WO2008075683A1 - Support d'enregistrement d'informations optiques - Google Patents

Support d'enregistrement d'informations optiques Download PDF

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Publication number
WO2008075683A1
WO2008075683A1 PCT/JP2007/074319 JP2007074319W WO2008075683A1 WO 2008075683 A1 WO2008075683 A1 WO 2008075683A1 JP 2007074319 W JP2007074319 W JP 2007074319W WO 2008075683 A1 WO2008075683 A1 WO 2008075683A1
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Prior art keywords
recording
alloy
recording film
optical information
film
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PCT/JP2007/074319
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English (en)
Japanese (ja)
Inventor
Hironori Kakiuchi
Hideo Fujii
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Kabushiki Kaisha Kobe Seiko Sho
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Publication of WO2008075683A1 publication Critical patent/WO2008075683A1/fr

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Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B7/2437—Non-metallic elements
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B7/2433—Metals or elements of Groups 13, 14, 15 or 16 of the Periodic Table, e.g. B, Si, Ge, As, Sb, Bi, Se or Te
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/2431—Metals or metalloids group 13 elements (B, Al, Ga, In)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24312—Metals or metalloids group 14 elements (e.g. Si, Ge, Sn)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24318—Non-metallic elements
    • G11B2007/2432—Oxygen

Definitions

  • the present invention relates to an optical information recording medium.
  • the optical information recording medium of the present invention is used as the current CD (Compact Disc) and DVD (Digital Versatile Disc), the next generation optical information recording medium HD DVD and BD (Blu-ray Disc), and in particular, blue-violet. It is suitably used as a write-once type high-density optical information recording medium.
  • Optical information recording media are roughly classified into three types: read-only, rewritable, and write-once types, depending on the recording and playback method.
  • write-once optical discs record data using changes in the physical properties of recording films (hereinafter also referred to as recording layers and optical recording films) irradiated with an energy beam such as laser light. To do.
  • a write-once optical disc can record information, but it cannot be erased or rewritten.
  • write-once optical discs such as CD-R, DVD-R, and DVD + R are used for applications that require data tampering prevention such as document files and image files.
  • organic dye materials such as cyanine dyes, phthalocyanine dyes, and azo dyes are known.
  • this organic dye material is irradiated with a laser beam, the dye and the substrate are decomposed, melted and vaporized by the heat absorption of the dye to form a recording mark.
  • organic dye material it is necessary to dissolve the dye in an organic solvent and then apply it onto the substrate, resulting in low productivity! There is also a problem in terms of long-term stable storage of recorded signals.
  • Non-patent Document 1 Patent Documents 1 to 9, etc.
  • phase change Te oxide
  • alloying Cu and Si laminated structure, etc.
  • Patent Document 1 discloses a single-layer type inorganic material thin film
  • Patent Document 2 discloses a two-layer type.
  • This punching method has a problem that the recording sensitivity is lower than the recording method due to phase change or alloying of the inorganic material thin film.
  • This local recording mark forming method is a method in which an inorganic material thin film as a recording film is melted with a laser beam to form holes, pits, and the like. For this reason, it is necessary to raise the temperature to above the melting point of the inorganic material thin film, and inevitably high laser power is required.
  • the thin film of the inorganic material is melted, and the melted film tends to remain like water droplets in a portion where holes, pits, and the like are formed.
  • the presence of the remaining droplet-like molten film hinders the change in reflectivity of the recording mark portion and prevents the signal modulation from increasing.
  • Non-Patent Document 1 discloses a technique of using a Te thin film having a low melting point and low thermal conductivity to make a recording mark hole with low laser power.
  • Patent Documents 3 and 4 disclose optical information recording films in which a reaction layer made of a Cu-based alloy containing A1 and a reaction layer containing Si or the like are laminated on a substrate.
  • the region where the elements contained in each reaction layer are mixed is partially formed on the substrate by the laser beam irradiation, and the reflectivity changes greatly. Therefore, it is described that recording can be performed with high sensitivity using a short wavelength laser such as a blue laser.
  • Patent Documents 5, 6 and 9 prevent a decrease in signal C / N ratio (carrier-to-noise ratio) due to a recording mark, and a high signal C / N and reflection.
  • An optical information recording medium having a high efficiency is disclosed, and a Cu-based alloy containing In as a recording film (Patent Document 5), an Ag-based alloy containing Bi (Patent Document 6), an Sn-based alloy containing Bi, etc. (Patent Document 9) are listed.
  • Patent Documents 7 and 8 relate to an optical information recording medium using a Sn-based alloy.
  • Patent Document 7 includes two or more elements that can be aggregated at least partially in the heat treatment step in the alloy layer.
  • An optical information recording medium is disclosed. Specifically, it is an optical information recording medium having a high melting point and a high thermal conductivity, comprising a Sn—Cu based alloy layer having a thickness including Bi and In;
  • Patent Document 8 discloses an optical information recording film in which an oxidizable substance that is easier to oxidize than Sn or Bi is added to an Sn-Bi alloy having excellent recording characteristics. It is emphasized that it shows excellent durability.
  • Patent Document 1 JP-A 52-130304
  • Patent Document 2 Japanese Patent Publication No. 53-31104
  • Patent Document 3 JP 2004-5922 Noriyuki
  • Patent Document 4 JP 2004-234717 A
  • Patent document 5 JP 2002-172861 A
  • Patent Document 6 JP 2002-144730 A
  • Patent Document 7 Japanese Patent Laid-Open No. 2-117887
  • Patent Document 8 JP 2001-180114 A
  • Patent Document 9 JP 2002-225433 A
  • Japanese Patent Laid-Open No. 2-117887 discloses 55 mass% 11-40 mass% 31-5 quality i% Cu alloy (in terms of atomic%, 53.5 atomic% 11-37.7 atoms % 31-8.8 atom% Cu alloy) is disclosed.
  • this optical recording film composition it is difficult to obtain a practical signal C / N ratio.
  • the thickness of the alloy layer disclosed in this patent document is 2 to 4 nm. For the above alloy composition, the film thickness is too thin, and thus a practically usable reflectance was not obtained.
  • Japanese Patent Application Laid-Open No. 2001-180114 discloses an optical recording film in which an Sn-Bi alloy is added with an oxidizable substance that is more easily oxidized than Sn or Bi.
  • a signal C / N ratio and recording sensitivity at levels exceeding those of the Sn-based alloy recording film of the present invention described later were not obtained.
  • Sn based alloy of the optical recording layer alloy composition is 84 atomic 0/0 Sn- 10 atoms 0/0 Z n- 6 atomic% 313 discloses ing.
  • the signal strength nor the Sn-base alloy provided a signal C / N ratio, recording sensitivity, or reflectivity that exceeded the level of the Sn-base alloy of the present invention described later.
  • the metal-based recording film has a great advantage that the material is remarkably stable as compared with the organic recording film, as described above. For this reason, the development of a practical recording film that satisfies the above-mentioned characteristics with metallic materials can be achieved by using BD (Blu-ray Disc) —R, HD DVD ( Digital Versatile Disc) —R is extremely important in providing users with R.
  • BD Blu-ray Disc
  • HD DVD Digital Versatile Disc
  • the present inventors have developed a next-generation blue-purple that satisfies the required characteristics shown in the above (1) to (4), has high recording accuracy, and is inexpensive in terms of cost. It was found that a 1n alloy having a low melting point and a low environmental load is suitable as a hole-drilling recording film with good recording sensitivity using a laser.
  • the recording film (optical information recording film) made of the In alloy can provide good recording characteristics, but the recording sensitivity (drilling sensitivity) is not sufficient. The problem of the need for high laser power was clarified.
  • the present invention has been made by paying attention to such a situation, and the object thereof is to enable drilling (recording) with a relatively low laser power, and while having good recording characteristics, It is an object of the present invention to provide an optical information recording medium having a recording film capable of obtaining a good signal modulation degree.
  • the gist of the optical information recording medium according to the present invention for achieving this object is an optical information recording medium having a recording film on which a recording mark is formed by irradiation of an energy beam. Is composed of a mixture of In alloy and oxide.
  • the In alloy in the recording film of the optical information recording medium preferably contains 1 to 65 atomic% of one or two kinds of Ni and Co, with the balance being In and inevitable impurities. Further, the content of one or two of Ni and Co in the In alloy is preferably 50 atomic% or less. Further, the content of one or two of Ni and Co in the In alloy is preferably 20 atomic% or more. In addition, the In alloying force containing Ni and Co, and further containing 19 atomic% or less (not including 0 atomic%) of one or more selected from Sn, Bi, Ge and Si S preferable.
  • the oxide in the recording film of the optical information recording medium is preferably one kind selected from silicon, aluminum and niobium oxides, or a composite oxide of two or more kinds thereof. Further, the mixing ratio of the In alloy and the oxide in the recording film of the optical information recording medium is a volume ratio of the In alloy to the oxide (In alloy volume) / (oxide volume) of 3 to 10; Preferred to be in the range! / ,.
  • the recording film of the optical information recording medium is composed of a mixture of an In alloy and an oxide that is a dielectric component, so that heat transfer of these mixture recording films (optical information recording film) is achieved.
  • the conductivity and suppressing the diffusion of heat input by the laser it becomes possible to use energy efficiently.
  • the thermal conductivity of a recording film made of a mixture of an In alloy and an oxide is significantly lower than that of a recording film formed only of an In alloy.
  • the diffusion of heat input by the laser in the recording film can be suppressed. Therefore, a recording film made of a mixture of In alloy and oxide can be melted with a lower laser power, and local recording marks (holes, pits, etc.) can be formed with a lower laser power. As a result, it is possible to obtain a recording film that has a good recording characteristic and a better signal modulation degree.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the optical information recording medium of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another embodiment of the optical information recording medium of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing another embodiment of the optical information recording medium of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing another embodiment of the optical information recording medium of the present invention.
  • FIG. 5 is an explanatory diagram showing the relationship between the recording laser power of the recording film and the signal modulation degree in Example 1.
  • FIG. 6 is an explanatory diagram showing the relationship between the recording laser power of the recording film and the signal C / N ratio in Example 1.
  • FIG. 7 is an explanatory view showing the result of measuring the thermal conductivity of the recording film in Example 1.
  • FIG. 8 is an explanatory diagram showing the relationship between the recording laser power of the recording film and the signal modulation degree in Example 2.
  • FIG. 9 is an explanatory diagram showing the relationship between the recording laser power of the recording film and the signal C / N ratio in Example 2.
  • FIG. 10 is an explanatory diagram showing the relationship between the recording laser power of the recording film and the signal modulation degree in Example 3.
  • FIG. 11 is an explanatory diagram showing the relationship between the recording laser power of the recording film and the signal C / N ratio in Example 3.
  • FIGS.! To 4 exemplify a write-once type optical information recording medium of the present invention capable of recording and reproducing data by irradiating a recording film with an energy beam such as a laser beam having a wavelength of about 350 to 700 nm.
  • an energy beam such as a laser beam having a wavelength of about 350 to 700 nm.
  • FIG. 1 and Fig. 2 (A) and Fig. 3 (B) and (B) and (D) in FIG. 4 are those in which the recording location is formed in a convex shape
  • FIG. 1, (B) in FIG. 2, (A) in FIG. 3 and (A) in FIG. (C) shows an example in which the recording location is concave.
  • An optical disc 10 in FIG. 1 includes a support substrate 1, an optical adjustment layer 2, dielectric layers 3 and 5, and a dielectric layer.
  • a recording film 4 sandwiched between 3 and 5 and a light transmission layer 6 are provided.
  • the optical disk 10 in FIG. 2 includes a support substrate 1, a 0th recording film group (a group of layers including an optical adjustment layer, a dielectric layer, and a recording film) 7A, an intermediate layer 8, and a first recording film.
  • a group (a group of layers including an optical adjustment layer, a dielectric layer, and a recording film) 7B and a light transmission layer 6 are provided.
  • Fig. 3 shows an example of a single-layer DVD-R, single-layer DVD + R, single-layer HD DVD-R type optical disc
  • Fig. 4 shows a double-layer DVD-R, dual-layer DVD + R, double-layer.
  • HD DVD Example of R type optical disc.
  • Reference numeral 8 denotes an intermediate layer
  • reference numeral 9 denotes an adhesive layer.
  • the group of layers constituting the 0th and 1st recording film groups 7A and 7B in Figs. 2 and 4 consist of only one recording film in addition to the three-layer structure or the two-layer structure. It doesn't matter.
  • the three-layer structure is composed of a dielectric layer / recording film / dielectric layer, a dielectric layer / recording film / optical adjustment layer, a recording film / dielectric layer / optical adjustment layer, etc. from the upper side of the figure.
  • the two-layer structure is composed of a recording film / dielectric layer, a dielectric layer / recording film, a recording film / optical adjustment layer, an optical adjustment layer / recording film, and the like from the upper side of the figure.
  • the recording film 4 is made of a mixture of an In alloy and an oxide such as SiO. It is characterized by enabling high density.
  • the optical information recording medium of the present invention selectively has dielectric layers 3 and 5 adjacent to the recording film 4 made of a mixture of this In alloy and oxide.
  • dielectric layers 3 and 5 are provided, Si
  • the main component is an oxide of an element selected from Mg, Ta, Zr, Mn, In and the like.
  • the dielectric layers 3 and 5 made of these oxides have a dielectric film and a recording film made of a mixture of an In alloy and an oxide when forming a local recording mark with laser power. Control the wettability of 4. This makes it possible to form local recording marks with laser power. In this way, it is possible to suppress the uneven distribution of the molten In in the form of water droplets and the uneven distribution of In as a mass, and to improve the formation of local recording marks. This prevents a decrease in signal modulation. Further, the dielectric layer made of these oxides also has a dielectric function (effect) that protects the recording film 4 and increases the reflectance and the signal C / N ratio as the dielectric layer.
  • the dielectric layers 3 and 5 are adjacent to the recording film 4 made of a mixture of In alloy and oxide in order to control the wettability of the recording film and perform the dielectric function.
  • the dielectric layer 3 is preferably located between the recording film 4 and the substrate 1.
  • the dielectric layer 5 is preferably located between the recording film 4 and the light transmission layer 6.
  • the force S for forming the recording film 4 from a mixture of an In alloy and an oxide such as SiO first, the composition of the In alloy will be described below.
  • the melting point of pure In is a low melting point of 156.6 ° C, which is significantly lower than that of Al at 660 ° C, Ag at 962 ° C, and Cu at 1085 ° C. For this reason, In can be melted and deformed even at a lower temperature with low laser power, and there is a possibility that the above-mentioned local recording marks (holes, pits, etc.) can be formed with good marking performance.
  • the melting point is too low, and the surrounding recording film not irradiated with the laser is melted at the time of the local recording mark by laser irradiation. Is likely to get worse.
  • the surface roughness of the formed recording film becomes rough, and there is a disadvantage that the reflectance and sensitivity are low in environmental resistance.
  • the composition of the In alloy preferably includes 1 to 65 atomic percent of one or two of Ni and Co, and the balance is In and unavoidable impurities.
  • the upper limit of the content of one or two of Ni and Co is preferably 50 atomic%.
  • the lower limit of the content of one or two of Ni and Co is preferably 20 atomic%. That is, the content range of one or two of Ni and Co is set to a narrow range of 1 to 50 atomic percent or a narrow range of 20 to 65 atomic percent with respect to the range of! Is preferably in a narrower range of 20 to 50 atomic%.
  • the composition of the In alloy is composed of the balance In and unavoidable impurities.
  • Examples of elements belonging to Group 8 of the periodic table having such effects include Fe, Ru, Rh, Pd, Os, Ir, Ni, Co, and Pt in addition to Ni and Co. However, the effects of Ni and Co are significantly greater than these elements. In addition, it is allowed to contain the above-mentioned Fe, Ru, Rh, Pd, Os, Ir, Pt, etc. as (unavoidable) impurities.
  • the composition of the In alloy is that, as described above, In contains one or two kinds of Ni and Co, and further contains one or more kinds of Sn, Bi, Ge and Si at 19 atomic% or less. Lower (not including 0 atomic%) can be included. By including these Sn, Bi, Ge and Si in addition to Ni and Co, the jitter value can be further reduced. Although this mechanism is not necessarily clear, it is presumed that Sn, Bi, Ge, and Si achieve lateral heat bleed suppression by lowering the thermal conductivity without increasing the melting point.
  • the composition of the In alloy includes 1 to 65 atomic% of one or two kinds of Ni and Co, and further 19 atomic% or less (0 atomic%) of one or more kinds of Sn, Bi, Ge and Si. Contained, and the remainder shall consist of In and inevitable impurities. At this time, the content of one or two of these Ni and Co may be made narrower within the above preferred ranges.
  • the recording film 4 is composed of such a mixture of In alloy and oxide.
  • the thermal conductivity of the recording film 4 is controlled.
  • the laser is used. This makes it possible to use the energy more efficiently by suppressing the diffusion of the input heat.
  • This oxide is one kind of force selected from silicon, aluminum and niobium oxides, or two or more kinds of these widely used as dielectric layer components as the dielectric layers 3 and 5.
  • a composite oxide is preferable. That is, the oxide is preferably composed of one (single) oxide selected from SiO, Al 2 O, NbO, NbO, Nb 2 O, or the like, or two or more (plural) complex oxides.
  • oxides used as the dielectric layer component include oxides of elements selected from Mg, Ta, Zr, Mn, In, and the like, which can be used. However, among these, it is mixed with In alloy to lower the thermal conductivity of the In alloy film, and the recording film 4 having the functions of the dielectric layers 3 and 5 is highly effective for silicon, aluminum and aluminum.
  • Niobium oxide is one kind of force selected from silicon, aluminum and niobium oxides, or two or more kinds of these widely used as dielectric layer components as the dielectric layers 3 and 5.
  • a composite oxide is preferable. That is
  • the thermal conductivity of the recording film 4 of this mixture becomes lower than that of the In alloy alone. For this reason, it is possible to suppress the diffusion of the heat input by the laser and to efficiently use the energy for forming the local recording mark.
  • the mixture of the In alloy and the oxide that is a dielectric component can be melted by a lower laser power, and local recording marks can be formed. Become. As a result, it is possible to obtain a recording film having better recording characteristics and a better signal modulation degree than that of the recording film 4 made of only In alloy.
  • the recording film 4 made of a mixture of In alloy mixed with an oxide can be melted and deformed even at a lower temperature than the low laser performance, but the surrounding recording film not irradiated with the laser is dissolved.
  • An appropriate melting point can be obtained without melting. This effect can be exhibited by low laser power marking of laser light of each wavelength of 810 nm to 405 nm used for marking.
  • the surface roughness of the recording film can be kept small, and high reflectivity, high sensitivity, and high environmental resistance can be obtained within the range of the film thickness of the recording film described later.
  • the recording film 4 made of a mixture of an In alloy and an oxide
  • the recording film 4 in which the dielectric layers 3 and 5 and the recording film 4 are mixed is formed.
  • the recording film 4 having the functions of the dielectric layers 3 and 5 is formed.
  • it is compatible with optical information recording and reproduction technology using short-wavelength lasers such as blue-violet lasers. Allows densification and guarantees.
  • (1) high-quality signal writing / reading such as (1) high signal C / N ratio and low jitter, (2) in addition to high recording sensitivity, (3) high reflection from recording film Rate, (4) high corrosion resistance, etc. can be made possible. Further, the recording accuracy is high and the cost is low, and a practical recording film can be obtained.
  • the mixing ratio of the In alloy and the oxide such as SiO in the recording film 4 (the mixing ratio of the oxide to the In alloy) is determined, and the volume of the In alloy and the oxide is determined.
  • the ratio (In alloy volume) / (oxide volume) is preferably 3 to 10;
  • the recording film 4 made of a mixture of the In alloy and the oxide has a thickness in the range of 1 to 50 nm, depending on the structure of the optical information recording medium, in order to form a reliable recording film with stable accuracy. It is good to do.
  • the recording film 4 consisting of a mixture of In alloy and oxide in this thickness range shows high recording sensitivity, especially for laser light with a wavelength in the range of 350 to 700 nm, and excellent optical information writing / reading accuracy. It becomes an optical information recording medium to be exhibited.
  • the thickness of the recording film is less than 1 nm, the optical recording film is too thin. Therefore, even if an optical adjustment layer or a dielectric layer is provided above or below the optical recording film, a pore is formed on the film surface of the optical recording film. If defects such as these are likely to occur, it will be difficult to obtain satisfactory recording sensitivity.
  • the more preferable thickness of the recording film is 8 nm or more and 30 nm or less, more preferably 12 nm or more and 20 nm or less when no dielectric layer or optical adjustment layer is provided.
  • the thickness is 3 nm or more and 30 nm or less, more preferably 5 nm or more and 20 nm or less.
  • the recording film 4 made of the mixture of In alloy and oxide of the present invention formed the recording film 4 in which the dielectric layers 3 and 5 and the recording film 4 were mixed. It can be said that the recording film 4 having the function of 5 was formed. Therefore, a mode in which the dielectric layers 3 and 5 are not provided is possible.
  • an oxide of a specific element selected from Si, Al, Nb, Mg, Ta, Zr, Mn, and In is used.
  • the dielectric layers 3 and 5 are preferably provided. Examples of these suitable oxides include SiO, Al 2 O, NbO, NbO, Nb 2 O, MgO, Ta 2 O, ZrO, MnO, and InO.
  • the dielectric layers 3 and 5 made of oxides of these elements control the wettability of the In-based alloy recording film 4 when a local recording mark is formed with laser power. Reduces signal modulation.
  • the dielectric layers 3 and 5 protect the recording film 4 as a dielectric layer, thereby greatly extending the storage period of recorded information (improves durability), and reflectivity and signal C / It also has the effect of increasing the N ratio.
  • the dielectric layers 3 and 5 made of oxides of these elements have the effect of the present invention of the dielectric layers on the formation of the dielectric layers, even if the dielectric layers are not only made of oxides of these elements. In the range that does not inhibit the above, it is allowed to contain oxides other than the oxides of these elements as impurities in the dielectric layer. Of course, if possible, a dielectric layer consisting essentially of oxides of these elements may be formed.
  • the thickness of these dielectric layers 3 and 5 is preferably in the range of 5 to 200 nm, depending on the structure of the optical information recording medium, in order to exert the effect of suppressing the decrease in the signal modulation. Is in the range of 10 to 150 nm. If the thickness is less than 5 nm, the dielectric layer is too thin. Even if a dielectric layer is provided, the above effect is not exhibited. On the other hand, if it is too thick, the effect is not improved. If it is too thick, there is a disadvantage that the productivity of the optical information recording medium is reduced. Therefore, it is not necessary to increase the thickness beyond 200 nm.
  • the means for forming the oxide layer of the specific element is not particularly limited, but the sputtering method is preferable!
  • the optical disk as a representative embodiment of the present invention includes the dielectric layers 3 and 5 including the dielectric layers 3 and 5 in the case where the oxide layer of the specific element other than the recording film 4 is not used.
  • the materials such as the optical adjustment layer 2 and the like are not particularly limited, and those usually used can be appropriately selected and used.
  • the material for the support substrate generally used polycarbonate resin (also referred to as PC substrate), norbornene-based resin, cyclic olefin-based copolymer, amorphous polyolefin and the like are preferably used.
  • As a material for the optical adjustment layer Ag, Au, Cu, Al, Ni, Cr, Ti, or an alloy thereof is preferably used.
  • the preferred wavelength of the laser beam irradiated for recording is in the range of 350 to 700 nm. If it is less than 35 Onm, light absorption by the cover layer (light transmission layer) becomes significant, making it difficult to write to and read from the optical recording film. become. Conversely, if the wavelength exceeds 700 nm and becomes excessive, the energy of the laser beam is reduced, making it difficult to form a recording mark on the optical recording film. From this point of view, the more preferable wavelength of the laser beam used for recording information is 350 nm or more and 660 or less, more preferably 380 or more and 650 or less.
  • the composition of the sputtering target used for forming the recording film or dielectric layer is basically the same as the desired alloy composition or oxide composition of the recording film or dielectric layer described above. Can be used. In other words, a set of sputtering targets By making the composition the same as the alloy composition and oxide composition of the recording film and dielectric layer described above, the recording film and dielectric layer formed by sputtering are formed into a desired alloy composition and oxide composition. be able to.
  • the recording film made of the mixture of the In alloy and the oxide of the present invention uses a separate In alloy target and an oxide target such as SiO, respectively, and a predetermined mixing ratio of the recording film described above.
  • the sputtering conditions are controlled so that each is sputtered simultaneously (co-sputtering), and DC sputtering or RF sputtering is used.
  • a single sputtering target was prepared by previously mixing an oxide such as SiO in the In alloy at a predetermined mixing ratio of the recording film described above, and this was performed by DC sputtering or RF sputtering.
  • the recording film of the present invention can be formed by sputtering.
  • the recording film of the present invention can be formed in which the In alloy and the oxide are uniformly dispersed and mixed, and the film quality of the mixture is homogenized.
  • the signal modulation degree and signal C / N ratio of each recording film made of a mixture of In alloy and oxide SiO were measured and evaluated.
  • an optical disk 10 of the type shown in FIG. 1 is prototyped, and a recording film 4 and a light transmission layer 6 are provided on the support substrate 1 in this order, and two layers are provided in that order.
  • Signal modulation and signal C / N ratio were measured and evaluated.
  • the results are shown in Figs.
  • the thermal conductivity of each recording film consisting of a mixture of In alloy and oxide SiO The rate was measured.
  • the result is shown in FIG. 5 and 6, the line connecting the diamond marks is Invention Example 1, the line connecting the square marks is Invention Example 2, the line connecting the triangle marks is Comparative Example 1, and the line connecting the X marks is Comparative Example 2. .
  • Inventive Examples 1 and 2 in FIGS. 5, 6 and 7 have a recording film made of an appropriate amount of a mixture of In alloy and SiO, as will be described later.
  • Comparative Example 1 is a recording film made of only an In alloy
  • Comparative Example 2 is a recording film in which the amount of SiO mixed is too large.
  • Invention Examples 1 and 2 having a recording film made of an appropriate amount of a mixture of In alloy and SiO have a laser power of about 8 mW compared to Comparative Example 1 and Comparative Example 2. Of course, even with a lower laser power of around 5 mW, the signal modulation and signal C / N ratio are high.
  • Invention Example 1 and Invention Example 2 which are recording films made of a mixture of In alloy and SiO, are formed only of In alloy! /, Compared with the recording film of Comparative Example 1. This confirms that the thermal conductivity is greatly reduced.
  • the light transmission layer 6 was directly provided on the film 4, and the optical adjustment layer 2 and the dielectric layers 3 and 5 were not provided.
  • a polycarbonate substrate (thickness 1. lmm, track pitch 0.32 111, groove width 0.116 111, groove depth 25 nm) was used.
  • an In—25at% Ni In alloy with a thickness of 12 nm was formed by DC sputtering using co-sputtering, and at the same time, SiO equivalent to 1.5 nm was formed by RF sputtering. did.
  • a recording film 4 having a total film thickness of 13.5 nm was formed so that the mixing ratio of In alloy / SiO dielectric was 8: 1 by volume.
  • the composition of each target used for film formation and the film composition of each recording film formed were measured by ICP emission spectrometry or ICP mass spectrometry.
  • an ultraviolet curable resin manufactured by Nippon Kayaku Co., Ltd., trade name: "BRD-1" 30 ” was spin-coated, and then cured by UV to form a light transmission layer 6 having a thickness of 100 ⁇ 15 m.
  • Inventive Example 2 used the same (condition) polycarbonate substrate as Inventive Example 1. On the substrate surface, an In-25at% Ni In alloy equivalent to 12 nm in thickness equivalent to that of Invention Example 1 was formed by DC sputtering using co-sputtering, and at the same time by RF sputtering as in Invention Example 1. A SiO film having a thickness of 3 nm was formed. Then, a recording film 4 having a total film thickness of 15 nm was formed such that the mixing ratio of In alloy / SiO 2 dielectric material was 4 in the volume ratio.
  • Comparative Example 1 used the same (condition) polycarbonate substrate as Invention Example 1. On the substrate surface, a recording film 4 made of only an In-25 at% Ni alloy equivalent to a thickness of 12 nm was formed by DC sputtering as in Invention Example 1.
  • Comparative Example 2 the same polycarbonate substrate (under the same conditions) as in Invention Example 1 was used. On the substrate surface, an In-25at% Ni In alloy equivalent to 12nm in thickness equivalent to that of Invention Example 1 was deposited by DC sputtering using co-sputtering. At the same time, RF sputtering method was used as in Invention Example 1. Thus, a SiO film having a thickness of 6 nm was formed. Then, a recording film 4 having a total film thickness of 18 nm was formed so that the mixing ratio of In alloy / SiO dielectric was 2: 1 by volume.
  • FIG. 5 shows the relationship between the recording laser power and the signal modulation degree in each of the optical recording media of Invention Examples 1 and 2 and Comparative Examples 1 and 2, respectively.
  • This measurement was performed using an optical disk evaluation device (ODU-1000 (trade name) manufactured by Pulstec Industrial Co., Ltd., recording laser wavelength: 405 nm, NA (numerical aperture): 0.85) and a digital oscilloscope (manufactured by Yokogawa Electric Corporation, Using the product name “DL1640L”), the degree of signal modulation was measured. More specifically, a recording mark of 0.660 111 in length was repeatedly formed at a linear velocity of 4.9 m / s in the range of laser power 4 mW to 12 mW, and the signal at the time of signal reading at laser power 0.3 mW The degree of modulation was measured.
  • ODU-1000 trade name
  • NA number of numerical aperture
  • the signal modulation degree means (signal intensity max—signal intensity min) / (signal intensity max) 100 (unit%) of the obtained signal. In order to obtain desired recording characteristics, It is generally considered that a signal modulation degree of 50% or more is required.
  • FIG. 6 shows the relationship between the recording laser power and the signal C / N ratio in each of the optical recording media of Invention Examples 1 and 2 and Comparative Examples 1 and 2, respectively.
  • the signal C / N ratio was measured using an optical disk evaluation apparatus (same as above) and a spectrum analyzer (trade name “R3131A”) at the same time as the signal modulation degree measurement of the optical disk in FIG. (Unit: dB) was measured. More specifically, a recording mark with a length of 0.60 m is repeatedly formed at a linear speed of 4.9 m / s in the range of laser power 4 mW to 12 mW, and 4.12 MHz when reading a signal with a laser power of 0.3 mW.
  • the signal C / N ratio (unit: dB), which is the ratio when the signal strength of the frequency component is the carrier (unit: dB) and the noise of the signal strength of the frequency component before and after that (unit: dB), was measured.
  • the C / N ratio of the same signal of the optical disc needs to be at least 45 dB! /.
  • the mixing ratio of SiO to the In alloy is too high at 2 in the volume ratio of In alloy volume / oxide volume.
  • the signal C / N ratio remained below 45 dB for all recording powers. This result confirms that when the mixing ratio of SiO to the In alloy is set to a certain level or more, there is an adverse effect that the signal quality is deteriorated. Therefore, the mixing ratio of SiO to In alloy is suitably in the range of 3 to 10 in terms of the volume ratio of In alloy to oxide (In alloy volume) / (oxide volume).
  • Equation 1 K: thermal conductivity (W / mK), ⁇ : electric conductivity (S / m), L: mouth one Lenz number (2. 45 X 10- 8 W ⁇ / K 2 ), T: Absolute temperature (K), respectively.
  • Invention Example 1 and Invention Example 2 which are recording films made of a mixture of In alloy and SiO, have a thermal conductivity as compared with the recording film of Comparative Example 1 formed only of In alloy. This confirms that the rate will decline significantly. As a result, the recording film made of a mixture of In alloy and SiO can suppress the diffusion of heat input by the laser, and a local recording mark can be formed with a lower laser power. As a result, as described above, it is proved that there is an effect of obtaining a recording film that has a good recording characteristic and can obtain a better signal modulation degree.
  • the signal modulation degree and signal C / N ratio of a recording film made of a mixture of an In alloy and oxides of Al 2 O and Nb 2 O were measured and evaluated.
  • the type shown in Fig. 1 is the same as in Example 1.
  • Invention Example 3 having an appropriate amount of mixture of In alloy and Al 2 O of the present invention, and an appropriate amount of mixture of In alloy and Nb 2 O Inventive example 4 having a recording film made of is superior in signal modulation degree and signal C / N ratio to Comparative Example 1 (same as Example 1) of a recording film made only of In alloy! /, It was.
  • FIGs. 8 and 9 the line connecting the diamond marks is again shown (same as in Example 1), Invention Example 2, the line connecting the square marks is Invention Example 3, the line connecting the triangle marks is Invention Example 4, The line connecting the X marks is Comparative Example 1.
  • Invention Example 1 The same (condition) polycarbonate substrate as in Invention Example 1 was used.
  • Invention Example 1 an In-25 at% Ni In alloy equivalent to a thickness of 12 nm was formed on the surface of the substrate by DC sputtering using co-sputtering, and at the same time, equivalent to 3 nm in thickness by RF sputtering.
  • a film of AlO was formed.
  • a recording film 4 having a total film thickness of 15 nm was formed so that the mixing ratio of In alloy / Al 2 O dielectric was 4 in the volume ratio.
  • Invention Example 3 and Invention Example 4 which are recording films made of a mixture of In alloy and Al 2 O or Nb 2 O
  • the laser power is 6 mW or less
  • the signal modulation degree is 50% or more
  • the signal It can be seen that the C / N ratio is 45 dB or more. That is, it is supported that the recording sensitivity can be greatly improved by using an In alloy / Al 2 O or Nb 2 O mixed recording film as compared with Comparative Example 1 in which only the In alloy is used.
  • FIG. 10 shows the relationship between the recording laser power and the signal modulation degree in each optical recording medium
  • FIG. 11 shows the relationship between the recording laser power and the signal C / N ratio.
  • the line connecting the black circles is Invention Example 5, and the line connecting the * marks is Comparative Example 3. From these FIGS. 10 and 11, in Comparative Example 3 in which the recording film is formed only of the In alloy, the laser power necessary for recording, that is, the signal modulation degree is 50% or more and the signal C / N ratio is A laser power of 45 m or more is required.
  • Invention Example 5 which is a recording film made of a mixture of In alloy and SiO, the laser power is 6 mW or less, the signal modulation is 50% or more, and the signal C / N ratio is 45 dB or more. I understand that.
  • the recording sensitivity can be greatly improved by using an In alloy / SiO mixed recording film as in the present invention.
  • the invention example has a laser power of about 8 mW as well as a laser power of about 5 mW, as compared with the comparative example of the recording film made only of the In alloy, as long as it is within the composition range of the present invention. Even with a lower laser power, the effect of high signal modulation and signal C / N ratio can be obtained.
  • a polycarbonate substrate having the same conditions as in Invention Example 1 was used as the substrate 1.
  • an In alloy containing Co—40 at% Co equivalent to 12 nm in thickness was formed by DC sputtering, and at the same time, SiO equivalent to 1.5 nm in thickness was formed by RF sputtering. (Cosputtering).
  • a recording film 4 having a total film thickness of 13.5 nm was formed so that the mixing ratio of In alloy / SiO dielectric was 8: 1 by volume.
  • a polycarbonate substrate having the same conditions as in Invention Example 1 was used.
  • a recording film 4 made of only an In-40 at% Co alloy equivalent to 12 nm in thickness was formed by DC sputtering as in Invention Example 5.
  • the same light transmission layer 6 as that of Invention Example 1 was formed on the recording film 4.
  • the sputtering conditions the ultimate vacuum: 3 X 10- 6 Torr or less, Ar gas pressure: 2 mTorr, DC spatter deposition power: was 100W.
  • the film thickness was adjusted in the range of 12 to 21 nm so that the unrecorded SUM2 signal level of the BD-R disc (output signal correlating with reflectivity) was 280 mV or more. Some alloys cannot secure more than 280mV).
  • a UV curable resin (trade name “BRD-130” manufactured by Nippon Kayaku Co., Ltd.) was spin-coated thereon, followed by UV curing to form a light transmission layer 3 having a thickness of 100 ⁇ 15 m. .
  • optical disk evaluation method is as follows: Optical disk evaluation device (trade name “ODU-1000” manufactured by Pulstec Industrial Co., Ltd., recording laser wavelength: 405 nm, NA (numerical aperture): 0 ⁇ 85), spectrum analyzer (Trade name “R3131R” manufactured by Advantest) was used.
  • the linear velocity is 4 ⁇ 9m / s, the unrecorded SUM2 level, and the recording laser power in the range of 4mW to 12mW, the length of 0.6 111 recording mark (corresponds to 811 signal of 2508 8111 & Disc)
  • the maximum C / N value at the time of recording / reproducing at the time of signal reading with a reproducing laser power of 0.3 mW was evaluated.
  • Table 1 shows examples in which the In alloy of the recording film 4 of the optical disc contains one or two of Ni and Co.
  • each example in Tables 1 and 2 means an example of a recording film made of only an In alloy within the composition range of the present invention in Tables 1 and 2, and in each of the above-described Examples;! To 3 It is different from the recording film made of a mixture of In alloy + oxide.
  • Comparative Examples 1 to 4 in Table 1 also mean a comparative example of a recording film consisting only of In alloy outside the composition range of the present invention in Table 1, and the Comparative Examples 1 to 3 in FIGS. Is different.
  • Table 2 shows examples (invention examples) each including one or more selected from Sn, Bi, Ge, and Si in addition to the In alloying force S, Ni, and Co of the recording film 4 of the optical disk. Recording power and jitter values (3 continuous tracks) with the minimum SUM2 level, C / N value during 8T signal recording and playback, and jitter value (during continuous 3 track recording) It is a table showing (at the time of recording).
  • the recording laser power that gives the maximum C / N value is in the range of 6 mW to 10 mW.
  • the unrecorded SUM2 level is over 280 mV. Those not satisfying are marked with X.
  • ⁇ is marked, and X is marked if it is less than this.
  • the optical disk with In alloy recording film 4 containing Ni and Co has a SUM2 level and C / N value that is higher than that of each comparative example (In alloy containing Pt, Au, or V). It can be seen that both have high recording properties. Therefore, the significance of Ni, Co content or Ni, Co content in the In alloy of the recording film comprising the mixture of In alloy and oxide of the present invention is supported.
  • the optical disc provided with the In alloy recording film 4 containing Bi, Sn, Ge, and Si also has the same SUM2 level and C / N value.
  • the jitter value is lower than that of the reference example corresponding to Example 1 in Table 1 that does not contain Bi, Sn, Ge, and Si, and has excellent recording characteristics. It turns out that But Therefore, the recording film comprising the mixture of In alloy and oxide of the present invention contains Bi, Sn, Ge, and Si in addition to Ni and Co in the In alloy or Bi, Sn, Ge, and Si. The significance of quantity is supported.
  • Example 31 In-Co-Ni-Sn Co 41.4at% Ni 8.5at% 12nm O309mV O ⁇ 50dB 6. Mechanical 6.9%
  • Example 32 In-Co-Ni-Sn Co 34.0at% Ni 16.6at% 12nrn O308mV O ⁇ 50dB 6.2mW 6.9%
  • Example 36 In-Co-Ni-Sn Co 32.2at% Ni 12.5at 11nm 0286mV O ⁇ 50dB 6.2mW 7.8%
  • an optical information recording medium having a recording film that enables punching (recording) with a relatively low laser power, has a good recording characteristic, and obtains a better signal modulation degree. can do.
  • the optical information recording medium of the present invention is used as a current CD (Compact Disc), DVD (Digital Versatile Disc), or next-generation optical information recording medium (HD DVD or Blu-ray Disc). It is suitably used as a write-once high-density optical information recording medium using a violet laser.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

L'invention concerne un support d'enregistrement d'informations optiques ayant un film d'enregistrement où un repère d'enregistrement est formé par l'application d'un faisceau d'énergie. Le film d'enregistrement est formé par un mélange d'un alliage à base de In et d'un oxyde. Le support d'enregistrement d'informations optiques est utilisé comme un CD actuellement utilisé (Disque compact), un DVD (Disque numérique polyvalent), un HD DVD (DVD haute définition) et un BD (Disque Blu-ray) en tant que support d'enregistrement d'informations optiques de la nouvelle génération, et en particulier en tant que support d'enregistrement d'informations optiques haute densité de type inscriptible une seule fois pour lequel un laser de couleur bleue-violette est utilisé.
PCT/JP2007/074319 2006-12-20 2007-12-18 Support d'enregistrement d'informations optiques WO2008075683A1 (fr)

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JP4969625B2 (ja) 2008-11-12 2012-07-04 株式会社神戸製鋼所 光情報記録媒体
WO2010055865A1 (fr) * 2008-11-12 2010-05-20 株式会社神戸製鋼所 Couche d'enregistrement pour support d'enregistrement d'informations optique, support d'enregistrement d'informations optique et cible de pulvérisation cathodique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61195943A (ja) * 1985-02-25 1986-08-30 Hitachi Ltd 分光反射率可変合金及び記録材料
JPS648521A (en) * 1987-06-30 1989-01-12 Sony Corp Optical recording medium
JP2004178673A (ja) * 2002-11-26 2004-06-24 Toshiba Corp 相変化光記録媒体
JP2005022409A (ja) * 2003-06-13 2005-01-27 Matsushita Electric Ind Co Ltd 光学情報記録媒体とその製造方法
JP2005190647A (ja) * 2003-12-03 2005-07-14 Ricoh Co Ltd 相変化型光記録媒体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61195943A (ja) * 1985-02-25 1986-08-30 Hitachi Ltd 分光反射率可変合金及び記録材料
JPS648521A (en) * 1987-06-30 1989-01-12 Sony Corp Optical recording medium
JP2004178673A (ja) * 2002-11-26 2004-06-24 Toshiba Corp 相変化光記録媒体
JP2005022409A (ja) * 2003-06-13 2005-01-27 Matsushita Electric Ind Co Ltd 光学情報記録媒体とその製造方法
JP2005190647A (ja) * 2003-12-03 2005-07-14 Ricoh Co Ltd 相変化型光記録媒体

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