METHOD AND APPARATUS FOR FORMING OXIDE THIN FILM

• US 20160336175A1
• Filed: 12/11/2014
• Published: 11/17/2016
• Est. Priority Date: 12/18/2013
• Status: Abandoned Application

• Current Assignee: National University Corporation Yamagata University
• Original Assignee: National University Corporation Yamagata University
• Inventors: HIROSE, Fumihiko, KANOMATA, Kensaku
• Application Number:
  US15/106,661
• Publication Number:
  US 20160336175A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/452 by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/505 using radio frequency discharges
• CPC Class Codes: C23C 16/52 Controlling or regulating the coating process C23C16/45557, C23C16/279 take precedence
• CPC Class Codes: H01J 2237/3321 CVD [Chemical Vapor Deposition]
• CPC Class Codes: H01J 37/3211 Antennas, e.g. particular shapes of coils
• CPC Class Codes: H01J 37/32724 Temperature
• CPC Class Codes: H01J 37/32926 Software, data control or modelling
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 29/517 the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence

Abstract

Disclosed is a method for forming an oxide thin film on a solid substrate, the method including the steps of placing a solid substrate s a in a reaction container 1, maintaining the solid substrate at a temperature of higher than 0° C. and 150° C. or lower, and filling the reaction container with an organometallic gas containing tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium; discharging the organometallic gas from the reaction container or filling the reaction container with an inert gas; treating a gas containing oxygen and water vapor with plasma, to thereby generate a plasma gas containing excited oxygen and water vapor, and feeding the plasma gas into the reaction container; and discharging the plasma gas from the reaction container or filling the reaction container with an inert gas; and repeating the series of steps.

Claims

1. A method for forming an oxide thin film on a solid substrate, characterized in that the method comprises a series of steps of:

placing the solid substrate in a reaction container, maintaining the solid substrate at a temperature of higher than 0°

C. and 150°

C. or lower, and filling the reaction container with an organometallic gas containing tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium;

discharging the organometallic gas from the reaction container or filling the reaction container with an inert gas;

treating a gas containing oxygen and water vapor with plasma, to thereby generate a plasma gas containing excited oxygen and water vapor, and feeding the plasma gas into the reaction container; and

discharging the plasma gas from the reaction container or filling the reaction container with an inert gas; and

repeating the series of steps.

2. An oxide thin film formation method according to claim 1, wherein the plasma gas is formed by feeding water vapor-added oxygen into an insulated tube, and applying high-frequency magnetic field to the insulated tube at an electric power of 3.8 W/cm² or greater per cross-section of the inside of the insulated tube, to thereby generate plasma inside the insulated tube.

3. An oxide thin film formation method according to claim 2, wherein the water vapor-added oxygen is formed by bringing oxygen into contact with water at a temperature higher than 0°

C. and not exceeding 80°

C.

4. An oxide thin film formation method according to claim 1, which further includes, before the first contact of the solid substrate with the organometallic gas, a step of treating the solid substrate with a plasma gas generated from a gas containing at least water vapor.

8. An oxide thin film formation method according to claim 2, which further includes, before the first contact of the solid substrate with the organometallic gas, a step of treating the solid substrate with a plasma gas generated from a gas containing at least water vapor.

9. An oxide thin film formation method according to claim 3, which further includes, before the first contact of the solid substrate with the organometallic gas, a step of treating the solid substrate with a plasma gas generated from a gas containing at least water vapor.

10. An oxide thin film formation method according to claim 1, wherein the dose of the organometallic gas which is tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium is adjusted to 1.0×

10<sup>−

2</sup> Torr·

s or higher or 1.0×

10⁵ Langmuir units or higher, at the surface of the substrate to be treated.

11. An oxide thin film formation method according to claim 2, wherein the dose of the organometallic gas which is tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium is adjusted to 1.0×

10<sup>−

2</sup> Torr·

s or higher or 1.0×

10⁵ Langmuir units or higher, at the surface of the substrate to be treated.

12. An oxide thin film formation method according to claim 3, wherein the dose of the organometallic gas which is tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium is adjusted to 1.0×

10<sup>−

2</sup> Torr·

s or higher or 1.0×

10⁵ Langmuir units or higher, at the surface of the substrate to be treated.

13. An oxide thin film formation method according to claim 4, wherein the dose of the organometallic gas which is tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium is adjusted to 1.0×

10<sup>−

2</sup> Torr·

s or higher or 1.0×

10⁵ Langmuir units or higher, at the surface of the substrate to be treated.

14. An oxide thin film formation method according to claim 8, wherein the dose of the organometallic gas which is tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium is adjusted to 1.0×

10<sup>−

2</sup> Torr·

s or higher or 1.0×

10⁵ Langmuir units or higher, at the surface of the substrate to be treated.

15. An oxide thin film formation method according to claim 9, wherein the dose of the organometallic gas which is tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium is adjusted to 1.0×

10<sup>−

2</sup> Torr·

s or higher or 1.0×

10⁵ Langmuir units or higher, at the surface of the substrate to be treated.

16. An oxide thin film formation method according to claim 1, wherein the dose of the plasma gas is adjusted to 0.15 Torr·

s or higher or 1.5×

10⁵ Langmuir units or higher, at the surface of the substrate to be treated.

5-7. -7. (canceled)

17. An apparatus for forming an oxide thin film, the apparatus comprising:

a reaction container having a mechanism for sustaining a substrate;

a temperature-controlling mechanism which can maintain the substrate at a temperature of higher than 0°

C. and 150°

C. or lower;

a source-feeding apparatus for feeding tetrakis(ethylmethylamino)hafnium or tetrakis(ethylmethylamino)zirconium;

a plasma gas generating apparatus adapted to feed water vapor-containing oxygen into a glass tube, and to apply high-frequency magnetic field to the glass tube, to thereby generate plasma inside the glass tube, thereby providing a plasma gas;

a first determination mechanism for determining the dose of tetrakis(ethylmethylamino)hafnium during feeding thereof in the reaction container; and

a second determination mechanism for determining the dose of the plasma gas in the reaction container.