# US 7,410,913 B2 · Method of manufacturing silicon rich oxide (SRO) and semiconductor device employing SRO

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- Number: US 7,410,913 B2
- Document ID: US7410913B2
- Status: Granted
- Kind: B2
- Application number: 11/519,083
- Filed: 2006-09-12
- Published: 2007-03-29
- Granted: 2008-08-12
- Earliest claimed: 2006-09-12
- Assignees: Samsung Electronics Co., Ltd.
- Inventors: Jung-Hyun Lee; Sang-Bong Bang
- Web page: https://patentgrep.com/patent/US7410913B2

## CPC

- C23C 16/401: {containing silicon}
- C23C 16/45525: {Atomic layer deposition [ALD]}
- C23C 16/45529: {specially adapted for making a layer stack of alternating different compositions or gradient compositions}
- H10P 14/416: {of highly doped semiconductor materials, e.g. polysilicon layers or amorphous silicon layers}
- H10D 30/0411: {of FETs having floating gates}
- H10D 30/0413: {of FETs having charge-trapping gate insulators, e.g. MNOS transistors}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/662: {Laminate layers, e.g. stacks of alternating high-k metal oxides (adhesion layers or buffer layers H10P14/6508, H10P14/6548)}
- H10P 14/69215: {the material being a silicon oxide, e.g. SiO2}
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

Provided are methods for manufacturing silicon rich oxide (SRO) layers useful in the fabrication of semiconductor devices, for example, non-volatile memory devices, and methods for fabricating semiconductor devices incorporating such SRO layers. The methods include absorbing a first silicon source gas onto the substrate, oxidizing the first absorbed layer to form a silicon oxide layer, absorbing a second silicon source gas onto the substrate and reducing the second absorbed layer to form a silicon layer. The combination of the silicon oxide layer(s) and the silicon layer(s) comprise, in turn, a composite SRO layer. These manufacturing methods facilitate control of the oxygen concentration in the SRO, the relative thicknesses of the silicon oxide and silicon layers, and provides improved step coverage, thus allowing the manufacturing of high quality semiconductor devices.

## Claims

### Claim 1

A method of forming a silicon rich oxide (SRO) layer on a substrate comprising:
a) introducing the substrate into a reaction chamber;
b) introducing a first silicon source gas into the reaction chamber under conditions whereby a portion of the first silicon source gas is absorbed on a first substrate surface to form a first silicon source layer, the first silicon source gas being substantially free of oxygen;
c) introducing a first reaction gas into the reaction chamber under conditions sufficient to form an oxidizing plasma;
d) reacting the first silicon source layer and the oxidizing plasma to form a silicon oxide layer on the first substrate surface;
e) introducing a second silicon source gas into the reaction chamber under conditions whereby a portion of the second silicon source gas is absorbed on a surface of the silicon oxide layer to form a second silicon source layer, the second silicon source gas being substantially free of oxygen;
f) introducing a second reaction gas into the reaction chamber under conditions sufficient to form a reducing plasma; and
g) reacting the second silicon source layer and the reducing plasma to form a silicon layer, wherein the combination of the silicon oxide layer and the silicon layer comprise the SRO layer.

### Claim 2 (depends on 1)

The method of forming a silicon rich oxide (SRO) layer according to claim 1, further comprising:
repeating steps b) through g) to form a plurality of silicon oxide layers, wherein the silicon oxide layers are separated by a plurality of silicon layers.

### Claim 3 (depends on 1)

The method of forming a silicon rich oxide (SRO) layer according to claim 1, further comprising:
repeating steps b) through d) to form a multilayer silicon oxide layer; and
repeating steps e) through g) to form a multilayer silicon layer on the multilayer silicon oxide layer.

### Claim 4 (depends on 1)

The method of forming a silicon rich oxide (SRO) layer according to claim 1, wherein:
first reaction gas is selected from a group consisting of H2O, H2O2, O2, O3 and mixtures thereof; and
the second reaction gas is selected from a group consisting of H2, NH3, HCl and mixtures thereof.

### Claim 5 (depends on 1)

The method of forming a silicon rich oxide (SRO) layer according to claim 1, wherein:
the first silicon source gas and the second silicon sources are selected from a group consisting of SiXaHb, Si2XcHd and mixtures thereof, wherein X represents a halogen selected from a group consisting of Cl, F, Br and mixtures thereof, and further wherein a, b, c and d are integers satisfying the expressions a+b=4 and c+d=6.

### Claim 6 (depends on 5)

The method of forming a silicon rich oxide (SRO) layer according to claim 5, wherein:
the first silicon source gas and second silicon source gas are identical.

### Claim 7 (depends on 6)

The method of forming a silicon rich oxide (SRO) layer according to claim 6, wherein:
the first and second silicon source gases are hexachlorodisilane (HCDS).

### Claim 8 (depends on 6)

The method of forming a silicon rich oxide (SRO) layer according to claim 6, wherein:
the first reaction gas is H2O; and
the second reaction gas is H2.

### Claim 9 (depends on 3)

The method of forming a silicon rich oxide (SRO) layer according to claim 3, wherein:
the first and second silicon source gases are HCDS.

### Claim 10 (depends on 9)

The method of forming a silicon rich oxide (SRO) layer according to claim 9, wherein:
the first reaction gas is H2O; and
the second reaction gas is H2.

### Claim 11

A method of manufacturing a semiconductor device comprising:
forming an active region on a semiconductor substrate;
forming a gate insulating layer on the active region; and
forming a gate electrode on the gate insulating layer for controlling an electrical field within the portion of the active layer underlying the gate electrode,
wherein forming the gate insulating layer further comprises fabricating a silicon rich oxide (SRO) layer by
a) absorbing a first silicon source gas onto a substrate surface to form a first silicon source layer, the first silicon source gas being substantially free of oxygen;
b) oxidizing the first silicon source layer to form a silicon oxide layer;
c) absorbing a second silicon source gas onto a substrate surface to form a second silicon source layer, the second silicon source gas being substantially free of oxygen; and
d) reducing the second silicon source layer to form a silicon layer;
wherein the silicon oxide layer and the silicon layer comprise the SRO layer.

### Claim 12 (depends on 11)

The method of manufacturing a semiconductor device according to claim 11, further comprising:
repeating steps a) through d) to form a multilayer SRO layer having alternating silicon oxide layers and silicon layers.

### Claim 13 (depends on 12)

The method of manufacturing a semiconductor device according to claim 12, wherein forming the multilayer SRO layer further comprises at least one operation selected from a group consisting of
repeating steps a) and b) to form a multilayer silicon oxide layer before forming a next silicon layer and
repeating steps c) and d) to form a multilayer silicon layer before forming a next silicon oxide layer.

### Claim 14 (depends on 12)

The method of manufacturing a semiconductor device according to claim 12, wherein:
steps a) and b) are repeated M times to form a silicon oxide layer before forming a next silicon layer; and
steps c) and d) are repeated N times to form a silicon layer before forming a next silicon oxide layer, wherein N and M are positive integers that satisfy the expression M>N.

### Claim 15 (depends on 11)

The method of manufacturing a semiconductor device according to claim 11, wherein:
the first silicon source gas and the second silicon sources are selected from a group consisting of SiXaHb, Si2XcHd and mixtures thereof, wherein X represents a halogen selected from a group consisting of Cl, F, Br and mixtures thereof, and further wherein a, b, c and d are integers satisfying the expressions a+b=4 and c+d=6.

### Claim 16 (depends on 11)

The method of manufacturing a semiconductor device according to claim 11, wherein:
the first silicon source gas and the second silicon sources are selected from a group consisting of SiClaHb, Si2ClcHd and mixtures thereof, and further wherein a, b, c and d are integers satisfying the expressions a+b=4 and c+d=6.

### Claim 17 (depends on 16)

The method of manufacturing a semiconductor device according to claim 16, wherein:
both the first silicon source gas and second silicon source gas are hexachlorodisilane (HCDS).

### Claim 18 (depends on 17)

The method of manufacturing a semiconductor device according to claim 17, wherein:
the first reaction gas is H2O; and
the second reaction gas is H2.

### Claim 19 (depends on 14)

The method of manufacturing a semiconductor device according to claim 14, wherein:
M and N define an M:N ratio of 4:1 to 7:1.

### Claim 20 (depends on 19)

The method of manufacturing a semiconductor device according to claim 19, wherein:
N is no greater than 2.

### Claim 21 (depends on 11)

The method of manufacturing a semiconductor device according to claim 11, wherein forming the active region further comprises:
forming a vertically elongated semiconductor fin structure extending from semiconductor substrate; and
forming the active region on vertical surfaces of the fin structure.

### Claim 22

A method of manufacturing SRO (Silicon Rich Oxide) having SiO2 and extra Si on a substrate, the method comprising:
absorbing a first silicon source gas containing no oxygen onto the substrate and forming a SiO2 layer by oxidation reaction between a reaction gas containing oxygen and the first silicon source gas; and
forming a Si layer as a result of reduction reaction between a second silicon source gas containing no oxygen and a reaction gas under conditions sufficient to form a reducing plasma corresponding to the second silicon source gas.

### Claim 23 (depends on 22)

The method of claim 22, wherein the forming of the SiO2 layer and the forming of the Si layer are alternately repeated with a predetermined period to form a multilayer stack of alternate SiO2 and Si layers by oxidation and reduction reactions.

### Claim 24 (depends on 22)

The method of claim 22, wherein the SiO2 layer and the Si layer each have a multilayer structure.

### Claim 25 (depends on 22)

The method of claim 22, wherein oxygen plasma is supplied during the forming of the SiO2 layer and hydrogen plasma is supplied during the forming of the Si layer.

### Claim 26 (depends on 22)

The method of claim 22, wherein the first and second silicon sources are the same precursor.

### Claim 27 (depends on 22)

The method of claim 22, wherein the first and second silicon sources are a SiCl-based precursor.

### Claim 28 (depends on 22)

The method of claim 22, wherein the first and second silicon sources are HCDS (Hexa-Chloro-Di-Silane).

### Claim 29 (depends on 27)

The method of claim 27, wherein the reaction gas for the first silicon source is H2O and the reaction gas for the second silicon source is H2.

### Claim 30 (depends on 24)

The method of claim 24, wherein the first and second silicon sources are HCDS.

### Claim 31 (depends on 30)

The method of claim 30, wherein the reaction gas for the first silicon source is H2O and the reaction gas for the second silicon source is H2.