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WO2017119335A1 - Procédé de fabrication d'un film réfléchissant - Google Patents

Procédé de fabrication d'un film réfléchissant Download PDF

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Publication number
WO2017119335A1
WO2017119335A1 PCT/JP2016/088675 JP2016088675W WO2017119335A1 WO 2017119335 A1 WO2017119335 A1 WO 2017119335A1 JP 2016088675 W JP2016088675 W JP 2016088675W WO 2017119335 A1 WO2017119335 A1 WO 2017119335A1
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WIPO (PCT)
Prior art keywords
layer
reflective
film
manufacturing
refractive index
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Ceased
Application number
PCT/JP2016/088675
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English (en)
Japanese (ja)
Inventor
仁一 粕谷
宗矩 川路
中村　新吾
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of WO2017119335A1 publication Critical patent/WO2017119335A1/fr
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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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors

Definitions

  • the present invention relates to a method for manufacturing a reflective film, and more particularly to a technique suitable for improving both reflectance and gas corrosion resistance.
  • Patent Document 1 Bi and / or Sb is contained in Ag to suppress a decrease in reflectance over time (paragraphs 0018 to 0022).
  • Patent Document 2 an oxide film of a predetermined metal such as Zr is formed as a second layer on an Ag film to improve sulfidation resistance and heat resistance and to suppress a decrease in reflectance (paragraph 0020). ⁇ 0024).
  • Patent Document 1 paragraphs 0031 to 0038
  • Patent Document 2 paragraphs 0062 to 0065
  • the reflective film is manufactured using the sputtering method.
  • a sputtering method for example, as shown in FIG. 9, when manufacturing a polyhedral reflector 50 such as a polygon mirror, simultaneously forming a reflective film on a plurality of film formation surfaces 52 Therefore, it is necessary to reduce the distance from the target 60 to the film formation surface 52, and unevenness in film thickness occurs between the film formation surfaces 52. In order to avoid this, it is necessary to perform film formation while switching the film formation surfaces 52 one by one, and the productivity is not good.
  • Patent Document 3 discloses a method for manufacturing a reflective film using a vapor deposition method (paragraph 0058).
  • the technique of Patent Document 3 since the film is formed by the vapor deposition method instead of the sputtering method, the distance from the vapor deposition source to the film formation surface is separated even when a polyhedral reflector such as a polygon mirror is manufactured. It is considered that the occurrence of film thickness unevenness can be suppressed, and since it is not necessary to switch the film formation surface, productivity can be improved and the above problem can be solved.
  • Patent Document 3 attempts to obtain a corrosion resistance and high spectral reflectance by forming a reflective film 52 of a Bi-containing silver alloy by vapor deposition (paragraphs 0028 and 0058).
  • an adhesion improving film 51 Cr film and Cu film
  • reflection film 52 Al—Bi film
  • intermediate film 54 Al 2 O 3 film
  • Reflection increasing film 53 ZrO 2 film, SiO 2 film, ZrO 2 film and SiO 2 film
  • Light reflecting mirror on which a water repellent film is formed is manufactured. Is forming.
  • an Ag—Bi alloy is used as the raw material evaporation material (paragraphs 0071, 0073, and 0078).
  • a main object of the present invention is to provide a method for manufacturing a reflective film using a vapor deposition method, and to provide a method for manufacturing a reflective film capable of improving both reflectivity and gas corrosion resistance. .
  • a method for manufacturing a reflective film reflecting one aspect of the present invention includes the following.
  • a method for producing a reflective film including at least a reflective layer Depositing AgBi as a raw material to form a reflective layer;
  • a method for producing a reflective film, wherein the composition ratio of Bi of the raw material is 0.01 to 0.8 atomic%.
  • the composition ratio of Bi as a raw material is optimized, and it is possible to improve both reflectance and gas corrosion resistance.
  • FIG. 1 It is a perspective view which shows schematic structure of a reflective mirror. It is sectional drawing which shows schematic structure of a reflecting film. It is a schematic flowchart which shows the manufacturing method of a reflecting film over time. It is a figure for demonstrating the formation method of a reflection layer. It is the schematic which shows the state which mounted the laser radar in the vehicle. It is a perspective view which shows schematic structure of the laser radar to which a reflective mirror is applied. It is a figure for demonstrating the relationship between an Ag-Bi layer and Cl suppression. It is a figure which shows the compositional analysis result of the depth direction of the reflecting film of the comparative example 3 and Example 3. FIG. It is a figure for demonstrating the problem of the conventional manufacturing method (sputtering).
  • the reflecting mirror 10 is a so-called polygon mirror that is a polyhedral reflecting mirror, and has a form in which two quadrangular pyramids are abutted.
  • the reflecting mirror 10 four trapezoidal reflecting surfaces 12 and 14 are arranged on the top and bottom, respectively, to form a total of eight reflecting surfaces 12 and 14.
  • a reflective film 30 is formed on each of the reflective surfaces 12 and 14 (see FIG. 2).
  • the reflecting mirror 10 includes a base material 20 and a reflective film 30 that is a thin film, and the reflective film 30 is formed on the surface of the base material 20 (respective reflecting surfaces 12 and 14).
  • the base material 20 is a member that becomes a base of the reflecting mirror 10, and has a flat optical surface 21 that is covered by the reflective film 30.
  • the substrate 20 is made of a resin material such as polycarbonate (PC), cycloolefin polymer (COP), acrylic resin (PMMA), polyethylene terephthalate (PET).
  • the substrate 20 is not limited to these resin materials, and may be formed of quartz, glass, ceramics, or other inorganic materials.
  • the reflective film 30 includes an adhesion layer 31 formed as a base on the base material 20, a reflection layer 32 formed on the adhesion layer 31, and an increased reflection layer 33 formed on the reflection layer 32. .
  • the reflection layer 32 is disposed between the adhesion layer 31 and the increased reflection layer 33.
  • a description will be given of a mode in which the reflective film 30 has a three-layer structure of the adhesion layer 31, the reflective layer 32, and the increased reflective layer 33.
  • the adhesion layer 31 may be composed of one layer or may be composed of two or more layers.
  • the term “two or more layers” means a layer of a material having good adhesion to the upper reflective layer 32 and a layer of a material having good adhesion to the lower substrate 20.
  • the adhesion layer 31 has a single-layer configuration, it is necessary to select a material that has good adhesion to both the reflective layer 32 and the substrate 20.
  • the influence of moisture from the substrate 20 must be taken into account. It is necessary to adjust the film stress of each film to achieve a balance between them in order to suppress film floating and cracks associated with stress on each film caused by high temperature and high humidity environment and high temperature dry environment. .
  • the layer mainly composed of aluminum oxide there are several media for blocking moisture in the adhesion layer 31, but one is preferably a layer mainly composed of aluminum oxide.
  • the layer mainly composed of aluminum oxide “Substance M2” or “Substance M3” manufactured by Merck Co., Ltd. in which La 2 O 3 is mixed with aluminum oxide in an amount of about 5 to 10% is used in addition to pure aluminum oxide. Including cases.
  • the layer mainly composed of aluminum oxide used in the adhesion layer 31 is formed without performing ion assist, the moisture blocking effect is recognized, but the tensile stress of the material itself is strong, and durability in a high temperature and high humidity environment is improved. Not suitable for holding. Therefore, it is preferable to make the film dense by using an ion assist method to achieve both the moisture blocking effect and the stress adjusting effect.
  • the resistance to high temperature and high humidity can be improved by adjusting the film formation conditions such as the ion assist output and the film formation rate in consideration of the correlation with the film stress of the entire layer.
  • a layer mainly made of aluminum oxide formed using an ion assist method is preferable.
  • the layer constituting the upper side of the adhesion layer 31 is preferably selected from at least one of LaTiO 3 , CeO 2 , Y 2 O 3 and SnO 2 as a material having good adhesion with silver.
  • the adhesion layer 31 may include a first layer 31a on the base material 20 side and a second layer 31b on the reflective layer 32 side. Both layers 31a and 31b have a thickness of about 10 to 200 nm, more preferably 20 to 120 nm.
  • the first layer 31a is a thin film layer that has a role of a buffer layer that directly adheres to the base material 20 and allows some permeation while blocking moisture.
  • the second layer 31b is a thin film layer that is in direct contact with the reflective layer 32 and has a role of reliably blocking moisture.
  • the first layer 31a on the substrate 20 side is a layer mainly made of aluminum oxide as described above, and is preferably formed using an ion assist method.
  • the second layer 31b on the reflective layer 32 side is a layer of a material selected from at least one of LaTiO 3 , CeO 2 , Y 2 O 3 and SnO 2 as described above, and is formed using an ion assist method. Preferably it is done.
  • both layers 31a and 31b have an effect of improving the adhesion even if the film thickness is less than 10 nm as a whole, if the film thickness is less than 10 nm, the thin film is being grown and sufficient moisture is formed from the continuity of the film.
  • the film thickness is preferably 10 nm or more.
  • the film thickness is preferably controlled to 200 nm or less.
  • the reflective layer 32 is a thin film formed of an alloy of Ag and Bi.
  • the reflective layer 32 is a layer formed by vapor deposition using AgBi as a raw material.
  • the composition ratio of Bi of the raw material is 0.01 to 0.8 atomic%, preferably 0.02 to 0.5 atomic%. Is done.
  • the reflective layer 32 has a thickness of about several tens to 100 nm, more preferably about 50 to 100 nm.
  • the increased reflection layer 33 is a dielectric multilayer film in which high refractive index material layers 33a and low refractive index material layers 33b are alternately stacked, and the uppermost layer is preferably formed of the low refractive index material layer 33b.
  • the number of layers of the high refractive index material layer 33a and the low refractive index material layer 33b is appropriately set.
  • the high refractive index material layer 33a has a refractive index of 1.8 or more
  • the low refractive index material layer 33b has a refractive index of 1.55 or less.
  • the material of the high refractive index material layer 33a is selected from at least one of TiO 2 , Nb 2 O 5 , Ta 2 O 5 , LaTiO 3 , ZrO 2, and a mixed material of these materials.
  • the material of the low refractive index material layer 33b is selected from at least one of SiO 2 and a mixed material obtained by mixing aluminum oxide with SiO 2 .
  • the high-refractive index material layer 33a and the low-refractive index material layer 33b are set to have a film thickness corresponding to the refractive index for each layer depending on the optical design, and even the same low-refractive index material layer 33b may have different thicknesses. Further, when the increased reflection layer 33 is composed of a plurality of high refractive index material layers 33a and a plurality of low refractive index material layers 33b, for example, the plurality of high refractive index material layers 33a are formed of different materials having different refractive indexes. can do.
  • the single low refractive index material layer 33b can be composed of a plurality of types of low refractive index material layers, and similarly, the single high refractive index material layer 33a is composed of a plurality of types of high refractive index material layers. You can also
  • the first reflective layer 33 may be formed with a first layer 33 f that is in direct contact with the reflective layer 32.
  • the first layer 33f is made of a material mainly containing aluminum oxide.
  • the reflection performance can be improved.
  • the first layer 33f has a refractive index of 1.55 or more and less than 1.80.
  • the first layer 33f in contact with the reflective layer 32 can be regarded as a medium refractive index material layer in terms of a higher refractive index than the uppermost low refractive index material layer 33b, but in a broad sense, the high refractive index material layer 33a. Therefore, it is called a low refractive index material layer.
  • the manufacturing method of the reflecting mirror 10 is mainly (I) Step S1 for preparing the base material 20; (Ii) Step S2 of forming the adhesion layer 31, (Iii) Step S3 of forming the reflective layer 32; (Iv) Step S4 of forming the increased reflection layer 33; It has.
  • a base member formed of a resin material such as polycarbonate (PC) is prepared.
  • a single ion beam assisted vapor deposition apparatus (deposition apparatus using a known ion assist method) is used while switching the presence or absence of an ion beam.
  • Each layer is preferably formed.
  • a material mainly composed of aluminum oxide is vapor-deposited on the base material 20 by using an ion assist method to form the first layer 31a. Thereafter, a material selected from at least one of LaTiO 3 , CeO 2 , Y 2 O 3 and SnO 2 is vapor-deposited on the first layer 31a by using an ion assist method to form the second layer 31b.
  • the denseness or density of the first layer 31a and the second layer 31b can be adjusted by adjusting the degree of ion beam irradiation.
  • the reflective layer 32 is formed using a normal vapor deposition method.
  • AgBi with a Bi composition ratio of 0.01 to 0.8 atomic% is used as a raw material to fill the vapor deposition source 40, and the vapor deposition source 40 is heated to form an Ag—Bi alloy base.
  • a reflective film 32 is formed by vapor deposition on the material 20 (second layer 31b of the adhesion layer 31).
  • the composition ratio of Bi as a raw material is preferably 0.02 to 0.5 atomic%.
  • the vapor deposition source 40 including the raw material it is preferable to preheat the vapor deposition source 40 including the raw material, and then perform main heating at a temperature higher than the preheating for vapor deposition.
  • an openable / closable shutter 42 is disposed between the vapor deposition source 40 and the substrate 20, and vapor deposition is performed with the shutter 42 closed, and then the shutter 42 is formed. Vapor deposition is recommended. That is, the raw material Bi has a lower melting point than Ag and evaporates first.
  • the heating temperature of the main heating is set higher than the heating temperature of the preheating in order to increase the film formation rate. If the film formation rate is increased, the kinetic energy increases and the strength of the reflective film 32 can be improved.
  • the reflective film 30 may be configured by only the reflective layer 32.
  • the reflective layer 32 may be directly formed on the base material 20 and may be used as the reflective mirror 10.
  • a material mainly composed of aluminum oxide is vapor-deposited on the reflection layer 32 by using an ordinary vapor deposition method to form the first layer 33f. Thereafter, a material selected from at least one of TiO 2 , Nb 2 O 5 , Ta 2 O 5 , LaTiO 3 , ZrO 2, and a mixed material of these materials is formed on the first layer 33 f using an ion assist method. To form a high refractive index material layer 33a.
  • the reflecting mirror 10 can be manufactured.
  • the reflecting mirror 10 can be applied to, for example, a vehicle laser radar. That is, as shown in FIG. 5, the laser radar LR is provided behind the front window 1a of the vehicle 1 or behind the front grille 1b. As shown in FIG. 6, the laser radar LR is mainly composed of a light projecting system LPS, a reflecting mirror 10, and a light receiving system RPS.
  • the light projecting system LPS includes a pulsed semiconductor laser LD that emits a laser beam, and a collimator lens CL that converts divergent light from the semiconductor laser LD into parallel light.
  • the laser light collimated by the collimator lens CL is reflected by the reflecting surfaces 12 and 14 of the reflecting mirror 10 and scanned and projected toward the object OBJ side (see FIG. 5). Can do.
  • the light receiving system RPS includes a lens LS that collects reflected light reflected by the object OBJ and reflected by the reflecting surfaces 14 and 12 of the reflecting mirror 10, and a photodiode PD that receives the light collected by the lens LS. And has.
  • the reflecting mirror 10 is held so as to be rotatable around a rotation axis RO that is an axis.
  • the divergent light intermittently emitted from the semiconductor laser LD in a pulsed manner is converted into a parallel light beam by the collimating lens CL, enters the point P1 of the reflecting surface 12 of the rotating reflecting mirror 10, is reflected here, and is reflected by the reflecting surface. 14 is further reflected at a point P2 on the reflecting surface 14 and is projected to the object OBJ side. Thereafter, the laser beam reflected by the object OBJ out of the projected light beam is incident again on the point P3 of the reflecting surface 14 of the reflecting mirror 10, is reflected here, travels along the rotation axis RO, and further The light is reflected at the point P4 on the reflection surface 12, collected by the lens LS, and detected by the light receiving surface of the photodiode PD.
  • the object OBJ can be detected by the distance measuring operation described above.
  • sample A reflective film was formed on the base material as follows using GENER-1300 manufactured by OPTRAN as a vapor deposition apparatus.
  • a polycarbonate (PC) H-3000R manufactured by Mitsubishi Engineering Plastics Co., Ltd. which was molded to a diameter of 30 mm and a thickness of 3 mm was used. Since the film formation surface (reflecting surface) of the actual product is located at a deposition incident angle of 45 degrees, the substrate is tilted by 45 degrees with respect to the surface orthogonal to the deposition source or the support surface of the deposition holder. Installed in.
  • Comparative Examples 1 to 3 and Examples 1 to 8 the reflective film was composed only of the reflective layer.
  • the reflective film was composed of an adhesion layer, a reflective layer, and an increased reflective layer. The structure of each layer is shown in Table 2 and Table 3.
  • Examples 1 and 2 KOBELCO KGB10 (Ag-0.01Bi) was loaded into a resistance heating boat made of molybdenum. Otherwise, in the same manner as in Comparative Example 1, an Ag—Bi layer (reflective layer) having a layer thickness of 80 nm and a Bi composition ratio of 0.01 atomic% was formed.
  • Kobelco KGB800 (Ag-0.8Bi) was loaded into a resistance heating boat made of molybdenum. Otherwise, in the same manner as in Comparative Example 1, an Ag—Bi layer (reflective layer) having a layer thickness of 80 nm and a Bi composition ratio of 0.8 atomic% was formed.
  • Example 3 no preheating was performed. Otherwise, in the same manner as in Example 3, an Ag—Bi layer (reflective layer) having a layer thickness of 80 nm and a Bi composition ratio of 0.02 atomic% was formed. In Example 4, no preheating was performed. Otherwise, in the same manner as in Example 4, an Ag—Bi layer (reflective layer) having a layer thickness of 80 nm and a Bi composition ratio of 0.5 atomic% was formed.
  • Example 3 the heating time (holding time) of preheating was doubled. Otherwise, in the same manner as in Example 3, an Ag—Bi layer (reflective layer) having a layer thickness of 80 nm and a Bi composition ratio of 0.02 atomic% was formed. In Example 4, the heating time (holding time) of preheating was doubled. Otherwise, in the same manner as in Example 4, an Ag—Bi layer (reflective layer) having a layer thickness of 80 nm and a Bi composition ratio of 0.5 atomic% was formed.
  • Example 10 Merck Al 2 O 3 was loaded into a copper crucible. After pressure in the vacuum tank was reduced to 1 ⁇ 10 -4 Pa, and heated with an electron gun and deposited in suitably adjusted to formation rate 5.0 nm / sec energization heating conditions of the electron gun, the thickness 60 nm Al 2 O Three layers (the first layer of the adhesion layer) were formed. During the vapor deposition, O 2 was introduced until 1.5 ⁇ 10 ⁇ 2 Pa was reached.
  • Mercury LaTiO 3 (Substance H4) was loaded into a copper crucible.
  • the vacuum chamber was depressurized to 1 ⁇ 10 ⁇ 4 Pa, and then heated with an electron gun, and the current and heating conditions of the electron gun were appropriately adjusted and deposited at a formation rate of 4.0 nm / second to form a LaTiO 3 layer having a layer thickness of 60 nm. (Second layer of the adhesion layer) was formed. In the formation of the adhesion layer, IAD (Ion Assisted Deposition) was used. The IAD conditions were as shown in Table 1.
  • Voltage [V] means the beam voltage of the ion gun
  • Current [A] means the beam current of the ion gun
  • ACC [V] means acceleration voltage
  • E / B [%] means the power ratio between Emission and Beam.
  • Emission is the power of the neutralizer that neutralizes ions
  • Beam is the power of ion assist.
  • Gas1, O2 [SCCM]”, “Gas2, Ar [SCCM]” and “Gas3, Ar [SCCM]” indicate the supply flow rates of oxygen and argon.
  • Gas2, Ar [SCCM] indicates the supply amount of the argon gas component to the ion gun
  • Gas3, Ar [SCCM] indicates the supply amount of the argon gas to the neutralizing gun.
  • Kobelco KGB250 (Ag-0.25Bi) was loaded into a molybdenum resistance heating boat. After depressurizing the vacuum chamber to 1 ⁇ 10 ⁇ 4 Pa, energize and heat the molybdenum resistance heating boat (preliminary heating). Thus, an Ag—Bi layer (reflective layer) having a layer thickness of 80 nm and a Bi composition ratio of 0.25 atomic% was formed. As preheating (conditions), the temperature was raised to 200 A in 10 seconds and held for 10 seconds, raised to 270 A in 10 seconds, held for 5 seconds, raised to 290 A in 5 seconds, and held for 85 seconds.
  • an Al 2 O 3 layer having a thickness of 25 nm (first layer of the reflective layer) was formed (here, IAD was not used).
  • a LaTiO 3 layer having a layer thickness of 75 nm (second layer of the increased reflection layer) was formed.
  • Merck SiO 2 was loaded into a copper crucible.
  • the vacuum chamber was depressurized to 1 ⁇ 10 ⁇ 4 Pa, and then heated with an electron gun, and the current-carrying heating conditions of the electron gun were appropriately adjusted and deposited at a formation rate of 8.0 nm / second, and a SiO 2 layer having a layer thickness of 15 nm (The third layer of the increased reflection layer) was formed.
  • a LaTiO 3 layer (fourth layer of the increased reflection layer) having a layer thickness of 75 nm was formed.
  • a SiO 2 layer having a thickness of 30 nm was formed in the same manner as the third layer of the increased reflection layer.
  • Example 11 ZnS was loaded into a molybdenum resistance heating boat. After depressurizing the vacuum chamber to 1 ⁇ 10 ⁇ 4 Pa, the resistance heating boat was energized and heated, the current heating conditions of the resistance heating boat were appropriately adjusted, and vapor deposition was performed at a formation rate of 4.0 nm / sec. A layer (adhesion layer) was formed.
  • Kobelco KGB250 (Ag-0.25Bi) was loaded into a molybdenum resistance heating boat. After depressurizing the vacuum chamber to 1 ⁇ 10 ⁇ 4 Pa, energize and heat the molybdenum resistance heating boat (preliminary heating), and then perform main heating at a temperature higher than the preheating while appropriately adjusting the energization heating conditions of the resistance heating boat. Thus, an Ag—Bi layer (reflective layer) having a layer thickness of 80 nm and a Bi composition ratio of 0.25 atomic% was formed. As preheating (conditions), the temperature was raised to 200 A in 10 seconds and held for 10 seconds, raised to 270 A in 10 seconds, held for 5 seconds, raised to 290 A in 5 seconds, and held for 85 seconds.
  • a ZnS layer having a thickness of 40 nm (second layer of the enhanced reflection layer) was formed in the same manner as the adhesion layer.
  • Example 12 TiO 2 was loaded into a copper crucible.
  • the vacuum chamber was depressurized to 1 ⁇ 10 ⁇ 4 Pa, and then heated with an electron gun, and the current was heated by an electron gun with appropriate adjustment and deposition was performed at a formation rate of 5.0 nm / second.
  • a TiO 2 layer having a layer thickness of 20 nm (First layer of the adhesion layer) was formed.
  • O 2 was introduced until 1.5 ⁇ 10 ⁇ 2 Pa was reached.
  • the IAD conditions were as shown in Table 1.
  • ZnS was loaded into a molybdenum resistance heating boat.
  • the resistance heating boat was energized and heated, the current heating conditions of the resistance heating boat were appropriately adjusted, and vapor deposition was performed at a formation rate of 4.0 nm / sec. A layer (second layer of the adhesion layer) was formed.
  • a ZnS layer having a thickness of 40 nm (the first layer of the increased reflection layer) was formed in the same manner as the second layer of the adhesion layer.
  • a 20 nm thick TiO 2 layer ( second layer of the increased reflection layer) was formed.
  • a SiO 2 layer having a layer thickness of 78 nm, a LaTiO 3 layer having a layer thickness of 110 nm, and a SiO 2 layer having a layer thickness of 20 nm were formed in the same manner as in the third to fifth layers of the increased reflection layer of Example 10. .
  • the Cu film When a Cu film or the like is formed as an adhesion layer as in Production Examples 1 and 2 of Patent Document 3, the Cu film may be oxidized in a high-temperature and high-humidity environment, and film peeling may occur.
  • Example 10 it can be seen that when an oxide layer is formed as the adhesion layer, the adhesion is excellent. It can be seen that it is useful to form an oxide layer as the adhesion layer in order to improve the adhesion between the substrate and the reflective layer.
  • the present invention can be particularly suitably used for providing a method for manufacturing a reflective film capable of improving both reflectance and gas corrosion resistance.

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Abstract

L'invention concerne un procédé de fabrication d'un film réfléchissant permettant d'améliorer à la fois la réflectance et la résistance à la corrosion par les gaz. Le procédé de fabrication d'un film réfléchissant ayant au moins une couche réfléchissante comprend une étape (S3) pour former la couche réfléchissante par dépôt en phase vapeur avec AgBi comme matière première, le rapport de composition Bi dans le matériau de départ allant de 0,01 à 0,8 % atomique dans l'étape (S3) de formation de couche réfléchissante.
PCT/JP2016/088675 2016-01-06 2016-12-26 Procédé de fabrication d'un film réfléchissant Ceased WO2017119335A1 (fr)

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JP2016000772A JP2019035100A (ja) 2016-01-06 2016-01-06 反射膜の製造方法

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CN109388008A (zh) * 2017-08-03 2019-02-26 精工爱普生株式会社 波长转换元件及其制造方法、光源装置及投影仪

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JP7805717B2 (ja) 2021-05-25 2026-01-26 キヤノン株式会社 光学素子

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