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KR-102962299-B1 - ELEMENT, AND EQUIPMENT

KR102962299B1KR 102962299 B1KR102962299 B1KR 102962299B1KR-102962299-B1

Abstract

The film contains an amorphous transition metal oxide as the main component and 1.0 at% or more of hydrogen.

Inventors

  • 아베 타츠키
  • 이시카와 쿄헤이
  • 호시노 카즈히로
  • 치바나 타카히토
  • 코바야시 히로아키

Assignees

  • 캐논 가부시끼가이샤

Dates

Publication Date
20260508
Application Date
20220509
Priority Date
20210520

Claims (20)

  1. A device comprising a gas and an optical structure formed on the gas, The above optical structure includes a first type of layer and a second type of layer alternately stacked, and The film constituting each of the above-mentioned first type of layer comprises an oxide of a transition metal of groups 3 to 11 and hydrogen, and The sum of the transition metal content of the above membrane and the oxygen content of the above membrane is greater than the hydrogen content of the above membrane, and each content is specified by the ratio of the number of atoms, and The above hydrogen content is 1.0 at% or more, and The above film is an amorphous device.
  2. A device comprising a gas and an optical structure formed on the gas, The film constituting the optical structure comprises oxides of transition metals of groups 3 to 11, hydrogen, and elements of group 18, and The sum of the transition metal content of the above membrane and the oxygen content of the above membrane is greater than the hydrogen content of the above membrane, and each content is specified by the ratio of the number of atoms, and The above hydrogen content is 1.0 at% or more, and The sum of the content of the transition metal, the content of oxygen, the content of hydrogen, and the content of the Group 18 element of the above film is 99.0 at% or more, and The above film is an amorphous device.
  3. In Article 1, The above hydrogen content is smaller than the above transition metal content and the above oxygen content, and larger than the content of the Group 18 element.
  4. In Article 1, A device in which the hydrogen content is less than or equal to half the transition metal content.
  5. In Article 1, The oxide of the above transition metal is an oxide of a transition metal of group 4 or 5.
  6. In Paragraph 5, The oxide of the above transition metal is an oxide of a transition metal of the 5th or 6th period, a device.
  7. In Paragraph 2, The oxide of the above transition metal is a device containing hafnium oxide.
  8. In Article 7, A device having a hydrogen content of 16.0 at% or less.
  9. In Article 7, A device having a hydrogen content of 6.0 at% or more.
  10. In Article 7, The above hafnium oxide contains zirconium, and the zirconium content is 0.05 at% or more and 0.5 at% or less, a device.
  11. In Article 7, A device having a refractive index of 2.15 or higher for light with a wavelength of 280 nm and an absorption rate of 0.2% or lower for light with a wavelength of 280 nm.
  12. In Article 1, The oxide of the above transition metal is a device containing tantalum oxide.
  13. In Paragraph 12, A device having a hydrogen content of less than 10.0 at%.
  14. In Paragraph 12, A device having a hydrogen content of 3.0 at% or more.
  15. In Paragraph 12, A device having an absorption rate of 0.40% or less for light with a wavelength of 313 nm and a refractive index of 2.40 or more for light with a wavelength of 313 nm.
  16. In Article 1, The above membrane further comprises a group 18 element, and A device in which the content of the Group 18 element of the above film is smaller than the content of the above hydrogen.
  17. In any one of paragraphs 1 through 16, A device having an argon content of 0.5 at% or more and 5.0 at% or less of the above film.
  18. In any one of paragraphs 1 through 16, A device in which the silicon content of the film, the carbon content of the film, and the nitrogen content of the film are each less than 0.5 at%.
  19. In any one of paragraphs 1 through 16, A device having a film thickness of 10 nm or more and 1000 nm or less.
  20. In any one of paragraphs 1 through 16, The above element is a lens.

Description

ELEMENT, AND EQUIPMENT The present invention relates to a film comprising a metal oxide. The application of metal oxides in the fields of optical devices, electrical devices, and semiconductor devices is being investigated. In various optical devices, such as photolithography equipment, optical elements are coated with optical films to improve optical properties, such as anti-reflection or reflection characteristics. In capacitive or semiconductor devices, insulating films are used to insulate capacitive electrodes, gate electrodes, etc., from other components. As standards for the performance of optical devices increase, the number of optical elements used within the device increases, and consequently, the number of optical surfaces requiring coating with optical films tends to increase. Furthermore, since the optical films used for coating do not necessarily need to be composed of a single layer but may be composed of multiple layers, the total number of layers installed tends to increase. In the field of optical devices, attempts are being made to coat optical components, such as lenses or filters, with a film containing metal oxide as an optical film. Japanese Patent Publication No. 10-217377 describes incorporating hydrogen into a dielectric multilayer film to suppress degradation of the dielectric multilayer film used in optical devices. The hydrogen contained in the dielectric film replenishes lattice defects that cause light absorption, thereby extending the lifespan of the dielectric multilayer film. Examples of dielectric multilayer films containing hydrogen include SiO₂ , Al₂O₃ , TiO₂ , Ta₂O₅ , HfO₂ , and ZrO₂ . Japanese Patent Publication No. 10-217377 discloses a technology for using a dielectric film containing hydrogen in SiO2 or TiO2 to provide a high-strength dielectric multilayer film for optical devices. As examples of dielectric materials other than SiO2 and TiO2 , hydrogen-containing Ta2O5 , HfO2 , Al2O3 , and ZrO2 are suggestively listed, but specific information is not disclosed. Japanese Patent Publication No. 2012-506950 (translation of PCT application) discloses a technique for reducing internal stress of a coating by adding 1 at% to 10 at% silicon to suppress light absorption and light scattering when hafnium oxide is used as an optical film. In the field of semiconductor devices, attempts are being made to use films containing hafnium oxide as gate insulators for transistors. However, when high-dielectric constant films containing hafnium oxide are used as gate insulators for transistors, there has been a problem in that crystallization occurs due to high-temperature treatment during the manufacturing process, leading to an increase in leakage current through grain boundaries or defect sequences. Japanese Patent Publication No. 2006-165589 discloses a technique for forming a silicon-containing high dielectric constant film by diffusing silicon into hafnium oxide to suppress crystallization of the high dielectric constant material and an increase in leakage current when high-temperature treatment is performed after forming a gate insulating film. Japanese Patent Publication No. 2017-83789 proposes a reflective optical element equipped with an optical film having a design center wavelength of 400 nm. Examples of materials used in the high dielectric constant layer of the optical film coating the reflective optical element include tantalum oxide ( Ta₂O₅ ), niobium oxide ( NbO₅ ), titanium oxide ( TiO₂ ), zirconium oxide ( ZrO₂ ), zinc oxide (ZnO), hafnium oxide ( HfO₂ ), aluminum nitride (AlN), and silicon nitride (SiN). Japanese Patent Publication No. 7-311393 discloses a nonlinear driving element comprising a metal tantalum as a bottom metal, tantalum oxide as an insulating film, and a transparent conductive film as a top metal, wherein the tantalum oxide as an insulating film has a hydrogen atom concentration of less than 1 at%. FIG. 1 is a schematic cross-sectional view of an optical element according to embodiment 1. FIG. 2 is a schematic diagram of a sputtering film deposition apparatus used to manufacture an optical element according to Embodiment 1. Figure 3 is a graph showing the light absorption rate characteristics with respect to the hydrogen content of the hafnium oxide film. Figure 4 is a graph showing the refractive index characteristics with respect to the hydrogen content of the hafnium oxide film. FIG. 5 is a graph showing the wavelength dependence of light absorption of Examples 1 and 3 of Embodiment 1. FIG. 6 is a graph showing the wavelength dependence of the refractive index of Examples 1 and 4 of Embodiment 1. FIG. 7 is a diagram showing the X-ray diffraction pattern of the hafnium oxide film of Example 1 of Embodiment 1. FIG. 8 is a diagram showing the X-ray diffraction pattern of the hafnium oxide film of Comparative Example 1 of Embodiment 1. FIG. 9 is a cross-sectional view showing the layer configuration of Examples 5 and 6 of Embodiment 1. FIG. 10 is a g