CN117865997A - 一种混配型酰胺基铪配合物及其制备方法和应用 - Google Patents
一种混配型酰胺基铪配合物及其制备方法和应用 Download PDFInfo
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- -1 hafnium amide Chemical class 0.000 title claims abstract description 50
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000010668 complexation reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 6
- 150000001408 amides Chemical class 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract description 3
- 238000000231 atomic layer deposition Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 238000003877 atomic layer epitaxy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Natural products C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
本发明公开一种混配型酰胺基铪配合物及其制备方法和应用，在惰性气体的保护下，将定量的二胺盐和无水金属氯化铪加入无水溶剂中进行反应；反应一段时间后，过滤，将定量的酰胺基盐加入滤液中继续进行反应；反应一段时间后，过滤，将滤液用减压蒸馏除去溶剂，得固体经过重结晶升华，即得到目标金属配合物。本发明提供一系列对衬底的污染小、合成方法简便，工艺操作简单，产率高，成本低的混配型酰胺基铪配合物的合成方法，此系列制备方法，易于合成，毒性低，简单易操作等特点。
Description
技术领域
本发明涉及金属有机配合物技术领域，具体为一种混配型酰胺基铪配合物及其制备方法和应用。
背景技术
随着集成电路的飞速发展，SiO2作为传统的栅介质将不能满足金属-氧化物-半导体场效应管（MOSFET）器件高集成度的要求，需要一种新型高K材料来代替传统的SiO2，这就要综合考虑以下几个方面的问题：①具有高介电常数、高的势垒和能隙；②在Si上有良好的热稳定性；③非晶态栅介质更理想；④具有良好的界面质量；⑤与Si基栅兼容；⑥处理工艺的兼容性；⑦具有良好的可靠性和稳定性。
目前被广泛研究用来替代传统SiO2栅极氧化物的高K材料主要有以下几种：Al2O3、ZrO2、HfO2、 (HfO2)x(Al2O3)1-x、La2O3、Pr2O3、Y2O3、Gd2O3和Nd2O3等等。其中研究最多是ZrO2、HfO2和它们相关的硅化物。稀土氧化物由于具有高势垒和能隙(Pr2O3~3.9, Gd2O3~5.6eV)、高介电常数(Gd2O3K=16, La2O3K=30, Pr2O3K=26-30)，以及在硅底物上优良的热力学稳定三大优点，最近也引起了人们极大的兴趣。
用来制备高K材料的原子层沉积(ALD)技术最初又叫原子层外延。其中ALD前驱体的制备在整个ALD技术中扮演着至关重要的角色。
ALD稀土类前驱体主要有如下几类：
(A) β-二酮化合物，(B) 烷氧基化合物，(C)有机胺化物，(D环戊二烯型化合物和(E)脒基化合物。
以铪基材料为例，铪的卤化物（例如HfCl4）作为前驱体在ALD中制备HfO2薄膜最为常见，也最为广泛。但是研究表明，制备的高K材料具有一些问题，如：缺陷密度、薄膜的均匀性等等。以HfCl4作为前驱体源制备的HfO2薄膜中Cl元素的含量非常高，而且氯元素还不能通过退火除去，还在退火中容易腐蚀硅衬底表面。HfCl4的气化温度较高，在ALD设备中运输效率比液态的前躯体运输效率低。所以，必须寻找一种无氯的HfO2高K材料前躯体来制备高质量的MOS栅介质薄膜，已成为研究的重要方向。
发明内容
针对现有技术的不足，本发明提供了一种混配型酰胺基铪配合物及其制备方法和应用，目的是提供一系列对衬底的污染小、合成方法简便，工艺操作简单，产率高，成本低的混配型酰胺基铪配合物的合成方法。此系列制备方法，易于合成，毒性低，简单易操作等特点。
为了达到上述目的，本发明所采用的技术方案是：
首先，本发明提供一种混配型酰胺基铪配合物，其特征在于：该配合物的结构通式为：
其中：
M =Hf；n= 1，2或3；
R1=CH3，CH2CH3，异丙基，叔丁基，环己基，苯基，环戊基或环戊二烯基；
R2= H，CH3，CH2CH3，异丙基，叔丁基，环己基，苯基，环戊基或环戊二烯基；
R3= -N(CH2CH3)2，-N(CH2CH3)CH3，-N(CH3)2或-N(SiMe3)2。
其次，本发明提供一种混配型酰胺基铪配合物的制备方法，其技术路径为：
其中：
M =Hf；M1= K，Na或Li； M2= K，Na或Li；n= 1，2或3；
R1=CH3，CH2CH3，异丙基，叔丁基，环己基，苯基，环戊基或环戊二烯基；
R2= H，CH3，CH2CH3，异丙基，叔丁基，环己基，苯基，环戊基或环戊二烯基；
R3= -N(CH2CH3)2，-N(CH2CH3)CH3，-N(CH3)2或-N(SiMe3)2。
前述的一种混配型酰胺基铪配合物的制备方法，所述金属M为铪，无水金属盐为无水氯化铪。
前述的一种混配型酰胺基铪配合物的制备方法，所述技术路径（2）中，金属M为铪：二胺盐与酰胺基盐的投料比为1:3或2:2或3:1；二胺盐与酰胺基盐与无水氯化铪的投料比为4:1。
前述的一种混配型酰胺基铪配合物的制备方法，所述无水有机溶剂为：甲苯、乙醚、乙二醇二甲醚、四氢呋喃、正己烷或者其中任意两种上述溶剂按照1:9-9:1的体积比例混合的混合溶剂
前述的一种混配型酰胺基铪配合物的制备方法，包括以下步骤，
（1）在惰性气体的保护下，将定量的二胺盐和无水氯化铪加入无水溶剂中进行反应；
（2）反应一段时间后，过滤，将定量的酰胺盐加入滤液中继续进行反应；
（3）在步骤（2）反应一段时间后，过滤，将滤液用减压蒸馏除去溶剂，得固体经过重结晶升华，即得到目标金属配合物。
前述的一种混配型酰胺基铪配合物的制备方法，步骤（1）中，二胺盐和无水金属氯化物反应时间：5-10小时，反应温度：0-40℃。
前述的一种混配型酰胺基铪配合物的制备方法，所述步骤（2）中，定量的酰胺盐加入滤液反应时间：5-12小时，反应温度：20-55℃。
另外，本发明提供一种前述的混配型酰胺基铪配合物的应用，包括在制备高k材料HfO2上的应用，和用于催化内酯或交酯开环聚合反应。
本发明的有益效果为：本发明合成简便，工艺稳定，原料简单，价格便宜。混配型酰胺基铪配合物的合成过程不带入其他杂质，制备工艺质量可靠稳定，符合ALD工艺的要求。
附图说明
图1为本发明混配型酰胺基铪配合物制备的HfO2薄膜的SEM图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例一：Hf[i-Bu(NCO)Ph]3[N(SiMe3)2]配合物的合成
在惰性气体氮气的保护下，将定量的[N,N-双(三甲基硅基)胺]锂Li[N(SiMe3)2](83.67 g, 0.500 mol)和无水氯化铪HfCl4( 160.15g, 0.500 mol)在无水甲苯中搅拌，反应温度15℃下搅拌6小时，过滤，保留滤液。将定量N-异丁基苯甲酰胺锂( 274.77 g, 1.500mol)加入滤液中，然后在30℃反应8h，溶液颜色由无色变为黄色，过滤，将滤液用减压蒸馏除去溶剂，重结晶得到配合物产品Hf[i-Bu(NCO)Ph]3[N(SiMe3)2]。检测数据如下：Yield,85.7 % (371.76 g).Anal. Calcd forC39H60HfN4O3Si2: C, 53.99; H, 6.97; Hf, 20.57;N, 6.46; O, 5.53; Si, 6.47, Found: C, 53.88; H,6.90; Hf, 20.45; N, 6.32; O,5.45; Si, 6.45.1HNMR(400 MHz,C6D6): δ 7.65~7.72 (m, 9H, Ph-H) 8.04 (dd, 6H,Ph-H), 3.78(m, 3H, CH(CH3)CH2CH3), 1.69(m, 6H, CH(CH3)CH 2CH3), 1.35(d, 9H, CH(CH 3)CH2CH3), 0.69(t, 9H, CH(CH3)CH2CH 3), 0.08(s, 18H, Si(CH 3)3)。
实施例二：Hf[t-Bu(NCO)i-Bu]2[NEt2]2配合物的合成
在惰性气体氮气的保护下，将定量的[二乙胺]钠Na[NEt2]( 114.14g, 1.200mol)和无水氯化铪HfCl4( 192.18g, 0.600mol)在无水四氢呋喃中搅拌，反应温度25℃下搅拌7小时，过滤，保留滤液。将定量N-叔丁基异丁基甲酰胺钠( 215.28g, 1.200 mol)加入滤液中，然后在60℃反应10 h，溶液颜色由无色变为黄色，过滤，将滤液用减压蒸馏除去溶剂，得到Hf[t-Bu(NCO)i-Bu]2[NEt2]2。检测数据如下：Yield, 85.8 % (327.02g).Anal.Calcd forC26H56HfN4O2: C, 49.16; H, 8.89; Hf, 28.10; N, 8.82; O, 5.04. Found:C, 49.07; H, 8.91; Hf,28.02; N, 8.79; O, 5.01.1HNMR(400 MHz,C6D6): δ2.57 (q,8H, NCH 2CH3),2.53(m, 2H, OCH(CH3) CH2CH3), 1.62(q, 4H, CH 2CH3),1.46 (s, 18H, N(CH 3)3), 1.23(d, 6H, OCH(CH 3)CH2CH3),1.05 (t, 12H, NCH2CH 3),1.02(t, 6H, CH2CH 3)。
实施例三：HfO2薄膜的制备
用实施例一制备的配合物（Hf[t-Bu(NCO)i-Bu]2[NEt2]2）为例作为前驱体，用原子层沉积的方法来生长La2O3薄膜材料,如图1所示。基底：Si，SiO2；载气：N2，Ar。反应的衬底温度为255℃，在气流量为：30-50sccm，反应腔工作压强保持在5×10-6Tor。一个周期内，铪配合物前驱体的脉冲长度为1.0s，H2O的脉冲长度为0.05s，HfO2的生长速率为0.50 Å/cycle,循环50个周期。利用原子层沉积技术制备的薄膜致密均匀，且平整度很好（RMS=0.35nm）。
综上，本发明合成简便，提供了一种混配型酰胺基铪配合物的制备方法，提供一系列对衬底的污染小、合成方法简便，工艺操作简单，产率高，成本低的混配型酰胺基铪配合物的合成方法。此系列制备方法，易于合成，毒性低，简单易操作等特点，工艺稳定，原料简单，价格便宜，混配型酰胺基铪配合物的合成过程不带入其他杂质，制备工艺质量可靠稳定，符合ALD工艺的要求。
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (9)
1.一种混配型酰胺基铪配合物，其特征在于：该配合物的结构通式为：
；
其中：
M =Hf；n= 1，2或3；
R1=CH3，CH2CH3，异丙基，叔丁基，环己基，苯基，环戊基或环戊二烯基；
R2= H，CH3，CH2CH3，异丙基，叔丁基，环己基，苯基，环戊基或环戊二烯基；
R3= -N(CH2CH3)2，-N(CH2CH3)CH3，-N(CH3)2或-N(SiMe3)2。
2.一种混配型酰胺基铪配合物的制备方法，其特征在于：技术路径为，
；
其中：
M=Hf；M1=K，Na或Li； M2 =K，Na，Li；n=1，2或3；
R1=CH3，CH2CH3，异丙基，叔丁基，环己基，苯基，环戊基或环戊二烯基；
R2= H，CH3，CH2CH3，异丙基，叔丁基，环己基，苯基，环戊基或环戊二烯基；
R3= -N(CH2CH3)2，-N(CH2CH3)CH3，-N(CH3)2或-N(SiMe3)2。
3.根据权利要求2所述的一种混配型酰胺基铪配合物的制备方法，其特征在于：所述金属M为铪，无水金属盐为无水氯化铪。
4.根据权利要求2所述的一种混配型酰胺基铪配合物的制备方法，其特征在于：所述技术路径中，金属M为铪：二胺盐与酰胺基盐的投料比为1:3或2:2或3;1；二胺盐与酰胺基盐与无水氯化铪的投料比为4:1。
5.根据权利要求2所述的一种混配型酰胺基铪配合物的制备方法，其特征在于：所述无水有机溶剂为：甲苯、乙醚、乙二醇二甲醚、四氢呋喃、正己烷或者其中任意两种上述溶剂按照1:9-9:1的体积比例混合的混合溶剂。
6.根据权利要求2所述的一种混配型酰胺基铪配合物的制备方法，其特征在于：包括以下步骤，
（1）在惰性气体的保护下，将定量的二胺盐和无水氯化铪加入无水溶剂中进行反应；
（2）反应一段时间后，过滤，将定量的酰胺基盐加入滤液中继续进行反应；
（3）在步骤（2）反应一段时间后，过滤，将滤液用减压蒸馏除去溶剂，得固体经过重结晶升华，即得到目标金属配合物。
7.根据权利要求6所述的一种混配型酰胺基铪配合物的制备方法，其特征在于：所述步骤（1）中，二胺盐和无水金属氯化物反应时间：5-10小时，反应温度：0-40℃。
8.根据权利要求6所述的一种混配型酰胺基铪配合物的制备方法，其特征在于：所述步骤（2）中，定量的酰胺基盐加入滤液反应时间：5-12小时，反应温度：20-55℃。
9.根据权利要求1所述的混配型酰胺基铪配合物或权利要求2-8任一项所制备的混配型酰胺基铪配合物的应用，其特征在于：在制备高k材料HfO2上的应用，或用于催化内酯或交酯开环聚合反应。
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