# US 7,611,959 B2 · Zr-Sn-Ti-O films

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- Number: US 7,611,959 B2
- Document ID: US7611959B2
- Status: Granted
- Kind: B2
- Application number: 11/084,968
- Filed: 2005-03-21
- Published: 2005-07-28
- Granted: 2009-11-03
- Earliest claimed: 2002-12-04
- Assignees: Micron Technology, Inc.
- Inventors: Kie Y. Ahn; Leonard Forbes
- Web page: https://patentgrep.com/patent/US7611959B2

## CPC

- H10P 14/69397: {the material containing two or more metal elements}
- C04B 35/49: containing also titanium oxides or titanates
- C23C 16/40: Oxides
- C23C 16/45529: {specially adapted for making a layer stack of alternating different compositions or gradient compositions}
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- C04B 2235/3293: Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
- C04B 2235/441: Alkoxides, e.g. methoxide, tert-butoxide
- C04B 2235/444: Halide containing anions, e.g. bromide, iodate, chlorite
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/69391: {the material containing aluminium, e.g. Al2O3}
- H10P 14/69394: {the material containing titanium, e.g. TiO2}
- H10P 14/69395: {the material containing zirconium, e.g. ZrO2}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- 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)

## Abstract

A dielectric layer containing a Zr—Sn—Ti—O film and a method of fabricating such a dielectric layer produce a reliable dielectric layer having an equivalent oxide thickness thinner than attainable using SiO2. In an embodiment, forming the Zr—Sn—Ti—O film on a substrate includes depositing materials of the Zr—Sn—Ti—O film substantially as atomic monolayers. In an embodiment, electronic devices include a dielectric layer having a Zr—Sn—Ti—O film such that Zr—Sn—Ti—O material is configured as substantially atomic monolayers. Dielectric layers containing such Zr—Sn—Ti—O films may have minimal reactions with a silicon substrate or other structures during processing.

## Claims

### Claim 1

A method of forming a dielectric film comprising:
forming a Zr—Sn—Ti—O film on a substrate by depositing materials of the Zr—Sn—Ti—O film substantially as atomic monolayers such that each metal of the Zr—Sn—Ti—O film is deposited independent of each of the other metals of the Zr—Sn—Ti—O film.

### Claim 2 (depends on 1)

The method of claim 1, wherein the method includes controlling material deposition to form the dielectric film as an amorphous Ti-rich Zr—Sn—Ti—O film.

### Claim 3 (depends on 1)

The method of claim 1, wherein the method includes controlling material deposition to form the dielectric film having a composition substantially of ZrySnxTi1-x-yO4 with 0.3<y<0.7 and 0<x<0.2.

### Claim 4 (depends on 1)

The method of claim 1, wherein the method includes controlling material deposition to form the dielectric film having a composition substantially of Zr0.2Sn0.2Ti0.6O2.

### Claim 5 (depends on 1)

The method of claim 1, wherein the method includes using metal chloride precursors.

### Claim 6

A method of forming a dielectric film comprising:
depositing a titanium-containing precursor and a first oxygen-containing precursor onto a surface;
depositing a zirconium-containing precursor and a second oxygen-containing precursor onto the surface; and
depositing a tin-containing precursor and a third oxygen-containing precursor onto the surface to form a Zr—Sn—Ti—O film substantially at an atomic monolayer level of deposition such that each metal of the Zr—Sn—Ti—O film is deposited independent of each of the other metals of the Zr—Sn—Ti—O film.

### Claim 7 (depends on 6)

The method of claim 6, wherein the method include using a TiCl4 precursor.

### Claim 8 (depends on 6)

The method of claim 6, wherein the method includes controlling formation of the dielectric film such that the dielectric film includes an amorphous Ti-rich Zr—Sn—Ti—O film.

### Claim 9 (depends on 6)

The method of claim 6, wherein the method includes controlling formation of the dielectric film such that the dielectric film includes a composition substantially of ZrySnxTi1-x-yO4 with 0.3<y<0.7 and 0<x<0.2.

### Claim 10 (depends on 6)

The method of claim 6, wherein the method includes controlling formation of the dielectric film such that the dielectric film includes a composition substantially of Zr0.2Sn0.2Ti0.6O2.

### Claim 11

A method of forming a dielectric film comprising:
forming TiO2 onto a surface;
depositing a zirconium-containing precursor and a second oxygen-containing precursor onto the surface; and
depositing a tin-containing precursor and a third oxygen-containing precursor onto the surface to form a Zr—Sn—Ti—O film substantially at an atomic monolayer level of deposition such that each metal of the Zr—Sn—Ti—O film is deposited independent of each of the other metals of the Zr—Sn—Ti—O film.

### Claim 12 (depends on 11)

The method of claim 11, wherein the method includes using a TiCl4 precursor.

### Claim 13 (depends on 11)

The method of claim 11, wherein the method includes using a ZrCl4 precursor.

### Claim 14 (depends on 11)

The method of claim 11, wherein the method includes using a SnCl4 precursor.

### Claim 15 (depends on 11)

The method of claim 11, wherein the method includes controlling formation of the dielectric film such that the dielectric film has a composition substantially of ZrySnxTi1-x-yO4 with 0.3<y<0.7 and 0<x<0.2.

### Claim 16 (depends on 11)

The method of claim 11, wherein the method includes controlling formation of the dielectric film such that the dielectric film has a composition substantially of Zr0.2Sn0.2Ti0.6O2.

### Claim 17

A method of forming a capacitor, comprising:
forming a first conductive layer on a substrate;
forming a Zr—Sn—Ti—O film on the first conductive layer by depositing materials of the Zr—Sn—Ti—O film substantially as atomic monolayers such that each metal of the Zr—Sn—Ti—O film is deposited independent of each of the other metals of the Zr—Sn—Ti—O film; and
forming a second conductive layer on the dielectric film.

### Claim 18 (depends on 17)

The method of claim 17, wherein forming a Zr—Sn—Ti—O film includes forming an amorphous Ti-rich Zr—Sn—Ti—O film.

### Claim 19 (depends on 17)

The method of claim 17, wherein forming a Zr—Sn—Ti—O film includes forming a dielectric film having a composition substantially of ZrySnxTi1-x-yO4 with 0.3<y<0.7 and 0<x<0.2.

### Claim 20 (depends on 17)

The method of claim 17, wherein the method includes regulating deposition of zirconium, tin, titanium, and oxygen to form a dielectric film having a dielectric constant in the range from about 50 to about 70.

### Claim 21 (depends on 17)

The method of claim 17, wherein the method includes regulating deposition of zirconium, tin, titanium, and oxygen to form a dielectric film having a dielectric constant in the range from about 33 to about 37.

### Claim 22 (depends on 17)

The method of claim 17, wherein forming a Zr—Sn—Ti—O film on the first conductive layer includes:
depositing a titanium-containing precursor and a first oxygen-containing precursor onto the first conductive layer;
depositing a zirconium-containing precursor and a second oxygen-containing precursor onto the first conductive layer; and
depositing a tin-containing precursor and a third oxygen-containing precursor onto the first conductive layer to form Zr—Sn—Ti—O substantially at an atomic monolayer level of deposition.

### Claim 23 (depends on 22)

The method of claim 22, wherein depositing titanium and oxygen includes forming TiO2 onto the first conductive layer.

### Claim 24 (depends on 22)

The method of claim 22, wherein the method includes using a TiCl4 precursor, a ZrCl4 precursor, and a SnCl4 precursor.

### Claim 25

A method of forming a transistor comprising:
forming a source region and a drain region in a substrate, the source region and the drain region separated by a body region;
forming a dielectric layer on the body region between the source and drain regions, the dielectric layer containing a Zr—Sn—Ti—O film, the Zr—Sn—Ti—O film formed by depositing materials of the Zr—Sn—Ti—O film substantially as atomic monolayers such that each metal of the Zr—Sn—Ti—O film is deposited independent of each of the other metals of the Zr—Sn—Ti—O film; and
coupling a gate to the dielectric layer.

### Claim 26 (depends on 25)

The method of claim 25, wherein coupling a gate to the dielectric layer includes coupling a floating gate to the dielectric layer.

### Claim 27 (depends on 25)

The method of claim 25, wherein forming a dielectric layer includes controlling material deposition to form the dielectric layer as an amorphous Ti-rich Zr—Sn—Ti—O film.

### Claim 28 (depends on 25)

The method of claim 25, wherein forming a dielectric layer includes controlling material deposition to form the dielectric layer as a composition substantially of ZrySnxTi1-x-yO4 with 0.3<y<0.7 and 0<x<0.2.

### Claim 29 (depends on 25)

The method of claim 25, wherein forming a dielectric layer includes controlling material deposition to form the dielectric layer as a composition substantially of Zr0.2Sn0.2Ti0.6O2.

### Claim 30 (depends on 25)

The method of claim 25, wherein forming a dielectric layer includes regulating deposition of zirconium, tin, titanium, and oxygen to form a dielectric layer having a dielectric constant in the range from about 50 to about 70.

### Claim 31 (depends on 25)

The method of claim 25, wherein forming a dielectric layer includes regulating deposition of zirconium, tin, titanium, and oxygen to form a dielectric layer having a dielectric constant in the range from about 33 to about 37.

### Claim 32 (depends on 25)

The method of claim 25, wherein forming a dielectric layer containing a Zr—Sn—Ti—O film includes:
depositing a titanium-containing precursor and a first oxygen-containing precursor onto the body region;
depositing a zirconium-containing precursor and a second oxygen-containing precursor onto the body region; and
depositing a tin-containing precursor and a third oxygen-containing precursor onto the body region to form Zr—Sn—Ti—O substantially at an atomic monolayer level of deposition.

### Claim 33 (depends on 32)

The method claim 32, wherein the method includes using a TiCl4 precursor.

### Claim 34 (depends on 32)

The method claim 32, wherein the method includes using a ZrCl4 precursor.

### Claim 35 (depends on 32)

The method claim 32, wherein the method includes using a SnCl4 precursor.

### Claim 36

A method of forming a memory comprising:
forming a number of access transistors, at least one of the access transistors including a dielectric layer on a body region between a source region and a drain region, the dielectric layer containing a Zr—Sn—Ti—O film, the Zr—Sn—Ti—O film formed by depositing materials of the Zr—Sn—Ti—O film substantially as atomic monolayers such that each metal of the Zr—Sn—Ti—O film is deposited independent of each of the other metals of the Zr—Sn—Ti—O film;
forming a number of word lines coupled to a number of the gates of the number of access transistors;
forming a number of source lines coupled to a number of the source regions of the number of access transistors; and
forming a number of bit lines coupled to a number of the drain regions of the number of access transistors.

### Claim 37 (depends on 36)

The method of claim 36, wherein the method includes forming the dielectric layer as an amorphous Ti-rich Zr—Sn—Ti—O film.

### Claim 38 (depends on 36)

The method of claim 36, wherein the method includes forming the dielectric layer as a composition substantially of ZrySnxTi1-x-yO4 with 0.3<y<0.7 and 0<x<0.2.

### Claim 39 (depends on 36)

The method of claim 36, wherein the method includes forming the Zr—Sn—Ti—O film by:
depositing a titanium-containing precursor and a first oxygen-containing precursor onto the body region;
depositing a zirconium-containing precursor and a second oxygen-containing precursor onto the body region; and
depositing a tin-containing precursor and a third oxygen-containing precursor onto the body region to form Zr—Sn—Ti—O substantially at an atomic monolayer level of deposition.

### Claim 40 (depends on 39)

The method of claim 39, wherein the method includes using metal chloride precursors.

### Claim 41

A method of forming an electronic system comprising:
providing a processor;
coupling a memory to the processor, wherein the memory includes at least one access transistor having a dielectric layer on a body region between a source region and a drain region, the dielectric layer containing a Zr—Sn—Ti—O layer, wherein forming the Zr—Sn—Ti—O layer includes forming a Zr—Sn—Ti—O film on a substrate by depositing materials of the Zr—Sn—Ti—O film substantially as atomic monolayers such that each metal of the Zr—Sn—Ti—O film is deposited independent of each of the other metals of the Zr—Sn—Ti—O film.

### Claim 42 (depends on 41)

The method of claim 41, wherein the method includes forming the dielectric layer as an amorphous Ti-rich Zr—Sn—Ti—O film.

### Claim 43 (depends on 41)

The method of claim 41, wherein the method includes forming the dielectric layer as a composition substantially of ZrySnxTi1-x-yO4 with 0.3<y<0.7 and 0<x<0.2.

### Claim 44 (depends on 41)

The method of claim 41, wherein forming a Zr—Sn—Ti—O film includes:
depositing a titanium-containing precursor and a first oxygen-containing precursor onto the body region;
depositing a zirconium-containing precursor and a second oxygen-containing precursor onto the body region; and
depositing a tin-containing precursor and a third oxygen-containing precursor onto the body region to form Zr—Sn—Ti—O substantially at an atomic monolayer level of deposition.

### Claim 45 (depends on 44)

The method claim 44, wherein the method includes forming the dielectric layer using metal chlorides.