Formulation for deposition of silicon doped hafnium oxide as ferroelectric materials

Patent metadata

Field	Value
Publication number	US-11081337-B2
Application number	US-201815914968-A
Country	US
Kind code	B2
Filing date	Mar 7, 2018
Priority date	Mar 15, 2017
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

Abstract

In one aspect, the invention is formulations comprising both organoaminohafnium and organoaminosilane precursors that allows anchoring both silicon-containing fragments and hafnium-containing fragments onto a given surface having hydroxyl groups to deposit silicon doped hafnium oxide having a silicon doping level ranging from 0.5 to 8 mol %, preferably 2 to 6 mol %, most preferably 3 to 5 mol %, suitable as ferroelectric material. In another aspect, the invention is methods and systems for depositing the silicon doped hafnium oxide films using the formulations.

First claim

The invention claimed is:

1. An Atomic Layer Deposition or a Plasma Enhanced Atomic Layer Deposition composition for depositing a silicon doped hafnium oxide film comprising:
1) at least one organoaminosilane precursor compound having a formula of R x R 3 Si(NR 1 R 2 ) 3-x ;
wherein
R is a linear or branched C 1 to C 6 alkyl;
R 1 , R 2 and R 3 are independently selected from linear or branched C 1 to C 6 alkyl; wherein
R 1 and R 2 in organoamino group are linked to form a cyclic ring structure; or not linked to form a cyclic ring structure; and
x=0, 1, or 2;

and
(b) at least one organoaminohafnium precursor compound having a formula of
L x Hf(NR 1 R 2 ) 4-x ;
wherein
L is cyclopentadienyl or alkyl substituted cyclopentadienyl;
R 1 and R 2 are independently selected from linear or branched C 1 to C 6 alkyl in organoamino group; wherein
R 1 and R 2 are linked to form a cyclic ring structure or R 1 and R 2 are not linked to form a cyclic ring structure; and

x=0, 1, or 2;
wherein melting point of the composition is ≤30° C.; and
the at least one organoaminosilane precursor and the at least one organoaminohafnium precursor have the same organoamino group.

2. The composition of claim 1 , wherein the at least one organoaminosilane precursor compound is selected from the group consisting of tris(dimethylamino)methylsilane, tris(diethylamino)methylsilane, tris(ethylmethylamino)methylsilane, tris(pyrrolidino)methylsilane, tris(dimethylamino)ethylsilane, tris(diethylamino)ethylsilane, tris(ethylmethylamino)ethylsilane, tris(pyrrolidino)ethylsilane, bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(pyrrolidino)dimethylsilane, bis(dimethylamino)diethylsilane, bis(diethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(pyrrolidino)diethylsilane, dimethylaminotrimethylsilane, diethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, pyrrolidinotrimethylsilane, dimethylaminotriethylsilane, diethylaminotriethylsilane, ethylmethylaminotriethylsilane, pyrrolidinotriethylsilane, dimethylaminophenyldimethylsilane, diethylaminophenyldimethylsilane, ethylmethylaminophenyldimethylsilane, pyrrolidinophenyldimethylsilane, tris(dimethylamino)phenylsilane, tris(diethylamino)phenylsilane, tris(ethylmethylamino)phenylsilane, tris(pyrrolidino)phenylsilane, 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1,1,1,4,4,4-hexakis(dimethylamino)-1,4-disilabutane, 2,5-bis(dimethylamino)-2,5-dimethyl-2,5-disilahexane and combinations thereof; and
the at least one organoaminohafnium precursor compound is selected from the group consisting of tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(pyrrolidino)hafnium, cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe 2 ) 3 ), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe 2 ) 3 ), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe 2 ) 3 ), cyclopentadienyltris(ethylmethylamino)hafnium (CpHf(NMeEt) 3 ), methylcyclopentadienyltris(ethylmethylamino)hafnium (MeCpHf(NMeEt) 3 ), ethylcyclopentadienyltris(ethylmethylamino)hafnium (EtCpHf(NMeEt) 3 ), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt 2 ) 3 ), methylcyclopentadienyltris(diethylamino)hafnium (MeCpHf(NEt 2 ) 3 ), ethylcyclopentadienyltris(diethylamino)hafnium (EtCpHf(NEt 2 ) 3 ), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp 2 Hf(NMe 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) 2 Hf(NMe 2 ) 2 ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) 2 Hf(NMe 2 ) 2 ), bis(cyclopentadienyl)bis(ethylmethylamino)hafnium (Cp 2 Hf(NMeEt) 2 ), bis(methylcyclopentadienyl)bis(ethylmethylamino)hafnium ((MeCp) 2 Hf(NMeEt) 2 ), bis(ethylcyclopentadienyl)bis(ethylmethylamino)hafnium ((EtCp) 2 Hf(NMeEt) 2 ), bis(cyclopentadienyl)bis(diethylamino)hafnium ((Cp 2 Hf(NEt 2 ) 2 ), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp) 2 Hf(NEt 2 ) 3 ), bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp) 2 Hf(NEt 2 ) 2 ), (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino] bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene, 1-ethanamino]bis(diethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino] bis(ethylmethylamino)hafnium, and combinations thereof.

3. The composition of claim 1 , wherein the at least one organoaminosilane precursor compound is bis(dimethylamino)dimethylsilane; and the at least one organoaminohafnium precursor compound is tetrakis(dimethylamino)hafnium.

4. The composition of claim 1 , wherein the at least one organoaminosilane precursor compound has a range selected from the group consisting of 0.10 to 99.90 wt. %, 0.10 to 30.00 wt. %, 0.10 to 20.00 wt. %, 0.10 to 10.00 wt. %, 5.00 to 30.00 wt. %, 5.00 to 20.00 wt. %, 5.00 to 10.00 wt. %, and 0.10 to 5.00 wt. %; and the at least one organoaminohafnium precursor compound has a range selected from the group consisting of 0.10 to 99.00 wt. %, 0.10 to 30.00 wt. %, 0.10 to 20.00 wt. %, 0.10 to 10.00 wt. %, 5.00 to 30.00 wt. %, 5.00 to 20.00 wt. %, 5.00 to 10.00 wt. %, and 0.10 to 5.00 wt. %.

5. The composition of claim 1 further comprises (c) a solvent selected from the group consisting of ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, siloxanes, tertiary aminoether, and combinations thereof; the at least one organoaminosilane precursor compound has a range selected from the group consisting of 0.10 to 99.90 wt. %, 10.00 to 90.00 wt. %, 20.00 to 80.00 wt. %, 30.00 to 70.00 wt. %,and 40.00 to 60.00 wt. %; and the at least one organoaminohafnium precursor compound has a range selected from the group consisting of 0.10 to 99.00 wt. %, 10.00 to 90.00 wt. %, 20.00 to 80.00 wt. %, 30.00 to 70.00 wt. %, and 40.00 to 60.00 wt. %.

6. A system to deposit a film comprising silicon, hafnium and oxygen onto a substrate, comprising:
the substrate in a reactor; and
an Atomic Layer Deposition or a Plasma Enhanced Atomic Layer Deposition composition comprising:
(i) at least one organoaminosilane precursor compound having a formula of
R x R 3 Si(NR 1 R 2 ) 3-x ;
wherein
R is a linear or branched Ci to C6 alkyl;
R 1 , R 2 and R 3 are independently selected from linear or branched C 1 to C 6 alkyl; wherein
R 1 and R 2 in organoamino group are linked to form a cyclic ring structure; or not linked to form a cyclic ring structure; and
x=0, 1, or 2;

and
(ii) at least one organoaminohafnium precursor compound having a formula of
L x Hf(NR 1 R 2 ) 4-x ;
wherein
L is cyclopentadienyl or alkyl substituted cyclopentadienyl;
R 1 and R 2 are independently selected from linear or branched C 1 to C 6 alkyl in organoamino group; wherein
R 1 and R 2 are linked to form a cyclic ring structure or R 1 and R 2 are not linked to form a cyclic ring structure; and

x=0, 1, or 2;

wherein
a melting point of the composition is ≤30° C.;
the at least one organoaminosilane precursor and the at least one organoaminohafnium precursor have the same organoamino group; and
the system is at a temperature ranging from 100° C. to 350° C.

7. The system of claim 6 , wherein the composition comprises the at least one organoaminosilane precursor compound is selected from the group consisting of tris(dimethylamino)methylsilane, tris(diethylamino)methylsilane, tris(ethylmethylamino)methylsilane, tris(pyrrolidino)methylsilane, tris(dimethylamino)ethylsilane, tris(diethylamino)ethylsilane, tris(ethylmethylamino)ethylsilane, tris(pyrrolidino)ethylsilane, bis(dimethylamino)dimethylsilane, bis(diethyla

Assignees

• Versum Mat Us Llc
• Versum Mat U S Llc

Inventors

• Lei Xinjian
• Macdonald Matthew R
• Kim Moo-Sung
• Lee Se-Won

Classifications

• H10P14/6687

  the compound comprising silicon and nitrogen · CPC title

• H10P14/6682

  the compound being a silane, e.g. disilane, methylsilane or chlorosilane · CPC title

• H10P14/6339

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• H10P14/6336

  in the presence of a plasma [PECVD] · CPC title

• H10P14/693 Primary

  the material containing hafnium, e.g. HfSiOx or HfSiON · CPC title