Vapor deposition of metal oxides, silicates and phosphates, and silicon dioxide

Patent metadata

Field	Value
Publication number	US-2016268121-A1
Application number	US-201615161903-A
Country	US
Kind code	A1
Filing date	May 23, 2016
Priority date	Sep 28, 2000
Publication date	Sep 15, 2016
Grant date	—

Abstract

Metal silicates or phosphates are deposited on a heated substrate by the reaction of vapors of alkoxysilanols or alkylphosphates along with reactive metal amides, alkyls or alkoxides. For example, vapors of tris(tert-butoxy)silanol react with vapors of tetrakis(ethylmethylamido) hafnium to deposit hafnium silicate on surfaces heated to 300° C. The product film has a very uniform stoichiometry throughout the reactor. Similarly, vapors of diisopropylphosphate react with vapors of lithium bis(ethyldimethylsilyl)amide to deposit lithium phosphate films on substrates heated to 250° C. Supplying the vapors in alternating pulses produces these same compositions with a very uniform distribution of thickness and excellent step coverage.

First claim

What is claimed is:

1 . A process for making an insulating metal oxide layer in a microelectronic device, the process comprising:
alternatingly exposing a substrate to a first reactant vapor comprising a metal alkylamide, the metal alkylamide comprising a metal attached to two or more different ligands, at least one of which is an alkylamide, so as to form a deposited metal alkylamide; and a second reactant vapor, so as to form a metal oxide, wherein the deposition of the metal alkylamide and the second reactant are self-limiting, and wherein said metal oxide comprises oxygen and the metal from the metal alkylamide.

2 . The process of claim 1 , wherein the metal oxide insulates a gate.

3 . The process of claim 1 , wherein the metal oxide insulates a capacitor.

4 . The process of claim 1 , wherein the substrate has a hole and the metal oxide conformally coats said hole.

5 . The process of claim 4 , wherein the hole has a length to diameter ratio of greater than 40.

6 . The process of claim 4 , wherein the hole comprises a trench.

7 . The process of claim 4 , wherein the substrate comprises silicon.

8 . The process of claim 4 , wherein the metal oxide has a thickness that varies by less than 1%.

9 . The process of claim 4 , wherein the metal oxide has a root mean square surface roughness less than 0.4 nm.

10 . The process of claim 1 , wherein the metal alkylamide is selected from the group consisting of Al(N(Et)CH 2 CH 2 NMe 2 )(NMe 2 ) 2 , Ga(N(Me)CH 2 CH 2 NMe 2 )(NMe 2 ) 2 , Ta(N t Bu)(NEt 2 ) 3 , Ta(NEt)(NEt 2 ) 3 , W(N t Bu) 2 (NH t Bu) 2 , W(N t Bu) 2 (NEtMe) 2 , V(O)(NMe 2 ) 3 , and W(N t Bu) 2 (NMe 2 ) 2 .

11 . The process of claim 10 , wherein the metal alkylamide is Al(N(Et)CH 2 CH 2 N Me 2 )(NMe 2 ) 2 .

12 . The process of claim 1 , wherein the metal from the metal alkylamide is selected from the group consisting of aluminum, gallium, tungsten, vanadium, and tantalum.

13 . The process of claim 1 , wherein the second reactant vapor is selected from the group consisting of alkoxysilanols, alkoxysilanediols, phosphorus(III) oxide, white phosphorus, arene hydrates, water, and alcohol.

14 . The process of claim 1 , wherein all of the two or more different ligands are alkylamides.

15 . The process of claim 1 , wherein the alternatingly exposing the substrate to the first reactant vapor and the second reactant vapor comprises a plurality of cycles.

16 . A microelectronic device comprising:
a substrate with a hole; and an insulating metal oxide layer conformally coating said hole, wherein the insulating metal oxide layer is prepared by a process comprising: alternatingly exposing said substrate to a first reactant vapor comprising a metal alkylamide, the metal alkylamide comprising a metal attached to two or more different ligands, at least one of which is an alkylamide, so as to form a deposited metal alkylamide; and a second reactant vapor so as to form the insulating metal oxide layer, wherein the deposition of the metal alkylamide and the second reactant are self-limiting, and wherein said insulating metal oxide layer comprises oxygen and the metal from the metal alkylamide.

17 . The microelectronic device of claim 16 , wherein the insulating metal oxide layer insulates a gate.

18 . The microelectronic device of claim 16 , wherein the insulating metal oxide layer insulates a capacitor.

19 . The microelectronic device of claim 16 , wherein the hole has a length to diameter ratio of greater than 40.

20 . The microelectronic device of claim 16 , wherein the hole comprises a trench.

21 . The microelectronic device of claim 16 , wherein the substrate comprises silicon.

22 . The microelectronic device of claim 16 , wherein the insulating metal oxide layer has a thickness that varies by less than 1%.

23 . The microelectronic device of claim 16 , wherein the insulating metal oxide layer has a root mean square surface roughness less than 0.4 nm.

24 . The microelectronic device of claim 16 , wherein the metal alkylamide is selected from the group consisting of Al(N(Et)CH 2 CH 2 NMe 2 )(NMe 2 ) 2 , Ga(N(Me)CH 2 CH 2 NMe 2 )(NMe 2 ) 2 , Ta(N t Bu)(NEt 2 ) 3 , Ta(NEt)(NEt 2 ) 3 , W(N t Bu) 2 (NH t Bu) 2 , W(N t Bu) 2 (NEtMe) 2 , V(O)(NMe 2 ) 3 , and W(N t Bu) 2 (NMe 2 ) 2 .

25 . The microelectronic device of claim 24 , wherein the metal alkylamide is Al(N(Et)CH 2 CH 2 NMe 2 )(NMe 2 ) 2 .

26 . The microelectronic device of claim 16 , wherein the metal from the metal alkylamide is selected from the group consisting of aluminum, gallium, tungsten, vanadium, and tantalum.

27 . The microelectronic device of claim 16 , wherein the second reactant vapor compound is selected from the group consisting of alkoxysilanols, alkoxysilanediols, phosphorus(III) oxide, white phosphorus, arene hydrates, water, and alcohol.

28 . The microelectronic device of claim 16 , wherein all of the two or more different ligands are alkylamides.

29 . A process for making an insulating metal oxide layer in a microelectronic device, the process comprising:
alternatingly exposing a surface to:
a first reactant vapor comprising a metal alkylamide, the metal alkylamide comprising a metal attached to two or more different ligands, at least one of which is an alkylamide, so as to form a deposited metal alkylamide; and
a second reactant vapor, so as to form a metal oxide,
wherein the deposition of the metal alkylamide and the second reactant are self-limiting, and wherein said metal oxide comprises oxygen and the metal from the metal alkylamide.

Assignees

• Harvard College

Inventors

• Gordon Roy Gerald
• Becker Jill S
• Hausmann Dennis
• Suh Seigi

Classifications

• H10P14/69397

  the material containing two or more metal elements · CPC title

• H10P14/69395

  the material containing zirconium, e.g. ZrO2 · CPC title

• H10P14/69392

  the material containing hafnium, e.g. HfO2 · CPC title

• H10P14/69391

  the material containing aluminium, e.g. Al2O3 · CPC title

• H10P14/6923

  the material being boron or phosphorus doped silicon oxides, e.g. BPSG, BSG or PSG · CPC title