# US 9,437,419 B2 · Method of forming a layer using a trialkylsilane silicon precursor compound

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- Number: US 9,437,419 B2
- Document ID: US9437419B2
- Status: Granted
- Kind: B2
- Application number: 14/173,381
- Filed: 2014-02-05
- Published: 2014-09-18
- Granted: 2016-09-06
- Earliest claimed: 2013-03-15
- Assignees: Samsung Electronics Co., Ltd.
- Applicants: Younsoo Kim; Sangyeol Kang; Hiroki Sato; Tsubasa Shiratori; Naoki Yamada; Chayoung Yoo; Younjoung Cho; Chin Moo Cho; Jaehyoung Choi
- Inventors: Younsoo Kim; Sangyeol Kang; Hiroki Sato; Tsubasa Shiratori; Naoki Yamada; Chayoung Yoo; Younjoung Cho; Chin Moo Cho; Jaehyoung Choi
- Web page: https://patentgrep.com/patent/US9437419B2

## CPC

- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- C23C 16/34: Nitrides {(C23C16/303 takes precedence)}
- C23C 16/401: {containing silicon}
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 14/69215: {the material being a silicon oxide, e.g. SiO2}
- H10P 14/69395: {the material containing zirconium, e.g. ZrO2}
- H10D 1/68: Capacitors having no potential barriers
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- 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)
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

A trialkylsilane-based silicon precursor compound may be expressed by Si(Ri)X, i=1-3, where each of “R1”, “R2”, and “R3” is a hydrogen or an alkyl having 1-5 carbon(s), all of “R1”, “R2”, and “R3” are not hydrogen, “X” is one of hydrogen, a hydroxyl group, an amide group, an alkoxide group, a halide group, or Si(R*)3, and “R*” is a hydrogen or an alkyl group having 1˜5 carbon(s).

## Claims

### Claim 1

A method of forming a layer, the method comprising:
forming a dielectric layer using a trialkylsilane-based silicon precursor compound expressed by the following chemical formula 1,
wherein each of R1, R2, and R3 is hydrogen or an alkyl having 3˜5 carbons; R1, R2, and R3 are not all hydrogen; X is one of hydrogen, a hydroxyl group, an amide group, an alkoxide group, a halide group, or Si(R*)3; R* is hydrogen or an alkyl group having 3˜5 carbon(s); and the dielectric layer is a silicon-doped metal oxide layer or a silicon-doped metal nitride layer,
wherein forming the dielectric layer includes alternately forming a first sub-dielectric layer and a second sub-dielectric layer; forming the first sub-dielectric layer includes forming m atomic layers of a metal oxide layer or a metal nitride layer; forming the second sub-dielectric layer includes forming n atomic layers of a silicon oxide layer or a silicon nitride layer; and m and n are positive integers, and
wherein the forming n atomic layers includes repeating n times:
supplying the trialkylsilane-based silicon precursor compound to a substrate such that the trialkylsilane-based silicon precursor compound is adsorbed onto the substrate; and
supplying the oxygen-containing gas or the nitrogen-containing gas to react with the trialkylsilane-based silicon precursor compound to form one atomic layer of the silicon oxide layer or the silicon nitride layer.

### Claim 2 (depends on 1)

The method of claim 1, wherein all of R1, R2, and R3 are propyl groups; and X is hydrogen.

### Claim 3 (depends on 1)

The method of claim 1, wherein the forming m atomic layers includes repeating m times:
supplying a metal precursor compound to the substrate such that the metal precursor compound is adsorbed onto the substrate; and
supplying an oxygen-containing gas or a nitrogen-containing gas to react with the metal precursor compound to form one atomic layer of the metal oxide layer or the metal nitride layer.

### Claim 4 (depends on 3)

The method of claim 3, wherein m is different from n.

### Claim 5 (depends on 3)

The method of claim 3, further comprising:
performing a thermal treatment to diffuse at least silicon atoms included in the second sub-dielectric layer into the first sub-dielectric layer.

### Claim 6 (depends on 3)

The method of claim 3, wherein the oxygen-containing gas includes at least one of oxygen (O2), ozone (O3), water vapor (H2O), and nitrous oxide (N2O); and the nitrogen-containing gas includes at least one of nitrogen (N2), ammonia (NH3), and hydrazine (N2H4).

### Claim 7 (depends on 3)

The method of claim 3, wherein the metal precursor compound has a chemical structure expressed by MLn; M being an element with an atomic number spanning from 3 to 92; L being hydrogen, alkyl, aryl, allyl, amide, alkoxide, beta-diketonate, beta-diiminate, dienyl, cyclopentadienyl, or alkylcyclopentadienyl; and n being a number ranging from 2 to 6.

### Claim 8 (depends on 3)

The method of claim 3, wherein the metal precursor compound has a chemical structure expressed by the following chemical formula 2,
M being titanium, zirconium, or hafnium; and each of L1, L2, L3, and Y being one of hydrogen, alkyl, aryl, allyl, amide, alkoxide, beta-diketonate, beta-diiminate, dienyl, cyclopentadienyl, or alkylcyclopentadienyl.

### Claim 9 (depends on 3)

The method of claim 3, wherein the trialkylsilane-based silicon precursor compound and the metal precursor compound have substantially constant deposition rates in a same temperature range.

### Claim 10 (depends on 1)

The method of claim 1, wherein the dielectric layer is used as a gate insulating layer or a capacitor dielectric layer.

### Claim 11 (depends on 1)

The method of claim 1, wherein a content of silicon atoms with respect to a total content of metal atoms and the silicon atoms in the dielectric layer is in the range of about 0.5 at % to about 50 at %.

### Claim 12 (depends on 1)

The method of claim 1, wherein forming the dielectric layer is performed by an atomic layer deposition method or an organic metal chemical vapor deposition method.

### Claim 13 (depends on 1)

The method of claim 1, wherein forming the dielectric layer is performed at a temperature of about 200° C. to 400° C.

### Claim 14

A method of forming a dielectric layer, comprising:
forming a first sub-dielectric layer of a metal oxide or a metal nitride;
forming a second sub-dielectric layer of a silicon oxide or a silicon nitride on the first sub-dielectric layer using a trialkylsilane-based silicon precursor compound expressed by the following chemical formula 1,
wherein each of R1, R2, and R3 is hydrogen or an alkyl having 3˜5 carbons; R1, R2, and R3 are not all hydrogen; X is one of hydrogen, a hydroxyl group, an amide group, an alkoxide group, a halide group, or Si(R*)3; R* is hydrogen or an alkyl group having 3˜5 carbons; and
heat treating the first sub-dielectric layer and the second sub-dielectric layer to diffuse silicon atoms from the second sub-dielectric layer into the first sub-dielectric layer.

### Claim 15 (depends on 14)

The method of claim 14, wherein the forming a first sub-dielectric layer and the forming a second sub-dielectric layer are alternately performed a plurality of times.

### Claim 16 (depends on 14)

The method of claim 14, wherein the heat treating is performed at a temperature of about 500 degrees Celsius or more.

### Claim 17 (depends on 14)

The method of claim 14, wherein the heat treating further includes diffusing metal atoms from the first sub-dielectric layer into the second sub-dielectric layer.

### Claim 18 (depends on 14)

The method of claim 14, wherein the heat treating is performed so as to achieve a substantially uniform distribution of the silicon atoms in the dielectric layer, the dielectric layer being a combination of the first sub-dielectric layer and the second sub-dielectric layer.

### Claim 19 (depends on 18)

The method of claim 18, wherein the heat treating is performed such that the dielectric layer is in a form of a metal silicate.

### Claim 20 (depends on 18)

The method of claim 18, wherein the heat treating is performed such that a content of the silicon atoms with respect to a total content of the silicon atoms and metal atoms in the dielectric layer is in a range of about 0.5 at % to about 50 at %.