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Source reagent compositions for CVD formation of high dielectric constant and ferroelectric metal oxide thin films and method of using same

Inactive Publication Date: 2006-05-25
BAUM THOMAS H +3
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  • Abstract
  • Description
  • Claims
  • Application Information

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Benefits of technology

[0017] One particularly preferred metal precursor species of the present invention has the formula M(thd)2(O-tBu)2 wherein M is Zr, Hf or Ti. In such precursor, the bulky t-butyl groups function to minimize deleterious isomerization reactions and enhance thermal stability of the precursor. The preferred M(thd)2(O-tBu)2 precursor can be synthesized by reacting M(O-tBu)4 with two equivalents of Hthd in a dry hydrocarbon or aryl solvent according to the following equation: M(O-tBu)4+2Hthd→M(thd)2(O-tBu)2+2HO-tBu  (1)
[0018] Another aspect of the present invention relates to a CVD source reagent composition comprising a metal precursor as described hereinabove, and a solvent medium in which the metal precursor is soluble or suspendable. Providing a source reagent composition in liquid (e.g., solution or suspension) form facilitates rapid volatilization (e.g., flash vaporization) of the source reagent composition and transport of the resultant precursor vapor to a deposition locus such as a CVD reaction chamber. Further, when used in solution the precursor stability is greatly improved over other prior art alkoxide analogs.

Problems solved by technology

Deleterious occurrence of side reactions, e.g., when the substrate is silicon, produce predominantly silicon dioxide (SiO2), locally doped SiO2, and / or other surface impurities, are desirably minimized, because formation of such surface impurities reduces the capacitance and therefore compromises performance of the deposited gate dielectric, high dielectric constant and / or ferroelectric metal oxide thin films.
Premature decomposition of source reagents not only results in undesirable accumulation of side products that will clog fluid flow conduits of the CVD apparatus, but also causes undesirable variations in composition of the deposited gate dielectric, high dielectric constant and / or ferroelectric metal oxide thin film.
Any change in chemical identity of source reagents in the solvent medium is deleterious since it impairs the ability of the CVD process to achieve repeatable delivery and film growth.

Method used

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  • Source reagent compositions for CVD formation of high dielectric constant and ferroelectric metal oxide thin films and method of using same
  • Source reagent compositions for CVD formation of high dielectric constant and ferroelectric metal oxide thin films and method of using same
  • Source reagent compositions for CVD formation of high dielectric constant and ferroelectric metal oxide thin films and method of using same

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NMR Characterization of Cis- and Trans-Equilibration of Zr(thd)2(O-iPr)2

[0112] A sample of Zr(thd)2(O-iPr)2 is dissolved in deuterated benzene solvent. FIGS. 4a-4c, show the 1H NMR (C6D6), δ(ppm), spectra of a single sample of Zr(thd)2(O-iPr)2 over a period of approximately fourteen days. The original sample in FIG. 4a shows the majority of the compound to be in the cis-phase 1.15 (s, 36H=4x-C(CH3)3 of thd ligands) and 5.92 (s, 2H=2xCH of thd ligands) with a detectable amount of the trans-isomer at 1.24 (s, 36H=4xC(CH3)3 of thd ligands) and 5.97 (s, 2H=2xCH of thd ligands). FIGS. 4b-4c further evidence the cis- to trans-equilibration of the sample over time as the peaks at 1.24(s, 36H=4x-C(CH3)3 of thd ligands) and 5.97 (s, 2H=2xCH of thd ligands) increase over the fourteen-day period (FIG. 4b time lapse=4 days, FIG. 4c time lapse=14 days). Such isomerization is accompanied by a disproportionation / dimerization reaction, leading to a less volatile, less soluble dinuclear species of ...

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Abstract

Chemical vapor deposition (CVD) precursor compositions for forming metal oxide high dielectric constant (κ) thin films. The precursor composition in one embodiment comprises a metal precursor having a general formula M(β-diketonate)2(OR)2, wherein M is Hf, Zr or Ti, and R is t-butyl. The precursor composition may also comprise a solvent medium selected from the group consisting of ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclic ethers, and compatible combinations of two or more of the foregoing.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This is a continuation of U.S. patent application Ser. No. 09 / 907,282 filed Jul. 17, 2001, which is a continuation-in-part of U.S. patent application Ser. No. 09 / 793,023 filed Feb. 26, 2001, which is a continuation-in-part of U.S. patent application Ser. No. 09 / 414,133 filed Oct. 7, 1999. The disclosures of all of said prior applications are hereby incorporated herein by reference in their respective entireties.BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates to metal precursors useful for chemical vapor deposition (CVD) of high dielectric constant (κ) and / or ferroelectric metal oxide thin films. [0004] 2. Description of the Related Art [0005] Zirconium and hafnium-containing silicates possess dielectric constant (κ) values in the range of from about 10 to 20, and therefore are highly useful as gate dielectric materials in various microelectronic structures and devices. Zirconium- and haf...

Claims

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Application Information

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IPC IPC(8): C23C16/40C07F7/00
CPCC07F7/006C09D1/00C23C16/40C23C16/401C23C16/405C23C16/409C07F7/003
Inventor BAUM, THOMAS H.ROEDER, JEFFREY F.XU, CHONGYINGHENDRIX, BRYAN C.
Owner BAUM THOMAS H
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