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CN-121974944-A - N-alkanoyl alkylamide lanthanum/gadolinium compound complex and preparation method and application thereof

CN121974944ACN 121974944 ACN121974944 ACN 121974944ACN-121974944-A

Abstract

The invention discloses an N-alkanoyl alkylamide lanthanum/gadolinium mixed complex, a preparation method and application thereof, wherein under the protection of inert gas, quantitative N-alkanoyl alkylamide and tri (diamine) lanthanum or tri (diamine) gadolinium compound are added into an anhydrous solvent; adding anhydrous solvent, reacting for a period of time, filtering, distilling the filtrate under reduced pressure to remove solvent and byproducts to obtain white solid, and recrystallizing and sublimating the obtained white solid to obtain the target metal complex. The complex synthesized by the method has the characteristics of small pollution to a substrate, simple and convenient synthesis method, simple technological operation, high yield and low cost, and the complex has the characteristics of high volatility, proper thermal stability, easiness in synthesis, low toxicity and the like, can be used for preparing high-K materials, and has good practical value and application prospect.

Inventors

  • SHEN YINGZHONG
  • SHEN KECHENG
  • TAO XIAN

Assignees

  • 江苏爱姆欧光电材料有限公司

Dates

Publication Date
20260505
Application Date
20251224

Claims (10)

  1. 1. The N-alkanoylalkylamide lanthanum/gadolinium mixed complex is characterized by comprising two ligands of N-alkanoylalkylamide and diamine, wherein the structural formula of the two ligands is shown as formula I: (formula I); wherein: M=la or Gd; n=1 or 2; R 1 =CH 3 ,CF 3 ,CH 2 CH 3 ,CH 2 CH 2 CH 3 ,CHCH 3 CH 3 ,CH 2 CH 2 CH 2 CH 3 ,CHCH 3 (CH 2 CH 3 ),C (CH 3 ) 3 ,Cp Or Ph; R 2 =CH 3 ,CF 3 ,CH 2 CH 3 ,CH 2 CH 2 CH 3 ,CHCH 3 CH 3 ,CH 2 CH 2 CH 2 CH 3 ,CHCH 3 (CH 2 CH 3 ),C (CH 3 ) 3 ,Cp Or Ph; R 3 = -N(CH 2 CH 3 ) 2 ,-N(CH 2 CH 3 )CH 3 ,-N(CH 3 ) 2 ,-N(SiMe 3 ) 2 .
  2. 2. A process for preparing a lanthanum/gadolinium N-alkanoylalkylamide complex according to claim 1, comprising the steps of, 1) Under the protection of inert gas, adding quantitative N-alkanoylalkanamide and lanthanum tri (diamine) or gadolinium tri (diamine) compound into an anhydrous solvent, and reacting for a period of time to obtain a crude product solution; 2) Filtering the crude product solution obtained by the reaction in the step 1), and distilling the filtrate under reduced pressure to remove the solvent and byproducts to obtain crude product solid; 3) And (3) carrying out recrystallization sublimation on the crude product solid obtained in the step (2) through reduced pressure distillation to obtain the target metal complex.
  3. 3. The method for preparing a lanthanum/gadolinium N-alkanoylalkylamide complex according to claim 1, wherein in step 1), the inert gas is nitrogen or argon.
  4. 4. The method for preparing a lanthanum/gadolinium N-alkanoylalkylamide complex according to claim 1, wherein in the step 1), the feeding ratio of the lanthanum tri (diamine) or gadolinium tri (diamine) compound to the N-alkanoylalkylamide is 1:2 or 2:1.
  5. 5. The preparation method of the lanthanum/gadolinium N-alkanoylalkylamide compound complex according to claim 1, wherein in the step 1), the anhydrous organic solvent is selected from any one or two of diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, toluene and N-hexane.
  6. 6. The preparation method of the N-alkanoylalkylamide lanthanum/gadolinium mixed complex according to claim 1, wherein in the step 1), the reaction temperature is-10-35 ℃ and the reaction time is 3-12 hours.
  7. 7. The preparation method of the N-alkanoylalkylamide lanthanum/gadolinium mixed complex according to claim 1, wherein in the step 2), the parameters of reduced pressure distillation are-50 to-99 kpa and 20-100 ℃.
  8. 8. The preparation method of the N-alkanoylalkylamide lanthanum/gadolinium mixed complex according to claim 1, wherein in the step 3), the specific process of recrystallization sublimation is that crude product solid obtained by reduced pressure distillation is recrystallized in the anhydrous organic solvent according to claim 5 at a low temperature of-40-0 ℃.
  9. 9. Use of an N-alkanoylalkylamide lanthanum/gadolinium compound complex according to claim 1 as precursor for the preparation of high K materials.
  10. 10. The application of the lanthanum/gadolinium N-alkanoylalkylamide compound complex according to claim 9, wherein the method for preparing the high-K material is an atomic layer deposition method, and the parameters are as follows: A substrate of Si or SiO2; Carrier gas, N2 or Ar; The temperature of the reacted substrate is 260-270 ℃; the flow rate of the carrier gas is 30-50 sccm; the working pressure of the reaction cavity is kept at 5 multiplied by 10 < -6 > Tor; In one period, the pulse length of the complex precursor is 1.5s, and the pulse length of H2O is 0.06s; The growth rate of the K material is 0.50A/cycle, and the cycle is 55-65 cycles.

Description

N-alkanoyl alkylamide lanthanum/gadolinium compound complex and preparation method and application thereof Technical Field The invention relates to the technical field of metal organic complexes, in particular to an N-alkanoyl alkylamide lanthanum/gadolinium mixed complex, a preparation method and application thereof. Background With the rapid development of microelectronic technology, the feature sizes of devices such as large-scale integrated circuits (LSI) and transistors are becoming smaller, and when the feature sizes of devices are below 45nm, the conventional gate dielectric material SiO 2 cannot meet the requirements, and SiO 2 needs to be replaced by a high-K material with a larger dielectric constant. In addition to ZrO 2(k=25),HfO2 (k=25) and Al2O3(k=9)（Niinistö L, Päiväsaari J, NiinistöJ, et al. phys. stat. sol. (a), 2004, 201(7): 1443~1452.）., the rare earth oxide has been a very promising high-K material in recent years (Leskel ä M, ritla m.j. Solid State chem., 2003,171 (1-2): 170-174) due to its very high stability and excellent electrical properties. Atomic Layer Deposition (ALD) is a thin film deposition technology developed in recent years, and it is critical to find a precursor suitable for ALD. For an ideal ALD precursor, two basic requirements must be met: (1) Sufficient volatility, large steric hindrance of ① ligand to prevent polymerization, single-core complex of ② without solvent coordination, low polarity of ③ molecule and small intermolecular attraction. (2) Suitable reactivity is ① that it does not decompose on its own in the deposition temperature range, ② is highly reactive towards oxygen sources (typically H2O), and ③ precursor must be able to adsorb or react with the substrate without corroding the substrate. ALD precursors of many oxides are currently studied and can be classified into six general classes as shown in FIG. 1, alkoxy compounds (A), beta-diketone compounds (B), organic amine compounds (C) and metal-organic compounds (cyclopentadiene compounds) (D), amidinate complexes (E), guanidinate complexes (F). However, these precursors all suffer from certain drawbacks: The alkoxy compound has poor thermal stability and low reactivity, is easy to generate non-self-limiting thermal decomposition or homogeneous gas phase reaction at the growth temperature to destroy an ALD process window, and has sometimes insufficient reactivity with water to cause low growth rate. Beta-diketones have contradictory volatility and thermal stability, and large steric ligands (such as thd) introduced by the beta-diketone compounds can seriously reduce the reactivity, so that the growth temperature is high, the rate is extremely low, carbon impurities can be introduced due to incomplete reaction, and the problems of volatility and sensitivity of a melting point to ligand structures exist. Organic amine compound is used as precursor, side reaction is more, reaction by-products (such as amine) can be re-adsorbed, carbon impurities are incorporated or non-ideal growth is caused, and the problem that the interface is excessively clean and natural oxide on the surface of a III-V substrate is excessively reduced, atoms (such as In and Ga) are caused to diffuse across the film, so that interface control is not facilitated. The cyclopentadiene compound is used as a precursor, the size is oversized, the steric hindrance is large, the growth rate is low, the ligand is difficult to remove, and even a strong oxidant is used for effectively removing the ligand, so that the film or the substrate is damaged. The amidino complex contains four rings, and the balance of monomers and dimers in the solid state or in solution affects the vapor pressure stability and delivery reproducibility. The guanidine-based complex has limited ligand (carbodiimide) sources and large synthesis challenges, and partial saturated bridging groups in the structure are unconjugated, so that a higher-order polymer is easy to form, the volatility is reduced, and in addition, the size of a ring substituent can influence the bond strength and the space rejection with a metal center, so that the film quality is finally influenced. In addition, the existing precursor synthesis processes are complicated, the structure is complex, the price is high, and popularization and application are not facilitated. Therefore, how to design and develop a balance of volatility, reactivity and thermal stability, and has the advantages of small pollution to the substrate, simple synthesis method and simple process operation, and the problem of preparing the precursor by the high-K material is still to be solved. Disclosure of Invention Aiming at the defects of the prior art and in order to achieve the purposes, the invention provides an N-alkanoylalkylamide lanthanum/gadolinium mixed complex, a preparation method and application thereof, wherein the N-alkanoylalkylamide and a tri (diamine) lanthanum or tri (diamine) gadolinium compound are used as raw mat