Germanium- and zirconium-containing composition for vapor deposition of zirconium-containing films

Patent metadata

Field	Value
Publication number	US-9868753-B2
Application number	US-201615297191-A
Country	US
Kind code	B2
Filing date	Oct 19, 2016
Priority date	Dec 23, 2014
Publication date	Jan 16, 2018
Grant date	Jan 16, 2018

Abstract

Disclosed are Germanium- and Zirconium-containing precursors having one of the following formulae:

wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from H; a C1-C5 linear, branched, or cyclic alkyl group; and a C1-C5 linear, branched, or cyclic fluoroalkyl groups. Also disclosed are methods of synthesizing the disclosed precursors and using the same to deposit Zirconium-containing films on substrates via vapor deposition processes.

First claim

We claim:

1. A process for the deposition of a Germanium doped Zirconium oxide film on a substrate, the process comprising the steps of: introducing a vapor of a Germanium- and Zirconium-containing precursor into a reactor having a substrate disposed therein and depositing at least part of the Germanium- and Zirconium-containing precursor onto the substrate and introducing an oxidizing gas into the reactor, the precursor having the following formula:

wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently selected from the group consisting of H; a C1-C5 linear, branched, or cyclic alkyl group; and a C1-C5 linear, branched, or cyclic fluoroalkyl group.

2. The process of claim 1 , wherein the Germanium- and Zirconium-containing precursor and the oxidizing gas are introduced into the reactor simultaneously and the reactor is configured for chemical vapor deposition.

3. The process of claim 1 , wherein the Germanium- and Zirconium-containing precursor and the oxidizing gas are introduced into the chamber sequentially and the reactor is configured for atomic layer deposition.

4. The process of claim 3 , wherein the Germanium- and Zirconium-containing precursor is selected from the group consisting of:
(trimethylgermyl)cyclopentadienyl tris(Dimethylamino) Zirconium(IV) (Zr(TMG-Cp) (NMe 2 ) 3 ); (trimethylgermyl)cyclopentadienyl tris(methylamino) Zirconium(IV) (Zr(TMG-Cp)(NHMe) 3 ); (trimethylgermyl)cyclopentadienyl tris(Diethylamino) Zirconium(IV) (Zr(TMG-Cp)(NEt 2 ) 3 ); (trimethylgermyl)cyclopentadienyl tris(ethylamino) Zirconium(IV) (Zr(TMG-Cp)(NHEt) 3 ); (trimethylgermyl)cyclopentadienyl tris(ethylmethylamino) Zirconium(IV) (Zr(TMG-Cp)(NEtMe) 3 );
(trimethylgermyl)cyclopentadienyl tris(Di n-propylamino) Zirconium(IV) (Zr(TMG-Cp) (NnPr 2 ) 3 ); (trimethylgermyl)cyclopentadienyl tris(n-propylamino) Zirconium(IV) (Zr(TMG-Cp)(NHnPr) 3 ); (trimethylgermyl)cyclopentadienyl tris(Di isopropylamino) Zirconium(IV) (Zr(TMG-Cp)(NiPr 2 ) 3 ); (trimethylgermyl)cyclopentadienyl tris(isopropylamino) Zirconium(IV) (Zr(TMG-Cp)(NHiPr) 3 );
(trimethylgermyl)cyclopentadienyl tris(Di n-butylamino) Zirconium(IV) (Zr(TMG-Cp) (NnBu 2 ) 3 ); (trimethylgermyl)cyclopentadienyl tris(n-butylamino) Zirconium(IV) (Zr(TMG-Cp)(NHnBu) 3 ); (trimethylgermyl)cyclopentadienyl tris(Di isobutylamino) Zirconium(IV) (Zr(TMG-Cp)(NiBu 2 ) 3 ); (trimethylgermyl)cyclopentadienyl tris(isobutylamino) Zirconium(IV) (Zr(TMG-Cp)(NHiBu) 3 );
(trimethylgermyl)cyclopentadienyl tris(Di sec-butylamino) Zirconium(IV) (Zr(TMG-Cp) (NsBu 2 ) 3 ); (trimethylgermyl)cyclopentadienyl tris(sec-butylamino) Zirconium(IV) (Zr(TMG-Cp)(NHsBu) 3 ); (trimethylgermyl)cyclopentadienyl tris(Di tert-butylamino) Zirconium(IV) (Zr(TMG-Cp)(NtBu 2 ) 3 ); (trimethylgermyl)cyclopentadienyl tris(tert-butylamino) Zirconium(IV) (Zr(TMG-Cp)(NHtBu) 3 ); (dimethylgermyl)cyclopentadienyl tris(Dimethylamino) Zirconium(IV) (Zr(DMG-Cp)(NMe 2 ) 3 );
(dimethylgermyl)cyclopentadienyl tris(methylamino) Zirconium(IV) (Zr(DMG-Cp) (NHMe) 3 ); (dimethylgermyl)cyclopentadienyl tris(Diethylamino) Zirconium(IV) (Zr(DMG-Cp)(NEt 2 ) 3 ); (dimethylgermyl)cyclopentadienyl tris(ethylamino) Zirconium(IV) (Zr(DMG-Cp)(NHEt) 3 ); (dimethylgermyl)cyclopentadienyl tris(ethylmethylamino) Zirconium(IV) (Zr(DMG-Cp)(NEtMe) 3 ); (dimethylgermyl)cyclopentadienyl tris(Di n-propylamino) Zirconium(IV) (Zr(DMG-Cp)(NnPr 2 ) 3 ); (dimethylgermyl)cyclopentadienyl tris(n-propylamino) Zirconium(IV) (Zr(DMG-Cp)(NHnPr) 3 );
(dimethylgermyl)cyclopentadienyl tris(Di isopropylamino) Zirconium(IV) (Zr(DMG-Cp) (NiPr 2 ) 3 ); (dimethylgermyl)cyclopentadienyl tris(isopropylamino) Zirconium(IV) (Zr(DMG-Cp)(NHiPr) 3 ); (dimethylgermyl)cyclopentadienyl tris(Di n-butylamino) Zirconium(IV) (Zr(DMG-Cp)(NnBu 2 ) 3 ); (dimethylgermyl)cyclopentadienyl tris(n-butylamino) Zirconium(IV) (Zr(DMG-Cp)(NHnBu) 3 ); (dimethylgermyl)cyclopentadienyl tris(Di isobutylamino) Zirconium(IV) (Zr(DMG-Cp)(NMe 2 ) 3 );
(dimethylgermyl)cyclopentadienyl tris(isobutylamino) Zirconium(IV) (Zr(DMG-Cp) (NHiBu) 3 ); (dimethylgermyl)cyclopentadienyl tris(Di sec-butylamino) Zirconium(IV) (Zr(DMG-Cp)(NsBu 2 ) 3 ); (dimethylgermyl)cyclopentadienyl tris(sec-butylamino) Zirconium(IV) (Zr(DMG-Cp)(NHsBu) 3 ); (dimethylgermyl)cyclopentadienyl tris(Di tert-butylamino) Zirconium(IV) (Zr(DMG-Cp)(NtBu 2 ) 3 ); (dimethylgermyl)cyclopentadienyl tris(tert-butylamino) Zirconium(IV) (Zr(DMG-Cp)(NHtBu) 3 );
(trifluorogermyl)cyclopentadienyl tris(Dimethylamino) Zirconium(IV) (Zr(F 3 Ge-Cp) (NMe 2 ) 3 ); (trifluorogermyl)cyclopentadienyl tris(methylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NHMe) 3 ); (trifluorogermyl)cyclopentadienyl tris(Diethylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NEt 2 ) 3 ); (trifluorogermyl)cyclopentadienyl tris(ethylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NHEt) 3 ); (trifluorogermyl)cyclopentadienyl tris(Ethylmethylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NEtMe) 3 );
(trifluorogermyl)cyclopentadienyl tris(Di n-propylamino) Zirconium(IV) (Zr(F 3 Ge-Cp) (NnPr 2 ) 3 ); (trifluorogermyl)cyclopentadienyl tris(n-propylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NHnPr) 3 ) (trifluorogermyl)cyclopentadienyl tris(Di isopropylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NiPr 2 ) 3 ); (trifluorogermyl)cyclopentadienyl tris(isopropylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NHiPr) 3 );
(trifluorogermyl)cyclopentadienyl tris(Di n-butylamino) Zirconium(IV) (Zr(F 3 Ge-Cp) (NnBu 2 ) 3 ); (trifluorogermyl)cyclopentadienyl tris(n-butylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NHnBu) 3 ); (trifluorogermyl)cyclopentadienyl tris(Di isobutylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NiBu 2 ) 3 ); (trifluorogermyl)cyclopentadienyl tris(isobutylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NHiBu) 3 );
(trifluorogermyl)cyclopentadienyl tris(Di sec-butylamino) Zirconium(IV) (Zr(F 3 Ge-Cp) (NsBu 2 ) 3 ); (trifluorogermyl)cyclopentadienyl tris(sec-butylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NHsBu) 3 ); (trifluorogermyl)cyclopentadienyl tris(Di tert-butylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NtBu 2 ) 3 ); (trifluorogermyl)cyclopentadienyl tris(tert-butylamino) Zirconium(IV) (Zr(F 3 Ge-Cp)(NHtBu) 3 ); (difluorogermyl)cyclopentadienyl tris(Dimethylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NMe 2 ) 3 );
(difluorogermyl)cyclopentadienyl tris(methylamino) Zirconium(IV) (Zr(F 2 HGe-Cp) (NHMe) 3 ); (difluorogermyl)cyclopentadienyl tris(Diethylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NEt 2 ) 3 ); (difluorogermyl)cyclopentadienyl tris(ethylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NHEt) 3 ); (difluorogermyl)cyclopentadienyl tris(Ethylmethylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NEtMe) 3 ); (difluorogermyl)cyclopentadienyl tris(Di n-propylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NnPr 2 ) 3 ); (difluorogermyl)cyclopentadienyl tris(n-propylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NHnPr) 3 );
(difluorogermyl)cyclopentadienyl tris(Di isopropylamino) Zirconium(IV) (Zr(F 2 HGe-Cp) (NiPr 2 ) 3 ); (difluorogermyl)cyclopentadienyl tris(isopropylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NHiPr) 3 ); (difluorogermyl)cyclopentadienyl tris(Di n-butylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NnBu 2 ) 3 ); (difluorogermyl)cyclopentadienyl tris(n-butylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NHnBu) 3 ); (difluorogermyl)cyclopentadienyl tris(Di isobutylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NiBu 2 ) 3 );
(difluorogermyl)cyclopentadienyl tris(isobutylamino) Zirconium(IV) (Zr(F 2 HGe-Cp) (NHiBu) 3 ); (difluorogermyl)cyclopentadienyl tris(Di sec-butylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NsBu 2 ) 3 ); (difluorogermyl)cyclopentadienyl tris(sec-butylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NHsBu) 3 ); (difluorogermyl)cyclopentadienyl tris(Di tert-butylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NtBu 2 ) 3 ); (difluorogermyl)cyclopentadienyl tris(tert-butylamino) Zirconium(IV) (Zr(F 2 HGe-Cp)(NHtBu) 3 );
(monofluorogermyl)cyclopentadienyl tris(Dimethyl

Assignees

• L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude
• L'Air Liquide Société Anonyme Our L'Etude Et L'Exploitation Des Procédés Georges Claude

Inventors

• Lansalot-Matras Clément
• Lieffrig Julien
• Ishii Hana
• Dussarrat Christian

Classifications

• C23C16/45553

  characterized by the use of precursors specially adapted for ALD · CPC title

• C23C16/407

  of zinc, germanium, cadmium, indium, tin, thallium or bismuth · CPC title

• C23C16/405 Primary

  of refractory metals or yttrium · CPC title

• C23C16/40

  Oxides · CPC title

• C07F17/00 Primary

  Metallocenes · CPC title