WO2021014904A1 - Lid material for light-emitting device, method for manufacturing lid material, and light-emitting device - Google Patents

Lid material for light-emitting device, method for manufacturing lid material, and light-emitting device Download PDF

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Publication number
WO2021014904A1
WO2021014904A1 PCT/JP2020/025716 JP2020025716W WO2021014904A1 WO 2021014904 A1 WO2021014904 A1 WO 2021014904A1 JP 2020025716 W JP2020025716 W JP 2020025716W WO 2021014904 A1 WO2021014904 A1 WO 2021014904A1
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WIPO (PCT)
Prior art keywords
film
layer
lid
lid material
emitting device
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PCT/JP2020/025716
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French (fr)
Japanese (ja)
Inventor
村上　達也
利治 辻原
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株式会社大真空
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Application filed by 株式会社大真空 filed Critical 株式会社大真空
Priority to JP2021533894A priority Critical patent/JP7173347B2/en
Priority to CN202080023443.6A priority patent/CN113646908A/en
Publication of WO2021014904A1 publication Critical patent/WO2021014904A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/483—Containers
    • H01L33/486—Containers adapted for surface mounting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/06—Containers; Seals characterised by the material of the container or its electrical properties
    • H01L23/08—Containers; Seals characterised by the material of the container or its electrical properties the material being an electrical insulator, e.g. glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages

Definitions

  • the present invention relates to a lid material used in a light emitting device equipped with an LED (Light Emitting Diode), a method for manufacturing the lid material, and a light emitting device.
  • LED Light Emitting Diode
  • a structure in which the LED is sealed inside a package to improve reliability is generally known.
  • the LED is housed in the cavity of the package base (for example, a ceramic package) and the cavity opening of the package base is sealed by a lid.
  • the lid needs to be transparent to the LED irradiation light.
  • the LED is a deep ultraviolet LED that irradiates deep ultraviolet rays
  • quartz glass is preferably used for the lid (for example, Patent Document 1).
  • the number of man-hours may increase in the element manufacturing process in the light emitting device.
  • using a crystal for the lid has the advantage of reducing man-hours.
  • Au-Sn alloy is used as a brazing material to seal the ceramic package with a quartz lid.
  • Quartz has low adhesion to Au—Sn alloy, so a base film is required to improve the adhesion. It should be noted that such a base film is also necessary when quartz glass is used for the lid. For this reason, when sealing a ceramic package with a lid, a lid material (lid and base film) in which a base film is formed in advance on the joint surface of the lid with the package is generally used. Further, in such a lid material, a brazing material is preliminarily fused to the base film.
  • a lid material using a quartz lid causes problems such as lid peeling and poor airtightness depending on the formation conditions of the underlying film. That is, when the base film was formed under the same conditions as when quartz glass was used for the lid, the adhesion was extremely low, and it was necessary to change the conditions significantly.
  • quartz glass even when quartz glass is used for the lid, it goes without saying that the reliability of the light emitting device will be improved if the adhesion with the Au—Sn alloy can be further improved.
  • a Cr (chromium) film as a base film for obtaining adhesion with an Au—Sn alloy, but in this case, Au—to the base film Diffusion of the Sn alloy is likely to occur, and there is ample room for improvement from the viewpoint of film peeling and adhesion.
  • the present invention has been made in view of the above problems, and is a lid material having a suitable base film that does not cause lid peeling or airtightness in a light emitting device in which an LED is arranged inside a package and sealed with a lid material. , A method of manufacturing a lid material and a light emitting device.
  • the lid material according to the first aspect of the present invention is a lid material used for a light emitting device in which an LED is sealed in a package, and the lid material is used for the irradiation light of the LED.
  • the first metallized film includes a transparent lid body and a first metallized film formed on the sealing surface of the lid body, and the first metallized film includes a first layer directly formed on the lid body.
  • the first layer includes a second layer formed on the first layer, the first layer is a layer containing a Ti film having a thickness of 20 to 700 nm, and the second layer is Ni, Ti, Au. It is characterized by having an alloy film containing Sn and Sn.
  • a lid material having a suitable base film that does not cause lid peeling or poor airtightness can be obtained.
  • the Ti film contained in the first layer can be configured to be a Ti film having a film thickness of 200 to 300 nm.
  • the first layer can be configured to have an oxide film made of titanium oxide on the surface.
  • the first layer has a structure in which an Au film and another Ti film are laminated in order from the side closer to the Ti film on the Ti film. be able to.
  • the second layer has a Ni alloy film on the inner peripheral edge side and the outer peripheral edge side thereof, and the alloy film containing Ni, Ti, Au and Sn is formed between these Ni alloy films. It can be a formed configuration.
  • the lid material can be configured such that the lid body is quartz.
  • the lid material manufacturing method is a lid material manufacturing method used for a light emitting device in which an LED is sealed in a package.
  • a step of forming a base film on the sealing surface of the lid body having transparency to the irradiation light of the LED a first layer containing a Ti film having a thickness of 20 to 700 nm is formed on the sealing surface of the lid body.
  • the Ti film formed in the first step can be configured to have a film thickness of 200 to 300 nm.
  • a buffer film composed of an Au film and another Ti film which are laminated in order from the side closer to the Ti film is formed on the Ti film. can do.
  • the undercoat has a pull-down structure in an upper layer portion including the arbitrary film in any film other than the lowermost film, and in the pull-down structure, the pull-down structure is obtained.
  • a structure in which the inner peripheral edge of the film included in the structure is pulled outward from the inner peripheral edge of the other film, and the outer peripheral edge of the film included in the lowered structure is pulled inward from the outer peripheral edge of the other film. Can be.
  • the method for manufacturing the lid material can be configured such that the lid body is made of quartz.
  • the light emitting device is a light emitting device in which an LED is sealed in a package, and the LED and the LED are placed in a cavity. It has a package base for storing and a lid material for sealing the cavity opening of the package base, and the lid material is characterized by being the lid material described above.
  • the package base can be configured to be made of aluminum nitride.
  • the LED can be configured to be a deep ultraviolet LED.
  • the present invention has an effect that in a light emitting device in which an LED is arranged inside a package and sealed with a lid material, a lid material having a suitable base film that does not cause lid peeling or poor airtightness can be obtained.
  • FIG. 1 It is sectional drawing which shows an example of the basic structure of the light emitting device to which this invention is applied. It is sectional drawing which shows typically the manufacturing method of the light emitting device of FIG. It is a bottom view of the lid material. It is a partial cross-sectional view which shows the structure of the base film formed in the film formation process of the lid material of Embodiment 1. FIG. It is sectional drawing which shows the fusion process of the lid material of Embodiment 1. FIG. It is an SEM photograph which photographed the cross section of a part of the bonding layer in the light emitting device after sealing. It is sectional drawing which shows the fusion process of the lid material of Embodiment 2.
  • the light emitting device 10 is roughly composed of a ceramic package 11, a crystal lid (lid body) 12, and an LED chip 13. That is, the light emitting device 10 has a structure in which the LED chip 13 is housed in the cavity 111 of the ceramic package 11 and the opening of the cavity 111 is sealed by the crystal lid 12.
  • the ceramic package 11 is a package base having a substantially rectangular parallelepiped shape, has an opening of a cavity 111 on the upper surface, and a sealing surface 11A with the crystal lid 12 is formed around the opening. Further, a mounting pad 112 for mounting the LED chip 13 is formed on the bottom surface of the cavity 111, and an external connection terminal 113 is formed on the lower surface of the ceramic package 11. The mounting pad 112 and the external connection terminal 113 are electrically connected to each other through a through hole (not shown).
  • the ceramic package 11 is preferably formed of a material having high thermal conductivity so that the heat generated from the LED chip 13 can be dissipated, and aluminum nitride can be preferably used. Although the case where the package base of the light emitting device 10 is a ceramic base is illustrated here, the package base may be a crystal base.
  • the crystal lid 12 is a rectangular crystal plate having a size substantially the same as that of the ceramic package 11 in a plan view.
  • the crystal lid 12 is bonded to the sealing surface 11A of the ceramic package 11 via a bonding layer 14.
  • the LED chip 13 is mounted on the ceramic package 11 by FCB (Flip Chip Bonding).
  • FCB Flip Chip Bonding
  • the present invention is not limited to this, and the LED chip 13 may be mounted on the ceramic package 11 by wire bonding.
  • the LED chip 13 is preferably a deep ultraviolet LED that irradiates deep ultraviolet rays.
  • Deep ultraviolet rays refer to ultraviolet rays with a relatively short wavelength, and are mainly used for sterilization and disinfection. Since the crystal lid 12 has transparency to deep ultraviolet rays, it can be used when the LED chip 13 is a deep ultraviolet LED.
  • the LED chip 13 is not limited to the deep ultraviolet LED as long as it irradiates light in the transmission wavelength range of the crystal.
  • quartz glass which has been conventionally used, but when quartz glass is used as a lid of the light emitting device 10, the number of test steps in the airtightness test may increase. ..
  • the use of the crystal lid 12 in the light emitting device 10 has an advantage that the number of test steps is reduced when the airtightness test is performed, and the airtightness test can be performed more easily.
  • FIG. 2 is a cross-sectional view schematically showing a manufacturing method of the light emitting device 10.
  • the light emitting device 10 is manufactured by joining the lid material 20 and the packaging material 30 via the joining material 40.
  • the lid material 20 has a first metallized film 41 formed on the lower surface (joining surface) of the crystal lid 12.
  • the first metallized film 41 is formed in an annular shape on the lower surface of the crystal lid 12 along the outer shape of the crystal lid 12.
  • the first metallized film 41 is formed by fusing a brazing material 41B (see FIG. 5) to a base film 41A (see FIGS. 4 and 5) for enhancing the adhesion between the crystal lid 12 and the bonding layer 14. Is.
  • the specific configuration of the first metallized film 41 will be described later.
  • the package material 30 is formed by forming a second metallized film 42 on the sealing surface 11A of the ceramic package 11 on which the LED chip 13 is mounted.
  • the second metallized film 42 is formed in an annular shape along the shape of the sealing surface 11A so as to overlap the first metallized film 41 when the lid material 20 and the packaging material 30 face each other.
  • the second metallized film 42 is a base film for enhancing the adhesion between the ceramic package 11 and the bonding layer 14.
  • the package base is a ceramic base
  • the second metallized film 42 preferably has a Ni alloy / Au film (or Ni / Au film) or the like formed on top of a metallized material such as tungsten or molybdenum.
  • the thickness of the second metallized film 42 is preferably in the range of 150 to 700 nm.
  • the second metallized film 42 may be a Ti alloy / Au film (or Ti / Au film).
  • the light emitting device 10 is manufactured by arranging the lid material 20 and the package material 30 in an overlapping manner and heating the lid material 20 and the package material 30 while applying a load to join them. I do. That is, the first metallized film 4 and the second metallized film 42 are melted by heating, and then cooled while applying a load. The melted first metallized film 41 and the second metallized film 42 are solidified by cooling to form the bonding layer 14 shown in FIG.
  • the lid material 20 has a first metallized film 41 formed on the lower surface of the crystal lid 12, and the first metallized film 41 is formed by fusing the brazing material 41B to the base film 41A. There is.
  • the first metallized film 41 is formed through a film forming step of the base film 41A and a fusion step of the brazing material 41B.
  • the base film 41A of the first metallized film 41 is configured to include the first metal layer 411 and the second metal layer 412.
  • the first metal layer 411 formed directly on the crystal lid 12 has a single layer structure made of a Ti (titanium) film.
  • the second metal layer 412 is formed on the first metal layer 411, and is laminated including the Ni—Ti (nickel-titanium) film 4121 and the Au (gold) film 4122 in order from the side closer to the first metal layer 411. It has a structure.
  • the Ni—Ti film 4121 in the second metal layer 412 preferably has a film thickness in the range of 50 to 1000 nm. Further, the Ni—Ti film 4121 can be replaced with another Ni alloy film.
  • a Ti film to be the first metal layer 411 is formed on one side of the crystal lid 12 (the surface facing the package material 30) by physical vapor deposition. Once the Ti film is formed, it is once taken out of the film forming apparatus and the surface of the Ti film is exposed to air. As a result, an oxide film made of titanium oxide is formed on the surface of the Ti film. Then, a Ni—Ti film 4121 is formed on the Ti film, which is the first metal layer 411, by physical vapor deposition, and an Au film 4122 is formed on the Ni—Ti film 4121 by physical vapor deposition. .. That is, the second metal layer 412 has a laminated structure of Ni—Ti film 4121 and Au film 4122.
  • the method of oxidizing the Ti film to form an oxide film on the surface thereof is not limited to the above-mentioned method of exposing the surface of the Ti film to air.
  • a method of introducing oxygen when forming a Ti film by sputtering to form a film as a Ti oxide film, or a method of promoting oxidation of the surface of the formed Ti film by oxygen plasma is also possible.
  • the brazing material 41B is subsequently fused onto the base film 41A by a fusion process.
  • the brazing material 41B is placed on the base film 41A and heat-treated (baking in a heating furnace). By this heat treatment, the base film 41A and the brazing material 41B are integrated to form the first metallized film 41.
  • the brazing material 41B before fusion is formed by preforming gold tin (Au-Sn) used as a brazing material into an annular shape having substantially the same shape as the base film 41A.
  • the thickness of the preformed brazing material 41B is preferably in the range of 10 to 20 ⁇ m.
  • the laminated structure of the second metal layer 412 (laminated structure of Ni—Ti film 4121 and Au film 4122) in the base film 41A before heating is lost. Specifically, by heating in the fusion step, the second metal layer 412 and the brazing material 41B are melted and alloyed (a eutectic bond is formed) to form an alloy layer 43 (see FIG. 6).
  • the first metal layer 411 is maintained in a layered state even after the fusion step and does not form a eutectic bond.
  • FIG. 6 is an SEM photograph of a part of the cross section of the bonding layer 14 taken in the light emitting device 10 after sealing.
  • the bonding layer 14 has a first metal layer 411, an alloy layer 43, a Ni—Sn alloy layer 422, and a Ni plating layer 421 in this order from the side closer to the crystal lid 12. Since the oxide film on the surface of the first metal layer 411, which is a Ti film, is extremely thin, it cannot be visually recognized as a clear layer in the SEM photograph of FIG. However, the reason why the first metal layer 411, which is a Ti film, is maintained as a layer without forming a eutectic bond is because the oxide film on the surface of the Ti film exists as a barrier film.
  • the alloy layer 43 is a layer in which the second metal layer 412 and the brazing material 41B in the base film 41A before heating form a eutectic bond by melting.
  • the alloy layer 43 in addition to the "Au-Sn ⁇ 'phase” and the “Au-Sn ⁇ phase” in gold tin (Au-Sn) which is the brazing material 41B, the second metal layer 412 and the brazing material 41B are formed.
  • “Ni-Sn alloy” and “Ti-Sn alloy” formed by mixing are included. That is, the alloy layer 43 is an alloy layer containing Ni, Ti, Au and Sn.
  • the Ni plating layer 421 is a layer contained in the second metallized film 42 of the packaging material 30.
  • the Ni—Sn alloy layer 422 is a layer formed by alloying the joint portion between the first metallized film 41 and the second metallized film 42. That is, the Ni—Sn alloy layer 422 is an alloy layer containing Ni, Ti, Au, and Sn, similarly to the alloy layer 43. More specifically, in the Ni—Sn alloy layer 422 formed by welding the lid material 20 to the package material 30, the Ni plating layer on the package material 30 side and the Sn of the Au—Sn alloy on the lid material 20 side are bonded to each other to form Ni. -Sn layer is formed. Therefore, the Au—Sn alloy is in a non-eutectic state. After welding the lid material 20 and the packaging material 30, such a non-eutectic state of the Au—Sn alloy is preferable.
  • the package material 30 of the light emitting device 10 is a crystal base and the first metallized film 41 is a Ti / Au film
  • a Ti—Sn layer is formed instead of the Ni—Sn alloy layer 422. That is, the Ti plating layer on the package material 30 side and the Sn of the Au—Sn alloy on the lid material 20 side are bonded to form a Ti—Sn layer.
  • the SEM photograph of FIG. 6 is a photograph of a cross section of the bonding layer 14 in the light emitting device 10 after sealing, but the first metallized film 41 in the lid material 20 before bonding is a first metal layer (first metal layer). It already contains the 1st layer) 411 and the alloy layer (2nd layer) 43.
  • the film thickness of the first metallized film 41 needs to be controlled in order to obtain suitable adhesion of the crystal lid 12 in the light emitting device 10.
  • the film thickness of the first metal layer 411 was changed as a parameter
  • the light emitting device 10 was manufactured by the above-mentioned manufacturing method, and the appearance evaluation and the airtightness evaluation by the airtightness test (helium leak test) were performed.
  • the appearance evaluation the discoloration of the metallized film seen from the crystal lid 12 side and the presence or absence of cracks in the crystal lid 12 were visually confirmed.
  • the Ni—Ti film 4121 and Au film 4122 of the second metal layer 412 were fixed at 300 nm and 50 nm, respectively.
  • the thickness of the Au-Sn preform which is the brazing material 41B, was fixed at 15 ⁇ m, and the second metallized film 42 was a Ni alloy / Au film, and the total film thickness was fixed at 5 ⁇ m.
  • the experimental results are shown in Table 1 below.
  • discoloration a relatively wide range of discoloration occurred under conditions 1 and 2 (film thickness 7 nm, 10 nm), and the evaluation was "x". Further, under conditions 3 to 6, 10 to 15 (film thickness 20 nm, 50 nm, 100 nm, 150 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm), slight discoloration occurred, and the evaluation was “ ⁇ ”. ing. Then, under conditions 7 to 9 (film thickness 200 nm, 250 nm, 300 nm), almost no discoloration occurred, and the evaluation was “ ⁇ ”.
  • This discoloration indicates that peeling has occurred between the crystal lid 12 and the metallized film which is the bonding layer 14. That is, when the thickness of the first metal layer 411 is not sufficient, Au and Sn are diffused from the bonding material 40 to the contact surface with the crystal lid 12 in the Ti film which is the first metal layer 411, and the first metal layer 411. It is probable that peeling (that is, discoloration) occurred by reducing the adhesion between the metal and the crystal lid 12. This is clear from the fact that a wide range of discoloration occurs under conditions 1 and 2 in which the film thickness of the first metal layer 411 is thin.
  • condition 1 where the film thickness of the first metal layer 411 is the thinnest, it is "x" in the airtightness evaluation (airtightness is poor).
  • condition 2 poor airtightness is not detected at the stage of airtightness evaluation, and the evaluation is “ ⁇ ”, but it is unlikely that airtightness can be maintained for a long period of time because the discoloration range is wide. Therefore, in conditions 1 and 2, the overall evaluation is set to "x".
  • Conditions 3 to 6 give an evaluation of " ⁇ " for discoloration
  • conditions 7 to 9 give an evaluation of " ⁇ " for discoloration.
  • the airtightness evaluation is also evaluated as “ ⁇ ", so that the conditions 3 to 6 are “ ⁇ ” and the conditions 7 to 9 are " ⁇ ".
  • the coefficient of thermal expansion is also different.
  • the first metal layer 411 has a thick film thickness and high adhesion
  • warpage occurs due to the difference in thermal expansion between the ceramic package 11 and the crystal lid 12, and the warp causes peeling.
  • the conditions 7 to 9 have lower adhesion than the conditions 10 to 15, even if a thermal expansion difference occurs between the ceramic package 11 and the crystal lid 12, the first metal layer 411 and the crystal lid 12 It is considered that the gap between the two was able to absorb the difference in thermal expansion, and the action of suppressing the peeling due to the warp worked.
  • cracks in the crystal lid 12 also occur, and it is considered that the cracks in the crystal were caused by warpage due to the difference in thermal expansion.
  • the difference in the coefficient of thermal expansion between the crystal and aluminum nitride is larger than the difference in the coefficient of thermal expansion between quartz glass and aluminum nitride. Therefore, when the crystal lid 12 is used, warpage due to a difference in thermal expansion is likely to occur as compared with the conventional configuration using a quartz glass lid, and it is necessary to consider such warpage.
  • the conditions 10 to 13 are “ ⁇ ” and the conditions 14 and 15 are “x”. This is because the airtightness was broken by the crack of the crystal lid 12 under the conditions 14 and 15. Therefore, the conditions 10 to 13 have a comprehensive evaluation of " ⁇ ", and the conditions 14 and 15 have a comprehensive evaluation of "x".
  • the film thickness of the first metal layer 411 is preferably in the range of 20 to 700 nm, and more preferably in the range of 200 to 300 nm.
  • the lid material 20 has a first metallized film 41 as a base film, and the first metallized film 41 has a high degree of adhesion to the crystal, and when the crystal lid 12 is used, the lid can be peeled off. It was explained that it is a suitable base film that does not cause poor airtightness. However, since the first metallized film 41 in the first embodiment has a high degree of adhesion, the light emitting device 10 may have a problem of lid cracking. In particular, when the sealing load is large (for example, 100 gf or more), lid cracking tends to occur easily in a thermal shock test or the like. In the second embodiment, a lid material that can prevent the lid from cracking even when the sealing load is large or in the thermal shock test will be described.
  • the first metallized film 41 in the lid material 20 is formed by fusing the brazing material 41B to the base film 41A.
  • the lid material 21 according to the second embodiment has a configuration in which the first metallized film 51 is provided instead of the first metallized film 41 of the lid material 20.
  • the metallized film 51 is formed by fusing the brazing material 41B to the base film 51A.
  • FIG. 8 is a partial cross-sectional view showing the configuration of the base film 51A in the lid material 21 according to the second embodiment.
  • the base film 51A includes a first metal layer (first layer) 511 and a second metal layer (second layer) 412. That is, the base film 51A in the lid material 21 has a configuration in which the first metal layer 411 is changed to the first metal layer 511 in the base film 41A of the lid material 20 according to the first embodiment.
  • the first metal layer 411 of the first embodiment has a single layer structure composed of only a Ti film, but the first metal layer 511 has a laminated structure composed of a Ti film 5111, an Au film 5112, and a Ti film 5113. doing.
  • the Ti film 5111 corresponds to the Ti film constituting the first metal layer 411 of the first embodiment. That is, the Ti film 5111 preferably has a film thickness of 20 to 700 nm, and more preferably 200 to 300 nm, like the Ti film of the first metal layer 411.
  • the Au film 5112 and Ti film 5113 in the first metal layer 511 are formed as a buffer film for preventing lid cracking when the sealing load is large or in a thermal shock test.
  • the ceramic package 11 and the crystal lid 12 in the light emitting device 10 are made of different materials, so that the coefficient of thermal expansion is also different. Therefore, warpage occurs due to the difference in thermal expansion between the ceramic package 11 and the crystal lid 12, and this warpage may cause crystal cracking.
  • the difference in thermal expansion between the ceramic package 11 and the crystal lid 12 can be absorbed by the deformation of the buffer film (that is, Au film 5112 and Ti film 5113). As a result, it is considered that the warp can be reduced and the crystal cracking can be suppressed.
  • a Ti film 5111, an Au film 5112, and a Ti film 5113 which become the first metal layer 511 by physical vapor deposition are sequentially formed on one side (the surface facing the package material 30) of the crystal lid 12.
  • the first metal layer 511 is formed, it is once taken out from the film forming apparatus, and the surface of the Ti film 5113 on the uppermost layer is exposed to air. As a result, an oxide film made of titanium oxide is formed on the surface of the Ti film 5113.
  • an oxide film made of titanium oxide is formed on the surface of the first metal layer 411, and in the second embodiment, the Ti film 5111 is the Ti film of the first metal layer 411 of the first embodiment. It is supposed to be equivalent to. However, since the oxide film made of titanium oxide serves as a boundary between the first metal layer and the second metal layer, in the lid material 21 according to the second embodiment, the oxide film made of titanium oxide is Ti. It is formed not on the film 5111 but on the surface of the Ti film 5113 on the uppermost layer of the first metal layer 511.
  • the method of forming an oxide film on the surface of the Ti film 5113 is the same as that of the first embodiment, that is, a method of introducing oxygen when forming a Ti film by sputtering, or a method of forming a film as a Ti oxide film. A method of promoting oxidation of the surface of the formed Ti film by oxygen plasma is also possible.
  • the method of forming the second metal layer 412 is the same as the method described in the first embodiment. By forming the first metal layer 511 and the second metal layer 412, the base film 51A is formed on the crystal lid 12.
  • the brazing material 41B is subsequently fused onto the base film 51A by a fusion process.
  • the brazing material 41B is placed on the base film 51A and heat-treated (baking in a heating furnace). By this heat treatment, the base film 51A and the brazing material 41B are integrated to form the first metallized film 51.
  • the film thickness control of the base film is effective in order to obtain the suitable adhesion of the crystal lid 12 in the light emitting device 10 and the effect of preventing crystal cracking.
  • it is effective to control the film thickness of the Au film 5112 in the first metal layer 511 within an appropriate range. The following is a discussion based on experiments.
  • each film thickness of the Ti film 5111, Au film 5112, and Ti film 5113 in the first metal layer 511 is changed as a parameter, and the light emitting device 10 is manufactured by the above-mentioned manufacturing method, and its appearance evaluation and airtightness test ( The airtightness was evaluated by the helium leak test). In the appearance evaluation, the discoloration of the metallized film seen from the crystal lid 12 side and the presence or absence of cracks in the crystal lid 12 were visually confirmed. In each of the manufactured light emitting devices 10, the Ni—Ti film 4121 and Au film 4122 of the second metal layer 412 were fixed at 300 nm and 50 nm, respectively.
  • the thickness of the Au—Sn preform which is the bonding material 40, was fixed at 15 ⁇ m, and the second metallized film 42 used a Ni alloy / Au film, and the total film thickness was fixed at 5 ⁇ m.
  • the experimental results are shown in Table 2 below.
  • the film thickness of the first metal layer in Table 2 the Ti film thickness in the left column indicates the film thickness of the Ti film 5111, and the Ti film thickness in the right column indicates the film thickness of the Ti film 5113.
  • Conditions 16 to 18 in Table 2 do not have Au film 5112 and Ti film 5113 as buffer films, but the larger the film thickness of Ti film 5111, the better the result. Then, the film thickness of the Ti film 5111, which is the preferable range in the first embodiment, is 250 nm (condition 3), and the overall evaluation is also “ ⁇ ”.
  • the overall evaluation is " ⁇ " or higher, and particularly under conditions 21 to 24, the overall evaluation is “ ⁇ ". It has become. Since the discoloration evaluation is “ ⁇ ” under the conditions 21 to 24, it can be seen that the adhesion of the crystal lid 12 in the light emitting device 10 is further improved. This is because in the light emitting device 10, the buffer film (that is, Au film 5112 and Ti film 5113) absorbs the difference in thermal expansion between the ceramic package 11 and the crystal lid 12, so that the warp is reduced, and as a result, the lid is peeled off. Is also considered to have been reduced. Further, this effect is improved by appropriately controlling the film thickness of the Au film 5112, and the film thickness of the Au film 5112 is preferably in the range of 100 to 700 nm, more preferably in the range of 300 to 600 nm. preferable.
  • the Ni—Ti film 4121 and Au film 4122 contained in the second metal layer 412 have the same forming width (metallizing width) of these films (Ni—Ti film 4121).
  • the Au film 4122 is formed on top of it (so that it is completely superimposed).
  • problems such as lid peeling and poor airtightness may occur at the evaluation stage.
  • a lid material capable of more reliably preventing lid peeling and poor airtightness will be described.
  • the lid material 22 according to the third embodiment has a configuration in which the first metallized film 61 is provided in place of the first metallized film 51 of the lid material 21, and the first metallized film 61 is configured. It is formed by fusing the brazing material 41B to the base film 61A.
  • FIG. 10 is a partial cross-sectional view showing the configuration of the base film 61A in the lid material 22 according to the third embodiment.
  • the base film 61A includes a first metal layer (first layer) 511 and a second metal layer (second layer) 612.
  • the lid material 22 according to the third embodiment is characterized by the structure of the second metal layer. Therefore, in the lid material 22 of FIG. 6, the first metal layer has the same structure as the first metal layer 511 of the lid material 21, but the first metal layer has the same structure as the first metal layer 411 of the lid material 20. May be good.
  • the second metal layer 612 has a laminated structure including a Ni—Ti film 6121 formed on the first metal layer 511 and an Au film 6122 formed on the Ni—Ti film 6121.
  • the Ni—Ti film 6121 can be a film similar to the Ni—Ti film 4121 in lid materials 20 and 20A. Further, the Au film 6122 is different from the Au film 4122 in the lid materials 20 and 21 only in the film forming width.
  • the Au film 6122 is formed with a narrower width than the Ni—Ti film 6121. More specifically, in the Au film 6122, the inner peripheral edge of the Au film 6122 is pulled outward from the inner peripheral edge of the Ni—Ti film 6121, and the outer peripheral edge of the Au film 6122 is lower than the outer peripheral edge of the Ni—Ti film 6121. It has a pull-down structure (a structure having a gap between the peripheral edge of the Au film 6122 and the peripheral edge of the Ni—Ti film 6121) that is pulled down inward.
  • the “inside” and “outside” here mean the “inside” and "outside” seen from the center of the lid material 22.
  • the pull-down width of the Au film 6122 inside and outside the base film 61A does not have to be the same, and as shown in FIG. 10, the pull-down width [ ⁇ m] on the inside is d1 and the pull-down width on the outside is d2. ..
  • the base film 61A is originally used. Only the second metal layer 412 melts to form a eutectic bond with the brazing filler metal 41B. However, depending on the manufacturing conditions (for example, if the sealing load at the time of bonding is large), the alloy formed by eutectic bonding (alloy containing Ni, Ti, Au and Sn) wraps around from the side surface of the bonding layer 14. It may reach the first metal layer 411.
  • the Au and Sn components of the alloy that have reached the first metal layer 411 infiltrate the first metal layer 411 to reduce the adhesion between the first metal layer 411 and the crystal lid 12, resulting in lid peeling and poor airtightness. It is considered to be a factor.
  • a similar problem occurs when the lid material 21 and the packaging material 30 are joined to manufacture the light emitting device 10.
  • the eutectic joint is formed only in a region substantially overlapping with the formation region of the Au film 6122.
  • Au is indispensable for the formation of eutectic junctions.
  • the alloy formed by the eutectic bonding wraps around from the side surface of the bonding layer 14 and the first metal layer 511 ( Alternatively, it can be prevented from reaching 411), and as a result, lid peeling and poor airtightness can be prevented.
  • the eutectic bond when the brazing material 41B is fused to the base film 61A is formed substantially corresponding to the formation region of the Au film 6122, and is formed in the peripheral region where the Au film 6122 is pulled down.
  • the alloy layer 43 formed by melting the second metal layer 412 and the brazing material 41B has a Ni alloy film (without eutectic bonding) on the inner peripheral side and the outer peripheral side peripheral portions thereof. It has a Ni—Ti film 6121) remaining on the surface, and an alloy film containing Ni, Ti, Au and Sn (an alloy film formed by eutectic bonding) is formed between these Ni alloy films.
  • the presence of the Ni alloy film that remains without eutectic bonding at the peripheral edge of the alloy layer 43 causes the alloy formed by eutectic bonding to wrap around from the side surface of the bonding layer 14 to form the first metal. It can be prevented from reaching layer 511 (or 411).
  • the film thicknesses of the Ti film 5111, Au film 5112, and Ti film 5113 in the first metal layer 511 were fixed to 250 nm, 500 nm, and 50 nm, respectively.
  • the film thicknesses of the Ni—Ti film 6121 and the Au film 6122 in the second metal layer 612 were fixed at 300 n and 50 nm, respectively.
  • the pull-down width of the Au film 6122 was changed as a parameter, the light emitting device 10 was manufactured by the above-mentioned manufacturing method, and the appearance evaluation and the airtightness evaluation by the airtightness test (helium leak test) were performed.
  • the present invention is not limited to this, and a pull-down structure may be applied to an upper layer portion including the film in any film other than the lowermost film (that is, Ti film 5111) of the base film 61A. ..
  • a pull-down structure may be applied at a portion that is an upper layer from the Au film 5112.
  • the present invention is not limited to this, and quartz glass may be used for the lid body. That is, in the conventional lid material using quartz glass, a Cr film is used as the base film, but when quartz glass is used as the lid body, if the above-mentioned base film 41A, 51A or 61A is used as the base film, It was confirmed that better performance can be obtained in terms of film peeling and adhesion. It is considered that this is because the diffusion of the brazing materials Au and Sn was suppressed by changing the base film from the Cr film to the base film 41A, 51A or 61A.
  • the bonding layer 14 for joining the ceramic package 11 and the crystal lid 12 is substantially entirely on the frame-shaped bonding surface of the ceramic package 11 and the crystal lid 12 (in the width direction of the frame). It is formed (without bias).
  • the present invention is not limited to this, and as shown in FIG. 13, the bonding layer 14 is formed closer to the inner peripheral side with respect to the frame-shaped bonding surface of the ceramic package 11 and the crystal lid 12. You may. When the bonding layer 14 is formed closer to the inner peripheral side with respect to the bonding surface in this way, the influence of stress due to the difference in thermal expansion between the ceramic package 11 and the crystal lid 12 can be reduced, and lid cracking or the like occurs. It becomes difficult.
  • the ceramic package 11 has a stepped U-shape and the crystal lid 12 has a flat plate shape in order to seal the LED 13 in the package.
  • the present invention is not limited to this, and as in the light emitting device 10'shown in FIG. 14, the flat plate-shaped ceramic base 11'and the stepped U-shaped crystal lid 12' are combined to form the LED13. You may form a package to seal. Even in this case, the bonding layer 14 for joining the ceramic base 11'and the stepped U-shaped crystal lid 12'can have the same configuration as the light emitting device 10 described above.

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Abstract

A light-emitting device (10) houses an LED chip (13) in a cavity (111) of a ceramic package (11) and seals an opening of the cavity (111) with a crystal lid (12). A lid material (20) before being sealed is obtained by using the crystal lid (12) as a lid body and forming a first metallization film (41) on a sealing surface of the crystal lid (12). The first metallization film (41) includes: a first metal layer (411) that is formed directly on the crystal lid (12); and an alloy layer (43) that contains a brazing material (Au-Sn) on the first metal layer (411). The first metal layer (411) has a single-layer structure that is formed from a Ti film having a film thickness of 20-700 nm.

Description

発光装置のリッド材、リッド材の製造方法および発光装置Lud material of light emitting device, manufacturing method of lid material and light emitting device
　本発明は、ＬＥＤ（Light Emitting Diode）を備えた発光装置に使用されるリッド材、リッド材の製造方法および発光装置に関する。 The present invention relates to a lid material used in a light emitting device equipped with an LED (Light Emitting Diode), a method for manufacturing the lid material, and a light emitting device.
　ＬＥＤを用いる発光装置においては、ＬＥＤをパッケージの内部に封止して信頼性を高めた構造が一般的に知られている。具体的な構造例としては、ＬＥＤをパッケージ基台（例えばセラミックパッケージ）のキャビティ内に格納し、パッケージ基台のキャビティ開口をリッドによって封止する構造が挙げられる。 In a light emitting device using an LED, a structure in which the LED is sealed inside a package to improve reliability is generally known. As a specific structural example, there is a structure in which the LED is housed in the cavity of the package base (for example, a ceramic package) and the cavity opening of the package base is sealed by a lid.
　このような構造では、リッドはＬＥＤの照射光に対して透過性を有する必要がある。ＬＥＤが深紫外線を照射する深紫外用ＬＥＤである場合、従来、リッドには石英ガラスの使用が好適とされていた（例えば、特許文献１）。 In such a structure, the lid needs to be transparent to the LED irradiation light. When the LED is a deep ultraviolet LED that irradiates deep ultraviolet rays, it has been conventionally considered that quartz glass is preferably used for the lid (for example, Patent Document 1).
特許第６２９４４１７号公報Japanese Patent No. 6294417
　しかしながら、リッドに石英ガラスを用いた場合、発光装置における素子製造工程で工数が多くなる場合がある。このような場合、リッドに水晶を使用することで工数削減できるメリットがある。 However, when quartz glass is used for the lid, the number of man-hours may increase in the element manufacturing process in the light emitting device. In such a case, using a crystal for the lid has the advantage of reducing man-hours.
　セラミックパッケージを水晶リッドで封止するには、Ａｕ－Ｓｎ合金がろう材として用いられる。水晶はＡｕ－Ｓｎ合金との密着性が低いため、密着性を高めるための下地膜が必要となる。尚、このような下地膜は、リッドに石英ガラスを用いる場合にも必要である。このため、セラミックパッケージをリッドで封止するときには、リッドにおけるパッケージとの接合面に予め下地膜を形成したリッド材（リッドおよび下地膜）が用いられることが一般的である。また、このようなリッド材では、下地膜にろう材を予め融着させておくことも行われている。 Au-Sn alloy is used as a brazing material to seal the ceramic package with a quartz lid. Quartz has low adhesion to Au—Sn alloy, so a base film is required to improve the adhesion. It should be noted that such a base film is also necessary when quartz glass is used for the lid. For this reason, when sealing a ceramic package with a lid, a lid material (lid and base film) in which a base film is formed in advance on the joint surface of the lid with the package is generally used. Further, in such a lid material, a brazing material is preliminarily fused to the base film.
　しかしながら、水晶リッドを用いたリッド材では、下地膜の形成条件によってはリッド剥離や気密不良などの問題が生じることが本願発明者により発見された。すなわち、リッドに石英ガラスを用いる場合と同様の条件で下地膜を形成すると、著しく密着性が低く、大幅な条件変更が必要であった。 However, it has been discovered by the inventor of the present application that a lid material using a quartz lid causes problems such as lid peeling and poor airtightness depending on the formation conditions of the underlying film. That is, when the base film was formed under the same conditions as when quartz glass was used for the lid, the adhesion was extremely low, and it was necessary to change the conditions significantly.
　また、リッドに石英ガラスを用いる場合においても、Ａｕ－Ｓｎ合金との密着性をより高めることができれば、発光装置の信頼性が向上することは言うまでもない。リッドに石英ガラスを用いる従来技術では、Ａｕ－Ｓｎ合金との密着性を得るための下地膜としてＣｒ（クロム）膜を用いることが一般的であったが、この場合は下地膜へのＡｕ－Ｓｎ合金の拡散が生じ易く、膜剥がれや密着性の観点からも改善の余地は十分にあった。 Further, even when quartz glass is used for the lid, it goes without saying that the reliability of the light emitting device will be improved if the adhesion with the Au—Sn alloy can be further improved. In the conventional technique of using quartz glass for the lid, it was common to use a Cr (chromium) film as a base film for obtaining adhesion with an Au—Sn alloy, but in this case, Au—to the base film Diffusion of the Sn alloy is likely to occur, and there is ample room for improvement from the viewpoint of film peeling and adhesion.
　本発明は、上記課題に鑑みてなされたものであり、ＬＥＤをパッケージの内部に配置し、リッド材で封止する発光装置において、リッド剥離や気密不良を生じさせない好適な下地膜を有するリッド材、リッド材の製造方法および発光装置を提供することを目的とする。 The present invention has been made in view of the above problems, and is a lid material having a suitable base film that does not cause lid peeling or airtightness in a light emitting device in which an LED is arranged inside a package and sealed with a lid material. , A method of manufacturing a lid material and a light emitting device.
　上記の課題を解決するために、本発明の第１の態様であるリッド材は、ＬＥＤをパッケージ内に封止してなる発光装置に用いられるリッド材であって、前記ＬＥＤの照射光に対して透過性を有するリッド本体と、前記リッド本体の封止面に形成される第１メタライズ膜とを含み、前記第１メタライズ膜は、前記リッド本体の上に直接形成される第１層と、前記第１層の上に形成される第２層とを含んでおり、前記第１層は、膜厚２０～７００ｎｍのＴｉ膜を含む層であり、前記第２層は、Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含む合金膜を有していることを特徴としている。 In order to solve the above-mentioned problems, the lid material according to the first aspect of the present invention is a lid material used for a light emitting device in which an LED is sealed in a package, and the lid material is used for the irradiation light of the LED. The first metallized film includes a transparent lid body and a first metallized film formed on the sealing surface of the lid body, and the first metallized film includes a first layer directly formed on the lid body. The first layer includes a second layer formed on the first layer, the first layer is a layer containing a Ti film having a thickness of 20 to 700 nm, and the second layer is Ni, Ti, Au. It is characterized by having an alloy film containing Sn and Sn.
　上記の構成によれば、ＬＥＤをパッケージの内部に配置し、リッド材で封止する発光装置において、リッド剥離や気密不良を生じさせない好適な下地膜を有するリッド材を得ることができる。 According to the above configuration, in a light emitting device in which an LED is arranged inside a package and sealed with a lid material, a lid material having a suitable base film that does not cause lid peeling or poor airtightness can be obtained.
　また、上記リッド材では、前記第１層に含まれる前記Ｔｉ膜は、膜厚２００～３００ｎｍのＴｉ膜である構成とすることができる。 Further, in the lid material, the Ti film contained in the first layer can be configured to be a Ti film having a film thickness of 200 to 300 nm.
　また、上記リッド材では、前記第１層は、表面に酸化チタンからなる酸化皮膜を有している構成とすることができる。 Further, in the lid material, the first layer can be configured to have an oxide film made of titanium oxide on the surface.
　また、上記リッド材では、前記第１層は、前記Ｔｉ膜の上に、前記Ｔｉ膜に近い側から順に積層されたＡｕ膜および他のＴｉ膜からなる緩衝膜を有している構成とすることができる。 Further, in the lid material, the first layer has a structure in which an Au film and another Ti film are laminated in order from the side closer to the Ti film on the Ti film. be able to.
　また、上記リッド材では、前記第２層は、その内周縁側および外周縁側においてＮｉ合金膜を有し、これらのＮｉ合金膜の間に、Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含む前記合金膜が形成されている構成とすることができる。 Further, in the lid material, the second layer has a Ni alloy film on the inner peripheral edge side and the outer peripheral edge side thereof, and the alloy film containing Ni, Ti, Au and Sn is formed between these Ni alloy films. It can be a formed configuration.
　また、上記リッド材は、前記リッド本体が水晶である構成とすることができる。 Further, the lid material can be configured such that the lid body is quartz.
　また、上記の課題を解決するために、本発明の第２の態様であるリッド材の製造方法は、ＬＥＤをパッケージ内に封止してなる発光装置に用いられるリッド材の製造方法であって、前記ＬＥＤの照射光に対して透過性を有するリッド本体の封止面に下地膜を形成する工程として、前記リッド本体の封止面に膜厚２０～７００ｎｍのＴｉ膜を含む第１層を形成する第１工程と、前記第１工程で形成された前記第１層の最上層にあるＴｉ膜を酸化させて、表面に酸化チタンからなる酸化皮膜を形成する第２工程と、前記第２工程後の前記第１層の上に、前記第１層に近い側から順に積層されるＮｉ合金膜およびＡｕ膜を含む第２層を形成する第３工程と、前記第３工程で形成された前記Ａｕ膜の上に、Ａｕ－Ｓｎプリフォームとして形成されたろう材を融着させる第４工程とを有することを特徴としている。 Further, in order to solve the above problems, the lid material manufacturing method according to the second aspect of the present invention is a lid material manufacturing method used for a light emitting device in which an LED is sealed in a package. As a step of forming a base film on the sealing surface of the lid body having transparency to the irradiation light of the LED, a first layer containing a Ti film having a thickness of 20 to 700 nm is formed on the sealing surface of the lid body. The first step of forming, the second step of oxidizing the Ti film on the uppermost layer of the first layer formed in the first step to form an oxide film made of titanium oxide on the surface, and the second step. A third step of forming a second layer including a Ni alloy film and an Au film laminated in order from the side closer to the first layer on the first layer after the step, and a third step formed in the third step. It is characterized by having a fourth step of fusing a brazing material formed as an Au-Sn preform on the Au film.
　また、上記リッド材の製造方法では、前記第１工程で形成される前記Ｔｉ膜は、２００～３００ｎｍの膜厚を有する構成とすることができる。 Further, in the method for producing a lid material, the Ti film formed in the first step can be configured to have a film thickness of 200 to 300 nm.
　また、上記リッド材の製造方法は、前記第１工程では、前記Ｔｉ膜の上に、前記Ｔｉ膜に近い側から順に積層されるＡｕ膜および他のＴｉ膜からなる緩衝膜を形成する構成とすることができる。 Further, in the method for producing the lid material, in the first step, a buffer film composed of an Au film and another Ti film which are laminated in order from the side closer to the Ti film is formed on the Ti film. can do.
　また、上記リッド材の製造方法では、前記下地膜は、最下層の膜を除く任意の膜において、前記任意の膜を含む上層部分で引き下がり構造を有しており、前記引き下がり構造では、前記引き下がり構造に含まれる膜の内周縁がその他の膜の内周縁よりも外側に引き下げられ、前記引き下がり構造に含まれる膜の外周縁がその他の膜の外周縁よりも内側に引き下げられて形成される構成とすることができる。 Further, in the method for producing a lid material, the undercoat has a pull-down structure in an upper layer portion including the arbitrary film in any film other than the lowermost film, and in the pull-down structure, the pull-down structure is obtained. A structure in which the inner peripheral edge of the film included in the structure is pulled outward from the inner peripheral edge of the other film, and the outer peripheral edge of the film included in the lowered structure is pulled inward from the outer peripheral edge of the other film. Can be.
　また、上記リッド材の製造方法は、前記リッド本体が水晶である構成とすることができる。 Further, the method for manufacturing the lid material can be configured such that the lid body is made of quartz.
　また、上記の課題を解決するために、本発明の第３の態様である発光装置は、ＬＥＤをパッケージ内に封止してなる発光装置であって、前記ＬＥＤと、前記ＬＥＤをキャビティ内に格納するパッケージ基台と、前記パッケージ基台のキャビティ開口を封止するリッド材とを有しており、前記リッド材は、前記記載のリッド材であることを特徴としている。 Further, in order to solve the above problems, the light emitting device according to the third aspect of the present invention is a light emitting device in which an LED is sealed in a package, and the LED and the LED are placed in a cavity. It has a package base for storing and a lid material for sealing the cavity opening of the package base, and the lid material is characterized by being the lid material described above.
　また、上記発光装置では、前記パッケージ基台は、窒化アルミニウムにより形成されている構成とすることができる。 Further, in the light emitting device, the package base can be configured to be made of aluminum nitride.
　また、上記発光装置では、前記ＬＥＤは、深紫外用ＬＥＤである構成とすることができる。 Further, in the light emitting device, the LED can be configured to be a deep ultraviolet LED.
　本発明は、ＬＥＤをパッケージの内部に配置し、リッド材で封止する発光装置において、リッド剥離や気密不良を生じさせない好適な下地膜を有するリッド材が得られるといった効果を奏する。 The present invention has an effect that in a light emitting device in which an LED is arranged inside a package and sealed with a lid material, a lid material having a suitable base film that does not cause lid peeling or poor airtightness can be obtained.
本発明が適用される発光装置の基本構造の一例を示す断面図である。It is sectional drawing which shows an example of the basic structure of the light emitting device to which this invention is applied. 図１の発光装置の製造方法を概略的に示す断面図である。It is sectional drawing which shows typically the manufacturing method of the light emitting device of FIG. リッド材の下面図である。It is a bottom view of the lid material. 実施の形態１のリッド材の成膜工程において形成される下地膜の構成を示す部分断面図である。It is a partial cross-sectional view which shows the structure of the base film formed in the film formation process of the lid material of Embodiment 1. FIG. 実施の形態１のリッド材の融着工程を示す断面図である。It is sectional drawing which shows the fusion process of the lid material of Embodiment 1. FIG. 封止後の発光装置において、接合層の一部の断面を撮影したＳＥＭ写真である。It is an SEM photograph which photographed the cross section of a part of the bonding layer in the light emitting device after sealing. 実施の形態２のリッド材の融着工程を示す断面図である。It is sectional drawing which shows the fusion process of the lid material of Embodiment 2. 実施の形態２のリッド材の成膜工程において形成される下地膜の構成を示す部分断面図である。It is a partial cross-sectional view which shows the structure of the base film formed in the film formation process of the lid material of Embodiment 2. 実施の形態３のリッド材の融着工程を示す断面図である。It is sectional drawing which shows the fusion process of the lid material of Embodiment 3. FIG. 実施の形態３のリッド材の成膜工程において形成される下地膜の構成を示す部分断面図である。It is a partial cross-sectional view which shows the structure of the base film formed in the film formation process of the lid material of Embodiment 3. 実施の形態３のリッド材の第１メタライズ膜の構成を示す部分断面図である。It is a partial cross-sectional view which shows the structure of the 1st metallized film of the lid material of Embodiment 3. 実施の形態３のリッド材における下地膜の他の構成を示す部分断面図である。It is a partial cross-sectional view which shows the other structure of the base film in the lid material of Embodiment 3. FIG. 本発明が適用される発光装置の基本構造の他の例を示す断面図である。It is sectional drawing which shows the other example of the basic structure of the light emitting device to which this invention is applied. 本発明が適用される発光装置の基本構造のさらに他の例を示す断面図である。It is sectional drawing which shows still another example of the basic structure of the light emitting device to which this invention is applied.
　［実施の形態１］
　以下、本発明の実施の形態について、図面を参照して詳細に説明する。 [Embodiment 1]
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
　〔発光装置の基本構造〕
　先ずは、本発明が適用される発光装置１０の基本構造を、図１を参照して説明する。図１に示すように、発光装置１０は、大略的には、セラミックパッケージ１１、水晶リッド（リッド本体）１２およびＬＥＤチップ１３により構成されている。すなわち、発光装置１０は、セラミックパッケージ１１のキャビティ１１１内にＬＥＤチップ１３を格納し、キャビティ１１１の開口を水晶リッド１２によって封止した構造とされている。 [Basic structure of light emitting device]
First, the basic structure of the light emitting device 10 to which the present invention is applied will be described with reference to FIG. As shown in FIG. 1, the light emitting device 10 is roughly composed of a ceramic package 11, a crystal lid (lid body) 12, and an LED chip 13. That is, the light emitting device 10 has a structure in which the LED chip 13 is housed in the cavity 111 of the ceramic package 11 and the opening of the cavity 111 is sealed by the crystal lid 12.
　セラミックパッケージ１１は、略直方体形状のパッケージ基台であり、上面にキャビティ１１１の開口を有し、この開口の周りが水晶リッド１２との封止面１１Ａとなっている。また、キャビティ１１１の底面にはＬＥＤチップ１３を実装するための実装パッド１１２が形成されており、セラミックパッケージ１１の下面には外部接続端子１１３が形成されている。実装パッド１１２と外部接続端子１１３とは、図示しないスルーホールを介して電気的に接続されている。尚、セラミックパッケージ１１は、ＬＥＤチップ１３から発生する熱を逃がすことができるように、熱伝導性の高い材料で形成されることが好ましく、好適には窒化アルミニウムが使用できる。尚、ここでは、発光装置１０のパッケージ基台をセラミックベースとした場合を例示しているが、パッケージ基台は水晶ベースであってもよい。 The ceramic package 11 is a package base having a substantially rectangular parallelepiped shape, has an opening of a cavity 111 on the upper surface, and a sealing surface 11A with the crystal lid 12 is formed around the opening. Further, a mounting pad 112 for mounting the LED chip 13 is formed on the bottom surface of the cavity 111, and an external connection terminal 113 is formed on the lower surface of the ceramic package 11. The mounting pad 112 and the external connection terminal 113 are electrically connected to each other through a through hole (not shown). The ceramic package 11 is preferably formed of a material having high thermal conductivity so that the heat generated from the LED chip 13 can be dissipated, and aluminum nitride can be preferably used. Although the case where the package base of the light emitting device 10 is a ceramic base is illustrated here, the package base may be a crystal base.
　水晶リッド１２は、平面視でセラミックパッケージ１１とほぼ同サイズの矩形形状の水晶板である。水晶リッド１２は、セラミックパッケージ１１の封止面１１Ａとの間に接合層１４を介して接合される。 The crystal lid 12 is a rectangular crystal plate having a size substantially the same as that of the ceramic package 11 in a plan view. The crystal lid 12 is bonded to the sealing surface 11A of the ceramic package 11 via a bonding layer 14.
　図１に示す発光装置１０では、ＬＥＤチップ１３は、セラミックパッケージ１１に対してＦＣＢ（Flip Chip Bonding）によって実装されている。しかしながら、本発明はこれに限定されるものではなく、ＬＥＤチップ１３は、セラミックパッケージ１１に対してワイヤボンディングによって実装されていてもよい。 In the light emitting device 10 shown in FIG. 1, the LED chip 13 is mounted on the ceramic package 11 by FCB (Flip Chip Bonding). However, the present invention is not limited to this, and the LED chip 13 may be mounted on the ceramic package 11 by wire bonding.
　ＬＥＤチップ１３は、好適には、深紫外線を照射する深紫外用ＬＥＤである。深紫外線は、紫外線の中でも比較的波長が短いものを指し、主に殺菌・消毒などの用途に使用される。水晶リッド１２は、深紫外線に対して透過性を有するため、ＬＥＤチップ１３が深紫外用ＬＥＤである場合に使用可能である。但し、ＬＥＤチップ１３は、水晶の透過波長域の光を照射するものであれば、深紫外用ＬＥＤに限定されるものではない。 The LED chip 13 is preferably a deep ultraviolet LED that irradiates deep ultraviolet rays. Deep ultraviolet rays refer to ultraviolet rays with a relatively short wavelength, and are mainly used for sterilization and disinfection. Since the crystal lid 12 has transparency to deep ultraviolet rays, it can be used when the LED chip 13 is a deep ultraviolet LED. However, the LED chip 13 is not limited to the deep ultraviolet LED as long as it irradiates light in the transmission wavelength range of the crystal.
　また、深紫外線に対して透過性を有する材料としては、従来使用されていた石英ガラスもあるが、石英ガラスを発光装置１０のリッドとして使用すると、気密試験における試験工程数が増加する場合がある。発光装置１０における水晶リッド１２の使用は、気密試験を行う場合に試験工程数が少なくなり、気密試験をより簡単に行えるといった利点がある。 Further, as a material having transparency to deep ultraviolet rays, there is quartz glass which has been conventionally used, but when quartz glass is used as a lid of the light emitting device 10, the number of test steps in the airtightness test may increase. .. The use of the crystal lid 12 in the light emitting device 10 has an advantage that the number of test steps is reduced when the airtightness test is performed, and the airtightness test can be performed more easily.
　〔発光装置の製造方法〕
　続いて、図１に示す発光装置１０の製造方法を示す。図２は、発光装置１０の製造方法を概略的に示す断面図である。 [Manufacturing method of light emitting device]
Subsequently, a method for manufacturing the light emitting device 10 shown in FIG. 1 will be shown. FIG. 2 is a cross-sectional view schematically showing a manufacturing method of the light emitting device 10.
　図２に示すように、発光装置１０は、リッド材２０とパッケージ材３０とを接合材４０を介して接合することで製造される。ここで、リッド材２０は、水晶リッド１２の下面（接合面）に、第１メタライズ膜４１を形成したものである。第１メタライズ膜４１は、図３に示すように、水晶リッド１２の下面において、水晶リッド１２の外形形状に沿った環状に形成されている。第１メタライズ膜４１は、水晶リッド１２と接合層１４との密着性を高めるための下地膜４１Ａ（図４、５参照）にろう材４１Ｂ（図５参照）を融着させて形成されるものである。尚、第１メタライズ膜４１の具体的構成については後述する。 As shown in FIG. 2, the light emitting device 10 is manufactured by joining the lid material 20 and the packaging material 30 via the joining material 40. Here, the lid material 20 has a first metallized film 41 formed on the lower surface (joining surface) of the crystal lid 12. As shown in FIG. 3, the first metallized film 41 is formed in an annular shape on the lower surface of the crystal lid 12 along the outer shape of the crystal lid 12. The first metallized film 41 is formed by fusing a brazing material 41B (see FIG. 5) to a base film 41A (see FIGS. 4 and 5) for enhancing the adhesion between the crystal lid 12 and the bonding layer 14. Is. The specific configuration of the first metallized film 41 will be described later.
　また、パッケージ材３０は、ＬＥＤチップ１３が実装されたセラミックパッケージ１１の封止面１１Ａ上に、第２メタライズ膜４２を形成したものである。第２メタライズ膜４２は、リッド材２０とパッケージ材３０とを対向させたときに第１メタライズ膜４１と重なり合うように、封止面１１Ａの形状に沿って環状に形成されている。第２メタライズ膜４２は、セラミックパッケージ１１と接合層１４との密着性を高めるための下地膜である。第２メタライズ膜４２としては、パッケージ基台がセラミックベースの場合は、タングステンあるいはモリブデン等のメタライズ材料の上部にＮｉ合金／Ａｕ膜（またはＮｉ／Ａｕ膜）等が形成されたものが好適に使用でき、また、第２メタライズ膜４２の膜厚は１５０～７００ｎｍの範囲とすることが好ましい。さらに、パッケージ基台が水晶ベースの場合は、第２メタライズ膜４２がＴｉ合金／Ａｕ膜（またはＴｉ／Ａｕ膜）とされていてもよい。 Further, the package material 30 is formed by forming a second metallized film 42 on the sealing surface 11A of the ceramic package 11 on which the LED chip 13 is mounted. The second metallized film 42 is formed in an annular shape along the shape of the sealing surface 11A so as to overlap the first metallized film 41 when the lid material 20 and the packaging material 30 face each other. The second metallized film 42 is a base film for enhancing the adhesion between the ceramic package 11 and the bonding layer 14. When the package base is a ceramic base, the second metallized film 42 preferably has a Ni alloy / Au film (or Ni / Au film) or the like formed on top of a metallized material such as tungsten or molybdenum. The thickness of the second metallized film 42 is preferably in the range of 150 to 700 nm. Further, when the package base is based on quartz, the second metallized film 42 may be a Ti alloy / Au film (or Ti / Au film).
　発光装置１０の製造は、図２に示すように、リッド材２０およびパッケージ材３０を重ねて配置し、リッド材２０とパッケージ材３０との間に荷重をかけながら加熱することで、これらの接合を行う。すなわち、第１メタライズ膜４および第２メタライズ膜４２を加熱によって溶融させ、その後、荷重をかけながら冷却する。溶融した第１メタライズ膜４１および第２メタライズ膜４２は、冷却によって固化し、図１に示す接合層１４を形成する。 As shown in FIG. 2, the light emitting device 10 is manufactured by arranging the lid material 20 and the package material 30 in an overlapping manner and heating the lid material 20 and the package material 30 while applying a load to join them. I do. That is, the first metallized film 4 and the second metallized film 42 are melted by heating, and then cooled while applying a load. The melted first metallized film 41 and the second metallized film 42 are solidified by cooling to form the bonding layer 14 shown in FIG.
　〔リッド材の構成および製造方法〕
　続いて、リッド材２０の構成および製造方法について説明する。 [Construction and manufacturing method of lid material]
Subsequently, the configuration and manufacturing method of the lid material 20 will be described.
　上述したように、リッド材２０は、水晶リッド１２の下面に第１メタライズ膜４１を形成したものであり、第１メタライズ膜４１は、下地膜４１Ａにろう材４１Ｂを融着させて形成されている。第１メタライズ膜４１は、下地膜４１Ａの成膜工程と、ろう材４１Ｂの融着工程を経て形成される。まずは、成膜工程によって形成される下地膜４１Ａの構成について図４を参照して説明する。 As described above, the lid material 20 has a first metallized film 41 formed on the lower surface of the crystal lid 12, and the first metallized film 41 is formed by fusing the brazing material 41B to the base film 41A. There is. The first metallized film 41 is formed through a film forming step of the base film 41A and a fusion step of the brazing material 41B. First, the configuration of the undercoat film 41A formed by the film forming step will be described with reference to FIG.
　図４に示すように、第１メタライズ膜４１の下地膜４１Ａは、第１金属層４１１および第２金属層４１２を含んで構成されている。 As shown in FIG. 4, the base film 41A of the first metallized film 41 is configured to include the first metal layer 411 and the second metal layer 412.
　水晶リッド１２の上に直接形成される第１金属層４１１は、Ｔｉ（チタン）膜からなる単層構造を有している。第２金属層４１２は、第１金属層４１１の上に形成されており、第１金属層４１１に近い側から順にＮｉ－Ｔｉ（ニッケル－チタン）膜４１２１およびＡｕ（金）膜４１２２を含む積層構造を有している。尚、第２金属層４１２におけるＮｉ－Ｔｉ膜４１２１は、その膜厚を５０～１０００ｎｍの範囲とすることが好ましい。また、Ｎｉ－Ｔｉ膜４１２１は、他のＮｉ合金膜に置き換えることも可能である。 The first metal layer 411 formed directly on the crystal lid 12 has a single layer structure made of a Ti (titanium) film. The second metal layer 412 is formed on the first metal layer 411, and is laminated including the Ni—Ti (nickel-titanium) film 4121 and the Au (gold) film 4122 in order from the side closer to the first metal layer 411. It has a structure. The Ni—Ti film 4121 in the second metal layer 412 preferably has a film thickness in the range of 50 to 1000 nm. Further, the Ni—Ti film 4121 can be replaced with another Ni alloy film.
　リッド材２０における下地膜４１Ａの製造方法としては、最初に、水晶リッド１２の片面（パッケージ材３０との対向面）に物理的気相成長によって第１金属層４１１となるＴｉ膜を形成する。Ｔｉ膜が形成されると、これを成膜装置から一旦取り出し、Ｔｉ膜の表面を空気に曝す。これにより、Ｔｉ膜の表面には酸化チタンからなる酸化皮膜が形成される。その後、第１金属層４１１であるＴｉ膜の上に物理的気相成長によってＮｉ－Ｔｉ膜４１２１を形成し、このＮｉ－Ｔｉ膜４１２１の上に物理的気相成長によってＡｕ膜４１２２を形成する。すなわち、第２金属層４１２は、Ｎｉ－Ｔｉ膜４１２１とＡｕ膜４１２２との積層構造を有している。 As a method for producing the base film 41A in the lid material 20, first, a Ti film to be the first metal layer 411 is formed on one side of the crystal lid 12 (the surface facing the package material 30) by physical vapor deposition. Once the Ti film is formed, it is once taken out of the film forming apparatus and the surface of the Ti film is exposed to air. As a result, an oxide film made of titanium oxide is formed on the surface of the Ti film. Then, a Ni—Ti film 4121 is formed on the Ti film, which is the first metal layer 411, by physical vapor deposition, and an Au film 4122 is formed on the Ni—Ti film 4121 by physical vapor deposition. .. That is, the second metal layer 412 has a laminated structure of Ni—Ti film 4121 and Au film 4122.
　尚、Ｔｉ膜を酸化させてその表面に酸化皮膜を形成する方法は、上述したＴｉ膜の表面を空気に曝す方法に限定されるものではない。例えば、スパッタリングによってＴｉ膜を形成するときに酸素を導入して酸化Ｔｉ膜として成膜する方法や、成膜されたＴｉ膜の表面を酸素プラズマによって酸化促進させる方法も可能である。 The method of oxidizing the Ti film to form an oxide film on the surface thereof is not limited to the above-mentioned method of exposing the surface of the Ti film to air. For example, a method of introducing oxygen when forming a Ti film by sputtering to form a film as a Ti oxide film, or a method of promoting oxidation of the surface of the formed Ti film by oxygen plasma is also possible.
　下地膜４１Ａが形成されると、続いて融着工程によって下地膜４１Ａの上にろう材４１Ｂが融着される。この融着工程では、図５に示すように、下地膜４１Ａの上にろう材４１Ｂを載せて熱処理（加熱炉によるベーキング）を行う。この熱処理により、下地膜４１Ａおよびろう材４１Ｂが一体化し、第１メタライズ膜４１となる。尚、融着前のろう材４１Ｂは、ろう材として使用される金錫（Ａｕ－Ｓｎ）を、下地膜４１Ａとほぼ同形状の環状にプリフォームして形成されたものである。プリフォームされたろう材４１Ｂの厚みは、１０～２０μｍの範囲とすることが好ましい。 When the base film 41A is formed, the brazing material 41B is subsequently fused onto the base film 41A by a fusion process. In this fusion step, as shown in FIG. 5, the brazing material 41B is placed on the base film 41A and heat-treated (baking in a heating furnace). By this heat treatment, the base film 41A and the brazing material 41B are integrated to form the first metallized film 41. The brazing material 41B before fusion is formed by preforming gold tin (Au-Sn) used as a brazing material into an annular shape having substantially the same shape as the base film 41A. The thickness of the preformed brazing material 41B is preferably in the range of 10 to 20 μm.
　融着工程後の第１メタライズ膜４１においては、加熱前の下地膜４１Ａにおける第２金属層４１２の積層構造（Ｎｉ－Ｔｉ膜４１２１とＡｕ膜４１２２との積層構造）は失われる。具体的には、融着工程の加熱によって、第２金属層４１２およびろう材４１Ｂが溶融して合金化し（共晶接合を形成し）、合金層４３（図６参照）を形成する。一方、第１金属層４１１は、融着工程後も層状に維持されており、共晶接合を形成していない。 In the first metallized film 41 after the fusion step, the laminated structure of the second metal layer 412 (laminated structure of Ni—Ti film 4121 and Au film 4122) in the base film 41A before heating is lost. Specifically, by heating in the fusion step, the second metal layer 412 and the brazing material 41B are melted and alloyed (a eutectic bond is formed) to form an alloy layer 43 (see FIG. 6). On the other hand, the first metal layer 411 is maintained in a layered state even after the fusion step and does not form a eutectic bond.
　図６は、封止後の発光装置１０において、接合層１４の一部の断面を撮影したＳＥＭ写真である。図６に示すように、接合層１４は、水晶リッド１２に近い側から順に、第１金属層４１１、合金層４３、Ｎｉ－Ｓｎ合金層４２２およびＮｉメッキ層４２１を有している。尚、Ｔｉ膜である第１金属層４１１表面の酸化皮膜は、その膜厚が極めて薄いため、図６のＳＥＭ写真では明確な層としては視認できない。しかしながら、Ｔｉ膜である第１金属層４１１が共晶接合を形成せずに層状に維持されているのは、Ｔｉ膜表面の酸化皮膜がバリア膜として存在しているためである。 FIG. 6 is an SEM photograph of a part of the cross section of the bonding layer 14 taken in the light emitting device 10 after sealing. As shown in FIG. 6, the bonding layer 14 has a first metal layer 411, an alloy layer 43, a Ni—Sn alloy layer 422, and a Ni plating layer 421 in this order from the side closer to the crystal lid 12. Since the oxide film on the surface of the first metal layer 411, which is a Ti film, is extremely thin, it cannot be visually recognized as a clear layer in the SEM photograph of FIG. However, the reason why the first metal layer 411, which is a Ti film, is maintained as a layer without forming a eutectic bond is because the oxide film on the surface of the Ti film exists as a barrier film.
　合金層４３は、加熱前の下地膜４１Ａにおける第２金属層４１２とろう材４１Ｂとが、溶融により共晶接合を形成した層である。合金層４３には、ろう材４１Ｂである金錫（Ａｕ－Ｓｎ）の中の“Ａｕ－Ｓｎζ'相”および“Ａｕ－Ｓｎδ相”の他に、第２金属層４１２とろう材４１Ｂとが混じり合ってできる“Ｎｉ‐Ｓｎ合金”や“Ｔｉ－Ｓｎ合金”が含まれている。すなわち、合金層４３は、Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含む合金層となる。 The alloy layer 43 is a layer in which the second metal layer 412 and the brazing material 41B in the base film 41A before heating form a eutectic bond by melting. In the alloy layer 43, in addition to the "Au-Snζ'phase" and the "Au-Snδ phase" in gold tin (Au-Sn) which is the brazing material 41B, the second metal layer 412 and the brazing material 41B are formed. "Ni-Sn alloy" and "Ti-Sn alloy" formed by mixing are included. That is, the alloy layer 43 is an alloy layer containing Ni, Ti, Au and Sn.
　Ｎｉメッキ層４２１は、パッケージ材３０の第２メタライズ膜４２に含まれる層である。また、Ｎｉ－Ｓｎ合金層４２２は、第１メタライズ膜４１と第２メタライズ膜４２との接合部分が合金化して形成された層である。すなわち、Ｎｉ－Ｓｎ合金層４２２は、合金層４３と同様にＮｉ、Ｔｉ、ＡｕおよびＳｎを含む合金層となる。より詳細には、リッド材２０をパッケージ材３０に溶着させてできるＮｉ－Ｓｎ合金層４２２では、パッケージ材３０側のＮｉめっき層とリッド材２０側のＡｕ－Ｓｎ合金のＳｎが結合し、Ｎｉ－Ｓｎ層を形成する。そのため、Ａｕ－Ｓｎ合金は非共晶状態になる。リッド材２０とパッケージ材３０と溶着後には、このようなＡｕ－Ｓｎ合金の非共晶状態が好ましい。 The Ni plating layer 421 is a layer contained in the second metallized film 42 of the packaging material 30. Further, the Ni—Sn alloy layer 422 is a layer formed by alloying the joint portion between the first metallized film 41 and the second metallized film 42. That is, the Ni—Sn alloy layer 422 is an alloy layer containing Ni, Ti, Au, and Sn, similarly to the alloy layer 43. More specifically, in the Ni—Sn alloy layer 422 formed by welding the lid material 20 to the package material 30, the Ni plating layer on the package material 30 side and the Sn of the Au—Sn alloy on the lid material 20 side are bonded to each other to form Ni. -Sn layer is formed. Therefore, the Au—Sn alloy is in a non-eutectic state. After welding the lid material 20 and the packaging material 30, such a non-eutectic state of the Au—Sn alloy is preferable.
　尚、発光装置１０のパッケージ材３０が水晶ベースであり、第１メタライズ膜４１がＴｉ／Ａｕ膜とされている場合は、Ｎｉ－Ｓｎ合金層４２２の代わりにＴｉ－Ｓｎ層が形成される。すなわち、パッケージ材３０側のＴｉめっき層とリッド材２０側のＡｕ－Ｓｎ合金のＳｎが結合し、Ｔｉ－Ｓｎ層を形成する。 When the package material 30 of the light emitting device 10 is a crystal base and the first metallized film 41 is a Ti / Au film, a Ti—Sn layer is formed instead of the Ni—Sn alloy layer 422. That is, the Ti plating layer on the package material 30 side and the Sn of the Au—Sn alloy on the lid material 20 side are bonded to form a Ti—Sn layer.
　尚、図６のＳＥＭ写真は、封止後の発光装置１０における接合層１４の断面を撮影したものであるが、接合前のリッド材２０における第１メタライズ膜４１は、第１金属層（第１層）４１１および合金層（第２層）４３を既に含んでいる。 The SEM photograph of FIG. 6 is a photograph of a cross section of the bonding layer 14 in the light emitting device 10 after sealing, but the first metallized film 41 in the lid material 20 before bonding is a first metal layer (first metal layer). It already contains the 1st layer) 411 and the alloy layer (2nd layer) 43.
　〔第１メタライズ膜の形成条件〕
　上述したリッド材２０では、発光装置１０における水晶リッド１２の好適な密着性を得るために、第１メタライズ膜４１において膜厚の制御が必要であることが確認された。特に、第１金属層４１１であるＴｉ膜の膜厚を適切な範囲に制御することが必要である。以下、実験に基づいた考察を行う。 [Conditions for forming the first metallized film]
In the lid material 20 described above, it was confirmed that the film thickness of the first metallized film 41 needs to be controlled in order to obtain suitable adhesion of the crystal lid 12 in the light emitting device 10. In particular, it is necessary to control the film thickness of the Ti film, which is the first metal layer 411, within an appropriate range. The following is a discussion based on experiments.
　ここでは、第１金属層４１１の膜厚をパラメータとして変化させ、上述した製造方法にて発光装置１０を製造し、その外観評価と気密試験（ヘリウムリークテスト）による気密評価とを行った。外観評価では、水晶リッド１２側から見たメタライズ膜の変色と、水晶リッド１２における割れの有無とを目視確認した。尚、製造した各発光装置１０において、第２金属層４１２のＮｉ－Ｔｉ膜４１２１およびＡｕ膜４１２２は、その膜厚を３００ｎｍおよび５０ｎｍにそれぞれ固定した。また、ろう材４１ＢであるＡｕ－Ｓｎプリフォームの厚みは１５μｍに固定し、第２メタライズ膜４２はＮｉ合金／Ａｕ膜を使用し、その膜厚は合計５μｍに固定した。実験結果を以下の表１に示す。 Here, the film thickness of the first metal layer 411 was changed as a parameter, the light emitting device 10 was manufactured by the above-mentioned manufacturing method, and the appearance evaluation and the airtightness evaluation by the airtightness test (helium leak test) were performed. In the appearance evaluation, the discoloration of the metallized film seen from the crystal lid 12 side and the presence or absence of cracks in the crystal lid 12 were visually confirmed. In each of the manufactured light emitting devices 10, the Ni—Ti film 4121 and Au film 4122 of the second metal layer 412 were fixed at 300 nm and 50 nm, respectively. The thickness of the Au-Sn preform, which is the brazing material 41B, was fixed at 15 μm, and the second metallized film 42 was a Ni alloy / Au film, and the total film thickness was fixed at 5 μm. The experimental results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　変色に関しては、条件１，２（膜厚７ｎｍ，１０ｎｍ）において比較的広範囲な変色が生じており、評価“×”となっている。また、条件３～６，１０～１５（膜厚２０ｎｍ，５０ｎｍ，１００ｎｍ，１５０ｎｍ，４００ｎｍ，５００ｎｍ，６００ｎｍ，７００ｎｍ，８００ｎｍ，９００ｎｍ）においては、僅かに変色が生じており、評価“○”となっている。そして、条件７～９（膜厚２００ｎｍ，２５０ｎｍ，３００ｎｍ）においては変色が殆ど生じておらず、評価“◎”となっている。 Regarding discoloration, a relatively wide range of discoloration occurred under conditions 1 and 2 (film thickness 7 nm, 10 nm), and the evaluation was "x". Further, under conditions 3 to 6, 10 to 15 (film thickness 20 nm, 50 nm, 100 nm, 150 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm), slight discoloration occurred, and the evaluation was “◯”. ing. Then, under conditions 7 to 9 (film thickness 200 nm, 250 nm, 300 nm), almost no discoloration occurred, and the evaluation was “⊚”.
　この変色は、水晶リッド１２と接合層１４であるメタライズ膜との間で剥離が生じていることを示している。すなわち、第１金属層４１１の膜厚が十分でない場合、接合材４０からＡｕおよびＳｎが第１金属層４１１であるＴｉ膜において水晶リッド１２との接触面にまで拡散し、第１金属層４１１と水晶リッド１２との密着性を低下させることによって剥離（すなわち変色）が生じたものと考えられる。このことは、第１金属層４１１の膜厚が薄い条件１，２において広範囲な変色が生じていることから明らかである。実際、第１金属層４１１の膜厚が最も薄い条件１では、気密評価において“×”となっている（気密不良が生じている）。また、条件２では、気密評価の段階で気密不良は検出されず、評価は“○”となっているが、変色範囲が広いことから長期にわたって気密性が維持できるとは考えにくい。このため、条件１，２は、総合評価を“×”としている。 This discoloration indicates that peeling has occurred between the crystal lid 12 and the metallized film which is the bonding layer 14. That is, when the thickness of the first metal layer 411 is not sufficient, Au and Sn are diffused from the bonding material 40 to the contact surface with the crystal lid 12 in the Ti film which is the first metal layer 411, and the first metal layer 411. It is probable that peeling (that is, discoloration) occurred by reducing the adhesion between the metal and the crystal lid 12. This is clear from the fact that a wide range of discoloration occurs under conditions 1 and 2 in which the film thickness of the first metal layer 411 is thin. In fact, under condition 1 where the film thickness of the first metal layer 411 is the thinnest, it is "x" in the airtightness evaluation (airtightness is poor). Further, under condition 2, poor airtightness is not detected at the stage of airtightness evaluation, and the evaluation is “◯”, but it is unlikely that airtightness can be maintained for a long period of time because the discoloration range is wide. Therefore, in conditions 1 and 2, the overall evaluation is set to "x".
　第１金属層４１１の膜厚が厚くなれば、第１金属層４１１であるＴｉ膜においてＡｕおよびＳｎの拡散が抑制され、水晶リッド１２と接合層１４であるメタライズ膜との密着性が向上する。条件３～６では変色に関して“○”の評価となっており、条件７～９では変色に関して“◎”の評価となっている。条件３～９では気密評価に関しても“○”の評価となっているため、総合評価は、条件３～６を“○”、条件７～９を“◎”としている。 When the thickness of the first metal layer 411 is increased, the diffusion of Au and Sn is suppressed in the Ti film which is the first metal layer 411, and the adhesion between the crystal lid 12 and the metallized film which is the bonding layer 14 is improved. .. Conditions 3 to 6 give an evaluation of "○" for discoloration, and conditions 7 to 9 give an evaluation of "◎" for discoloration. In the conditions 3 to 9, the airtightness evaluation is also evaluated as "○", so that the conditions 3 to 6 are "○" and the conditions 7 to 9 are "◎".
　条件１０～１５では、第１金属層４１１の膜厚がさらに厚くなっているが、変色に関しての評価は“○”となっており、条件７～９に比べて評価は下がっている。但し、このことは、条件１０～１５における水晶リッド１２の密着性が、条件７～９における水晶リッド１２の密着性よりも低いことを意味しているのではない。条件１０～１５において、変色に関しての評価が“○”となっているのは、以下の理由によるものと考えられる。 Under conditions 10 to 15, the film thickness of the first metal layer 411 is further thickened, but the evaluation regarding discoloration is "○", which is lower than that of conditions 7 to 9. However, this does not mean that the adhesion of the crystal lid 12 under the conditions 10 to 15 is lower than the adhesion of the crystal lid 12 under the conditions 7 to 9. It is considered that the reason why the evaluation regarding discoloration is "○" under the conditions 10 to 15 is as follows.
　発光装置１０において、セラミックパッケージ１１と水晶リッド１２とでは、材質が異なるため、熱膨張率も異なる。そして、条件１０～１５では、第１金属層４１１の膜厚が厚く密着性が高いことから、セラミックパッケージ１１と水晶リッド１２との熱膨張差から反りが発生し、この反りによって剥離が生じたと考えられる。すなわち、条件７～９は、条件１０～１５に比べると密着性が低いため、セラミックパッケージ１１と水晶リッド１２との間に熱膨張差が生じても、第１金属層４１１と水晶リッド１２との間にずれが生じて熱膨張差を吸収することができ、反りによる剥離を抑制する作用が働いたと考えられる。実際、条件１４，１５では、水晶リッド１２の割れも発生しており、この水晶割れは熱膨張差による反りによって生じたものと考えられる。 In the light emitting device 10, since the materials of the ceramic package 11 and the crystal lid 12 are different, the coefficient of thermal expansion is also different. Then, under conditions 10 to 15, since the first metal layer 411 has a thick film thickness and high adhesion, warpage occurs due to the difference in thermal expansion between the ceramic package 11 and the crystal lid 12, and the warp causes peeling. Conceivable. That is, since the conditions 7 to 9 have lower adhesion than the conditions 10 to 15, even if a thermal expansion difference occurs between the ceramic package 11 and the crystal lid 12, the first metal layer 411 and the crystal lid 12 It is considered that the gap between the two was able to absorb the difference in thermal expansion, and the action of suppressing the peeling due to the warp worked. In fact, under conditions 14 and 15, cracks in the crystal lid 12 also occur, and it is considered that the cracks in the crystal were caused by warpage due to the difference in thermal expansion.
　尚、セラミックパッケージ１１の材質を窒化アルミニウムとする場合、水晶と窒化アルミニウムとの熱膨張率の差は、石英ガラスと窒化アルミニウムとの熱膨張率の差よりも大きい。したがって、水晶リッド１２を用いる場合は、石英ガラスのリッドを用いる従来構成に比べて熱膨張差による反りが生じ易く、このような反りに対する考慮も必要となる。 When the material of the ceramic package 11 is aluminum nitride, the difference in the coefficient of thermal expansion between the crystal and aluminum nitride is larger than the difference in the coefficient of thermal expansion between quartz glass and aluminum nitride. Therefore, when the crystal lid 12 is used, warpage due to a difference in thermal expansion is likely to occur as compared with the conventional configuration using a quartz glass lid, and it is necessary to consider such warpage.
　条件１０～１５の気密評価に関しては、条件１０～１３は○”、条件１４，１５は“×”となっている。これは、条件１４，１５では、水晶リッド１２の割れによって気密が破れたためである。このため、条件１０～１３は総合評価を“○”、条件１４，１５は総合評価を“×”としている。 Regarding the airtightness evaluation of the conditions 10 to 15, the conditions 10 to 13 are "○" and the conditions 14 and 15 are "x". This is because the airtightness was broken by the crack of the crystal lid 12 under the conditions 14 and 15. Therefore, the conditions 10 to 13 have a comprehensive evaluation of "○", and the conditions 14 and 15 have a comprehensive evaluation of "x".
　以上のように、本実施の形態に係るリッド材２０では、第１金属層４１１の膜厚は、薄すぎても厚すぎても、発光装置１０において確実な気密が得られなくなる。上記表１の結果から明らかなように、第１金属層４１１の膜厚は、２０～７００ｎｍの範囲とすることが好ましく、２００～３００ｎｍの範囲とすることがさらに好ましい。 As described above, in the lid material 20 according to the present embodiment, if the film thickness of the first metal layer 411 is too thin or too thick, the light emitting device 10 cannot obtain reliable airtightness. As is clear from the results in Table 1 above, the film thickness of the first metal layer 411 is preferably in the range of 20 to 700 nm, and more preferably in the range of 200 to 300 nm.
　［実施の形態２］
　〔リッド材の構成および製造方法〕
　上記実施の形態１では、リッド材２０は下地膜となる第１メタライズ膜４１を有しており、この第１メタライズ膜４１は水晶に対する密着度が高く、水晶リッド１２を用いる場合にリッド剥離や気密不良を生じさせない好適な下地膜であることを説明した。しかしながら、実施の形態１における第１メタライズ膜４１は、密着度が高いゆえに発光装置１０にリッド割れの問題が生じる場合があった。特に、封止荷重が大きい場合（例えば１００ｇｆ以上）や冷熱衝撃試験などにおいてリッド割れが発生しやすい傾向があった。本実施の形態２では、封止荷重が大きい場合や冷熱衝撃試験においてもリッド割れを防止できるリッド材について説明する。 [Embodiment 2]
[Construction and manufacturing method of lid material]
In the first embodiment, the lid material 20 has a first metallized film 41 as a base film, and the first metallized film 41 has a high degree of adhesion to the crystal, and when the crystal lid 12 is used, the lid can be peeled off. It was explained that it is a suitable base film that does not cause poor airtightness. However, since the first metallized film 41 in the first embodiment has a high degree of adhesion, the light emitting device 10 may have a problem of lid cracking. In particular, when the sealing load is large (for example, 100 gf or more), lid cracking tends to occur easily in a thermal shock test or the like. In the second embodiment, a lid material that can prevent the lid from cracking even when the sealing load is large or in the thermal shock test will be described.
　リッド材２０における第１メタライズ膜４１は、図５に示すように、下地膜４１Ａにろう材４１Ｂを融着させて形成されるものである。これに対し、本実施の形態２に係るリッド材２１は、図７に示すように、リッド材２０の第１メタライズ膜４１に代えて第１メタライズ膜５１を有する構成とされており、第１メタライズ膜５１は下地膜５１Ａにろう材４１Ｂを融着させて形成される。 As shown in FIG. 5, the first metallized film 41 in the lid material 20 is formed by fusing the brazing material 41B to the base film 41A. On the other hand, as shown in FIG. 7, the lid material 21 according to the second embodiment has a configuration in which the first metallized film 51 is provided instead of the first metallized film 41 of the lid material 20. The metallized film 51 is formed by fusing the brazing material 41B to the base film 51A.
　図８は、本実施の形態２に係るリッド材２１における下地膜５１Ａの構成を示す部分断面図である。ここで、下地膜５１Ａは、図８に示すように、第１金属層（第１層）５１１および第２金属層（第２層）４１２を含んで構成されている。すなわち、リッド材２１における下地膜５１Ａは、実施の形態１に係るリッド材２０の下地膜４１Ａにおいて、第１金属層４１１を第１金属層５１１に変更した構成である。 FIG. 8 is a partial cross-sectional view showing the configuration of the base film 51A in the lid material 21 according to the second embodiment. Here, as shown in FIG. 8, the base film 51A includes a first metal layer (first layer) 511 and a second metal layer (second layer) 412. That is, the base film 51A in the lid material 21 has a configuration in which the first metal layer 411 is changed to the first metal layer 511 in the base film 41A of the lid material 20 according to the first embodiment.
　実施の形態１の第１金属層４１１はＴｉ膜のみからなる単層構造を有していたが、第１金属層５１１は、Ｔｉ膜５１１１、Ａｕ膜５１１２およびＴｉ膜５１１３からなる積層構造を有している。ここでは、Ｔｉ膜５１１１が、実施の形態１の第１金属層４１１を構成するＴｉ膜に相当する。すなわち、Ｔｉ膜５１１１は、第１金属層４１１のＴｉ膜と同様に、膜厚２０～７００ｎｍであることが好ましく、膜厚２００～３００ｎｍであることがより好ましい。 The first metal layer 411 of the first embodiment has a single layer structure composed of only a Ti film, but the first metal layer 511 has a laminated structure composed of a Ti film 5111, an Au film 5112, and a Ti film 5113. doing. Here, the Ti film 5111 corresponds to the Ti film constituting the first metal layer 411 of the first embodiment. That is, the Ti film 5111 preferably has a film thickness of 20 to 700 nm, and more preferably 200 to 300 nm, like the Ti film of the first metal layer 411.
　第１金属層５１１におけるＡｕ膜５１１２およびＴｉ膜５１１３は、封止荷重が大きい場合や冷熱衝撃試験においてのリッド割れを防止するための緩衝膜として形成されている。上記実施の形態１でも説明したように、発光装置１０におけるセラミックパッケージ１１と水晶リッド１２とでは、材質が異なるため、熱膨張率も異なる。このため、セラミックパッケージ１１と水晶リッド１２との熱膨張差から反りが発生し、この反りが水晶割れの要因となる場合がある。これに対し、リッド材２１を用いた発光装置１０では、セラミックパッケージ１１と水晶リッド１２との間の熱膨張差を緩衝膜（すなわちＡｕ膜５１１２およびＴｉ膜５１１３）の変形によって吸収することができ、その結果、反りを低減して水晶割れを抑制できると考えられる。 The Au film 5112 and Ti film 5113 in the first metal layer 511 are formed as a buffer film for preventing lid cracking when the sealing load is large or in a thermal shock test. As described in the first embodiment, the ceramic package 11 and the crystal lid 12 in the light emitting device 10 are made of different materials, so that the coefficient of thermal expansion is also different. Therefore, warpage occurs due to the difference in thermal expansion between the ceramic package 11 and the crystal lid 12, and this warpage may cause crystal cracking. On the other hand, in the light emitting device 10 using the lid material 21, the difference in thermal expansion between the ceramic package 11 and the crystal lid 12 can be absorbed by the deformation of the buffer film (that is, Au film 5112 and Ti film 5113). As a result, it is considered that the warp can be reduced and the crystal cracking can be suppressed.
　リッド材２１の製造方法としては、水晶リッド１２の片面（パッケージ材３０との対向面）に物理的気相成長によって第１金属層５１１となるＴｉ膜５１１１、Ａｕ膜５１１２およびＴｉ膜５１１３を順次形成する。第１金属層５１１が形成されると、これを成膜装置から一旦取り出し、最上層にあるＴｉ膜５１１３の表面を空気に曝す。これにより、Ｔｉ膜５１１３の表面には酸化チタンからなる酸化皮膜が形成される。 As a method for manufacturing the lid material 21, a Ti film 5111, an Au film 5112, and a Ti film 5113 which become the first metal layer 511 by physical vapor deposition are sequentially formed on one side (the surface facing the package material 30) of the crystal lid 12. Form. When the first metal layer 511 is formed, it is once taken out from the film forming apparatus, and the surface of the Ti film 5113 on the uppermost layer is exposed to air. As a result, an oxide film made of titanium oxide is formed on the surface of the Ti film 5113.
　尚、実施の形態１では、第１金属層４１１の表面に酸化チタンからなる酸化皮膜が形成され、本実施の形態２では、Ｔｉ膜５１１１が実施の形態１の第１金属層４１１のＴｉ膜に相当するものとされている。しかしながら、酸化チタンからなる酸化皮膜は、第１金属層と第２金属層との境界となるものであるため、本実施の形態２に係るリッド材２１では、酸化チタンからなる酸化皮膜は、Ｔｉ膜５１１１ではなく、第１金属層５１１の最上層にあるＴｉ膜５１１３の表面において形成される。また、Ｔｉ膜５１１３の表面に酸化皮膜を形成する方法は、実施の形態１と同様に、スパッタリングによってＴｉ膜を形成するときに酸素を導入して酸化Ｔｉ膜として成膜する方法や、成膜されたＴｉ膜の表面を酸素プラズマによって酸化促進させる方法も可能である。第１金属層５１１の形成後、第２金属層４１２の形成方法は、実施の形態１で説明した方法と同様である。第１金属層５１１および第２金属層４１２の形成により、水晶リッド１２上に下地膜５１Ａが形成される。 In the first embodiment, an oxide film made of titanium oxide is formed on the surface of the first metal layer 411, and in the second embodiment, the Ti film 5111 is the Ti film of the first metal layer 411 of the first embodiment. It is supposed to be equivalent to. However, since the oxide film made of titanium oxide serves as a boundary between the first metal layer and the second metal layer, in the lid material 21 according to the second embodiment, the oxide film made of titanium oxide is Ti. It is formed not on the film 5111 but on the surface of the Ti film 5113 on the uppermost layer of the first metal layer 511. Further, the method of forming an oxide film on the surface of the Ti film 5113 is the same as that of the first embodiment, that is, a method of introducing oxygen when forming a Ti film by sputtering, or a method of forming a film as a Ti oxide film. A method of promoting oxidation of the surface of the formed Ti film by oxygen plasma is also possible. After the formation of the first metal layer 511, the method of forming the second metal layer 412 is the same as the method described in the first embodiment. By forming the first metal layer 511 and the second metal layer 412, the base film 51A is formed on the crystal lid 12.
　下地膜５１Ａが形成されると、続いて融着工程によって下地膜５１Ａの上にろう材４１Ｂが融着される。この融着工程では、図７に示すように、下地膜５１Ａの上にろう材４１Ｂを載せて熱処理（加熱炉によるベーキング）を行う。この熱処理により、下地膜５１Ａおよびろう材４１Ｂが一体化し、第１メタライズ膜５１となる。 When the base film 51A is formed, the brazing material 41B is subsequently fused onto the base film 51A by a fusion process. In this fusion step, as shown in FIG. 7, the brazing material 41B is placed on the base film 51A and heat-treated (baking in a heating furnace). By this heat treatment, the base film 51A and the brazing material 41B are integrated to form the first metallized film 51.
　〔第１メタライズ膜の形成条件〕
　上述したリッド材２１では、発光装置１０における水晶リッド１２の好適な密着性と水晶割れの防止効果とを得るために、下地膜において膜厚の制御が有効であることが確認された。特に、第１金属層５１１におけるＡｕ膜５１１２の膜厚を適切な範囲に制御することが有効である。以下、実験に基づいた考察を行う。 [Conditions for forming the first metallized film]
In the lid material 21 described above, it was confirmed that the film thickness control of the base film is effective in order to obtain the suitable adhesion of the crystal lid 12 in the light emitting device 10 and the effect of preventing crystal cracking. In particular, it is effective to control the film thickness of the Au film 5112 in the first metal layer 511 within an appropriate range. The following is a discussion based on experiments.
　ここでは、第１金属層５１１におけるＴｉ膜５１１１、Ａｕ膜５１１２およびＴｉ膜５１１３の各膜厚をパラメータとして変化させ、上述した製造方法にて発光装置１０を製造し、その外観評価と気密試験（ヘリウムリークテスト）による気密評価とを行った。外観評価では、水晶リッド１２側から見たメタライズ膜の変色と、水晶リッド１２における割れの有無とを目視確認した。尚、製造した各発光装置１０において、第２金属層４１２のＮｉ－Ｔｉ膜４１２１およびＡｕ膜４１２２は、その膜厚を３００ｎｍおよび５０ｎｍにそれぞれ固定した。また、接合材４０であるＡｕ－Ｓｎプリフォームの厚みは１５μｍに固定し、第２メタライズ膜４２はＮｉ合金／Ａｕ膜を使用し、その膜厚は合計５μｍに固定した。実験結果を以下の表２に示す。表２の第１金属層の膜厚においては、左側欄のＴｉ膜厚がＴｉ膜５１１１の膜厚を示しており、右側欄のＴｉ膜厚がＴｉ膜５１１３の膜厚を示している。 Here, each film thickness of the Ti film 5111, Au film 5112, and Ti film 5113 in the first metal layer 511 is changed as a parameter, and the light emitting device 10 is manufactured by the above-mentioned manufacturing method, and its appearance evaluation and airtightness test ( The airtightness was evaluated by the helium leak test). In the appearance evaluation, the discoloration of the metallized film seen from the crystal lid 12 side and the presence or absence of cracks in the crystal lid 12 were visually confirmed. In each of the manufactured light emitting devices 10, the Ni—Ti film 4121 and Au film 4122 of the second metal layer 412 were fixed at 300 nm and 50 nm, respectively. The thickness of the Au—Sn preform, which is the bonding material 40, was fixed at 15 μm, and the second metallized film 42 used a Ni alloy / Au film, and the total film thickness was fixed at 5 μm. The experimental results are shown in Table 2 below. Regarding the film thickness of the first metal layer in Table 2, the Ti film thickness in the left column indicates the film thickness of the Ti film 5111, and the Ti film thickness in the right column indicates the film thickness of the Ti film 5113.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２の条件１６～１８は、緩衝膜としてのＡｕ膜５１１２およびＴｉ膜５１１３を有していないが、Ｔｉ膜５１１１の膜厚が大きくなるほど結果が良好となっている。そして、実施の形態１で好適範囲とされているＴｉ膜５１１１の膜厚２５０ｎｍ（条件３）で、総合評価も“○”となっている。 Conditions 16 to 18 in Table 2 do not have Au film 5112 and Ti film 5113 as buffer films, but the larger the film thickness of Ti film 5111, the better the result. Then, the film thickness of the Ti film 5111, which is the preferable range in the first embodiment, is 250 nm (condition 3), and the overall evaluation is also “◯”.
　一方、緩衝膜としてのＡｕ膜５１１２およびＴｉ膜５１１３を有している条件１８～２５では何れも総合評価も“○”以上となっており、特に条件２１～２４では総合評価が“◎”となっている。条件２１～２４では、変色評価が“◎”であることから、発光装置１０における水晶リッド１２の密着性がより向上していることが分かる。これは、発光装置１０において、セラミックパッケージ１１と水晶リッド１２との間の熱膨張差を緩衝膜（すなわちＡｕ膜５１１２およびＴｉ膜５１１３）が吸収することで反りが低減され、その結果、リッド剥離も低減されたものと考えられる。また、この効果は、Ａｕ膜５１１２の膜厚を適切に制御することで向上し、Ａｕ膜５１１２の膜厚は１００～７００ｎｍの範囲とすることが好ましく、３００～６００ｎｍの範囲とすることがより好ましい。 On the other hand, under conditions 18 to 25 having Au film 5112 and Ti film 5113 as buffer films, the overall evaluation is "○" or higher, and particularly under conditions 21 to 24, the overall evaluation is "◎". It has become. Since the discoloration evaluation is “⊚” under the conditions 21 to 24, it can be seen that the adhesion of the crystal lid 12 in the light emitting device 10 is further improved. This is because in the light emitting device 10, the buffer film (that is, Au film 5112 and Ti film 5113) absorbs the difference in thermal expansion between the ceramic package 11 and the crystal lid 12, so that the warp is reduced, and as a result, the lid is peeled off. Is also considered to have been reduced. Further, this effect is improved by appropriately controlling the film thickness of the Au film 5112, and the film thickness of the Au film 5112 is preferably in the range of 100 to 700 nm, more preferably in the range of 300 to 600 nm. preferable.
　尚、表２の条件２６～２７は、緩衝膜を有してはいるが、気密評価が“×”（総合評価も“×”）となっている。また、条件２７では水晶割れでも評価が“×”となっている。これらの結果は、緩衝膜を厚くし過ぎた結果、下地膜のトータル膜厚が大きくなり、応力による影響で不具合が生じたためと考えられる。すなわち、下地膜のトータル膜厚が大きくなると、下地膜全体での膜厚に不均一が生じ、膜厚が不均一であることで水晶リッド１２にかかる応力が増加して水晶割れを引き起こしたと考えられる。これより、緩衝膜の膜厚には上限が存在することも示唆される。 In addition, the conditions 26 to 27 in Table 2 have a buffer film, but the airtightness evaluation is "x" (the overall evaluation is also "x"). Further, under the condition 27, the evaluation is “x” even if the crystal is cracked. It is probable that these results are due to the fact that the total film thickness of the undercoat film became large as a result of making the buffer film too thick, and problems occurred due to the influence of stress. That is, it is considered that when the total film thickness of the base film becomes large, the film thickness of the entire base film becomes non-uniform, and the stress applied to the crystal lid 12 increases due to the non-uniform film thickness, causing crystal cracking. Be done. This also suggests that there is an upper limit to the film thickness of the buffer film.
　［実施の形態３］
　〔リッド材の構成〕
　上記実施の形態１，２では、第２金属層４１２に含まれるＮｉ－Ｔｉ膜４１２１およびＡｕ膜４１２２が、これらの膜の形成幅（メタライズ幅）が同じになるように（Ｎｉ－Ｔｉ膜４１２１の上にＡｕ膜４１２２が完全に重畳するように）形成されている。しかしながら、この場合、発光装置１０の製造条件などによっては、評価段階でリッド剥離や気密不良の課題が生じることがあった。本実施の形態３では、リッド剥離や気密不良をより確実に防止することのできるリッド材について説明する。 [Embodiment 3]
[Composition of lid material]
In the first and second embodiments described above, the Ni—Ti film 4121 and Au film 4122 contained in the second metal layer 412 have the same forming width (metallizing width) of these films (Ni—Ti film 4121). The Au film 4122 is formed on top of it (so that it is completely superimposed). However, in this case, depending on the manufacturing conditions of the light emitting device 10, problems such as lid peeling and poor airtightness may occur at the evaluation stage. In the third embodiment, a lid material capable of more reliably preventing lid peeling and poor airtightness will be described.
　本実施の形態３に係るリッド材２２は、図９に示すように、リッド材２１の第１メタライズ膜５１に代えて第１メタライズ膜６１を有する構成とされており、第１メタライズ膜６１は下地膜６１Ａにろう材４１Ｂを融着させて形成される。 As shown in FIG. 9, the lid material 22 according to the third embodiment has a configuration in which the first metallized film 61 is provided in place of the first metallized film 51 of the lid material 21, and the first metallized film 61 is configured. It is formed by fusing the brazing material 41B to the base film 61A.
　図１０は、本実施の形態３に係るリッド材２２における下地膜６１Ａの構成を示す部分断面図である。下地膜６１Ａは、図１０に示すように、第１金属層（第１層）５１１および第２金属層（第２層）６１２を含んで構成されている。但し、本実施の形態３に係るリッド材２２は、第２金属層の構成に特徴を有するものである。このため、図６のリッド材２２では、第１金属層をリッド材２１の第１金属層５１１と同じ構成としているが、第１金属層はリッド材２０の第１金属層４１１と同じ構成としてもよい。 FIG. 10 is a partial cross-sectional view showing the configuration of the base film 61A in the lid material 22 according to the third embodiment. As shown in FIG. 10, the base film 61A includes a first metal layer (first layer) 511 and a second metal layer (second layer) 612. However, the lid material 22 according to the third embodiment is characterized by the structure of the second metal layer. Therefore, in the lid material 22 of FIG. 6, the first metal layer has the same structure as the first metal layer 511 of the lid material 21, but the first metal layer has the same structure as the first metal layer 411 of the lid material 20. May be good.
　第２金属層６１２は、第１金属層５１１の上に形成されるＮｉ－Ｔｉ膜６１２１と、Ｎｉ－Ｔｉ膜６１２１の上に形成されるＡｕ膜６１２２とを含む積層構造を有している。Ｎｉ－Ｔｉ膜６１２１は、リッド材２０および２０ＡにおけるＮｉ－Ｔｉ膜４１２１と同様の膜とすることができる。また、Ａｕ膜６１２２は、リッド材２０および２１におけるＡｕ膜４１２２とは膜の形成幅が異なるのみである。 The second metal layer 612 has a laminated structure including a Ni—Ti film 6121 formed on the first metal layer 511 and an Au film 6122 formed on the Ni—Ti film 6121. The Ni—Ti film 6121 can be a film similar to the Ni—Ti film 4121 in lid materials 20 and 20A. Further, the Au film 6122 is different from the Au film 4122 in the lid materials 20 and 21 only in the film forming width.
　すなわち、下地膜６１Ａにおいては、Ａｕ膜６１２２はＮｉ－Ｔｉ膜６１２１に比べて狭い幅で形成されている。より具体的には、Ａｕ膜６１２２は、Ａｕ膜６１２２の内周縁がＮｉ－Ｔｉ膜６１２１の内周縁よりも外側に引き下げられ、Ａｕ膜６１２２の外周縁がＮｉ－Ｔｉ膜６１２１の外周縁よりも内側に引き下げられた引き下がり構造（Ａｕ膜６１２２の周縁部とＮｉ－Ｔｉ膜６１２１の周縁部との間にギャップを有する構造）を有している。尚、ここでの“内側”，“外側”とは、リッド材２２の中心から見た“内側”，“外側”を意味している。また、下地膜６１Ａの内側および外側でのＡｕ膜６１２２の引き下がり幅は同じである必要はなく、図１０に示すように、内側の引き下がり幅［μｍ］をｄ１、外側の引き下がり幅をｄ２とする。 That is, in the undercoat film 61A, the Au film 6122 is formed with a narrower width than the Ni—Ti film 6121. More specifically, in the Au film 6122, the inner peripheral edge of the Au film 6122 is pulled outward from the inner peripheral edge of the Ni—Ti film 6121, and the outer peripheral edge of the Au film 6122 is lower than the outer peripheral edge of the Ni—Ti film 6121. It has a pull-down structure (a structure having a gap between the peripheral edge of the Au film 6122 and the peripheral edge of the Ni—Ti film 6121) that is pulled down inward. The "inside" and "outside" here mean the "inside" and "outside" seen from the center of the lid material 22. Further, the pull-down width of the Au film 6122 inside and outside the base film 61A does not have to be the same, and as shown in FIG. 10, the pull-down width [μm] on the inside is d1 and the pull-down width on the outside is d2. ..
　実施の形態１において説明したように、下地膜６１Ａにろう材４１Ｂを融着させるとき、およびリッド材２２とパッケージ材３０とを接合して発光装置１０を製造するとき、本来は下地膜６１Ａの第２金属層４１２のみが溶融してろう材４１Ｂとの共晶接合を形成する。しかしながら、製造条件によっては（例えば、接合時の封止荷重が大きければ）、共晶接合によって形成される合金（Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含む合金）が接合層１４の側面から回り込んで第１金属層４１１に達する恐れがある。この場合、第１金属層４１１に達した合金のＡｕやＳｎ成分が第１金属層４１１に浸潤して第１金属層４１１と水晶リッド１２との密着性を低下させ、リッド剥離や気密不良の要因になると考えられる。同様の問題は、リッド材２１とパッケージ材３０とを接合して発光装置１０を製造するときにも生じる。 As described in the first embodiment, when the brazing material 41B is fused to the base film 61A and when the lid material 22 and the package material 30 are joined to manufacture the light emitting device 10, the base film 61A is originally used. Only the second metal layer 412 melts to form a eutectic bond with the brazing filler metal 41B. However, depending on the manufacturing conditions (for example, if the sealing load at the time of bonding is large), the alloy formed by eutectic bonding (alloy containing Ni, Ti, Au and Sn) wraps around from the side surface of the bonding layer 14. It may reach the first metal layer 411. In this case, the Au and Sn components of the alloy that have reached the first metal layer 411 infiltrate the first metal layer 411 to reduce the adhesion between the first metal layer 411 and the crystal lid 12, resulting in lid peeling and poor airtightness. It is considered to be a factor. A similar problem occurs when the lid material 21 and the packaging material 30 are joined to manufacture the light emitting device 10.
　これに対し、リッド材２２とパッケージ材３０とを接合して発光装置１０を製造する場合には、共晶接合はＡｕ膜６１２２の形成領域とほぼ重畳する領域においてのみ形成される。これは、共晶接合の形成には、Ａｕが不可欠となるためである。リッド材２２では、Ａｕ膜６１２２はＮｉ－Ｔｉ膜６１２１に対して引き下がり構造を有しているため、共晶接合によって形成される合金が接合層１４の側面から回り込んで第１金属層５１１（または４１１）に達することを防止でき、その結果、リッド剥離や気密不良を防止することができる。 On the other hand, when the lid material 22 and the package material 30 are joined to manufacture the light emitting device 10, the eutectic joint is formed only in a region substantially overlapping with the formation region of the Au film 6122. This is because Au is indispensable for the formation of eutectic junctions. In the lid material 22, since the Au film 6122 has a pull-down structure with respect to the Ni—Ti film 6121, the alloy formed by the eutectic bonding wraps around from the side surface of the bonding layer 14 and the first metal layer 511 ( Alternatively, it can be prevented from reaching 411), and as a result, lid peeling and poor airtightness can be prevented.
　より具体的には、下地膜６１Ａにろう材４１Ｂを融着させるときの共晶接合は、Ａｕ膜６１２２の形成領域にほぼ対応して形成され、Ａｕ膜６１２２が引き下げられた周辺領域には形成されない。すなわち、図１１に示すように、第２金属層４１２とろう材４１Ｂとの溶融により形成される合金層４３は、その内周側および外周側の周縁部においてＮｉ合金膜（共晶接合せずに残ったＮｉ－Ｔｉ膜６１２１）を有し、これらのＮｉ合金膜の間に、Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含む合金膜（共晶接合による合金膜）が形成される構成となる。このように、合金層４３の周縁部において、共晶接合せずに残ったＮｉ合金膜が存在することで、共晶接合によって形成される合金が接合層１４の側面から回り込んで第１金属層５１１（または４１１）に達することを防止できる。 More specifically, the eutectic bond when the brazing material 41B is fused to the base film 61A is formed substantially corresponding to the formation region of the Au film 6122, and is formed in the peripheral region where the Au film 6122 is pulled down. Not done. That is, as shown in FIG. 11, the alloy layer 43 formed by melting the second metal layer 412 and the brazing material 41B has a Ni alloy film (without eutectic bonding) on the inner peripheral side and the outer peripheral side peripheral portions thereof. It has a Ni—Ti film 6121) remaining on the surface, and an alloy film containing Ni, Ti, Au and Sn (an alloy film formed by eutectic bonding) is formed between these Ni alloy films. In this way, the presence of the Ni alloy film that remains without eutectic bonding at the peripheral edge of the alloy layer 43 causes the alloy formed by eutectic bonding to wrap around from the side surface of the bonding layer 14 to form the first metal. It can be prevented from reaching layer 511 (or 411).
　〔第１メタライズ膜の形成条件〕
　上述したリッド材２２では、発光装置１０における水晶リッド１２の好適な密着性を得るために、第２金属層６１２におけるＡｕ膜６１２２の形成幅の制御が有効であることが確認された。以下、実験に基づいた考察を行う。 [Conditions for forming the first metallized film]
In the lid material 22 described above, it was confirmed that control of the formation width of the Au film 6122 in the second metal layer 612 is effective in order to obtain suitable adhesion of the crystal lid 12 in the light emitting device 10. The following is a discussion based on experiments.
　ここでは、第１金属層５１１におけるＴｉ膜５１１１、Ａｕ膜５１１２およびＴｉ膜５１１３の各膜厚を２５０ｎｍ、５００ｎｍおよび５０ｎｍにそれぞれ固定した。また、第２金属層６１２におけるＮｉ－Ｔｉ膜６１２１およびＡｕ膜６１２２の各膜厚は３００ｎおよび５０ｎｍにそれぞれ固定した。そして、Ａｕ膜６１２２における引き下がり幅をパラメータとして変化させ、上述した製造方法にて発光装置１０を製造し、その外観評価と気密試験（ヘリウムリークテスト）による気密評価とを行った。外観評価では、水晶リッド１２側から見たメタライズ膜の変色と、水晶リッド１２における割れの有無とを目視確認した。また、接合材４０であるＡｕ－Ｓｎプリフォームの厚みは１５μｍに固定し、第２メタライズ膜４２はＮｉ合金／Ａｕ膜を使用し、その膜厚は合計５μｍに固定した。実験結果を以下の表３に示す。 Here, the film thicknesses of the Ti film 5111, Au film 5112, and Ti film 5113 in the first metal layer 511 were fixed to 250 nm, 500 nm, and 50 nm, respectively. The film thicknesses of the Ni—Ti film 6121 and the Au film 6122 in the second metal layer 612 were fixed at 300 n and 50 nm, respectively. Then, the pull-down width of the Au film 6122 was changed as a parameter, the light emitting device 10 was manufactured by the above-mentioned manufacturing method, and the appearance evaluation and the airtightness evaluation by the airtightness test (helium leak test) were performed. In the appearance evaluation, the discoloration of the metallized film seen from the crystal lid 12 side and the presence or absence of cracks in the crystal lid 12 were visually confirmed. The thickness of the Au—Sn preform, which is the bonding material 40, was fixed at 15 μm, and the second metallized film 42 used a Ni alloy / Au film, and the total film thickness was fixed at 5 μm. The experimental results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３の条件２８～３０の比較より、引き下がり構造を有していない条件２８では変色が生じて気密評価が“×”（総合評価も“×”）となっているのに対し、引き下がり構造を有している条件２９，３０では気密評価が“○”（総合評価も“○”）となっている。これより、リッド材２２におけるＡｕ膜６１２２の引き下がり構造は、共晶接合によって形成される合金の回り込みによるリッド剥離や気密不良を低減するのに有効であることが分かる。また、この引き下がり構造における引き下がり幅は、少なくとも２５μｍ以上あれば、その効果を発揮できることが分かる。 From the comparison of conditions 28 to 30 in Table 3, under condition 28 which does not have a pull-down structure, discoloration occurs and the airtightness evaluation is “x” (comprehensive evaluation is also “x”), whereas the pull-down structure is used. Under the conditions 29 and 30, the airtightness evaluation is "○" (the overall evaluation is also "○"). From this, it can be seen that the pull-down structure of the Au film 6122 in the lid material 22 is effective in reducing lid peeling and poor airtightness due to wraparound of the alloy formed by eutectic bonding. Further, it can be seen that the effect can be exhibited if the pulling width in this pulling structure is at least 25 μm or more.
　また、表３の条件３０～３５の比較より、Ａｕ膜６１２２のメタライズ幅によって変色の評価に違いが生じることが分かる。すなわち、条件３１，３２では、変色の外観評価が“◎”（総合評価も“◎”）となっているが、Ａｕ膜６１２２のメタライズ幅がこれよりも広い条件３０では、変色の外観評価が“○”（総合評価も“○”）となっている。これは、Ａｕ膜６１２２のメタライズ幅が広くなることで、下地膜における密着力の大きい領域面積も広くなり、発光装置１０のより外側の領域まで高い密着力で水晶リッド１２とセラミックパッケージ１１とが接合されたためと考えられる。すなわち、発光装置１０において、高い密着力で接合される領域が広くなることで、水晶リッド１２とセラミックパッケージ１１との熱膨張差による影響を受けやすくなり、その結果、条件３０は条件３１，３２に比べて変色が生じ易くなったと考えられる。 Further, from the comparison of the conditions 30 to 35 in Table 3, it can be seen that the evaluation of discoloration differs depending on the metallizing width of the Au film 6122. That is, under conditions 31 and 32, the appearance evaluation of discoloration is "◎" (the overall evaluation is also "◎"), but under condition 30 where the metallizing width of the Au film 6122 is wider than this, the appearance evaluation of discoloration is It is "○" (comprehensive evaluation is also "○"). This is because the metallizing width of the Au film 6122 is widened, so that the area of the base film having a large adhesive force is also widened, and the crystal lid 12 and the ceramic package 11 are brought together with a high adhesive force to the outer region of the light emitting device 10. It is probable that it was joined. That is, in the light emitting device 10, the region to be joined with high adhesion is widened, so that the crystal lid 12 and the ceramic package 11 are easily affected by the difference in thermal expansion. It is considered that discoloration is more likely to occur as compared with.
　また、Ａｕ膜６１２２のメタライズ幅が条件３１，３２よりも狭い条件３３～３５では、メタライズ幅が狭くなるほど変色の外観評価が低下し、総合評価も低下している。これは、Ａｕ膜６１２２のメタライズ幅が狭くなりすぎると、下地膜における密着力の大きい領域面積が小さくなり、水晶リッド１２とセラミックパッケージ１１との熱膨張差に十分に耐えることができなくなってリッド剥離が生じ易くなるためと考えられる。 Further, under conditions 33 to 35 in which the metallizing width of the Au film 6122 is narrower than the conditions 31 and 32, the appearance evaluation of discoloration is lowered as the metallizing width is narrowed, and the overall evaluation is also lowered. This is because if the metallizing width of the Au film 6122 becomes too narrow, the area of the base film having a large adhesive force becomes small, and the lid cannot sufficiently withstand the difference in thermal expansion between the crystal lid 12 and the ceramic package 11. This is thought to be because peeling is likely to occur.
　さらに、表３の条件３１～３４と条件３６～３９との比較より、Ａｕ膜６１２２の引き下がり幅を内側と外側とで異ならせる場合には、内側の引き下がり幅を外側よりも大きくする外寄せパターン（条件３６～３９）よりも、外側の引き下がり幅を内側よりも大きくする内寄せパターン（条件３１～３４）とする方が好ましいことが分かる。すなわち、外寄せパターンは、内寄せパターンに比べて、冷熱衝撃試験による水晶割れが発生しやすいことが明らかとなっている。これは、発光装置１０のより外側の領域において高い密着力で水晶リッド１２とセラミックパッケージ１１とが接合されると、水晶リッド１２とセラミックパッケージ１１との熱膨張差による影響を受けやすくなり、その結果、冷熱衝撃試験による水晶割れが生じ易くなると考えられる。 Furthermore, based on the comparison between conditions 31 to 34 and conditions 36 to 39 in Table 3, when the pulling width of the Au film 6122 is different between the inside and the outside, the pulling width on the inside is made larger than that on the outside. It can be seen that it is preferable to use an inward alignment pattern (conditions 31 to 34) in which the outer pull-down width is larger than that of the inner side than (conditions 36 to 39). That is, it has been clarified that the outer alignment pattern is more likely to cause crystal cracking in the thermal impact test than the inward alignment pattern. This is because when the crystal lid 12 and the ceramic package 11 are joined with a high adhesion force in the outer region of the light emitting device 10, it is easily affected by the difference in thermal expansion between the crystal lid 12 and the ceramic package 11. As a result, it is considered that crystal cracking is likely to occur in the thermal shock test.
　尚、本実施の形態３における上記説明では、下地膜６１Ａの最上層であるＡｕ膜６１２２のみが引き下がり構造を有する構成を例示している。しかしながら、本発明はこれに限定されるものではなく、下地膜６１Ａの最下層の膜（すなわちＴｉ膜５１１１）を除く任意の膜において、その膜を含む上層部分で引き下がり構造を適用してもよい。例えば、図１２に示すように、Ａｕ膜５１１２から上層となる部分で引き下がり構造を適用してもよい。 Note that the above description in the third embodiment illustrates a configuration in which only the Au film 6122, which is the uppermost layer of the base film 61A, has a pull-down structure. However, the present invention is not limited to this, and a pull-down structure may be applied to an upper layer portion including the film in any film other than the lowermost film (that is, Ti film 5111) of the base film 61A. .. For example, as shown in FIG. 12, a pull-down structure may be applied at a portion that is an upper layer from the Au film 5112.
　今回開示した実施形態は全ての点で例示であって、限定的な解釈の根拠となるものではない。したがって、本発明の技術的範囲は、上記した実施形態のみによって解釈されるものではなく、特許請求の範囲の記載に基づいて画定される。また、特許請求の範囲と均等の意味および範囲内での全ての変更が含まれる。 The embodiment disclosed this time is an example in all respects and does not serve as a basis for a limited interpretation. Therefore, the technical scope of the present invention is not construed solely by the above-described embodiments, but is defined based on the description of the claims. It also includes all changes within the meaning and scope of the claims.
　例えば、上記説明では、発光装置１０のリッド材２０～２２において、リッド本体を水晶リッド１２とする場合を例示した。しかしながら、本発明はこれに限定されるものではなく、リッド本体には、石英ガラスを用いるものであってもよい。すなわち、従来の石英ガラスを用いたリッド材では下地膜にＣｒ膜が用いられていたが、石英ガラスをリッド本体とした場合に、下地膜として上述の下地膜４１Ａ，５１Ａまたは６１Ａを用いれば、膜剥がれや密着性の点でより優れた性能が得られることが確認された。これは、下地膜をＣｒ膜から下地膜４１Ａ，５１Ａまたは６１Ａに変更したことで、ろう材であるＡｕおよびＳｎの拡散が抑制されたことに起因すると考えられる。 For example, in the above description, in the lid materials 20 to 22 of the light emitting device 10, a case where the lid body is a crystal lid 12 is illustrated. However, the present invention is not limited to this, and quartz glass may be used for the lid body. That is, in the conventional lid material using quartz glass, a Cr film is used as the base film, but when quartz glass is used as the lid body, if the above-mentioned base film 41A, 51A or 61A is used as the base film, It was confirmed that better performance can be obtained in terms of film peeling and adhesion. It is considered that this is because the diffusion of the brazing materials Au and Sn was suppressed by changing the base film from the Cr film to the base film 41A, 51A or 61A.
　また、上記説明の発光装置１０では、セラミックパッケージ１１と水晶リッド１２とを接合する接合層１４は、セラミックパッケージ１１および水晶リッド１２における枠形状の接合面に対してほぼ全面に（枠の幅方向に対して偏りなく）形成されている。しかしながら、本発明はこれに限定されるものではなく、図１３に示すように、接合層１４は、セラミックパッケージ１１および水晶リッド１２における枠形状の接合面に対して内周側寄りに形成されていてもよい。このように、接合層１４を接合面に対して内周側寄りに形成した場合、セラミックパッケージ１１と水晶リッド１２との熱膨張差による応力の影響を少なくすることができ、リッド割れなどが生じにくくなる。 Further, in the light emitting device 10 described above, the bonding layer 14 for joining the ceramic package 11 and the crystal lid 12 is substantially entirely on the frame-shaped bonding surface of the ceramic package 11 and the crystal lid 12 (in the width direction of the frame). It is formed (without bias). However, the present invention is not limited to this, and as shown in FIG. 13, the bonding layer 14 is formed closer to the inner peripheral side with respect to the frame-shaped bonding surface of the ceramic package 11 and the crystal lid 12. You may. When the bonding layer 14 is formed closer to the inner peripheral side with respect to the bonding surface in this way, the influence of stress due to the difference in thermal expansion between the ceramic package 11 and the crystal lid 12 can be reduced, and lid cracking or the like occurs. It becomes difficult.
　さらに、上記説明の発光装置１０では、ＬＥＤ１３をパッケージ内に封止するために、セラミックパッケージ１１を段面コ字形状とし、水晶リッド１２を平板形状としている。しかしながら、本発明はこれに限定されるものではなく、図１４に示す発光装置１０’のように、平板形状のセラミックベース１１’と段面コ字形状の水晶リッド１２’とを組み合わせて、ＬＥＤ１３を封止するパッケージを形成してもよい。この場合でも、セラミックベース１１’と段面コ字形状の水晶リッド１２’とを接合する接合層１４は、上記説明の発光装置１０と同様の構成とすることができる。 Further, in the light emitting device 10 described above, the ceramic package 11 has a stepped U-shape and the crystal lid 12 has a flat plate shape in order to seal the LED 13 in the package. However, the present invention is not limited to this, and as in the light emitting device 10'shown in FIG. 14, the flat plate-shaped ceramic base 11'and the stepped U-shaped crystal lid 12' are combined to form the LED13. You may form a package to seal. Even in this case, the bonding layer 14 for joining the ceramic base 11'and the stepped U-shaped crystal lid 12'can have the same configuration as the light emitting device 10 described above.
１０，１０’　　発光装置
１１　　セラミックパッケージ（パッケージ基台）
１１’　　セラミックベース（パッケージ基台）
１１１　　キャビティ
１２，１２’　　水晶リッド（リッド本体）
１３　　ＬＥＤチップ
１４　　接合層
２０，２１，２２　　リッド材
３０　　パッケージ材
４１，５１，６１　　第１メタライズ膜
４１Ａ，５１Ａ，６１Ａ　　下地膜（リッド材の下地膜）
４１Ｂ　　ろう材
４２　　第２メタライズ膜
４１１，５１１　　第１金属層（第１層）
５１１１　　Ｔｉ膜
５１１２　　Ａｕ膜（緩衝膜）
５１１３　　Ｔｉ膜（緩衝膜）
４１２，６１２　　第２金属層
４１２１，６１２１　　Ｎｉ－Ｔｉ膜
４１２２，６１２２　　Ａｕ膜
４３　　合金層（第２層） 10,10'Light emitting device 11 Ceramic package (package base)
11'Ceramic base (package base)
111 Cavity 12, 12'Crystal lid (lid body)
13 LED chip 14 Bonding layer 20,21,22 Lid material 30 Package material 41,51,61 First metallized film 41A, 51A, 61A Base film (base film of lid material)
41B Brazing material 42 Second metallized film 411,511 First metal layer (first layer)
5111 Ti film 5112 Au film (buffer film)
5113 Ti membrane (buffer membrane)
421,612 Second metal layer 4121,6121 Ni— Ti film 4122,6122 Au film 43 Alloy layer (second layer)

Claims (16)

  1. 　ＬＥＤをパッケージ内に封止してなる発光装置に用いられるリッド材であって、
    　前記ＬＥＤの照射光に対して透過性を有するリッド本体と、
    　前記リッド本体の封止面に形成される第１メタライズ膜とを含み、
    　前記第１メタライズ膜は、前記リッド本体の上に直接形成される第１層と、前記第１層の上に形成される第２層とを含んでおり、
    　前記第１層は、膜厚２０～７００ｎｍのＴｉ膜を含む層であり、
    　前記第２層は、Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含む合金膜を有していることを特徴とするリッド材。     A lid material used in a light emitting device in which an LED is sealed in a package.
    A lid body that is transparent to the LED irradiation light,
    Including a first metallized film formed on the sealing surface of the lid body,
    The first metallized film includes a first layer formed directly on the lid body and a second layer formed on the first layer.
    The first layer is a layer containing a Ti film having a film thickness of 20 to 700 nm.
    The second layer is a lid material having an alloy film containing Ni, Ti, Au and Sn.
  2. 　請求項１に記載のリッド材であって、
    　前記第１層に含まれる前記Ｔｉ膜は、膜厚２００～３００ｎｍのＴｉ膜であることを特徴とするリッド材。     The lid material according to claim 1.
    The Ti film contained in the first layer is a lid material having a film thickness of 200 to 300 nm.
  3. 　請求項１または２に記載のリッド材であって、
    　前記第１層は、表面に酸化チタンからなる酸化皮膜を有していることを特徴とするリッド材。     The lid material according to claim 1 or 2.
    The first layer is a lid material having an oxide film made of titanium oxide on its surface.
  4. 　請求項１から３の何れか１項に記載のリッド材であって、
    　前記第１層は、前記Ｔｉ膜の上に、前記Ｔｉ膜に近い側から順に積層されたＡｕ膜および他のＴｉ膜からなる緩衝膜を有していることを特徴とするリッド材。     The lid material according to any one of claims 1 to 3.
    The lid material is characterized in that the first layer has a buffer film made of an Au film and another Ti film laminated in order from the side closer to the Ti film on the Ti film.
  5. 　請求項１から４の何れか１項に記載のリッド材であって、
    　前記第２層は、その内周縁側および外周縁側においてＮｉ合金膜を有し、これらのＮｉ合金膜の間に、Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含む前記合金膜が形成されていることを特徴とするリッド材。     The lid material according to any one of claims 1 to 4.
    The second layer has a Ni alloy film on the inner peripheral edge side and the outer peripheral edge side thereof, and the alloy film containing Ni, Ti, Au and Sn is formed between these Ni alloy films. Lid material to be.
  6. 　請求項１から５の何れか１項に記載のリッド材であって、
    　前記リッド本体が水晶であることを特徴とするリッド材。     The lid material according to any one of claims 1 to 5.
    A lid material characterized in that the lid body is quartz.
  7. 　ＬＥＤをパッケージ内に封止してなる発光装置に用いられるリッド材の製造方法であって、
    　前記ＬＥＤの照射光に対して透過性を有するリッド本体の封止面に下地膜を形成する工程として、
    　前記リッド本体の封止面に膜厚２０～７００ｎｍのＴｉ膜を含む第１層を形成する第１工程と、
    　前記第１工程で形成された前記第１層の最上層にあるＴｉ膜を酸化させて、表面に酸化チタンからなる酸化皮膜を形成する第２工程と、
    　前記第２工程後の前記第１層の上に、前記第１層に近い側から順に積層されるＮｉ合金膜およびＡｕ膜を含む第２層を形成する第３工程と、
    　前記第３工程で形成された前記Ａｕ膜の上に、Ａｕ－Ｓｎプリフォームとして形成されたろう材を融着させる第４工程とを有することを特徴とするリッド材の製造方法。     A method for manufacturing a lid material used in a light emitting device in which an LED is sealed in a package.
    As a step of forming a base film on the sealing surface of the lid body having transparency to the irradiation light of the LED,
    The first step of forming a first layer containing a Ti film having a film thickness of 20 to 700 nm on the sealing surface of the lid body, and
    A second step of oxidizing the Ti film on the uppermost layer of the first layer formed in the first step to form an oxide film made of titanium oxide on the surface.
    A third step of forming a second layer containing a Ni alloy film and an Au film, which are laminated in order from the side closer to the first layer, on the first layer after the second step.
    A method for producing a lid material, which comprises a fourth step of fusing a brazing material formed as an Au—Sn preform on the Au film formed in the third step.
  8. 　請求項７に記載のリッド材の製造方法であって、
    　前記第１工程で形成される前記Ｔｉ膜は、２００～３００ｎｍの膜厚を有することを特徴とするリッド材の製造方法。     The method for manufacturing a lid material according to claim 7.
    A method for producing a lid material, wherein the Ti film formed in the first step has a film thickness of 200 to 300 nm.
  9. 　請求項７または８に記載のリッド材の製造方法であって、
    　前記第１工程では、前記Ｔｉ膜の上に、前記Ｔｉ膜に近い側から順に積層されるＡｕ膜および他のＴｉ膜からなる緩衝膜を形成することを特徴とするリッド材の製造方法。     The method for producing a lid material according to claim 7 or 8.
    The first step is a method for producing a lid material, which comprises forming a buffer film composed of an Au film and another Ti film which are laminated in order from the side closer to the Ti film on the Ti film.
  10. 　請求項７から９の何れか１項に記載のリッド材の製造方法であって、
    　前記下地膜は、最下層の膜を除く任意の膜において、前記任意の膜を含む上層部分で引き下がり構造を有しており、
    　前記引き下がり構造では、前記引き下がり構造に含まれる膜の内周縁がその他の膜の内周縁よりも外側に引き下げられ、前記引き下がり構造に含まれる膜の外周縁がその他の膜の外周縁よりも内側に引き下げられて形成されることを特徴とするリッド材の製造方法。     The method for manufacturing a lid material according to any one of claims 7 to 9.
    The undercoat film has a pull-down structure in an upper layer portion including the arbitrary film in any film other than the lowermost layer film.
    In the pull-down structure, the inner peripheral edge of the film included in the pull-down structure is pulled outward from the inner peripheral edge of the other film, and the outer peripheral edge of the film included in the pull-down structure is inward of the outer peripheral edge of the other film. A method for producing a lid material, which is characterized by being pulled down and formed.
  11. 　請求項７から１０の何れか１項に記載のリッド材の製造方法であって、
    　前記リッド本体が水晶であることを特徴とするリッド材の製造方法。     The method for manufacturing a lid material according to any one of claims 7 to 10.
    A method for manufacturing a lid material, wherein the lid body is made of quartz.
  12. 　ＬＥＤをパッケージ内に封止してなる発光装置であって、
    　前記ＬＥＤと、
    　前記ＬＥＤをキャビティ内に格納するパッケージ基台と、
    　前記パッケージ基台のキャビティ開口を封止するリッド材とを有しており、
    　前記リッド材は、前記請求項１から６の何れか１項に記載のリッド材であることを特徴とする発光装置。     A light emitting device in which an LED is sealed in a package.
    With the LED
    A package base for storing the LED in the cavity and
    It has a lid material that seals the cavity opening of the package base.
    The light emitting device, wherein the lid material is the lid material according to any one of claims 1 to 6.
  13. 　請求項１２に記載の発光装置であって、
    　前記パッケージ基台は、窒化アルミニウムにより形成されていることを特徴とする発光装置。     The light emitting device according to claim 12.
    The package base is a light emitting device characterized by being formed of aluminum nitride.
  14. 　請求項１２または１３に記載の発光装置であって、
    　前記ＬＥＤは、深紫外用ＬＥＤであることを特徴とする発光装置。     The light emitting device according to claim 12 or 13.
    The LED is a light emitting device characterized by being a deep ultraviolet LED.
  15. 　請求項１２から１４の何れか１項に記載の発光装置であって、
    　前記パッケージ基台および前記リッド材は、接合層を介して接合されており、
    　前記接合層は、前記リッド本体に近い順から形成される第１層、第２層、第３層および第４層を有しており、
    　前記第１層は、前記リッド本体の上に直接形成され、膜厚２０～７００ｎｍのＴｉ膜を含む層であり、
    　前記第２層は、Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含む合金層であり、
    　前記第３層は、Ｎｉ、Ｔｉ、ＡｕおよびＳｎを含み、前記第２層に比べてＡｕの含有量が少ない合金層であり、
    　前記第４層は、Ｎｉメッキ層であることを特徴とする発光装置。     The light emitting device according to any one of claims 12 to 14.
    The package base and the lid material are joined via a joining layer.
    The bonding layer has a first layer, a second layer, a third layer, and a fourth layer formed in the order closest to the lid body.
    The first layer is a layer formed directly on the lid body and containing a Ti film having a film thickness of 20 to 700 nm.
    The second layer is an alloy layer containing Ni, Ti, Au and Sn.
    The third layer is an alloy layer containing Ni, Ti, Au and Sn, and has a lower Au content than the second layer.
    The fourth layer is a light emitting device characterized by being a Ni-plated layer.
  16. 　前記第２層は共晶状態の合金層であり、前記第３層は非共晶状態の合金層であることを特徴とする発光装置。 A light emitting device characterized in that the second layer is an alloy layer in a eutectic state and the third layer is an alloy layer in a non-eutectic state.
PCT/JP2020/025716 2019-07-25 2020-06-30 Lid material for light-emitting device, method for manufacturing lid material, and light-emitting device WO2021014904A1 (en)

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