# US 2022/0178028 A1 · Organoaminodisilazanes for high temperature atomic layer deposition of silicon oxide thin films

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- Number: US 2022/0178028 A1
- Document ID: US20220178028A1
- Status: Published application
- Kind: A1
- Application number: 17/606,438
- Filed: 2020-04-17
- Published: 2022-06-09
- Earliest claimed: 2019-04-25
- Assignees: Versum Materials US, LLC
- Applicants: Versum Materials US, LLC
- Inventors: LEI XINJIAN; MING LI; MATTHEW R. MACDONALD; MEILIANG WANG
- Web page: https://patentgrep.com/patent/US20220178028A1

## CPC

- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C01B 33/126: {Preparation of silica of undetermined type}
- C07F 7/10: containing nitrogen {having a Si-N linkage}
- C23C 16/401: {containing silicon}
- C23C 16/402: {Silicon dioxide}
- C23C 16/4408: {by purging residual gases from the reaction chamber or gas lines}
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C01P 2006/10: Solid density
- C01P 2006/80: Compositional purity
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

An atomic layer deposition (ALD) process for formation of silicon oxide at a temperature greater than 500° C. is performed using at least one organoaminodisilazane precursor having the following Formula I: wherein R1 and R2 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group with a proviso that R1 and R2 cannot be both hydrogen; R3 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; and either R1 and R2 are linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure.

## Claims

### Claim 1

A process to deposit a silicon oxide film onto a substrate comprises:
a) providing a substrate in a reactor;
b) introducing into the reactor at least one organoaminodisilazane precursor having the following Formula IA:
wherein R1 and R2 are independently selected from a C1 to C6 alkyl group; R3 is selected from hydrogen, a linear or branched C1 to C6 alkyl group, and a C6 to C10 aryl group; and either R1 and R2 are linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure;
c) purging the reactor with purge gas to purge away unconsumed reactants and/or reaction byproducts;
d) introducing an oxygen source into the reactor to react with the precursor and form the silicon oxide film; and
e) purging the reactor with purge gas to purge away unconsumed reactants and/or reaction byproducts;
wherein steps b through e are repeated until a desired thickness of the silicon oxide film is deposited, wherein the process in conducted at one or more temperatures ranging from 500 to 800° C. and one or more pressures ranging from 50 miliTorr (mT) to 760 Torr.

### Claim 2 (depends on 1)

The process of claim 1, wherein the at least one organoaminodisilazane precursor is selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisilazane, 1-diethylamino-1,1,3,3,3-pentamethyldisilazane, 1-methylethylamino-1,1,3,3,3-pentamethyldisilazane, 1-pyrrolidino-1,1,3,3,3-pentamethyldisilazane, 1-(2-methylpyrrolidino)-1,1,3,3,3-pentamethyldisilazane, 1-(2,5-dimethylpyrrolidino)-1,1,3,3,3-pentamethyldisilazane, 1-piperidino-1,1,3,3,3-pentamethyldisilazane, 1-(2,5-dimethylpiperidino)-1,1,3,3,3-pentamethyldisilazane, 1-pyrrolyl-1,1,3,3,3-pentamethyldisilazane, 1-imidazolyl-1,1,3,3,3-pentamethyldisilazane, 1-dimethylamino-1,1,2,3,3,3-hexamethyldisilazane, 1-diethylamino-1,1,2,3,3,3-hexamethyldisilazane, 1-methylethylamino-1,1,2,3,3,3-hexamethyldisilazane, 1-pyrrolidino-1,1,2,3,3,3-hexamethyldisilazane, 1-(2-methylpyrrolidino)-1,1,2,3,3,3-hexamethyldisilazane, 1-(2,5-dimethylpyrrolidino)-1,1,2,3,3,3-hexamethyldisilazane, 1-piperidino-1,1,2,3,3,3-hexamethyldisilazane, 1-(2,6-dimethylpiperidino)-1,1,2,3,3,3-hexamethyldisilazane, 1-pyrrolyl-1,1,2,3,3,3-hexamethyldisilazane, 1-imidazolyl-1,1,2,3,3,3-hexamethyldisilazane, 1-dimethylamino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-diethylamino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-methylethylamino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-pyrrolidino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-(2-methylpyrrolidino)-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-2,5-dimethylpyrrolidino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-piperidino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-(2,6-dimethylpiperidino)-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-pyrrolyl-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-imidazolyl-2-ethyl-1,1,3,3,3-pentamethyldisilazane, and mixtures thereof.

### Claim 3 (depends on 1)

The process of claim 1, wherein the purge gas is selected from the group consisting of nitrogen, helium, argon, and mixtures thereof.

### Claim 4 (depends on 1)

The process of claim 1, wherein the oxygen source is selected from the group consisting of oxygen, peroxide, oxygen plasma, water vapor, water vapor plasma, hydrogen peroxide, ozone source, and mixtures thereof.

### Claim 5 (depends on 1)

The process of claim 1 wherein the oxygen-containing source comprises a plasma.

### Claim 6 (depends on 5)

The process of claim 5 wherein the plasma is generated in situ.

### Claim 7 (depends on 5)

The process of claim 5 wherein the plasma is generated remotely.

### Claim 8 (depends on 4)

The process of claim 4 wherein the silicon oxide film has a density of about 2.0 g/cm3 or greater.

### Claim 9 (depends on 1)

The process of claim 1 wherein the silicon oxide film further comprises carbon.

### Claim 10 (depends on 9)

The process of claim 9 wherein the silicon oxide film has a density of at least about 1.8 g/cm3.

### Claim 11 (depends on 9)

The process of claim 9 wherein the carbon content of the silicon oxide film is at least 0.5 atomic weight percent (at. %) as measured by x-ray photospectroscopy.

### Claim 12

A composition for depositing a silicon oxide film or a carbon doped silicon oxide film using a vapor deposition process, wherein the composition comprises at least one silicon precursor having a structure represented by Formula IA:
wherein R1 and R2 are selected from a C1 to C6 alkyl group; R3 is selected from hydrogen, a linear or branched C1 to C6 alkyl group, and a C6 to C10 aryl group; and either R1 and R2 are linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure.

### Claim 13 (depends on 12)

The composition of claim 12, wherein the at least one silicon precursor is selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisilazane, 1-diethylamino-1,1,3,3,3-pentamethyldisilazane, 1-methylethylamino-1,1,3,3,3-pentamethyldisilazane, 1-pyrrolidino-1,1,3,3,3-pentamethyldisilazane, 1-(2-methylpyrrolidino)-1,1,3,3,3-pentamethyldisilazane, 1-(2,5-dimethylpyrrolidino)-1,1,3,3,3-pentamethyldisilazane, 1-piperidino-1,1,3,3,3-pentamethyldisilazane, 1-(2,5-dimethylpiperidino)-1,1,3,3,3-pentamethyldisilazane, 1-pyrrolyl-1,1,3,3,3-pentamethyldisilazane, 1-imidazolyl-1,1,3,3,3-pentamethyldisilazane, 1-dimethylamino-1,1,2,3,3,3-hexamethyldisilazane, 1-diethylamino-1,1,2,3,3,3-hexamethyldisilazane, 1-methylethylamino-1,1,2,3,3,3-hexamethyldisilazane, 1-pyrrolidino-1,1,2,3,3,3-hexamethyldisilazane, 1-(2-methylpyrrolidino)-1,1,2,3,3,3-hexamethyldisilazane, 1-(2,5-dimethylpyrrolidino)-1,1,2,3,3,3-hexamethyldisilazane, 1-piperidino-1,1,2,3,3,3-hexamethyldisilazane, 1-(2,6-dimethylpiperidino)-1,1,2,3,3,3-hexamethyldisilazane, 1-pyrrolyl-1,1,2,3,3,3-hexamethyldisilazane, 1-imidazolyl-1,1,2,3,3,3-hexamethyldisilazane, 1-dimethylamino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-diethylamino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-methylethylamino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-pyrrolidino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-(2-methylpyrrolidino)-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-2,5-dimethylpyrrolidino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-piperidino-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-(2,6-dimethylpiperidino)-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-pyrrolyl-2-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-imidazolyl-2-ethyl-1,1,3,3,3-pentamethyldisilazane, and combinations thereof.

### Claim 14 (depends on 12)

The composition of claim 12 wherein the at least one silicon precursor is substantially free of one or more impurities selected from the group consisting of a halide, metal ions, metal, and combinations thereof.

### Claim 15 (depends on 14)

The composition of claim 14 wherein the composition is substantially free of one or more impurities selected from the group consisting of halide compounds, metal ions, metal, and combinations thereof.

### Claim 16 (depends on 15)

The composition of claim 15, wherein the halide compounds comprise chloride-containing species.

### Claim 17 (depends on 16)

The composition of claim 16, wherein the chloride concentration is less than 50 ppm measured by IC.

### Claim 18 (depends on 16)

The composition of claim 16, wherein the chloride concentration is less than 10 ppm measured by IC.

### Claim 19 (depends on 16)

The composition of claim 16, wherein the chloride concentration is less than 5 ppm measured by IC.

### Claim 20 (depends on 1)

A film obtained by the method of claim 1.

### Claim 21 (depends on 20)

The film of claim 20 comprising at least one of the following characteristics: a density of at least about 2.0 g/cm3; a wet etch rate that is less than about 2.5 Å/s as measured in a solution of 1:100 of HF to water (0.5 wt. % dHF) acid; an electrical leakage of less than about 1×10−8 A/cm2 up to 6 MV/cm; and a hydrogen impurity of less than about 4×1021 at/cc as measured by SIMS.