WO2008123575A1 - Matériau de métallisation sous vide et film optique fin obtenu à partir de celui-ci - Google Patents

Matériau de métallisation sous vide et film optique fin obtenu à partir de celui-ci Download PDF

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Publication number
WO2008123575A1
WO2008123575A1 PCT/JP2008/056643 JP2008056643W WO2008123575A1 WO 2008123575 A1 WO2008123575 A1 WO 2008123575A1 JP 2008056643 W JP2008056643 W JP 2008056643W WO 2008123575 A1 WO2008123575 A1 WO 2008123575A1
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Prior art keywords
vapor deposition
lanthanum
niobium
deposition material
film
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PCT/JP2008/056643
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English (en)
Japanese (ja)
Inventor
Shuhei Takahashi
Kaneo Kosaka
Hitoshi Okada
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Fuji Titanium Industry Co., Ltd.
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Application filed by Fuji Titanium Industry Co., Ltd. filed Critical Fuji Titanium Industry Co., Ltd.
Priority to KR1020097022512A priority Critical patent/KR101462294B1/ko
Priority to CN2008800077082A priority patent/CN101636518B/zh
Priority to JP2009509292A priority patent/JP5358430B2/ja
Publication of WO2008123575A1 publication Critical patent/WO2008123575A1/fr
Priority to HK10103623.7A priority patent/HK1138334A1/xx

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/221—Ion beam deposition
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings

Definitions

  • the present invention relates to a vapor deposition material for forming an optical thin film on a substrate and an optical thin film formed using the same, and in particular, an optical thin film that transmits the visible and near-ultraviolet regions and has a high refractive index.
  • the present invention relates to an evaporation material for forming and an optical thin film formed using the same. Background technology
  • the optical thin film refers to a thin film formed by applying the interference phenomenon of light generated in a film having a thickness of about the wavelength of light to give functions such as antireflection and increased reflection.
  • Such an optical thin film is formed by providing a single layer film or a laminated film of about two to a hundred layers on a base material based on a pre-designed film configuration that expresses a desired optical function.
  • optical functions such as antireflection, increased reflection, light filtering in a narrow wavelength band, polarization control, and the like can be imparted to optical members such as camera lenses and spectacle lenses.
  • a vacuum deposition method as a vacuum deposition method, but a vacuum deposition method that is excellent in terms of cost is often used as a film formation rate.
  • a film is formed on a substrate by vaporizing the evaporation material loaded in a vessel such as a boat or a crucible in a vacuum by a heating means such as resistance heating or electron beam heating.
  • vacuum deposition may be further divided into resistance heating deposition and electron beam deposition.
  • the electron beam evaporation method is often used because, in principle, a material having a high melting point or a low vapor pressure can be deposited.
  • the vapor deposition material is a vapor deposition source used to form a film in the vacuum vapor deposition method. Generally, it is classified as a high refractive index material, a medium refractive index material, and a low refractive index material according to the degree of the refractive index of the formed film.
  • the refractive index of the film formed by changing the film formation conditions is set to a desired value. Specifically, the refractive index is lower than the material. It is possible to form a film having For example, if a film formation condition is set so that a medium refractive index film is intentionally formed using a high refractive material (relaxation is reduced), the obtained film is equivalent to the medium refractive index.
  • the packing density is small and it is easy to absorb moisture in the atmosphere. Therefore, the refractive index fluctuation is large, and it takes a long time for the fluctuation to settle.
  • the refractive index of the film is usually determined not by setting the film forming conditions but by selecting and combining appropriate materials.
  • High refractive index materials are composed of oxides of titanium, niobium, or tantalum, or these oxides. Multi-component oxides and binary oxides of titanium and zirconium are known.
  • the “multi-element oxide” refers to a mixed oxide, composite oxide, solid solution oxide, or the like containing two or more metal elements.
  • the film formed using titanium, niobium, or tantalum-based materials does not have a problem with light transmission in the visible region, but has a large absorption in the near-ultraviolet wavelength region and is used in the near-ultraviolet region. It is difficult to apply to optical members.
  • the vapor deposition material is a material in which the material solid is directly vaporized without melting (sublimation property), the material is melted and soon vaporizes (semi-melting property) material, melting It can be classified into three types of materials that vaporize after passing through the state (melting property). Of these, the fusible material can make the vapor deposition process the most stable.
  • the above-mentioned binary oxide of titanium and zirconium is a sublimable or semi-meltable material, and it is difficult to form a uniform and homogeneous film using this. Therefore, if a multi-component material having a composition in which a predetermined amount of an additive that does not absorb in the near-ultraviolet region is added to the above-described titanium, niobium, or tantalum-based material, the possibility of solving the above-described problems remains. It can be said that.
  • multi-component materials generally do not evaporate according to the composition of the materials (ratio of each component) due to the different vapor pressures of each component when the vacuum deposition method is used. That is, the composition of the evaporated vapor does not necessarily match the composition of the material. Therefore, the composition of the material changes with the deposition time and the number of depositions, and the composition of the formed film also changes.Therefore, it is often difficult to produce a film having a desired characteristic many times in succession. . This means that it is necessary to reduce the number of times the material is replenished as much as possible so that the vapor deposition material once loaded in the container is used up, as in the case of a film forming operation with a large number of film layers such as a light fill.
  • vapor deposition that is performed a plurality of times after the vapor deposition material is once loaded in the container and then replenished is referred to as “continuous vapor deposition”.
  • continuous vapor deposition Even a meltable material is not suitable for continuous vapor deposition in the case of a multi-component material whose material composition changes with the vapor deposition time and the number of vapor depositions.
  • a multi-element film can be formed by using a plurality of heating evaporation sources and evaporating the vapor deposition material as each element component independently (multi-element vapor deposition).
  • multi-source deposition is rarely used except for research purposes because it is difficult to optimize the deposition conditions to obtain the desired film composition and the cost is high.
  • Patent Documents 1 and 2 disclose binary oxides of titanium and lanthanum
  • Patent Document 3 discloses binary oxides of titanium and samarium.
  • the material of Patent Document 1 can only form a film having a refractive index of about 2.1 at the maximum, which is sufficient as the refractive index of a high refractive index material. It was not so high. Furthermore, although there is no absorption in the wavelength range from the near ultraviolet (short wavelength) to the near infrared (long wavelength) through the visible part (transparent), the shortest wavelength without absorption is approximately 3 60 close to the visible part. nm.
  • Patent Documents 2 and 3 can form a film having a refractive index higher than 2.1, as in Patent Document 1, the shortest wavelength without absorption is still close to the visible region. It was 0 nm, and it was not possible to transmit light in the near ultraviolet region sufficiently (no absorption). Thus, a deposition material for forming a film having a refractive index higher than 2.1 and transmitting light in the near ultraviolet region as well as the visible region has not been known so far.
  • electron beam vapor deposition is mainly used in vacuum vapor deposition.
  • Film formation by electron beam vapor deposition using a meltable vapor deposition material is generally performed as follows. First, as a pretreatment, the molten material is melted by electron beam heating to form a molten pool. Next, a film is formed on the substrate by irradiating the molten pool again with an electron beam to generate material vapor.
  • the melt pool is continuously irradiated with the electron beam during film formation, even if the meltable material is the same, (1) the heat from the beam is appropriately diffused from the beam irradiation point to the entire melt pool to maintain a smooth evaporation surface. Because of easy control of evaporation rate As a result, a material that can easily form a film having desired characteristics. (2) Heat concentrates only in the vicinity of the beam irradiation point, and the molten pool deforms into a concave shape or the like with the deposition time and is smooth. Since the evaporation surface cannot be maintained, it is difficult to control the evaporation rate, and there are materials that require frequent replenishment.
  • Patent Documents 1 to 3 correspond to the latter (2), and if continuous deposition is performed so as to reduce the replenishment frequency of the material as much as possible, the deposition operation is performed to avoid concentration of heat.
  • special measures such as film formation while changing the irradiation position of the electron beam appropriately were necessary.
  • the heat distribution state given to the molten pool was likely to fluctuate, and eventually it was difficult to control the evaporation rate.
  • a multi-component deposition material that can easily form a desired high-refractive-index film without special measures for electron beam operation has not been known so far.
  • Patent Document 1 Japanese Patent No. 2 7 2 0 9 5 9
  • Patent Document 2 Japanese Patent Laid-Open No. 2 0 0 2-2 2 6 9 6 7
  • Patent Document 3 Japanese Patent Laid-Open No. 2 0 0 0-1 8 0 6 0 4
  • the object of the present invention is to eliminate all of the above-mentioned problems, that is, it is meltable and can be continuously evaporated, and the evaporation rate can be easily controlled even if the electron beam evaporation method is used.
  • An evaporation material for forming an optical thin film capable of transmitting light in a wider wavelength range than that of the prior art, particularly in the near ultraviolet region, and having a high refractive index, and an optical thin film obtained by using the vapor deposition material The object is to provide a method for producing a thin film.
  • the present inventors have come to focus on vapor deposition materials composed of binary oxides of niobium and lanthanum.
  • composition of the vapor generated from the vapor deposition material by this combination of components is not necessarily determined simply by the vapor pressure of each component as conventionally known.
  • the present inventors have found that the above-described problems can be solved only in the vapor deposition materials having the composition ratios described above and optical thin films formed using these materials, and have completed the present invention. Disclosure of the invention
  • the present invention relates to the following inventions.
  • a vapor deposition material composed of a binary oxide of niobium and lanthanum, or in addition to metal niobium and / or metal lanthanum, wherein the molar ratio of niobium and lanthanum in the vapor deposition material is 25: 7 Vapor deposition material, wherein 5 to 90:10.
  • a method for producing an optical thin film characterized by being formed by a vacuum vapor deposition method using the vapor deposition material described in the above 1 to 4.
  • the vapor deposition material of the present invention is composed of a binary oxide of niobium and lanthanum, and the molar ratio of the niobium and lanthanum is 25:75 to 90:10.
  • binary oxide of niobium and lanthanum means a mixture of niobium oxide and lanthanum oxide, a composite oxide of niobium and lanthanum, a mixture of two or more of these composite oxides, niobium and A mixture of lanthanum oxide and niobium oxide, a mixture of niobium and lanthanum oxide and lanthanum oxide, a solid solution oxide of niobium and lanthanum, etc., composed of niobium, lanthanum and oxygen Refers to all substances.
  • lanthanum oxide, niobium oxide, and complex oxides of niobium and lanthanum are acid Lanthanum (III) (L a 2 0 3 ), niobium oxide (V) (Nb 2 0 5 ), L a 3 Nb 0 7 , L aNb 0 4 , L aNb 3 0 9 , L aNb 5 0 14 , L a other conventional chemically most stable oxides in an atmosphere such as N b 7 ⁇ L 9, L nitrous oxide lanthanum like A_ ⁇ , Ya Nb0 2, Nb 2 ⁇ 3, niobium suboxide as NbO
  • a sub-oxide such as a composite oxide in a sub-oxidation state such as LaNb 7 12 may be used.
  • suboxide vapor deposition materials are materials having a lower oxygen content. Desorption of oxygen gas is unlikely to occur during melting as a treatment. Therefore, it is easy to control the atmospheric pressure in the vapor deposition apparatus during vapor deposition, and it is easy to form a film having desired characteristics.
  • the nitrous oxide evaporation material of the present invention other L ANB 7 ⁇ 12 already described, Nb_ ⁇ + L ANb_ ⁇ 4, Nb_ ⁇ 2 + L ANb_ ⁇ 4 and Nb_ ⁇ 2 + L a 3 Nb0 7 + L the aNb0 binary oxides of structure such as 4 can be exemplified.
  • the second vapor deposition material of the present invention is a vapor deposition material comprising a) a binary oxide of niobium and lanthanum, and b) metal niobium and / or metal lanthanum, the mole of niobium and lanthanum in the vapor deposition material.
  • the ratio is 25:75 to 90:10.
  • the definition of “binary oxide of niobium and lanthanum” is as described above.
  • Nb + L a 2 ⁇ 3, L a + Nb 2 ⁇ 5, Nb + L a + Nb 2 0 5, Nb + L aO, Nb + L aNb0 4, Nb + L aNb 7 0 12, Nb + La 3 Nb0 7 + L aNb0 43 ⁇ 4 Nb + L a 3 NbO y + laNb 7 ⁇ 12, N b + N b O 2 + L a 3 N B_ ⁇ 9 + L a N the b O 4 and N b + N b O + Nb_ ⁇ 2 + L a 3 Nb_ ⁇ 9 + L ANb_ ⁇ 4 can be exemplified.
  • metal-containing vapor deposition material such a vapor deposition material containing niobium metal and / or metal lanthanum is referred to as a “metal-containing vapor deposition material”. Since the metal-containing vapor deposition material is also a material having a smaller oxygen content like the suboxide vapor deposition material, it is easy to form a film having desired characteristics for the reasons described above.
  • the vapor deposition material of the present invention does not impair the effects of the present invention described above. That is, up to 5 mo 1% of the binary oxides of niobium and lanthanum does not prevent the addition of materials other than niobium and lanthanum oxides. Examples of such materials include aluminum oxide, gadolinium oxide, dysprosium oxide, ytterbium oxide, and the like.
  • a material in which the molar ratio of niobium and lanthanum is outside the range of 25:75 to 90:10 is not suitable for continuous deposition because the molar ratio varies greatly with the deposition time and the number of depositions.
  • the variation in the refractive index and the optical wavelength range of the film successively formed by continuous vapor deposition becomes extremely small.
  • a film having certain characteristics over a long period of time and many times can be produced, which is preferable.
  • the refractive index variation can be suppressed to about 0.01.
  • the form of the vapor deposition material of the present invention is not particularly limited, but it is preferable that the vapor deposition material has a shape of a molded body such as a granule or evening bullet rather than the raw material powder itself or a mixture. This is because powders are not handled well during vapor deposition, and material splashing is likely to occur, making it difficult to form a film with desired optical characteristics.
  • the size of the molded body is about 0.1 to 10 mm because replenishment of the material during continuous vapor deposition is difficult.
  • L a 2 0 3 and L a O such containing chromatic ratio of lanthanum oxide is not more than 5% by weight.
  • Lanthanum oxide is highly hygroscopic, and when the content exceeds 5% by weight, it reacts with the moisture in the air and has a lower density of lanthanum hydroxide. This is because if it is chemically transformed into a molded body, sintered body, or melt, it expands and collapses into a powder.
  • a vapor deposition material containing a large amount of lanthanum hydroxide as well as this powder is used for vapor deposition as it is, not only will splash of the material occur during heating, but also significant moisture will be released, and the formed film will be lost. A physical defect occurs and it is not preferable from the viewpoint of maintenance of the vapor deposition apparatus.
  • the vapor deposition material of the present invention can be produced, for example, by the following method.
  • niobium oxide (V) and lanthanum oxide (III) powders are used as starting materials, mixed at a predetermined ratio, and the resulting mixture powder is granulated and / or molded.
  • a molded body having a size of about 0.1 to 10 mm can be produced and then fired at a predetermined temperature in the air, in a vacuum, or in an inert gas such as argon.
  • argon inert gas such as argon.
  • a melt it can be produced by melting the mixture powder or its molded body at a predetermined temperature.
  • the optimum firing temperature and melting temperature differ depending on the molar ratio of niobium and lanthanum constituting the vapor deposition material, but if the firing temperature is approximately 900 to 1700 t: It is appropriate that the melting temperature is approximately 1 3 5 0 to 1 90 0.
  • niobium oxide is used as a starting material.
  • metal niobium and metal or lanthanum metal may be used.
  • a metal and an oxide can be chemically reacted at the time of firing or melting, and a suboxide deposition material can be produced.
  • niobium oxide and / or lanthanum oxide may be used as a starting material instead of niobium oxide (V) and / or lanthanum oxide (I I I).
  • it can also be produced by deoxygenating a vapor deposition material produced using only niobium oxide (V) and lanthanum oxide (I I I) as starting materials. Examples of the deoxygenation method include heat treatment under a reducing gas such as hydrogen.
  • the composition of the starting material is sub-oxidation. This is the same as the case of the material vapor deposition material. However, the manufacturing conditions different from those for the suboxide deposition material are applied (for example, the firing temperature is slightly lowered or the firing time is shortened at the time of firing), so that the metal itself remains. To complete the manufacturing. In this way, a metal-containing vapor deposition material can be produced.
  • niobium and lanthanum can be produced by adding niobium metal and Z or metal lanthanum to the vapor deposition material of the binary oxide of niobium and lanthanum, and in some cases further firing or melting.
  • vapor deposition material of the present invention By using the vapor deposition material of the present invention described above, it is possible to transmit not only the entire visible light region but also the near ultraviolet region, which is a shorter wavelength region than 360 nm, and is refracted in the vicinity of a wavelength of 450 nm.
  • An optical thin film having a high refractive index of about 2.15 to 2.35, preferably about 2.20 to 2.35 can be formed.
  • the method for producing an optical thin film of the present invention is characterized in that it is formed by a vacuum deposition method using the vapor deposition material of the present invention.
  • the “vacuum evaporation method” in the present invention includes an ion plating method and an ion assist method in which an auxiliary means for film formation processing is added to this method.
  • the heat given to the material by the beam is appropriately diffused from the beam irradiation point to the entire material, and the evaporation surface is kept smooth even after the evaporation time, so the evaporation rate is easy. Can be controlled.
  • an optical thin film having desired characteristics can be easily produced.
  • the replenishment frequency of the vapor deposition material can be made lower, continuous vapor deposition can be performed for a longer time and many times.
  • the desired optical thin film can be obtained even if the electron beam irradiation position is fixed during film formation, for example, without requiring any special measures for electron beam operation. Can be easily manufactured.
  • the irradiation position of the electron beam at this time is preferably the central portion of the container, for example, when a vapor deposition material is loaded into a cylindrical container.
  • the evaporation rate is easily controlled and continuous evaporation can be achieved by configuring the evaporation material with a specific element combination of niobium and lanthanum. be able to.
  • FIG. 1 is an X-ray diffraction pattern of the vapor deposition material obtained in Example 1.
  • FIG. 2 is a photograph showing the state of the molten pool after film formation in Example 1.
  • FIG. 3 is a photograph showing the state of the molten pool after completion of film formation in Comparative Example 3.
  • FIG. 4 is a photograph showing the state of the molten pool after completion of film formation in Comparative Example 4.
  • the molar ratio of niobium and lanthanum is 37.5: 62.5
  • the powder mixture is granulated into granules of 1 to 3 mm, and fired at 1300 ° C for 4 hours in the atmosphere.
  • a granular deposition material was obtained.
  • the material was identified by X-ray diffraction pattern shown in Figure 1 and L a 3 Nb_ ⁇ 7 and L aNb0 4.
  • the was loaded evaporation material copper hearth liner (crucible) was set in a commercially available vacuum deposition instrumentation ⁇ , was evacuated to the interior of the apparatus to 1.
  • OX 10- 3 P a the deposition material by electron beam heating Melted to form a molten pool.
  • the total pressure by introducing oxygen to be 1.0X 10- 2 P a again, an electron beam is irradiated only to the center portion of the molten pool, to generate material vapor
  • a set 300 in the apparatus in advance Films were formed on the substrate that had been heated to a thickness of 0.9 nmZ seconds until the physical film thickness reached 250 nm. This film formation is performed without replacing the deposition material while replacing only the base material. I went twice.
  • the refractive index at a wavelength of 4 ⁇ 0 nm was determined by a spectrophotometer, and the molar ratio of niobium to lanthanum was determined by ICP-MS composition analysis.
  • the results are shown in Tables 1 and 2.
  • the refractive index and the molar ratio are uniform regardless of the number of depositions, and no absorption was observed from 285 nm to the visible region. As this 285 nm, when the wavelength is shortened from the visible region side to the ultraviolet region side, the light absorption of the film begins to occur, and the wavelength at which the spectral transmittance begins to drop rapidly, Called the “shortest transmission wavelength”.
  • Fig. 2 shows a photograph of the vapor deposition material (molten pool) after the film formation described above. Even though the electron beam was irradiated only at the center of the melt pool, a smooth evaporation surface was maintained. I understand that
  • the method for calculating the refractive index at a wavelength of 450 nm is as follows. Measure the spectral transmittance with a commercially available spectrophotometer to obtain a spectral curve.
  • the SELLME I ER dispersion formula is a formula often used for the purpose of obtaining the relationship between the wavelength of light and the refractive index, and is expressed by the following formula.
  • ⁇ is the refractive index
  • ⁇ is the wavelength
  • ⁇ and ⁇ are coefficients that determine the relationship between wavelength and refractive index.
  • SQL represents calculating the square root of the above [] part.
  • niobium oxide (V), lanthanum oxide (III) and metal niobium in a weight ratio of 45.5: 46.5: 8.0 (molar ratio of niobium to lanthanum is 60.0: 40.0).
  • V niobium oxide
  • III lanthanum oxide
  • metal niobium in a weight ratio of 45.5: 46.5: 8.0 (molar ratio of niobium to lanthanum is 60.0: 40.0).
  • the material was identified by X-ray diffraction pattern with L ANb_ ⁇ 4 and NbO.
  • the refractive index and the shortest transmission wavelength at a wavelength of 4 ⁇ 0 nm were obtained.
  • the molar ratio of Abu to lanthanum was determined. The results are shown in Tables 1 and 2. The refractive index and the molar ratio were uniform regardless of the number of film formation, and the shortest transmission wavelength was 305 nm.
  • Niobium oxide (V) and lanthanum oxide (III) powders were mixed at a weight ratio of 80.3: 19.7 (molar ratio of niobium and lanthanum was 83.3: 16.7), and the powder mixture was formed into a 1 to 3 mm tablet. And was fired in the atmosphere for 1200 x 4 hours to obtain an evening bullet-like vapor deposition material.
  • the material was identified as LaNb 5 0 14 from the X-ray diffraction pattern.
  • the refractive index at the wavelength of 450 nm, the shortest transmission wavelength, and the molar ratio of niobium to lanthanum were determined for each film obtained by forming a film in the same manner as in Example 1. .
  • the results are shown in Tables 1 and 2.
  • the refractive index and the molar ratio were uniform regardless of the number of depositions, and the shortest transmission wavelength was 330 nm.
  • niobium oxide (V) and lanthanum oxide (III) in a weight ratio of 25.9: 74.1 (molar ratio of niobium and lanthanum is 30.0: 70.0). Then, it was calcined in the atmosphere at 1500 ° C for 4 hours to obtain a granular deposition material.
  • the material was identified by X-ray diffraction pattern as L a 3 Nb_ ⁇ 7 and L ANb_ ⁇ 4.
  • the refractive index at the wavelength of 450 nm, the shortest transmission wavelength, and the molar ratio of niobium to lanthanum were determined for each film obtained by forming a film in the same manner as in Example 1. .
  • the results are shown in Tables 1 and 2.
  • the refractive index and the molar ratio were uniform regardless of the number of film formation, and the shortest transmission wavelength was 270 nm.
  • the refractive index at the wavelength of 450 nm, the shortest transmission wavelength, and the molar ratio of niobium to lanthanum were determined for each film obtained by forming a film in the same manner as in Example 1. .
  • the results are shown in Tables 1 and 2.
  • the refractive index and the molar ratio were uniform regardless of the number of film formation, and the shortest transmission wavelength was 290 nm.
  • V niobium oxide
  • ⁇ lanthanum oxide
  • metal niobium in a weight ratio of 26.8: 68.5: 4.7 (molar ratio of niobium to lanthanum is 37.5: 62.5).
  • V niobium oxide
  • ⁇ lanthanum oxide
  • metal niobium in a weight ratio of 26.8: 68.5: 4.7 (molar ratio of niobium to lanthanum is 37.5: 62.5).
  • the material was identified from the X-ray diffraction pattern as L a 3 Nb0 7, L a N B_ ⁇ 4 and N b.
  • the refractive index at the wavelength of 450 nm, the shortest transmission wavelength, and the molar ratio of niobium to lanthanum were determined for each film obtained by forming a film in the same manner as in Example 1. .
  • the results are shown in Tables 1 and 2.
  • the refractive index and the molar ratio were uniform regardless of the number of film formation, and the shortest transmission wavelength was 290 nm.
  • Niobium oxide (V), lanthanum oxide (III), and metal niobium powder were mixed at a weight ratio of 53.3: 21.8: 24.9 (molar ratio of niobium to lanthanum was 83.3: 16.7). Molded into 1 to 3 mm evening bullets and fired in vacuum at 1300 ° C for 3 hours to obtain evening bullet-like deposition materials. The material was identified as L aNb 3 09 , LaNb 0 4 , Nb 0 2 , NbO and Nb from the X-ray diffraction pattern.
  • the refractive index at the wavelength of 450 nm and the shortest transmission wavelength were obtained for each film obtained by forming the film in the same manner as in Example 1.
  • the molar ratio of Abu to lanthanum was determined. The results are shown in Tables 1 and 2.
  • the refractive index and the molar ratio were uniform regardless of the number of depositions, and the shortest transmission wavelength was 335 nm.
  • Niobium oxide (V) and lanthanum oxide (III) powders were mixed at a weight ratio of 90.4: 9.6 (the molar ratio of niobium and lanthanum was 92.3: 7.7).
  • the refractive index at the wavelength of 450 nm, the shortest transmission wavelength, and the molar ratio of niobium to lanthanum were determined for each film obtained by forming a film in the same manner as in Example 1. .
  • the results are shown in Tables 1 and 2.
  • the refractive index decreases and the molar ratio also changes, and even though the shortest transmission wavelength is 365 nm, it can sufficiently transmit light in the near ultraviolet region. It was not.
  • the powder mixture is granulated into 1 to 3 mm granules, and calcined in the atmosphere at 1500t: x4 hours to deposit condylar particles Obtained material.
  • the material was identified from its X-ray diffraction pattern L a 3 N b O 7 ⁇ beauty L a 2 ⁇ 3 (lanthanum oxide). Increased mass was observed due to moisture absorption. The granules did not collapse. The content of lanthanum oxide calculated from the increased mass was 2.5% by weight.
  • the refractive index at the wavelength of 450 nm, the shortest transmission wavelength, and the molar ratio of niobium to lanthanum were determined for each film obtained by forming a film in the same manner as in Example 1. .
  • the results are shown in Tables 1 and 2.
  • the shortest transmission wavelength is 260 nm, which sufficiently transmits the near-ultraviolet region, the refractive index increased and the molar ratio changed as the number of film formations increased. Comparative Example 3
  • Titanium oxide (IV), lanthanum oxide (III) and titanium metal powder were mixed at a weight ratio of 29.3: 68.2: 2.5 (molar ratio of titanium to lanthanum was 50.0: 50.0).
  • Granulated vapor-deposited material was obtained by granulating into ⁇ 3mm granules and firing in vacuum at 1700 ° CX for 5 hours.
  • a film was formed in the same manner as in Example 1 except that the number of film formation was one.
  • Fig. 3 shows a photograph of the vapor deposition material after the film formation, and it can be seen that the position irradiated with the electron beam is greatly recessed. The center of the dent is dug deep enough to reach the bottom of the hearth liner (the distance between the center surface and the hearth liner bottom is about 3mm) Continuous deposition was impossible at all.
  • Niobium oxide (V) and yttrium oxide (III) powders were mixed at a weight ratio of 44.0: 56.0 (molar ratio of niobium and yttrium was 40.0: 60.0). And then fired in vacuum for 1700 x 4 hours to obtain a granular deposition material.
  • a film was formed in the same manner as in Example 1 except that the number of film formation was one.
  • Fig. 4 shows a photograph of the vapor deposition material after the completion of the above film formation, but the position where the electron beam was irradiated was greatly recessed despite the fact that the film was formed only once. It can be seen that a part of the bottom is exposed. As in Comparative Example 3, continuous vapor deposition was not possible at all.
  • Comparative Example 5 A granular deposition material was obtained in the same manner as in Example 4 except that it was calcined at 120 ° C. for 4 hours in the air. The material was identified by X-ray diffraction pattern with L a N b 0 4, L a 3 N B_ ⁇ 7 and L a 2 ⁇ 3. An increase in mass was observed due to moisture absorption, and the granules collapsed and turned into powder one day after production. When the content of lanthanum oxide was calculated from the increased mass, it was 6.3% by weight.
  • the powdered copper hearth liner loaded with deposited material was set in a vacuum deposition apparatus available on the market, it was evacuated to the interior of the apparatus to 1. 0 X 1 0- 3 P a, was heated to a higher electron beam However, the material was scattered violently, so the film formation was interrupted.
  • the vapor deposition material which has the following characteristics, the optical thin film formed using it, and the manufacturing method of the optical thin film can be provided.
  • Evaporation rate can be easily controlled even using electron beam evaporation. That is, the heat generated by the beam diffuses moderately from the beam irradiation point * f to the entire molten pool and maintains a smooth evaporation surface, so that the evaporation rate can be easily controlled, resulting in uniform desired characteristics. A film can be easily formed.
  • An optical thin film having a high refractive index can be formed.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • General Physics & Mathematics (AREA)
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  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un matériau de métallisation sous vide composé d'un oxyde bicomposant de niobium et de lanthane, ou un matériau de métallisation sous vide composé de l'oxyde bicomposant et de niobium métal et/ou de lanthane métal. Ce matériau de métallisation sous vide est caractérisé par un rapport molaire entre le niobium et le lanthane situé entre 25/75 et 90/10. Il est décrit également un film optique fin obtenu à partir d'un tel matériau de métallisation sous vide.
PCT/JP2008/056643 2007-03-30 2008-03-27 Matériau de métallisation sous vide et film optique fin obtenu à partir de celui-ci WO2008123575A1 (fr)

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KR1020097022512A KR101462294B1 (ko) 2007-03-30 2008-03-27 증착재료 및 그로부터 얻어지는 광학박막
CN2008800077082A CN101636518B (zh) 2007-03-30 2008-03-27 蒸镀材料及利用该材料制得的光学薄膜
JP2009509292A JP5358430B2 (ja) 2007-03-30 2008-03-27 蒸着材料及びそれより得られる光学薄膜
HK10103623.7A HK1138334A1 (en) 2007-03-30 2010-04-14 Vapor deposition material and optical thin film obtained from the same

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CN105506737B (zh) * 2015-12-28 2018-02-09 常州瞻驰光电科技有限公司 一种非化学计量比氧化铌多晶镀膜材料及其生长技术
CN110078504B (zh) * 2019-04-26 2020-10-30 清华大学 一种原位合成赝二元复相稀土铌酸盐陶瓷及其制备方法

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JP2000180604A (ja) * 1998-12-17 2000-06-30 Oputoron:Kk 高屈折率の光学薄膜材料および該材料を用いた光学薄膜
JP2002226967A (ja) * 2000-12-29 2002-08-14 Merck Patent Gmbh 高屈折率光学層製造用蒸着材料および蒸着材料の製造方法
JP2005031297A (ja) * 2003-07-10 2005-02-03 Asahi Techno Glass Corp 液晶表示装置の反射防止膜付き透明基板
JP2006195301A (ja) * 2005-01-17 2006-07-27 Konica Minolta Opto Inc 光学素子
JP2006519923A (ja) * 2003-02-19 2006-08-31 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング 高屈折率光学層を製造するための蒸着材料

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US6327087B1 (en) * 1998-12-09 2001-12-04 Canon Kabushiki Kaisha Optical-thin-film material, process for its production, and optical device making use of the optical-thin-film material
JP2005154885A (ja) * 2003-03-26 2005-06-16 Mitsubishi Heavy Ind Ltd 遮熱コーティング材料
KR100997068B1 (ko) * 2003-10-21 2010-11-30 우베 마테리알즈 가부시키가이샤 산화마그네슘 증착재

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Publication number Priority date Publication date Assignee Title
JP2000180604A (ja) * 1998-12-17 2000-06-30 Oputoron:Kk 高屈折率の光学薄膜材料および該材料を用いた光学薄膜
JP2002226967A (ja) * 2000-12-29 2002-08-14 Merck Patent Gmbh 高屈折率光学層製造用蒸着材料および蒸着材料の製造方法
JP2006519923A (ja) * 2003-02-19 2006-08-31 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング 高屈折率光学層を製造するための蒸着材料
JP2005031297A (ja) * 2003-07-10 2005-02-03 Asahi Techno Glass Corp 液晶表示装置の反射防止膜付き透明基板
JP2006195301A (ja) * 2005-01-17 2006-07-27 Konica Minolta Opto Inc 光学素子

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JPWO2008123575A1 (ja) 2010-07-15
KR101462294B1 (ko) 2014-11-14
JP5358430B2 (ja) 2013-12-04
CN101636518B (zh) 2011-06-08
TW200848530A (en) 2008-12-16
TWI382101B (zh) 2013-01-11
KR20090127365A (ko) 2009-12-10
HK1138334A1 (en) 2010-08-20

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