Non-linear optical recording medium

Abstract: An optical information recording medium, which is not deteriorated after repeating reading out and writing in, is provided by forming a glass thin film (2), on a substrate (1), and providing a recording film, a protective film, and a reflecting film thereon. The thin glass film (1) has non-linear intensity distributions of irradiated and transmitted light. The glass may contain cobalt oxide.

Description: BACKGROUND OF THE INVENTION The present invention relates to an information recording medium, particularly, to an optical information recording medium, which is capable of reading out or recording with a high recording density, having a high reliability in repeating record and regeneration operations. Conventionally, compact disks (CD), laser disks (LD), and the like are used widely as optical information recording media. Currently, DVD having a seven times recording density of the CD have come to practical use. The DVD has been developing as an erasable recording-regenerating medium in addition to as a read only ROM (DVD-ROM), wherein information is directly written onto the substrate. Furthermore, the practical use of DVD as a RAM for computer is under investigation. With the DVD, high density recording can be achieved by using a laser having a shorter wave length such as 650 nm than the laser used for the CD (wave length approximately 780 nm). However, in order to handle a large amount of information such as computer graphics and the like, it is necessary to achieve a higher recording density such as 1.5 to 2 times of the conventional high density recording. In order to achieve the above recording density, a semiconductor laser of green to blue color having a shorter wave length (wave length 520-410 nm) than ever is under development. As another technology to achieve the higher recording density, a super resolution film can be pointed out. The super resolution film is a thin film formed at lower plane of the recording medium, and the high recording density can be achieved by decreasing the size of a beam spot of the incident light through the film. One of the mechanisms of the super resolution effect is an absorption-saturation phenomenon, which is a phenomenon utilizing such a non-linear optical characteristics of the super resolution film that the film allows the light having a larger intensity than the amount of its absorption-saturation pass through the film, and absorbs the light having an intensity less than the amount of its absorption-saturation. The spatial intensity of laser beam utilized in reading and writing has a Gaussian distribution. Therefore, when the laser beam passes through the super resolution film, the laser in the lower end portion of the Gaussian distribution, where the intensity is low, is absorbed by the film, and the laser in the middle portion of the Gaussian distribution, where the intensity is high, passes through the film. Accordingly, the diameter of the laser beam after passing through the super resolution film can be decreased. An organic thin film of phthalocyanine group disclosed in JP-A-8-96412 (1996), chalcogenide, fine particles of compound semiconductor, and the like are known at the present as the super resolution film explained above. Additionally, trials to use some organic materials such as thermochromic materials disclosed in JP-A-6-162564 (1994), and photochromic materials disclosed in JP-A-6-267078 (1994) as the super resolution film are known. However, respective of the above materials has problems in reliability, and productivity. That is, the organic thin film has a concern about gradual deterioration of the film after repeated recording and regenerating operations, because an energy density of the laser beam is locally increased significantly at the recording and regenerating operations. Therefore, a sufficient guarantee period for the recording and regenerating operations is scarcely obtained under a severe using condition, wherein the recording and regenerating operations are performed frequently, such as RAM and the like for computers. The chalcogenide is chemically unstable, and a long guarantee period can not be obtained. The fine particles of compound semiconductor has difficulty in production process. EP-A-580346 discloses a high density optical disk having a shutter layer, formed directly or indirectly on a substrate, for tightening a light beam to be irradiated to read or write information. The shutter layer is formed on the side of the substrate where pits are present, and has semiconductor fine particles dispersed in a matrix of glass or resin, thus exhibiting a third order non-linear effect. SUMMARY OF THE INVENTION One of the objects of the present invention is to provide an optical recording medium having a super resolution film, which can guarantee the repeated recording and regenerating operations for a sufficiently long time, having a preferable productivity and a high resolution effect. The present invention provides in a first aspect an optical information recording medium as set out in claim 1. The substrate is desirably transparent to light, for instance, inorganic materials such as glass and the like, and organic materials such as polycarbonate, polyethylene terephthalate, and the like are desirable. Here, the glass means amorphous solid oxides, and general amorphous materials containing the above oxide as a main component. The glass layer on the substrate may be formed onto the surface of the substrate directly, or formed onto the surface of the substrate indirectly via another layer, for instance, a protection layer. In accordance with the above composition, an information recording disk, which has a large capacity, and less deterioration after repeated reading out and writing, can be provided. The recording layer can be a pit pattern recording information. The pit pattern means a device which records the information by the arrangement of pits provided onto the surface of the substrate. In accordance with this recording method, the recorded information can not be rewritten. However, once a master die of the substrate recorded information is made, a large number of same substrates can be manufactured readily. Therefore, this recording method is used for recording movies, music, and computer programs. The recording layer can also be a device for recording information with an optical energy. The device for recording information with an optical energy means an information recording substrate using so-called phase changing organic materials or inorganic materials, of which crystalline structure varies by irradiation of light, as the recording layer. A second : aspect of the present invention is an optical information recording medium as set out in claim 5. Such a reflection type information recording disk can have a large capacity, and less deterioration after repeated reading out and writing. The second aspect is an information recording substrate of a type, which reflects incident light with a reflecting film provided at lower portion of the recording film, and reads the information with the reflected light. For the transition metal elements and the rare earth metal elements, particularly,at least an element selected from Ti, V, Cr, Mn, Fe, Co, Ni, Nd, Ce, Pr, Sm, Eu, Tb, Ho, Er, and Tm is desirable. When the transition metal element, or the rare earth metal element forms a glass film, the metal element is desirably contained in the range from 20 % by weight to 90 % by weight as oxide to total weight of glass. When the metal element forms a glass substrate, the metal element is desirably contained in the range from 0.1 % by weight to 29 % by weight as oxide to total weight of glass. In the first aspect , the glass desirably contains as oxide the following compounds: SiO 2 : 6 - 80 % by weight, R 2 O : 0 - 20 % by weight (R = alkali metal element), B 2 O 3 : 0 - 30 % by weight, and CoO : 20 - 90 % by weight. In the second aspect, the glass desirably contains cobalt oxide as CoO in the range of 0.1 - 29 % by weight. FIG. 8 is a graph indicating a relationship between the recording frequency and the output on the information recording media with and without the super resolution film of the present invention. The medium with the super resolution film can record signals of higher frequency components, because the spot size of the laser ray reaching at the recording layer is decreased. The above composition indicates an index which indicates how high frequency component can be recorded. BRIEF DESCRIPTION OF THE DRAWINGS The above and further objects and novel feature of the present invention will more fully appear from the following detailed description when the same is read in connection with the accompanying drawings. It is to be expressly understood, however, that the drawings are for purpose of illustration only and are not intended as a definition of the limits of the invention. FIG. 1 is a schematic cross section of RAM disk manufactured by the present invention, FIG. 2 is a schematic cross section of simulated sample manufactured by the present invention, FIG. 3 is a graph indicating a dependency of transmittance on wave length of the glass thin film manufactured by the present invention, FIG. 4 is an XPS of Co of glass thin film manufactured by the present invention, FIG. 5 is a graph indicating a relationship between transmittance for light of 650 nm and CoO content, FIG. 6 is a SIMS of glass thin film formed onto a glass substrate having a target composition, FIG. 7 is a schematic cross section of ROM disk manufactured by the present invention, FIG. 8 is a graph indicating a reading out frequency dependence of output obtained from the ROM disk shown in FIG. 7, FIG. 9 is a graph indicating a relationship between mark length and variation in output obtained from the RAM disk shown in FIG. 1, FIG. 10 is a graph indicating a dependency of output on repeating operations obtained from the RAM disk shown in FIG. 1, FIG. 11 is a graph indicating a relationship between CoO content and variation in reading out output obtained from the RAM disk shown in FIG. 1, FIG. 12 is a schematic cross section of RAM disk manufactured by the present invention, FIG. 13 is a schematic cross section of ROM disk manufactured by the present invention, FIG. 14 is a graph indicating variations of laser beam diameter when the glass film of the present invention is formed and not formed, and FIG. 15 is flow chart indicating a composition of the apparatus using the photo disk of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS (Embodiment 1) Details of the present invention is explained hereinafter using the preferred embodiments. The composition of glass targets investigated in the present embodiment are indicated in Table 1. No. Composition (% by weight) Target (kind) Film Q SiO 2 Na 2 O CaO MgO Al 2 O 3 Co 3 O 4 CoO 1 70.4 13.6 7.8 4.0 1.3 2.9 - glass ○ 2 69.0 13.3 7.6 3.9 1.3 4.9 - glass ○ 3 51.8 10.0 5.7 2.9 1.0 28.6 - glass ○ 4 45.3 8.8 5.0 2.6 0.9 37.4 sint . ○ 5 29.0 5.6 3.2 1.6 0.6 60.0 sint. ○ 6 14.5 2.8 1.6 0.8 0.3 80.0 sint. ○ 7 5.9 1.4 0.5 0.2 0.1 91.9 sint. × 8 - - - - - 100 sint. × 9 51.8 10.0 5.7 2.9 1.0 - 28.6 glass ○ 10 29.0 5.6 3.2 1.6 0.6 - 60.0 sint. ○ 11 14.5 2.8 1.6 0.8 0.3 - 80.0 sint. ○ 12 5.9 1.4 0.5 0.2 0.1 - 91.9 sint. × 13 - - - - - - 100 sint. × In accordance with Table 1, the column of the film quality was filled with ○ when an uniform film was obtained in view of transparency, uniformity, and the like, and with × when the obtained film was not uniform. In the present embodiment, a soda-lime group glass was used as a mother glass, and a cobalt oxide, which had a large absorption in the vicinity of 650 nm, was used as the transition metal. As raw materials for the cobalt oxide, Co 3 O 4 and CoO were used. The targets No. 1 - No. 7 are composed of soda-lime glass and Co 3 O 4 . Among them, No. 1 - No. 3 were targets of glass block, because they were vitrified. No. 4 - No. 7 were not vitrified, because the content of Co 3 O 4 was too much to be vitrified. Therefore, a sintered body of a mixture of glass powder and Co 3 O 4 was prepared as a sintered target. No. 8 is a comparative example of a sintered target made of only Co 3 O 4 . In No. 9 - No. 13, CoO was used as the raw material for cobalt oxide. In these cases, No. 9 was a glass target, because No. 9 had a Co content of 28.6 % by weight and was vitrified. Because No . 10 - No . 12 were not vitrified, a sintered target of the mother glass raw material and CoO was used. No. 13 is a comparative example of a sintered target made of only CoO. The glass block for the target was obtained by the steps of; weighing a designated amount of raw materials powder, charging the raw materials powder into a crucible, made of platinum, heating the crucible to approximately 1500 °C in an electric furnace to melt the raw materials, pouring the molten glass into a graphite mold, which was pre-heated at approximately 400 °C, after the raw materials were molten completely, cooling rapidly, performing a stress relief by reheating to approximately 600 °C and cooling gradually, and polishing back side of the obtained glass block. The sintered target was obtained by the steps of; granulating a designated amount of raw materials powder, fabricating the powder into a fabricated body in a die, and hot pressing the fabricated body at a designated temperature after dewaxing. The temperature for heat treatment was 900 °C when the cobalt raw material was Co 3 O 4 , and was 1200 °C when the cobalt raw material was CoO. As a previous step for the evaluation in a shape of disk, a glass sample for preliminary test in a shape of thin film as shown in FIG. 2 was prepared, and fundamental material characteristics of the glass thin film were determined. In accordance with FIG. 2, the numeral mark 1 indicates a substrate, and 2 is the glass thin film. In the present investigation, a soda-lime glass of 0.55 mm thick and 30 mm square was used as the substrate 1. The structure of the prepared film was evaluated by a thin film X-ray diffraction method. Then, it was found that all the prepared films were amorphous irrelevant to whether the target was glass or sintered body, and that glass films were formed. FIG. 3 indicates the dependence of transmittance of the glass thin films formed using the targets shown in Table 1 on wave length. The transmittance was measured using monochromatic light obtained by treating white light from a light source with a monochromator. In accordance with No. 1, the peak indicating an absorption was hardly observed around 300 nm, because of too small content of Co 3 O 4 . In accordance with No. 2 - No. 4, the peak indicating the absorption by Co could be observed, even it be small, in the region of 500 nm - 700 nm. No. 3 glass had a transmittance of approximately 85 % at wave length of 650 nm. With the thin films of No. 5 and 6, the values of the transmittance were sufficiently low. However, the transmittance was decreased in accordance with decreasing wave length, and it was indicated that the decrease in the transmittance was caused by scattering . The glass of No . 7 and the Co 3 O 4 of No . 8 had a sufficiently low transmittance. However, they were reduced in a spattering atmosphere, and film having a metallic luster were obtained. Therefore, the transmittance was decreased by reflection. On the other hand, in accordance with the glasses of No. 9 - No. 11, of which CoO was a raw material, the peak indicating the absorption by Co was observed in the vicinity of the region of 500 nm - 700 nm. The transmittance were decreased in accordance with the increase in Co content. The thin film of No. 11 containing 80 % of Co had the transmittance of approximately 5 % at wave length of 650 nm. The glass of No. 12 containing CoO of 91.9 %, and the film of No . 13, which was 100 % CoO, indicated the same results as No. 8. In order to investigate the difference in spectrum of the transmittance curves in FIG. 3, valence and oxide conditions of the Co were analyzed by XPS. The XPS spectra of Co in thin f ilms of No . 3 and 5 are indicated in FIG. 4. In the spectrum of the thin film of No. 3, a peak called a shake up peak exists around 786 eV. It indicates the presence of a large amount of Co 2+ . On the contrary, the shake up peak can not be observed in the spectrum of the thin film of No. 5. It indicates an oxide condition of Co 3 O 4 coexisting with Co 3+ . Accordingly, scattering was occurred, and the profile indicated in FIG. 3 was obtained. The same investigation were performed with other thin films, and it was found that, if cobalt existed in the condition of Co 2+ , the spectrum became the peak of absorption typical for Co such as No. 2, 3, 10, and 11, and, if Co 3+ is existed, the spectrum became a curve accompanying with scatter such as No. 5 and 6. FIG. 5 indicates relationship between the plotted transmittance at wave length of 650 nm versus Co ion content in the target based on the thin films transmittance curves of No. 2, 3, 10, and 11. The transmittance was decreased in accordance with increasing the CoO content, and the transmittance became approximately 30 % when the CoO content was 60 %. Then, in order to evaluate the Co content in the prepared glass thin films, composition analysis of the film was performed with a secondary ion mass spectrometer (SIMS). A plate cut out from glass having the same composition as the target was used as a substrate, and a thin film having the same composition was spattered onto the substrate. The analysis was performed from in a film forming direction to in a depth direction, so that the compositions of the film and the substrate could be evaluated continuously . In the present embodiment, the investigation was performed using No. 3 as the target composition. The results of the analysis are indicated in FIG. 6. It was found that the Co content in the thin film was larger than that in the substrate. The Si content in the thin film was smaller than that in the substrate. However, the amounts of their changing were small, and a large deflection in the composition could not be expected. Therefore, the film composition can be regarded approximately as same as that of the target composition. In accordance with the above investigation, the Co oxide content in the glass thin film is desirably in the range of from 4.5 % by weight to 85 % by weight as an oxide of CoO, and of from 4.9 % by weight to 91 % by weight as an oxide of Co 3 O 4 . If CoO is less than 4.5 % by weight, it is difficult to obtain a sufficient absorption of light. If CoO exceeds 85 % by weight, the film bears metallic luster, and the transmittance is decreased. (Embodiment 2) Then, the super resolution effect was evaluated by manufacturing ROM disks, whereon the glass film of the present invention was formed. FIG. 15 indicates the flow chart indicating the composition of the optical recording apparatus used in the present invention. Using the optical recording apparatus having the above composition, performance of the ROM disk of the present invention was evaluated. The same apparatus was used on other embodiments. FIG. 7 indicates a schematic cross section of the manufactured ROM disk. In FIG. 7, the numeral mark 1 is polycarbonate substrate, 2 is glass thin film, 5 is SiO 2 protective film, 4 is Al reflector, and 6 are pits written by information. The ROM disk was manufactured by the following steps. First, a pit pattern having information was formed onto a photoresist by laser. The pit pattern was duplicated onto a Ni die, and substrates were formed by injection molding polycarbonate into the Ni die. A glass f ilm of 160 nm thick was formed onto the substrate by spattering, and after a SiO 2 protective film of 140 nm thick was formed thereon, an aluminum reflecting film of 100 nm thick was formed. In the present embodiment, No. 11 film was formed as the glass thin film. As a comparative example, a ROM disk without forming the glass film was manufactured. A frequency dependency of the regenerating output intensity of the manufactured ROM disk was analyzed with a spectrum analyzer. The results are indicated in FIG. 8. The regenerated laser power is 4 mW. It was revealed that, a case when the glass thin film of No. 11 was formed, the output level was high until the higher frequency components than a case when the glass thin film was not formed. Since the high frequency components of a signal are written with finer pit pattern on the ROM disk, the above result indicated that the output was regenerated by reading out finer pit pattern when the glass film was formed. Therefore, it was found that, when the glass film was formed, the super resolution effect had been obtained. Same investigations as the above were performed on other glass films in Table 1, and the same super resolution effect was confirmed on the glass films of No. 3 - 6, and No. 9 - 11. Then, a RAM disk, wherein the glass thin films investigated above were formed on the substrate, was manufactured, and its characteristics were evaluated. A schematic cross section of the RAM manufactured by the present invention is indicated in FIG. 1. In FIG. 1, the numeral mark 1 is polycarbonate substrate, 2 is glass super resolution film, 3 is recording film, 4 is reflecting film, and 5, 5' are protective films. In accordance with the present invention, a circular plate of 0.6 mm thick and 120 mm in diameter was used as the polycarbonate substrate 1. A glass film 2 of 300 nm thick was formed thereon by a spattering method. After forming a ZnS-SiO 2 protective film of 80 nm thick thereon, a Ge-Sb-Te group phase changing film as the recording film was formed approximately 20 nm thick thereon by the same spattering method. Then, after forming a protective film of approximately 90 nm thick, an AlTi reflecting film of 200 nm thick was formed thereon. The glass thin film was formed by the following steps. That is, a glass block or a sintered body of 5 mm in thickness and 120 mm in diameter was manufactured as a target, and a backing plate made of copper was adhered onto the back side of the target with an organic adhesive agent for vacuum. Spattering was performed using Argon gas. The power was 200 mW. The f ilm was formed uniformly by rotating the substrate during the spattering. In the present embodiment, the sample No. 11 was used as the glass film. As the comparative example, a RAM disk, whereon the glass film was not formed, was manufactured. FIG. 9 indicates a relationship of recording mark length versus regenerating output intensity of the RAM disk, whereon recording marks of a same shape were formed with an equal interval. The laser power for reading out was 2 mW. In accordance with FIG. 9, it was revealed that the present embodiment, whereon the glass film of No. 11 was formed, had higher regenerating outputs than the comparative example, which did not have the glass film, in the shorter mark length region. Therefore, it was revealed that the regeneration was possible to the shorter mark length when the glass film is formed. Accordingly, the super resolution effect could be confirmed with the RAM disk. The same results as the case of the RAM disk were obtained when all the glass films shown in Table 1 were investigated. Then, a spatial intensity distribution of the reflecting light in the cases when the above super resolution effect were obtained was investigated. FIG. 14 indicates schematically the intensity distribution of laser light in the laser beam forwarding direction in the both cases when the glass film was formed and the super resolution effect was obtained, and when the glass film was not formed. In accordance with FIG. 14, it was revealed that the spatial intensity distribution was approximately a Gaussian distribution in the case when the glass film was not formed, but the distribution of the beam was deflected toward the laser beam forwarding direction when the glass film was formed. Simultaneously, it was revealed that the beam diameter Q' at the beam intensity necessary for reading out became smaller in comparison with the case when the glass film was not formed. In accordance with the above results, it was revealed that the intensity and the intensity distribution of the reading out light could be varied by forming the glass film such as the present embodiment. Furthermore, it was revealed that the super resolution effect could be obtained in the above case. (Embodiment 3) Next, deterioration of the film by repeating regeneration was evaluated. The evaluation was performed by irradiating repeatedly the manufactured RAM disk with regeneration signal light, and detecting the regenerated output. The pit pitch was 0.3 µm. The glass thin film of No. 11 was used. As a comparative example, a phthalocyanine group organic thin film was selected, and the same evaluation was performed. FIG. 10 indicates a relationship between the output versus the repeated number. In accordance with FIG. 10, it was revealed that the output of the disk formed with the organic group thin film was decreased gradually over the repeated number of approximately 10, 000 times . On the contrary, the output of the disk formed with the glass thin film of the present invention was hardly decreased by repeating the regeneration over 10,000 times. As explained above, it was revealed that the optical disk of the present invention maintained the super resolution effect even after repeating the regeneration. The high stability against the repeated regeneration could be obtained when the glass thin film, with which the super resolution effect was obtained in the above embodiment 2, among other glass films in Table 1 was used as the glass thin film. (Embodiment 4) Then, composition of the glass thin film was investigated. First, paying an attention to the content of cobalt oxides in the glass film, a relationship between the cobalt content and the output power was investigated by manufacturing the same RAM disk as the disk in the embodiment 2. The mark length was 0.3 µ m. The laser power was 2 mW. FIG. 11 indicates a relationship between the cobalt content and the output. The output power was increased in accordance with increasing the cobalt content, and it was found that the high output could be obtained even with the small mark length. In other words, it was found that the super resolution effect could be increased in accordance with increasing the cobalt content. Furthermore, it was found that the output exceeded 5 dB when the cobalt content was equal to or more than 20 %, and it was possible to treat the output as a signal. However, when the cobalt content was less than 20 %, the output was less than 5 dB, and it was impossible to treat the output as a signal. The ROM disk shown in FIG. 7 was manufactured, and the output to the high frequency component was evaluated by a spectrum analyzer . Then, it was revealed that the high frequency component could be read out when the cobalt content was equal to or more than 20 %, but when the cobalt content was less than 20 %, any significant effect of adding cobalt could not be observed. In accordance with the above investigation, the cobalt content is des irably equal to or more than 20 % by weight in any case of both ROM and RAM. In accordance with investigation in the embodiment 1, the cobalt content is desirably equal to or less than 91 %. Furthermore, chemical elements to be contained in the glass film were investigated. The mother glass was soda lime glass. The glass containing an oxide of at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co and Ni among transition metallic elements, and Nd, Ce, Pr, Sm, Eu, Tb, Ho, Er and Tm among rare earth elements had an absorbing spectrum typical for respective element, and the same super resolution effect as the embodiment 2 could be obtained by using laser beam having the wavelength band generating the absorption. In accordance with the above results, an optical disk having the super resolution effect could be obtained by using the glass thin film containing at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Nd, Ce, Pr, Sm, Eu, Tb, Ho, Er, and Tm among transition metallic elements and rare earth elements. Next, composition of the mother glass was investigated. In the above embodiments, soda lime glass was used as the mother glass. However, the same effect could be obtained by using borosilicate glass containing boron. However, when the content of SiO 2 was less than 6 % by weight, the stability as glass was low, and crystallization and the like could be occurred by containing an oxide of the transition element or the rare earth element. When the content of SiO 2 exceeded 80 % by weight, the above oxide be hardly included into the glass structure, and it was difficult to obtain stable glass. In accordance with the above results, the content of SiO 2 is desirably in the range from 6 % by weight to 80 % by weight. When the content of alkaline oxide in the glass exceeded 20 % by weight, durability of the glass was decreased, and obtaining stable glass was difficult. Accordingly, the content of the alkaline oxide is desirably equal to or less than 20 % by weight. Furthermore, when the content of boron oxide in the glass exceeded 30 % by weight, the oxide of the transition metal or the rare earth element was hardly included into the glass structure, and obtaining stable glass was difficult. Therefore, the content of boron oxide is desirably equal to or less than 30 % by weight. In addition to the above indispensable components, an oxide of alkaline earth elements, alumina, zirconia, and the like are desirably contained in the glass as a glass stabilizing agent. (Embodiment 5) Next, the super resolution effect was investigated by manufacturing glass substrates containing the transition metallic element. FIG. 12 indicates schematically a cross section of the manufactured RAM disk. In accordance with FIG. 12, the numeral mark 12 indicates glass substrate, 3 is recording film, 4 is reflecting film, and 5, 5' are protective films. The thickness of the substrate was 0.6 mm, and a track was formed onto the surface of the substrate by reactive ion etching using photoresist as a mask. FIG. 13 indicates schematically the cross section of the ROM disk manufactured using a same substrate. In accordance with FIG. 13, the numeral mark 12 indicates glass substrate, 4 is reflecting film, and 6 is recording mark written with information. In the present embodiment, soda lime glass was used as the mother glass, and CoO was contained as the transition metallic oxide. The super resolution effect was investigated using the same evaluating method as the embodiment 2 by varying the content of CoO in the range of 0.01 - 30 % by weight. The composition of the manufactured glass substrate, evaluated results in vitrification and the super resolution are indicated in Table 2. In the evaluated results of the vitrification, the case when glass was formed without causing crystallization was indicated with ○, and the case when crystallization or devitrification was caused was indicated with ×. The evaluated results of the super resolution effect were indicated by the mark length of 0.3 µm and the output at the space length. The reading out laser wavelength was 650 nm. No. Composition (% by weight) Vitrification S.R.E. (output/dB) SiO 2 Na 2 O CaO MgO Al 2 O 3 CoO 14 72.5 14.0 8.0 4.1 1.4 0.01 ○ 5 15 72.5 14.0 8.0 4.1 1.4 0.05 ○ 5 16 72.5 14.0 8.0 4.1 1.4 0.10 ○ 10 17 71.8 13.9 7.9 4.0 1.4 1.00 ○ 16 18 65.9 12.7 7.3 3.7 1.3 9.1 ○ 33 19 51.8 10.0 5.7 2.9 1.0 28.6 ○ 41 20 50.7 9.8 5.6 2.9 1.0 30.0 × - 21 66 9 B 2 O 3 9 1 5 10.0 ○ 33 22 49 9 26 1 5 10 ○ 35 23 43 9 32 1 5 10 × - In accordance with the specimens No. 14 - 19, and 21 - 23, no crystallization not devitrification were observed, and stable glasses could be manufactured. The glass of No. 20 caused a phase separation after pouring, and any stable glass could not be obtained. In view of the above result, the content of CoO in the glass is desirably equal to or less than 29 %. The glasses of No. 21 - 23 were same as the glasses of No. 14 - 19 except replacing their CaO with B 2 O 3 . Regarding regenerating output, the outputs not less than 10 dB could be obtained when the cobalt content was equal to or more than 0.10 % by weight, and it was possible to read out as signals. On the contrary, when the cobalt content was equal to or less than 0.05 % by weight, the outputs were as small as less than 5 dB, and it was impossible to read out. In accordance with the above results, the content of cobalt is desirably in the range of 0.10 - 29 % by weight. The above effects were similar with the glasses which contained B 2 O 3 instead of CaO. In accordance with the present invention, an information recording disk having a large capacity, and small deterioration against repeated reading out and writing in, can be provided. The present invention can provide an optical disk having a large capacity by manufacturing with a conventional optical disk manufacturing process.

Claims: An optical information recording medium, which regenerates information by being irradiated with light, comprising a substrate (1) and on said substrate (1) a glass layer (2) in which intensity distributions of the irradiated light and transmitted light vary non-linearly, and wherein either (a) information is recorded as a pit pattern (6) in the substrate (1) or (b) a recording layer (3) for recording information is provided on said glass layer (2), characterised in that said glass layer (2) is a glass comprising at least one element selected from Ti, V, Cr, Mn, Fe, Co, Ni, Nd, Ce, Pr, Sm, Eu, Tb, Ho, Er and Tm. An optical information recording medium as claimed in claim 1, wherein said recording layer (2) is provided and is adapted to record information by optical energy. An optical information recording medium as claimed in claim 1 or 2, wherein said at least one element is present in the glass in an amount in the range of 20-90% by weight converted to an oxide relative to the total weight of the glass. An optical information recording medium as claimed in claim 3, wherein said glass comprises: SiO 2 : 6 - 80% by weight converted to an oxide, R 2 O : 0 - 20% by weight converted to an oxide (where R = an alkali metal element), B 2 O 3 : 0 - 30% by weight converted to an oxide, and CoO : 20 - 90% by weight converted to an oxide. An optical information recording medium comprising a substrate (12) wherein either (a) information is recorded as a pit pattern (6) in the substrate (12) or (b) a recording layer (3) for recording information is provided on said substrate, and wherein a reflecting film (4) for reflecting light is provided on said recording layer, characterised in that said substrate (12) is made of glass in which optical transmittance increases non-linearly with increasing intensity of irradiated light, said glass comprising at least one element selected from transition metal elements and rare earth elements. An optical information recording medium as claimed in claim 5, wherein said at least one element is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Nd, Ce, Pr, Sm, Eu, Tb, Ho, Er and Tm. An optical information recording medium according to claim 6, wherein the amount of said at least one element is in the range of 0.1 - 29% by weight converted to an oxide relative to the total weight of the glass. An optical information recording medium according to claim 7, wherein said glass comprises cobalt oxides in the range of 0.1 - 29% by weight converted to CoO.

Inventors: NAITO TAKASHI, NAMEKAWA TAKASHI, SHINTANI TOSHIMICHI, SUZUKI YASUTAKA, TAKAHASHI KEN, TERAO MOTOYASU, YAMAMOTO HIROKI, NAITO, TAKASHI, NAMEKAWA, TAKASHI, SHINTANI, TOSHIMICHI, SUZUKI, YASUTAKA, TAKAHASHI, KEN, TERAO, MOTOYASU, YAMAMOTO, HIROKI
Applicants: HITACHI LTD, HITACHI, LTD.
Application year: 1998
Main classification: G11B7
IPC codes: G11B7, C03C8, C03C3