OPTICAL DATA RECORDING MEDIUM

Abstract: Improved optical data recording medium comprises a recording thin film-made of a three-component system consisting of GeTe alloy, Sb2Te3 alloy and excess Sb - formed on a substrate. This thin film furnishes the following characteristics, (i) when irradiated with laser light its temp. increases and it melts, and then becomes amorphous upon sudden cooling, and (ii) by irradiating laser light on the film in an amorphous condition its temp. increase and it becomes crystalline. The excess amount of Sb in the three-component system should satisfy the condition that it is more than 10 mol% and less than 30 mol%. The mole ratio (b) of the excess amount of Sb to Sb2Te3 lies between 0.3 and 0.8. The mole ratio (g) of GeTe alloy to Sb2Te3 alloy lies between 0.5 and 2.0. This optical data recording medium has four layers and is produced by the following process, (1) an electric induction layer is formed on a base, (2) a thin film made of the three-component system is formed on 1), 3) another electrical induction layer is formed on (2), and (4) a reflection layer is formed on (3).

Description: OPTICAL INFORMATION RECORDING MEDIUM TECHNICAL FIELD This invention relates to optical information recording mediums which enable information to be recorded, reproduced and erased by means of laser beams in high density and in large capacity. TECHNICAL BACKGROUND There is known as an optical disk memory a disk of the write-once type using a thin film of TeO x (0<x<2.0) mainly composed of Te and TeO₂. A chalcogen material, Ge₁₅Te₈₁Sb₂S₂, is also known as reported by S. R. Ovshinsky.This material is utilizable for recording information by heating and melting it by application of a laser beam and quenching for amorphization. The recorded information can be erased by heating by irradiation with a laser beam and subsequent gradual cooling for crystallization. Moreover, thin films made of combinations of chalcogens and the elements of the Group V or VI of the Periodic Table such as Ge, e.g. As₂S₃, As₂Se₃ or Sb₂S₃, are widely know, e.g. from EP-A-0 217 293, JP-A-62 196181 and JP-A-62 53886. One of procedures of recording information on these thin films by means of a laser beam and erasing the information is described. A thin film is initially crystallized and a laser beam with about 1µmø whose intensity is modulated according to information is applied, for example, to a recording disk having a thin film thereon under conditions of rotation of the disk. Portions where irradiated with the laser beam are heated to a temperature higher than the melting point of the thin film and then quickly cooled, thereby causing the information to be recorded as amorphous dots. For the erasure of the information, a spot beam which is elongated along the direction of rotating track or tracks of the disk is irradiated, so that the thin film is heated and is then recrystallized by the effect of gradual cooling with the elongated spot beam. In recording mediums where information is recorded and erased through heating · temperature rise · melting · quenching and heating · temperature rise · gradual cooling, respectively, by laser beam irradiation of the thin film, the quality of signals may vary in correspondence with the heating cycle. The variation is considered to result from thermal · mechanical damages of a material for substrate which are produced by repetition of a number of cycles of rapid heating over 400°C by application of a recording spot beam and an erasing spot beam and cooling. In addition, the recording thin film may suffer thermal · mechanical damages. Depending on the composition, the recording thin film may undergo a local change in the composition · component of the film or so-called segregation. A problem has been involved in that where the substrate or recording film undergoes such a change as mentioned above, an increasing number of noises generate and the cycle characteristic deteriorates during the recording, reproducing and erasing cycles. DISCLOSURE OF THE INVENTION This invention relates to the art of recording and erasure of optical information by thermally changing the state of thin film by irradiation, for example, of a laser beam and has for its object the improvement in the cycle characteristics of recording and erasure. The object of the invention is achieved by a recording medium as set out in Claim 1. When Sb₂Te₃ (melting point: 622°C) is converted into a thin film, an amorphous film is obtained. This film undergoes a change between amorphization and crystallization and is usable for recording. However, its blackening (involving crystallization) temperature is as low as 100°C and is thus thermally unstable. Mixing of GeTe having a high melting point, Tm = 725°C, can raise the blackening (crystallization) temperature over 180°C. Although the thin film of the mixture has good thermal stability, the quality of signal is liable to lower when repeating the cycle of recording (amorphization) · erasure (crystallization) or the cycle of the reverse mode of erasure · recording. To overcome the above drawback, excess Sb is added. Sb has the action of inhibiting the phase separation between GeTe and Sb₂Te₃ components and improves the cycle characteristic. Further, it is expected to work as nuclei for the crystallization and to bring about an improvement in recording and erasing sensitivities, making it possible to overwrite by the use of a single laser beam. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a triangular diagram for the composition of recording thin film used in an optical information recording medium according to one embodiment of the invention; Fig. 2 is a graph showing the dependence of the recording sensitivity (C/N ratio) of the medium on the ratio of excess Sb/Sb₂Te₃; and Fig. 3 is a triangular diagram for the composition of recording thin film used in an optical information recording medium according to another embodiment of the invention. BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention are described. (Example 1) A resin substrate on which a laser beam guide groove or grooves have been preliminarily formed is provided as a substrate on which a thin film used as a recording layer is to be formed. On the surface of the resin substrate is formed an inorganic dielectric layer which has a good heat resistance and is made, for example, of ZnS or SiO₂. The dielectric layer is preferably a ZnS dielectric layer which contains not less than 15 mole% of SiO₂. A thin film of a mixture of Sb₂Te₃, Gete and excess Sb is formed on the dielectric layer. The thin film may be formed by vacuum deposition or sputtering. In the triangular diagram of Fig. 1 consisting of Sb₂Te₃, GeTe and Sb, the composition of the thin film should preferably be selected from region 1 including point A of Sb₂Te₃ (35 mole%), GeTe (41 mole%) and excess Sb (24 mole%), point B of Sb₂Te₃ (27 mole%), GeTe (51 mole%) and excess Sb (22 mole%), and point C of Sb₂Te₃ (425 mole%), GeTe (29 mole%) and excess Sb (29 mole%). This may be represented by a ratio of GeTe to Sb₂Te₃ and a ratio of excess Sb to Sb₂Te₃, which are, respectively, selected from the following ranges that 0.5<GeTe/Sb₂Te₃<2.0 and 10<excess Sb<30. In the triangular diagram, the compositional range is around dotted line 2 where the excess Sb content is about 25 mole%. The compositional points around the 25 mole% line are the most important. In Fig. 2, there is shown the relation between the sensitivity and the composition of the respective films. In this figure, GeTe/Sb₂Te₃ ≒ 1.2 and the values of excess Sb/Sb₂Te₃ are 10, 18 and 30, respectively. As the excess Sb increases, the C/N value in a low laser power region of 6 mw increases as shown by curve 3. Thus, the sensitivity is improved. However, for the laser power of 9 mW, the C/N value is about 55 dB in any compositional points as shown by curve 4. When the GeTe/Sb₂Te₃ ratio increases so that GeTe becomes rich, the sensitivity lowers. Moreover, the relationship between the cycle characteristic and the composition may be expressed in such a manner that when a variation of C/N relative to the number of cycles is taken as Δ C/N, the magnitude of Δ C/N in connection with excess Sb/Sb₂Te₃ is in the following order. Δ C/N₁₀<ΔC/N₁₈<Δ C/N₃₀. Preferably, Sb/Sb₂Te₃>20. The recording medium of this example has so high a crystallization rate that a single beam may be used for recording · erasing procedures. In the triangular diagram of Fig. 1, at points E and H where the excess Sb is smaller than the 25 mole% line of Sb the cycle characteristic deteriorates considerably. Moreover, at point J where the excess Sb content is larger than the 25 mole% line, the deterioration of the cycle characteristic also increases. At point D where the Sb content is higher than at point J, the recording sensitivity and C/N ratio lower. (Example 2) The composition of a mixed thin film consisting of Sb₂Te₃, GeTe and excess Sb is selected from the region between the lines b = Sb/Sb₂Te₃ = 0.3 and b = Sb/Sb₂Te₃ = 0.8 in the triangular diagram for Sb₂Te₃, GeTe and Sb shown in Fig. 3. In the compositional region where b is less than 0.3, inclusive, crystallization is unlikely to occur smoothly during recording · erasing cycles of information. On the contrary, in the compositional region where b is 0.8 or over, amorphization is not likely to occur smoothly during recording · erasing cycles of information. The cycle characteristic becomes stabler in the region of 0.3< b < 0.8. As for g = Sb/Sb₂Te₃, when g is not larger than 0.5, the transition temperature for crystallization lowers with a lowering of thermal stability. A disk of 130 mmø at compositional point A where g = 1.2 and b = 0.5 was made. When this disk was subjected to measurement of an overwrite cycle characteristic of a signal of f₁ = 3.43 MHz and a signal of f₂ = 1.6 MHz at a frequency of 180 r.p.m., the C/N ratio and an erasure rate do not deteriorate over 10⁵ cycles or over for both a high power level of 16 mw and a low power level of 8 mw. Higher recording sensitivity is obtained at a smaller value of g or b. With regard to the thermal stability, it becomes better at a higher value of g or b. The values of g and b can be properly selected from the triangular diagram in correspondence with the number of disk rotation. At compositional point B where g = 2.0 and b = 0.5, the C/N ratio and the erasure rate do not lower over 10⁵ cycles or over for a recording power level of 18 mw and an erasing power level of 10 mw. However, the sensitivity is lower than at compositional point b. At compositional point C which is outside from b = 0.3, the sensitivity is improved at a point where g = 1.2 and b = 0.2, but crystallization slightly varies at about 10⁴ cycles At compositional point D which is outside from b = 0.8, the sensitivity for amorphization is slightly improved at g = 1.2 and b = 1.0, but amorphization slightly varies at about 10⁴ cycles. INDUSTRIAL UTILIZATION In a recording member for recording, reproducing and erasing information by the use of a laser beam, a recording thin film of a composition consisting of GeTe-Sb₂Te₃-Sb wherein excess Sb is contained can reduce a variation in crystallization or amorphization and ensures a good cycle performance. Further, the disk sensitivity and thermal stability are improved. Accordingly, there can be provided a useful recording medium which is capable of recording reproduction · erasure in optical disk files or the like. LIST OF REFERENCE NUMERALS IN THE DRAWINGS 1...........compositional region providing good characteristics 2...........25 mole% Sb line 3............C/N ratio at a laser power level of 6.5 mW 4...........C/N ratio at a laser powder level of 9 mW 5...........line where b = Sb/Sb₂Te₃ = 0.3 6...........line where b = Sb/Sb₂Te₃ = 0.8 7...........line where g = GeTe/Sb₂Te₃ = 0.5 8...........line where g = GeTe/Sb₂Te₃ = 2.0

Claims: An optical information recording medium comprising a recording thin film formed on a substrate, said recording thin film containing a GeTe alloy and an Sb₂ Te₃ alloy and having the capability of being heated and melded by irradiation of a laser beam and being converted into amorphization by quenching and having the capability of crystallization by heating the thin film in the amorphous state by irradiation of a laser beam characterized in that said recording thin film is made of three components of a GeTe alloy, and Sb₂ Te₃ alloy and excess Sb. An optical information recording medium according to Claim 1, characterized in that the amount of the excess Sb in the three components of GeTe, Sb₂Te₃ and excess Sb is selected such that 10 mole%<excess Sb<30 mole%. An optical information recording medium according to Claim 2, characterized in that the ratio of the excess Sb and the Sb₂Te₃ in the GeTe, Sb₂Te₃ and excess Sb is selected such that 0.3<b<0.8 (wherein b = excess Sb/Sb₂Te₃). An optical information recording medium according to Claim 2 or 3, characterized in that the ratio of GeTe and Sb₂Te₃ in the GeTe, Sb₂Te₃ and excess Sb is selected such that 0.5<g<2.0 (wherein g = GeTe/Sb₂Te₃). An optical information recording medium according to Claim 1, characterized in that said medium comprises the substrate having a dielectric layer formed thereon, the recording thin film consisting of the GeTe, Sb₂Te₃ and excess Sb and formed on the dielectric layer, a dielectric layer formed on the thin film, and a reflection layer formed on the second-mentioned dielectric layer.

Inventors: KOTERA, KOICHI, MATSUBARA, KUNIHIRO YAKUMO HAITSU 105, OHTA, TAKEO, UCHIDA, MASAMI
Applicants: MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1988
Main classification: G11B7
IPC codes: G11B7, B41M5