Titanium-containing film forming compositions for vapor deposition of titanium-containing films

Patent metadata

Field	Value
Publication number	US-9790591-B2
Application number	US-201514954319-A
Country	US
Kind code	B2
Filing date	Nov 30, 2015
Priority date	Nov 30, 2015
Publication date	Oct 17, 2017
Grant date	Oct 17, 2017

Abstract

Titanium-containing film forming compositions are disclosed as well as methods of synthesizing the same and methods of forming Titanium-containing films on substrates via vapor deposition processes using the Titanium-containing film forming compositions. The Titanium-containing film forming compositions comprise a precursor having the formula Ti(R 5 Cp) 2 (L), wherein each R is independently H, an alkyl group, or R′ 3 Si, with each R′ independently being H or an alkyl group; L is selected from the group consisting of formamidinates (N R,R′ -fmd) or amidinates (N R,R′ R″-amd).

First claim

We claim:

1. A Titanium-containing film forming composition comprising a liquid precursor having the formula
Ti(R 5 Cp) 2 (L)

wherein Cp is cyclopentadienyl, each R is independently H, an alkyl group, or R′ 3 Si, with each R′ independently being H or an alkyl group; and L is a formamidinate ligand having the chemical formula R—N—C(H)═N—R′, shown as:

(N R′,R′ -fmd or N R -fmd when R═R′) or am idinate ligand having the chemical formula R—N—C(R″)═N—R′, shown as:

(N R′,R′ R″-amd or N R R″-amd when R═R′), wherein R and R′ are alkyl groups or SiMe 3 and R″ is an alkyl group.

2. The Titanium-containing film forming composition of claim 1 , wherein the liquid precursor has the formula Ti(R 5 Cp) 2 (N R′,R′ -fmd) or Ti(R 5 Cp) 2 (N R -fmd) when R═R′.

3. The Titanium-containing film forming composition of claim 2 , wherein the liquid precursor is selected from the group consisting Ti(Cp) 2 (N Me -fmd), Ti(Cp) 2 (N Et -fmd), Ti(Cp) 2 (N iPr -fmd), Ti(Cp) 2 (N nPr -fmd), Ti(Cp) 2 (N iBu -fmd), Ti(Cp) 2 (N nBu -fmd), Ti(Cp) 2 (N tBu -fmd), Ti(Cp) 2 (N sBu -fmd), Ti(Cp) 2 (N tAm -fmd), Ti(Cp) 2 (N TMS -fmd), Ti(MeCp) 2 (N Me -fmd), Ti(MeCp) 2 (N Et -fmd), Ti(MeCp) 2 (N iPr -fmd), Ti(MeCp) 2 (N nPr -fmd), Ti(MeCp) 2 (N iBu -fmd), Ti(MeCp) 2 (N nBu -fmd), Ti(MeCp) 2 (N tBu -fmd), Ti(MeCp) 2 (N sBu -fmd), Ti(MeCp) 2 (N tAm -fmd), Ti(MeCp) 2 (N TMS -fmd), Ti(EtCp) 2 (N Me -fmd), Ti(EtCp) 2 (N Et -fmd), Ti(EtCp) 2 (N iPr -fmd), Ti(EtCp) 2 (N nPr -fmd), Ti(EtCp) 2 (N iBu -fmd), Ti(EtCp) 2 (N nBu -fmd), Ti(EtCp) 2 (N tBu -fmd), Ti(EtCp) 2 (N sBu -fmd), Ti(EtCp) 2 (N tAm -fmd), Ti(EtCp) 2 (N TMS -fmd), Ti(iPrCp) 2 (N Me -fmd), Ti(iPrCp) 2 (N Et -fmd), Ti(iPrCp) 2 (N iPr -fmd), Ti(iPrCp) 2 (N nPr -fmd), Ti(iPrCp) 2 (N iBu -fmd), Ti(iPrCp) 2 (N nBu -fmd), Ti(iPrCp) 2 (N tBu -fmd), Ti(iPrCp) 2 (N sBu -fmd), Ti(iPrCp) 2 (N tAm -fmd), Ti(iPrCp) 2 (N TMS -fmd), Ti(tBuCp) 2 (N Me -fmd), Ti(tBuCp) 2 (N Et -fmd), Ti(tBuCp) 2 (N iPr -fmd), Ti(tBuCp) 2 (N nPr -fmd), Ti(tBuCp) 2 (N nBu -fmd), Ti(tBuCp) 2 (N nBu -fmd), Ti(tBuCp) 2 (N tBu -fmd), Ti(tBuCp) 2 (N sBu -fmd), Ti(tBuCp) 2 (N tAm -fmd), Ti(tBuCp) 2 (N TMS -fmd), Ti(iPr 3 Cp) 2 (N Me -fmd), Ti(iPr 3 Cp) 2 (N Et -fmd), Ti(iPr 3 Cp) 2 (N iPr -fmd), Ti(iPr 3 Cp) 2 (N nPr -fmd), Ti(iPr 3 Cp) 2 (N iBu -fmd), Ti(iPr 3 Cp) 2 (N nBu -fmd), Ti(iPr 3 Cp) 2 (N tBu -fmd), Ti(iPr 3 Cp) 2 (N sBu -fmd), Ti(iPr 3 Cp) 2 (N tAm -fmd), Ti(iPr 3 Cp) 2 (N TMS -fmd), Ti(Cp*) 2 (N Me -fmd), Ti(Cp*) 2 (N Et -fmd), Ti(Cp*) 2 (N iPr -fmd), Ti(Cp*) 2 (N nPr -fmd), Ti(Cp*) 2 (N iBu -fmd), Ti(Cp*) 2 (N nBu -fmd), Ti(Cp*) 2 (N tBu -fmd), Ti(Cp*) 2 (N sBu -fmd), Ti(Cp*) 2 (N tAm -fmd), Ti(Cp*) 2 (N TMS -fmd), Ti(Me 3 SiCp) 2 (N Me -fmd), Ti(Me 3 SiCp) 2 (N Et -fmd), Ti(Me 3 SiCp) 2 (N iPr -fmd), Ti(Me 3 SiCp) 2 (N nPr -fmd), Ti(Me 3 SiCp) 2 (N iBu -fmd), Ti(Me 3 SiCp) 2 (N nBu -fmd), Ti(Me 3 SiCp) 2 (N tBu -fmd), Ti(Me 3 SiCp) 2 (N sBu -fmd), Ti(Me 3 SiCp) 2 (N tAm -fmd), Ti(Me 3 SiCp) 2 (N TMS -fmd), Ti(Cp)(Cp*)(N Me -fmd), Ti(Cp)(iPr 3 Cp)(N Me -fmd), Ti(Cp)(MeCp)(N Et -fmd), Ti(Cp)(EtCp)(N iPr -fmd), Ti(Cp)(iPrCp)(N nPr -fmd), Ti(Cp)(nPrCp)(N iBu -fmd), Ti(Cp)(iBuCp)(N nBu -fmd), Ti(Cp)(tBuCp)(N tBu -fmd), Ti(Cp)(tAmCp)(N sBu -fmd), Ti(Cp) 2 (N Et, tBu -fmd), Ti(MeCp) 2 (N Et, tBu -fmd) or Ti(EtCp) 2 (N Et, tBu -fmd).

4. The Titanium-containing film forming composition of claim 3 , wherein the liquid precursor is Ti(EtCp) 2 (N iPr -fmd).

5. The Titanium-containing film forming composition of claim 1 , wherein the liquid precursor has the formula Ti(R 5 Cp) 2 (N R′,R′ R″-amd) or Ti(R 5 Cp) 2 (N R R″-amd) when R═R′.

6. The Titanium-containing film forming composition of claim 5 , wherein the liquid precursor is selected from the group consisting of Ti(Cp) 2 (N Me Me-amd), Ti(Cp) 2 (N Et Me-amd), Ti(Cp) 2 (N nPr Me-amd), Ti(Cp) 2 (N iBu Me-amd), Ti(Cp) 2 (N nBu Me-amd), Ti(Cp) 2 (N sBu Me-amd), Ti(Cp) 2 (N tAm Me-amd), Ti(Cp) 2 (N TMS Me-amd), Ti(MeCp) 2 (N Me Me-amd), Ti(MeCp) 2 (N Et Me-amd), Ti(MeCp) 2 (N nPr Me-amd), Ti(MeCp) 2 (N iBu Me-amd), Ti(MeCp) 2 (N nBu Me-amd), Ti(MeCp) 2 (N tBu Me-amd), Ti(MeCp) 2 (N sBu Me-amd), Ti(MeCp) 2 (N tAm Me-amd), Ti(MeCp) 2 (N TMS Me-amd), Ti(EtCp) 2 (N Me Me-amd), Ti(EtCp) 2 (N Et Me-amd), Ti(EtCp) 2 (N iPr Me-amd), Ti(EtCp) 2 (N nPr Me-amd), Ti(EtCp) 2 (N iBu Me-amd), Ti(EtCp) 2 (N nBu Me-amd), Ti(EtCp) 2 (N tBu Me-amd), Ti(EtCp) 2 (N sBu Me-amd), Ti(EtCp) 2 (N tAm Me-amd), Ti(EtCp) 2 (N TMS Me-amd), Ti(iPrCp) 2 (N Me Me-amd), Ti(iPrCp) 2 (N Et Me-amd), Ti(iPrCp) 2 (N iPr Me-amd), Ti(iPrCp) 2 (N nPr Me-amd), Ti(iPrCp) 2 (N iBu Me-amd), Ti(iPrCp) 2 (N nBu Me-amd), Ti(iPrCp) 2 (N tBu Me-amd), Ti(iPrCp) 2 (N sBu Me-amd), Ti(iPrCp) 2 (N tAm Me-amd), Ti(iPrCp) 2 (N TMS Me-amd), Ti(tBuCp) 2 (N Me Me-amd), Ti(tBuCp) 2 (N Et Me-amd), Ti(tBuCp) 2 (N iPr Me-amd), Ti(tBuCp) 2 (N nPr Me-amd), Ti(tBuCp) 2 (N iBu Me-amd), Ti(tBuCp) 2 (N nBu Me-amd), Ti(tBuCp) 2 (N tBu Me-amd), Ti(tBuCp) 2 (N sBu Me-amd), Ti(tBuCp) 2 (N tAm Me-amd), Ti(tBuCp) 2 (N TMS Me-amd), Ti(iPr 3 Cp) 2 (N Me Me-amd), Ti(iPr 3 Cp) 2 (N Et Me-amd), Ti(iPr 3 Cp) 2 (N iPr Me-amd), Ti(iPr 3 Cp) 2 (N nPr Me-amd), Ti(iPr 3 Cp) 2 (N iBu Me-amd), Ti(iPr 3 Cp) 2 (N nBu Me-amd), Ti(iPr 3 Cp) 2 (N tBu Me-amd), Ti(iPr 3 Cp) 2 (N sBu Me-amd), Ti(iPr 3 CO 2 (N tAm Me-amd), Ti(iPr 3 Cp) 2 (N TMS Me-amd), Ti(Cp*) 2 (N Me Me-amd), Ti(Cp*) 2 (N Et Me-amd), Ti(Cp*) 2 (N iPr Me-amd), Ti(Cp*) 2 (N nPr Me-amd), Ti(Cp*) 2 (N iBu Me-amd), Ti(Cp*) 2 (N nBu Me-amd), Ti(Cp*) 2 (N tBu Me-amd), Ti(Cp*) 2 (N sBu Me-amd), Ti(Cp*) 2 (N tAm Me-amd), Ti(Cp*) 2 (N TMS Me-amd), Ti(Me 3 SiCp) 2 (N Me Me-amd), Ti(Me 3 SiCp) 2 (N Et Me-amd), Ti(Me 3 SiCp) 2 (N iPr Me-amd), Ti(Me 3 SiCp) 2 (N nPr Me-amd), Ti(Me 3 SiCp) 2 (N iBu Me-amd), Ti(Me 3 SiCp) 2 (N nBu Me-amd), Ti(Me 3 SiCp) 2 (N tBu Me-amd), Ti(Me 3 SiCp) 2 (N sBu Me-amd), Ti(Me 3 SiCp) 2 (N tAm Me-amd), Ti(Me 3 SiCp) 2 (N TMS Me-amd), Ti(Cp)(Cp*)(N Me Me-amd), Ti(Cp)(iPr 3 Cp)(N Me Me-amd), Ti(Cp)(MeCp)(N Et Me-amd), Ti(Cp)(EtCp)(N iPr Me-amd), Ti(Cp)(iPrCp)(N nPr Me-amd), Ti(Cp)(nPrCp)(N iBu Me-amd), Ti(Cp)(iBuCp)(N nBu Me-amd), Ti(Cp)(tBuCp)(N tBu Me-amd), Ti(Cp)(tAmCp)(N sBu Me-amd), Ti(Cp) 2 (N iPr Et-amd), Ti(Cp) 2 (N iPr nPr-amd), Ti(Cp) 2 (N iPr iPr-amd), Ti(Cp) 2 (N iPr tBu-amd), Ti(Cp) 2 (N iPr iBu-amd), Ti(Cp) 2 (N iPr sBu-amd), Ti(MeCp) 2 (N iPr Et-amd), Ti(MeCp) 2 (N iPr nPr-amd), Ti(MeCp) 2 (N iPr iPr-amd), Ti(MeCp) 2 (N iPr tBu-amd), Ti(MeCp) 2 (N iPr nBu-amd), Ti(MeCp) 2 (N iPr iBu-amd), Ti(MeCp) 2 (N iPr sBu-amd), Ti(EtCp) 2 (N iPr Et-amd), Ti(EtCp) 2 (N iPr nPr-amd), Ti(EtCp) 2 (N iPr iPr-amd), Ti(EtCp) 2 (N iPr tBu-amd), Ti(EtCp) 2 (N iPr nBu-amd), Ti(EtCp) 2 (N iPr iBu-amd), and Ti(EtCp) 2 (N iPr sBu-amd).

7. The Titanium-containing film forming composition of claim 6 , wherein the liquid precursor is Ti(EtCp) 2 (N iPr Me-amd).

8. The Titanium-containing film forming composition of claim 1 , the composition comprising between approximately 95.0% w/w and approximately 100.0% w/w of the liquid precursor.

9. The Titanium-containing film forming composition of claim 1 , the composition comprising between approximately 0.0% w/w and approximately 5.0% w/w impurities.

10. A method of forming a Titanium-containing film, the method comprising introducing into a reactor having a substrate therein a vapor of a Titanium-containing film forming composition comprising a liquid precursor having the formula
Ti(R 5 Cp) 2 (L)

wherein Cp is cyclopentadienyl, each R is independently H, an

Assignees

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

Inventors

• Ko Changhee
• Gatineau Julien
• Lansalot-Matras Clément
• Lieffrig Julien
• Ishii Hana

Classifications

• C23C16/4402

  Reduction of impurities in the source gas · CPC title

• C23C16/405

  of refractory metals or yttrium · CPC title

• C23C16/34

  Nitrides {(C23C16/303 takes precedence)} · CPC title

• C23C16/18 Primary

  from metallo-organic compounds · CPC title