-30 | Akhtar; Masud | Method of depositing metal oxides |
| DE4108731A1 (de) * | 1991-03-18 | 1992-09-24 | Solvay Barium Strontium Gmbh | Neuartige erdalkalimetall-heptandionat-verbindungen |
| US5403620A (en) * | 1992-10-13 | 1995-04-04 | Regents Of The University Of California | Catalysis in organometallic CVD of thin metal films |
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| US5908947A (en) * | 1996-02-09 | 1999-06-01 | Micron Technology, Inc. | Difunctional amino precursors for the deposition of films comprising metals |
| US6159855A (en) * | 1998-04-28 | 2000-12-12 | Micron Technology, Inc. | Organometallic compound mixtures in chemical vapor deposition |
| US6090992A (en) * | 1998-12-08 | 2000-07-18 | Phillips Petroleum Company | Isomerization catalyst system, method of making and method of using such catalyst system in the isomerization of saturated hydrocarbons |
| US6297539B1 (en) * | 1999-07-19 | 2001-10-02 | Sharp Laboratories Of America, Inc. | Doped zirconia, or zirconia-like, dielectric film transistor structure and deposition method for same |
| US6060755A (en) * | 1999-07-19 | 2000-05-09 | Sharp Laboratories Of America, Inc. | Aluminum-doped zirconium dielectric film transistor structure and deposition method for same |
| JP2001214270A (ja) * | 2000-01-28 | 2001-08-07 | Horiba Ltd | Ｐｚｔ薄膜の合成方法およびｐｌｚｔ薄膜の合成方法 |
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