OPTICAL STORAGE MEDIUM

Abstract: An optical recording medium includes a substrate (S3) carrying first and second adjacent thin layers (A, B) or different materials, which, upon marking with an energy beam, form a marked area having optical properties different from the op­ tical properties of the unmarked area. The optical properties of the marked areas has contrast sufficiently different from the opt­ ical properties of the unmarked area so that the marked area can be reliably sensed. The first thin layer comprises a metal and the second thin layer comprises a metal or a semiconduc­ tor selected from the group comprising germanium or silicon.

Description: OPTICAL STORAGE MEDIUM. AND METHOD OF RECORD INC DATA THEREON This invention relates to optical storage media and methods of recording thereon. In optical storage of data, use of lasers to record data optically has been employed in forming pits in a recording medium to change the reflectivity of the medium. Pits are formed by evaporation, melting, or ablation. Recording can be employed which uses changes of reflectivity or transmission of light to indicate data. Bell and Spong in "Anti-reflection Structures for Optical Recording" IEEE Journal of Quantum Electronics QEl4, No. 7, 487495 (July 1978) describes on page 489 a monolayer structure of bismuth, titanium, or rhodium. A bi-layer anti-reflection structure can include Al or a dielectric stack of TiO2/NgF2/TiO2. Organic dyes such as fluorescein have been used in such recording media. Another structure mentioned on page 493 of Bell and Spong is an Al reflector covered with 2 dielectric spacer and a Ti absorbing layer. Numerous optical recording variations have been proposed but they will not all be discussed here. The problem with the above alternatives is that they will not provide long-life storage of information without employing strong laser beams. US 3,959,799 teaches read-only storage media consisting of adjacent thin layers of two or more materials which react, upon heating, to form a reaction product different from those of the reactants. More specifically, a storage medium is described which comprises alternate aluminium and selenium layers which react to form a transparent product, A12Se3, by locally heating the layers such as by the employment of a laser pulse. U.S. patent 4,069,487 suggests that a laser optical storage system can be used in which a metallic element (selected from Pt, Ph, Au, Ag, Pd, Ir, Cr, No, Ta, Zn, Cu, Al, In, Sn, Pb, and Bi Col. 8) can be layered with a non-metallic layer such as a chalcogen compound, inorganic oxide or resin (dye or pigment). The chalcogens include a chalcogen element such as S, Se and Te. Widely publicised optical storage materials such as Te and Te-based alloys suffer from relatively short lifetimes primarily because of corrosion of these very thin films on the order of 100 atomic layers. An archival storage system is required to provide data integrity for a period of at least 10 years in an ordinary environment. U.S. 4,000,492 shows thin metal films upon a transparent substrate with a first layer of Bi, In or Sn and a second layer closer to the laser source composed of BiS3, SbS and Se. There have been knows in the art optical recording media which result in the removal of material in regions approximating the diffraction-limited spot size of the recording laser. While high contrast between the written and unwritten areas has generally -been achieved, the signal-to-noise ratio has been limited in some cases by edge effects around the periphery of the spots, which cause some scattering of the read beam. Additionally, these media, such as those based on Te and Te alloys, suffer from corrosion effects. There have also been known a number of other optical recording media and other means of marking these media, however, the ones of these media which have achieved long-life recording of information have required higher laser power levels than is desirable, i.e., higher than that achieved with Te-based alloys. An object of this invention is to provide an optical storage medium which provides extremely high densities of machine readable data. Another object of this invention is to provide archival level storage of data with assurance of both clarity of the data and long-term retention of the data. Another inject of this invention is to provide an optical recording medium which is capable of storing information in response to a laser beam of acceptable power level and which will also have sufficient lifetime for archival storage purposes. According to this invention there is provided an optical storage medium including first and second adjacent layers of different materials which, upon marking with an energy beam, form a marked area having optical properties different from the optical properties of the unmarked areas, said first layer comprising a metal; and said second layer comprising â metal or semiconductor. Preferably the semiconductor of the second layer is silicon, and the metal of the first layer is a transition metal. The metals preferred of the first layer include the group vs, VIE, VIIB and VIII elements on the periodic chart, plus Mg and Au. The more advantageous metals include V, NE, T , Cr, Mo, W, Mn, Fe, Co, Ph, Ni, PG, Pt and Au. Those metals which are most effective include Pd, Pt, Cr, Ta, Rh, V and Co. The layer in contact with the silicon layer is preferably of a material which can be locally combined or reacted with silicon by local heating to produce silicide which is an optically distinguishable mark and which is stable. The silicon layer may be the outer layer so that the other layer is not exposed by prolonged storage in standard ranges of ambient environmental conditions such as those found in offices and conventional manufacturing environments. The materials of the first and second layers can endothermically combine or react together to form the optically distinguishable marked area. The metals are selected from the group comprising Al, Au, Pb, and Sn and the semiconductors are chosen from the group comprising Ge and Si. The endothermically formed marked area comprises an alloy or mixture of the materials The materials disclosed here produce an optical recording medium capable of recording ir orr,ation at high recording density with acceptable laser power levels and which has lifetime characteristics suitable for archival storage purposes. According to another aspect of the invention, there is provided a method of recording data for subsequent optical readout, in which an energy beam is used to apply local heating to first and second adjacent layers, one of which layers is of metal and the other of which layers is of metal or semiconductor which can be locally combined or reacted with the metal of the first layer by local heating, to produce an optically distinguIshable mark and which is stable. The relatively short lifetime associated with the conventional Te-based alloys due to corrosion is increased to at least 1G years by use of the materials disclosed herein. The scope of the invention is defined by the appended claims; and how it can be carried into effect is hereinafter particularly described with reference to the accompanying drawings, in which FIGURE 1 is a schematic drawing of one embodiment of optical storage medium in accordance with this invention; FIGURE 2 is a simIlar drawing of another embodiment; FIGURE 3 is a sectional schematic drawing of a multilayer optical storage medium according to this invention; FIGURES 4 and 5 show differences in reflectivity between Pd and Pd2Si and a black reference ; FIGURE 6 is a schematic drawing of an arrangement by which reflectivity was measured; FIGURE 7 shows percentage of reflectivity versus wavelength for two bi-layers in accordance with this invention; ; FIGURE 8 shows glancing-incidence Seeman-Bohlin x-ray diffraction spectra of an Rh/Si film as a function of annealing time; FIGURE 9 shows percentage of reflectivity versus wavelength for Rh/Si bi-layers; FIGURE 10 shows reflectivity versus wavelength for Rh/Si before and after annealing; FIGURE 11 shows percentage of reflectivity versus wavelength for Rh/Si bi-layers; FIGURE 12 shows percent of reflectivity versus silicon thickness for an Rh/Si bi-layer; FIGURE 13 is a TEN bright field photograph of a mark written by a laser on a Co/Si bi-layer; FIGURE 14 is a photograph in the dark field mode of the same mark as in FIG. 13; FIGURES 15 to 17 show TEN photographs of marks on Au/Si bi-layers of varying compositions; FIGURE 18 shows reflectivity versus wavelength for a Si/Au bi-layer; ; FIGURE 19 shows reflectivity versus wavelength curves for various Si/Pd bi-layers; FIGURE 20 shows reflectivity percentage versus laser power for Te and Rh/Si bi-layers; FIGURE 21 shows power versus pulse width as a function for various substrates carrying Te or Rh/Si bi-layers. FIGURE 22 is a side view of another embodiment of an optical recording medium in accordance with this invention; FIGURE 23 is side view of an alternate embodiment of the optical recording medium in accordance with this invention; FIGURE 24 is a side view of a further embodiment of the optical recording medIum in accordance wilh this invention; CURE 25 is a side view partially in section snowing the recording of a marked area in accordance with this Invention; FIGURE 26 is a side view partially in sectIon showing the recorded marked area of the recordIng medIum in accordance with this invention; and FIGURE 27 is a plan view of the recording medium showing the recorded marked area o FIG. 5. fIGURE 1 s z schematic representation of an optical storage medium accorting tt one embodiment of the invention. The medium comprises substrate S which can be transparent or opaque, depending upon the applicaton or which the medium is to be employed. Upon the substrate is a layer in the form of a thin film of silicon (Si). Upon the silicon layer is another layer @ in the form of a thin film of a metal Ml which when heated sufficiently (by means such as laser beam B1) can combine with the silicon to provide a mark readable by a sensor, such as an optical sensor of the type employed in optical recording devices. The data recorded can be store with such high density that visual inspection is possible only with optical magnification. In general, the metal film R1 upon tne top of tre silicon provides high reflectivity of light. About 65% and more of beam El is reflected. In general, high writing energy is required to heat the metal Ml sufficiently to form a mark because o tne high level of reflectivity. In addition, the metal film Ml is exposed to ambient conditions which will tend to shorten the life of the medium because of oxidation due to humidity causing oxygen to react wit the metal. Such oxidation wili spoil the reflectivity of the metal thereby destroying the contrast in reflectivity required for storing data. However, if the substrate S1 is transparent, then the silacon can be exposed to the energy from a source, such as a laser beam B2, whIch strikes the silicon which has a low value of reflectavier less tnan or equal to about 58. This leads to a low writing enter because little neatlng ss required to ra; a the silicon enoug temperature to heat the interface between the metal Ml ana the s silicon to tne temperature required to form a mark. In addition, in tne case of exposure of the medium through the substrate, tne metal Ml can be covered with a protective layer to inhibit de- gradation of the metal film. The preferred metals Ml for use in the metal layer are rhodium, cobalt, palladium, platinum, chromium, tantalum and vanadium. In general, the group VB metals V, Nb and Ta are all useful in this connection. Group VIB, VIIB, VIII metals, Mg and Au are all applicable in particular among all other metals. Specifically, the group VIB metals are Cr, Mo, and W. The group VIIB metals are Mn, Tc, and Re. The group VIII metals are Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt. Au is, of course, the nearest neighbour of Pt on the periodic chart although it is a group 13 metal Another embodIment of the inventIon (Fig. 2) is similar to that of Fig.l with substrate S2 being composed of any substrate material suitable for a recording medIum. A metal layer M2 in the form of a thin film is deposited upon the substrate S2 first. Next, a thin film silicon layer is deposited upon the metal M2 In this case, it is preferred to write upon the upper surface of the medium with laser beam 33 (or alternative radiation other than a laser beam) rather than with a beam B4 passing through the substrate to heat the metal directly, as with beam 1 in Fig.l. Another advantage of the structure of Fig.2 is that the silicon layer on the metal layer M2 provides a passivation layer, per se, requiring no additional film to protect the natal layer M2, because the substrate protects the lower surface. In another embodiment of the invention, a multi-layer optical storage medium (FIg. 3) has a substrate S3 which may be a recording disk for : - storage. The next layer is rei1ectve mirror layer MR, which may he if titanium or other metal which is highly reflective and which is sufficiently refractory. Ti has a melting point of 1668 C so tnat it is suitable for use without degradation. Upon mirror layer MR is deposite dielectric spacer layer sP which is preferably composed of material, such as SIC, which is of an appropriate thickness to maximize the wavelength of the laser beam 3 which is directed upon a pair of thin f ilms A and 3 which are respectively 2 metal layer and silicon aver. The materials of films A and 3 are interchangeable, so that the metal may be on top as film A (as in Fig. 1) or below as film 3 (as in Fig.2). In either case, the light which passes through the fIlms A and 3 is reflected back to heat the upper films so as to increase the efficiency of the laser beam B5, thereby requiring less energy from beam B5 to write data at a given point. Again, the placement of the sIlicon as the upper film A should enhance the efficiency of the data recording function. Films of silicide (a compound of metal and silicon) have been widely studied for their applications in micro-electronic devices as contact materials. K N Th and J W mayor, chapter 10 in "Thin Films - Interdiffusion and Reactions" vÅa. by J M Poate, K N Tu and J W Mayer, Wiley-Interscience, New York (1978). In forming silicide contacts by reacting a deposited metallic film with Si, a large optical contrast between the silicide and the unreacted metallic film has often been observed. C J Kircher, Solid State Electron. 14,507 (1971). The present invention arises from a study of optical contrasts. For example, Fig. 9 shows the dark spot of a Pd2Si contact 0.025nm in diemeter in an etched hole on an oxidized Sj wafer surrounded by a much Pi area. Fig. 5 shows differences in reflectivity between ness and a black reference. These suggested that silicide films could be considered as potentIal materIals for archival optical storage, provided that the contrast between the silicide and the metal (or Si) In reflection is large enough for the application. Other crucial requIrements for materials in arhival optical storage are a long lifetime, over 10 years at room temperature and non-toxicity. FindIngs on reflectivity change and stability of silicide films for the storage application are dIscussed below. The difference in optical reflectivity between metallic films and their silicides formed on Si wavers was measured. Several transition metal films of thicknesses shown In Table I were prepared by E-beam deposition in a vacuum chamber of 13.33224 x 10-6 Pa (10-7 torr) onto [10] oriented Si wafers of about 32mm in diameter, as shown in Fig. 6. OptIcal reflect- ivity (R0) shown in Table 1 is the value measured at # = 643.7nm (Kr laser). with 8 the angle of incidence of light upon the film being zero. These films were then annealed at proper conditions to form silicides, and reflectivity values were measured again as shown in Table I As can be seen, most pairs of a metal and Its silicide show a dIfference in reflectivity ssR greater than 30%. The largest difference observed is that between. Pd and Pd2Si, about 53% The difference has been found to vary with the wavelength of light used, and Fig.7 shows variations in optical reflectivity of films of Pd, Pt, Pd-Pd2Si and Pt-PtS pairs measured on Si wafers as a function of wavelength of light used. In the wavelength range shown in fIG. 7 @R between Pd and Pd2Si shows a larder change than that between Pt and Ptsi. TARTS I OPTICAL REFLECTIVITY OF BULX SILICIDES Metal@ Thickness (A) Ro(%) Silicide R1(%) #R(%) Pd 2000 81 Pd2Si 28 53 Pt 1300 83 PtSi 44 39 Ta 2000 58.5 TaSi2 32.5 26 2000 67 RilSi 37 30 V 3000 48.5 VSi2 30 18.5 Co 500 68 CoSi 47 21 @=643.7nm *Metal films on Si waver PalladIum and SilIcon and Platinum and Silicon Pd2Si and PtsI are two compounds which have many desirable properties including stability ana optical contrast. Pd2Si and PtSi are both formed when local spots are heated by a laser beam during recording. Fig.l shows 2 schematic drawing of a structure in which the readout is done by reflection. A substrate of Si or a thin film of Si is deposited onto a suitable substrate by means of vacuum deposition technique or EVD process. A thin layer of Pd or Pt film is then deposited onto the Si film, where the thickness of Pd and Pt may range from 20 nm to 60 nm (200@ to 630). The percentage of optical reflectivity of these films ranges from 80t for Pd to 84% for Pt at a wavelength of interest, say 640nm (6400 ). The spectra 3nown in Fig. are for clnS of 10C nm (1000 ) thickness. Digital information is recorded by local heating of spots moving the sterace film or bv scanning the aser tear- ty moving ins storage film or by scanning the laser beam over he starionary storage film. The temperature of the local spots may exceed severa hundred degrees nelsius, and this causes the formation of compounds such as Pd2Si and PtSi by therrmal diffusion or melting. The percencage of optical reflectivity of these compounds is very low, typically less tnan 40%. For example, at the wavelength of interest, at 64Onm (6400 ), the percent of reflectivity is 28% for Pd2Si and 44% or PtSi, as show in Fig.7 and Table I. TABLE II ------- PUBLISHED PHYSICAL DATA ---------------------- Activation Formation energy of -Growth Melting silicides Temp. C growth, eV rate Point C ----------- ------------- -------------- --------------- ------------------------ Fd3Si 100 - 700 1.3 - 1.5 t 1/2 1330 Pt2Si 200 - 500 1.1 - 1.6 t 1/2 1100 t = time From P.376, Thin Films -- iNTERDIFUSSION and Reactions, w . by Poate, Tu, and Mayer, John Wiley & Sons (1978) As to the lifetime of such devices, consider the diffusion of Pd into si at room temperature. Taking 1.4 ev as the average activation energy, the diffusion distance in 13 years turns out to be 0.55nm. Although not shown in Fis.l, a dielectric thin film in the thickness range of lOOnm (1000 ) may be deposited over the Pd surface as an antireflection coating which may also serve as a passivalion layer, to enhance the corrosion resistance. In an optacal storage disk (Fig. 5) the active layerers A abd B nat be Rh on Si or Si on Rh and can be deposited on a Sio2 dielectric spacer layer SP. The thickness of each active layer, typically less than 15nm, is chosen such that there IS maximum contrast between the laser written spot and the unreactes background. When thin fIlm of rhodium is in contact with a layer of silicon and heated to a temperature higher than 400 C, reaction takes place at the interface that forms RhSí. Below 377 C no reaction was observed to take place (D. J. Coe, E. H. Rhoderick, P. H. Gerzon, and A. W. Ginsley, "Siliclde Formation in Rh-S1 Schottky barrier diodes", Inst. of Phys. Conf. Ser. 22, p. 74, 1974), and this makes the Rh system more attractive for long-term Storage applications. The active layers A and 3 (Si+Rh or Rh;Si) are on a Ti mirror (4G to 5D nm thick) separated by an SiO2 dielectric spacer (90 to 100 nm thick). Information is stored by local heating of spots with a laser beam where heating causes reaction of Rh and Si to form silicides. The difference in optical reflectivity before and after formation of silicide is sufficient to give an adequate contrast ratio for readback. For example, the reflectivity of a Rh film of 200 nm (2000A) on Si at the wavelength of interest (643.7 nm) is typically 67%, and this reduces to 378 after formation of RhSi by annealing at 500 c for 60 minutes. The main advantage of this is that it avoids the difficult process of ablating perfectly circular holes as used in conventional low-temperature storage materials such as Te and Te-based alloys. The element Rh is known to be almost corrosion free, and other optical files fabricated with Rh film (with very high laser energy) are certified to be archival by the National Bureau of Standards in the United States.of Americe. Rhodium offers resistance to atmospheric corrosion of the disk, thus providing a longer lifetime than metals wnicn are more reactive. Althaugn a ti-layer structure is shown or the actIve layer in FIG. 3, any ariation in tne structure may be used, for example a trilayer structure oc i-Rh-si can te employed to optimize the optical properties. The lifetime of media is determIned largely by degradation of the film caused by corrosion or interfacial diffusion. Corrosion With respect to corrosion, Pt/Si, Rh/si and Pd/si films (where the metal is deposited first and the silicon later) are much less easily corroded than conventional storage media such as Te. Interfacial Diffusion Room temperature lifetime of these bi-layer film structures has to be estimated by an accelerated test and by extrapolation using the known silicide growth rate in thicker films measured at higher temperatures. In the case of 200nm Rh films on Si wafers, the growth of RhSi around 400 C was observed to be diffusion-controlled with an activation energy of 1.9eV. See the following references. D. J. Cos, E. H. Rhoderick, D. H. Gerzon and A. W. Ginsely, in "Metal-Semiconductor Contacts", Conference Series No. 22, Institute of Physics, London 1974, S. Petersson, R. Anderson, J. Dempsey, W. Hammer, F. 'Heurle and S. Luplaex. J. Appl. Phys. 51,373 (1980), By extrapolating it to xoom temperature, a diffusion-lik,e kinetic constant of 10-31 cm2/sec and an estimated growth of RhSi of lnm in 2 period of 10 years are expected, which practically means no growth of Rh8i. However, to check experimentally if an under estImate had been made for the reaction rate in very thin films used here, an accelerated test was performed by annealing the Si/Rn bi-layer films at 150 C for periods of up to 98 days. Fig.8 how cancin-inclcence secman-Boinlin x-ray dIffraction spectra of a Si (25nm)/.kh (lSnm) film as deposited, annealed at 150 C for 49 days and 98 days. The extra reflections in (d) belong to RhSi. The intensity of tne reflections in (a) is less than those of (b) and (d) due to shorter counting time. Only after 98 days Is some RhSi formation observed; anout 30nm of Rh has been transformed to RhSi estimated from the relative intensity change of Rh reflections before and after the annealing. If the reported 1.9eV activation energy is used to estimate the growth of RhSi at 1500C after 98 days, a growth of about lnm of RhSi is obtained, which is quite close to the value measured. It is concluded that the bi- layer film structure of Si/Rh will be stable at room temperature over 10 years. However, the same measurement showed that the bi-layer structure of Si/Pt will be marginally stable though satisfactory and SI/Pd will transform to Pd2 SI probably in less than 10 years at room temperature. In summary, it has been demonstrated that bi-layer film structure of Si and transition metals are promising materials for archival optical storage. They show a large reflectivity change before and after silicide formation and some of them, such as Si/Rh, have extremely good stability at room temperature. Furthermore, they are non-toxic. Although the large AR observed is interesting, the thick films used experimentally are not suitable for optical storage application because they require relatively high laser power in writing. Much thinner bi-layer thin films of Si/metal have been prepared by consecutive deposition on oxidized Si wafers, fused quartz, and photoresist coated quartz for reflectivity and stability measurements. The bi-layer configuration of Si/metal/substrate of Fig.2 rather than metal/Si/substrate of Fig.l was selected because of lower reflectivity, lower writIng energy, and better surface passivation by the Si. Three near-noble metals, Pd, Pt and Rh were chosen to form the bi-layers because their silicides are easier to form than those of refractory metals. This wi 1 sae power during laser writing. yet it Is noted that there is a =rae-off in lifetime ii the ailicide forms very easily. The thickness or either the Si or the metal in the bi-layer structure has been varied in order to investigate the effect of interfacial interference on reflectivity. For example, FIG. 9 shows reflectivity-wavelength curves for six Si/Rh films cn cuart with 25nm Rh covered by 15, 25, 25, 3, 35 and 40nm Si films. The reflectivity shows maxima and minima ane they vary with film thickness. it is noted that these curves show a much stronger dependence of reflcetivity on wavelength than those in FIG. 7. After annealing at 700 C for 30 minutes to form RhSi silicide, the reflectivitywavelength curve for the annealed sample Si (25nrn)/Rh (25nm) for example, is shown by the broken line in FIG. 9. Before z nealing, the sample showed a reflectivity minimum at tE,6630nm. At this wavelength, which is desirable for writing, a #R of about 47z is observed. Characterization of Optical Storage Materials Laser beam writing on Pt/Si and Rh/Si bi-layer films shows that thermal conductivities of substrates carrying the bi-layer films play an im- portant role in determining power requirements for the write operation. With an argon laser (508 duty cycle), only 0.5 - 1.mw is needed to write 10 m diameter spots with Rh/Si fIlms on 400A thick Si N window structures; 10 - 20mw is needed for films on glass substrates, and more than 35mw is needed for films own higher thermal conductivity Si substriates For comparison, 2-3mw is typically necessary to write on me films on glass substrates. Laser written spots on the Pt/Si and Rh/Si bi-layer films can also be described in terms of their apparent colours when viewed by back reflection of white light, or in terms of the local change in reflectivity for monochromatic light, e.g., argon laser illumination # =514.nNm found that blue, red, and yellow spots written on Rh/Si bi-1ayers, had reflectivity changes of < 5% Tbluc)-37% (red) and +688 (yellow), in comparison with adjacent unwritten areas. Transmission icroscopy and diffraction were used to determine the struct ara@ redifications responsible to one various colour and reflectivity enanges. For Rh/Si films on thin Si3N4 windows, blue areas were assessated simply with grain growth of the metallic Rh. More intense laser illumination produced red areas, associated with solid state -- of the Rh and Si films and formation of a fine grain silicide of underermined structure and composition. Still higher laser powers prodices yellow areas, with larger crystals of orthorhombic Rh5Si3 and of an unidentified cubie phase (a = 4.72 ). FIG. 9 snows the reflectivity of a bi-layei of FIG. 2 for indicated thicknesses of Rh and Si. Note that for a wavelength of 600nm of light from a laser beam or the like the reflectance of Curve B is zero. Note the contrast With the RhSi compound curve shown in dotted form. Curve C is for 250A each of Rh and Si and it has a minimum slightly above zero at about 660nm. The curve in FIG. 10 shows slightly different results for Rh nominally 250A and Si 250 after annealing at 700 C for 30 minutes. At the preferred frequency (of a gallium arsenide laser) the difference in reflectivity is 478. Just above 7000A the difference in reflectivity is very large in percentage terms, nearly infinite according to the data shown. FIG. 11 shows the curves of reflectivity percent as a function of wavelength for a thinner 150 thick film of Rh. Thicknesses G, H and J of Si are comparable to those for curves C, D and E in FIG. 9, and it can be seen that one minimum or zero at about 780nm of curve H differs very substantially from the result shown for curve D in FIG. 9. The percentage contrast is much greater also at 810nm. It can be seen that at 600nm a red laser can be used with curve B in Fig.9 and curve G in Fig. ll to achieve extremely large ratios of reflectivity. Thus optimization will be enhanced by employing curves of this type for the materia used for recording. Fig.12 shows the percentages of reflectivity as a function of Si thickness for the bi-layer of Fig.2 and the silicide of rhodium in tne dotted tine curve. For nese thicknesses, it can be seen that the maximum difference in reflectivity is provided at 150A, for an 8GOnm laser beam. These thicknesses correspond to those for curve in Fig.9, but no such data is shown in F-g.ll. Fig.13 is of a photograph magnified 30k times of a bright field transmission electron micrograph (TEM) of a mark made by a 5600 Argstrom wavelength laser beam on a cobalt/silicon bi-layer as in Fig.2 Fig.14 is of a photograph also magnified 30k times of the same mark in the dark field mode. In the centre (dark in Fig.13 is a thinner layer of amorphous Cox Siy which has been heated more by the laser beam than the surrounding area. The next oval ring (lighter in Fig.12) is composed of Cox Siy amorphous materIal which is thicker. The dark r ne about the light rins in Fig.12 is composed of crystalline CoSI compound material. The surrounding grey area is the bi-layer of Co/Si which is in its unexposed state. The optical contrast of the inner oval wIth the surrounding area is quite sharp as can be seen. Rhodium forms similar patterns with two amorphous Rhx Siy inner portions. The thinned amorphous centre surrounded by a thicker rim is caused by writing with a level of laser power exceeding the optimum value. ghis pattern indicates the beginning of formation of a hole in the amorphous centre, where material has been driven away towards the rim. Slightly lower levels of power of the laser beam does not lead to a thickened rim around the amorphous centre. Fig. 15 is of a EM magnified 20k times which shows three marks made by the same laser on a i-layer of AUjSi in accordance with Fig.2 where the ratio of Au to Si is 84 atomic percent in the Au/si Bi-layer accordIng to a microprobe analysis. The centre of the mark is black the amorinous material is located. Around the amorpuous material is a ring of crystalline materIal. In the TEM photograp magnified 30k times of Fig. 16, the bi-layer is 9 atomic percent silicon and 21 atomic percent gold. The same laser team applIed to this gold rich material produced a crystalline marK which has poor characteristics or an optical record because of tne low contrast between the mark and Its surroundings. Fig.17 is a EM magnified 20k times of a set of marks made in a medium rich in silicon wit 67 atomic percent Si and 13 atomic percent Au. In this case the centre has been transformed to the amorphous AuxSiy material with the formation of a bubble of material lifted slightly off the substrate as can be seen by the curvature shadIng at the lower portion of the photographs of the TEMS. At the periphery is the crystalline Au Si compound and then the surrounding material is shown. Application of a greater period or intensity of laser radiation would cause the central bubble of amorphous material either to thin out or to collapse so that the contrast would be better, similarly to the marks in Fig.15. For optical reflectivity it does not matter whether the mixed bi-layer in the mark is amorphous or crystalline. The percentage of optical reflectivity of an Si Au bilayer on an Sio2 spacer layer on an Al mirror layer on a substrate is shown in Fig.18 for various wavelengths. Fig. 19 shows 2 Pd/Si chart of reflectivity fraction as a function of wavelength for a 250A base of Pd coated with six different thicknesses of Si. For the SlOCA GaAs laser, curve N with 300A thickness of si will provide the greatest contrast, as can be seen. Curves L and M have similar minima for lasers in the 5500A and 6700 ranges. Fig. 20 shows a comparison of laser writing with tellurium (Te) and a Fig. 14 shows a somgarison of laser writing with telluritun (Te) and a h@S1 bi-layer as a function of power. A power level below 30mw of a 741 waveiength laser is required to make a mark on Te/ Tje cirve rops rapidly to telow 10% refloctivity at 20mw power. For rhodium/silicon bl-layers of SODA each, the reflectivity of the Fi-layer is low up to about 20mw cc cower and peaks at about 37mw of power rearing about 45%. nat happens with a Te coated medIum is that the laser begins to open noles in the Te immediately. With the bi-layer, the first portion of ne curve involves the reflectivity change as Rn and Si mix, and as the eflectivlty curve for Rh/si declines above 40mw of power, holes open in ne Rh/Si bi-iayer. In addition, with Te there is ablation whereas with the bi-layer of Rh/si there is no ablation below 30mw, but there is instead a reaction of the two layers, at least until the power level is raised high enough to form holes in the materIal. Table III shows the writing power required to produce a mark with various media most of which are thin film bi-layers in accordance with this invention. ComparIson with tellurium is made in the last two entries. Palladium covered with silicon requIres only @ short pulse as do Si/Pd and Rh/Si with the power required being less for Pf/Si, increasing for Rh/Si and greatest for Si/Pd because of the reflectivity of the metal Pd being so much higher than Si In the other two cases. With Mo/Si, the power required to form silicides Is only 35mw with a longer pulse of SOOns. For Zr/Si, the power is the same but the pulse length increases to 800ns and for Nb/Si, the power is less at 30mw but the time of the pulse required is greater at 1000ns. For Si/Co and Co/Si the power levels required are low, but the length of the pulse is 1000ns, which makes the writing speed slow. Au/Ge and Te are included in the table for the purpose of comparison. The power required to open a hole is higher and the pulse length is long. TABLE III COMPARISON OF WRITING POWER BILAYER STRUCTURE ON GLASS SUBSTRATES MAT Rtt)THICK(A) POWER (mw) PULSE (ns) Pd - S1 54 250 - 500 13* # 64** 100 S1 - Pd 72 250 - 500 70 # 77 100 Rh - S1 7 300 - 300 98 # 61 100 Si - Co 68 300 - 300 27 # 68 1000 Co - Si 32 300 - 300 20 # 52 1000 S-Si 11 300-200 33 1000 Mo-Si 10 300-200 35 509 Zr - Si 15 300 35 800 Nb-Si 13 300-200 30 1000 Au-Ge 81 500 62 1000 Te 64 500 16 50 Te 64 500 10 100 *Power required to form silicides. **Power required to open holes. Wavelength: 647.lnm. In summary, Rh/Si provides a high data rate of only 100ns pulse length. WhIle Te is superior on this basis, requiring lower power or shorter pulses, it loses in comparison of lifetime. In terms of lifetimes, the life of Rh is extremely long, Pt is long, Pd less long, and Te extremely short. FIG. 20 shows the curves of power requIred to write on various materIals on different substrates. Except for the Te on PMMA curve, the rest of tne curves are Rh/Si in thicknesses of 300A/300 and 150A/300A. It can be seen that polyester and PMMA appear to require less energy. The glass suffers in this comparison from the fact that the thickness of the Rh was greater. Clearly, Te requeres less power to provide a mark for a given pulse width, and is far more easy to mark than Rh/S1 150A/300A on the PMMA ----substrate. Also, as is obvious, less tower is required as the pulse width increases. The slope of the curve seems to be greater for PMMA. a a snort pulse width of less than 50ns, the polyester requIres a lower power. Laser Written spots in Met l/Silicon Bilayer with a Thickness Varying From 300 to 500A Single pulse laser wrIting on Pd/Si. Co/Si and V/Si bi-layer films with 2 thickness varying from 300 to 500A, showed that films on A resist on glass can te written with 0.88w whereas on glass no effect was observed with less than 1.2w. The N2 pumped dye laser had a sIngle pulse width of 5ns and was focused to a spot size of about 1 m. Scanning microscopy showed that although at > 2.5w holes were blown in the film, intermediate to no effect at < 0.8w the film shows shallow mounds in the centre of the spot with one or more concentrIc grooves towards the edge. In the cases of Pd/Si and Co/Si, the centre was found to be amorphous but not SO in V/5i. All the spots showed silicide formation. No major difference was found in the size of spots witn 2 or 10 consecutive pulses into the same area. These results have demonstrated the writing ability of laser on silicide forming films. TABLE. IV SILICID FORMATION BY CONTACT REACTION EMI23.1 <tb> <SEP> ELEMENTS <SEP> SILICIDES <tb> <SEP> METAL-RICH <SEP> MONO <SEP> SILICIDES <SEP> DISILICIDES <tb> <SEP> SILICIDES <tb> <SEP> Pt, <SEP> Pd <SEP> Pt2Si <SEP> PtSi <SEP> (end <SEP> phase) <tb> <SEP> 1.3-1.5eV* <SEP> 1.6eV* <tb> Mg <SEP> Mg2Si <tb> <SEP> (only <SEP> phase) <tb> <SEP> Ni, <SEP> Co <SEP> Ni2Si <SEP> NiSi <SEP> NiSi2 <tb> <SEP> 1.5eV <SEP> (end <SEP> phase) <tb> Ti, <SEP> Zr, <SEP> Hf <SEP> HfSi <SEP> RhSi <SEP> HfSi2 <tb> <SEP> FE, <SEP> Rh, <SEP> Mn <SEP> 2.5eV* <SEP> 1.9eV* <tb> <SEP> V, <SEP> Nb, <SEP> Ta <SEP> VSi2 <tb> Cr, <SEP> Mo, <SEP> W <SEP> 2.9eV* <tb> *activation energy Silicide formation is quite systematic. It always starts with metal rich silicides and progresses towards the silicon rich silicides. Near noble metal silicides are easier to form, i.e., form at low temperatures, than silicides of refractory metals. For specific transition metals, Table IV shows the sequence of formation. The lower the acti7ation energy shown, the easier it is to form the silicide. In the embodIment of the recording mecium, according tc the invention snown In FIG. 22, the medium. IC comprises a substrate 12 whIch can be transparent or opaque depending upon the application for which the medium is to be used. A layer 14 of a first materIal is deposited upon me substrate 12 and this first material is preferably a metal. A layer 16 of a second material is deposited upon the first layer 14, and the second material is preferably a metal or a semiconductor. A passivating layer IS is deposited upon the medium 1G to protect the materials comprising layers 14 and 16 from corrosion due to exposure to environmental factors during the lifetime of the medium. inormation is recorded in medium 1Q by directing an energy beam of suitable power level to the medium. The energy beam is absorbed in layer 16 and, to a lesser extent in layer 14, to cause localized heating in the adjoining areas of layers 14 and 16 of sufficient magnitude to produce a change in the optical propertIes of the materials comprising layers 14 and 16. The energy beem, such as beam 31 shown in the drawing is preferably directed toward the surface 11 of the medium to produce a recorded spot 19. However, should the substrate 12 be transparent to the radiation in the energy beam, beam B2 could as well be utilized to produce recorded spot 19 by directing beam E2 through substrate 12. In this case, the materials comprising layers 14 and 16 would be interchanged. The exact nature of the change that takes place is not fully understood since the heating takes place in a time which is in the order of 20 nanoseconds. FIG 25 shows what is believed to occur during recording with localized melting in layers 14 and 16 due to heating by the beam 31 and a mixing of the component materials across their interface as shown by the small arrows. FIGS. 26 and 27 show the recorded area 19 after recording. Examination of the recorded area 19 with a Scanning Electron Microscope (SEM) shows a flat recorded spot on a flat background, and no noticeable change in composition from inside to outside the recorded spot. The optical changes are believed to result from either an alloying or mixture of the two materials comprising layers 14 and 16 or an inversion of these layers. ReferrIng to FIG. 23, the configuration of the medium 20 is very similar to the FIG. 22 embodiment with substrate 22 composed of any substrate material suitable for a recordIng medium. Layer 24 is deposIted upon the substrate and this layer is preferably a metal. Layer 26 is deposited upon layer 24, and layer 26 is preferably a semiconductor. Note that in this case, a separate passivation layer is not required since the semiconductor layer 26 also serves as a passivation layer. Suitable semIconductor materials can be chosen from germanium or silicon. The embodiment of the invention shown in FIG. 24 shows a further configuration of 2 medium 30 comprising a suitable substrate 32, a first recording layer 34 which preferably comprises a metal, a second recording layer 36 which prefer ably comprises either a metal or a semiconductor, and a thick passivation layer 38. In this case, passivatlon layer 38 can be several thousand Angstroms thick and may comprise poly(methylmethacrylate) (PEES) or other suitable polymeric materials. In this embodiment, the passivation layer 35 is sufficiently thick so that Its surface 40 is not in the same focal plane as the recording layers 34, 36. This construction has the advantage that minor amounts of dust or other contaminants on the surface 40 of the medium 30 do not adversely affect either recording or playback operations. The preferred medium comprises a 200 Angstrom thick layer of Al deposited on a PiA substrate, followed by deposition on the Al of a 230 Angstrom thick layer of Ge, and a passivating layer of SiO2 substantially as shown in FIG. 1. This medium had spots recorded with a dye laser at a wavelength of 5500 Angstrom, using a pulse width of 10 nanoseconds. No attempt was made to optimize the laser power requirements, but the tests indicated a power level requirement no greater than that required for a standard SiO2 overcoated Te Optical Recording Mater-al. The recorded spots, when examined by SEM, showed flat recorded spots along with flat background The contrast was sufficiently high that reliable reading could be accomplished. A similar medium was fabricated using a 200 Angstrom thick layer of Al deposited on a 9S S substrate. A layer of Si 350 Angstrom thick was deposited on the Al layer and overcoated with a passivating layer of MgO. The writing energy for a 1000 Angstrom thickness of MgO was slightly higher than that for Ge-Al. The contrast was also less, but the contrast could be varied with the thickness of the MgO layer. The S & showed a slightly domed spot, but no material was removed, and the reflectivity within the spot was consistently higher than ontside the spot A medium was made with a 300 Angstrom thickness Pb layer deposited on a FMMA substrate. A 320 Angstrom thick layer of Sn was then deposited over the Pb followed by a 1000 Angstrom thick passivating layer of 5102 The writing energy to form recorded spot was a actor of 2 greater than for the Ge-Al medium. The constrast was also lower than that for other media tested. The SBM snows a segmented effect in the film with individual segments being fully "written" or else completely unwritten". While the medium was regarded as unsuitable for some applications, it could be used in a digital form of recording. A medium which may require the lowest laser power comprises a 300 Angstrom thick layer of In deposited on a PMA substrate, overcoated with a 230 Angstrom thick Ge layer and a passivating layer of SiO2. Based on the melting point of this combination of materials, the laser power required should be the lowest, however, this has not yet been established by actual tests.

Claims: CLAIMS 1. An optical storage medium including first and second adjacent layers (A, ) of different materials which, upon marking With an energy beam, form a marked area having optical properties different from the optical properties of the unmarked areas, said first layer comprising metal; and said second layer comprising a metal or a semiconductor. A A medium according to claim 1, in which the semiconductor is silIcon. 3. A medium accordIng to claim 2, in which the metal of the first aver 5 a transition metal. A A medium according to claim t in which the metal oS the fIrst layer is selected from the broçp consisting cf the group VS, VIP, VIlS and VII elements on the periodic chart, plus Mg and Au. 5. A medium according to claim 2, in which the metal of the first layer iS selected from the group consisting of V, Nb, Ta, Cr, No, W, Mn, Fe, Co, Rh, Ni, Pd, Pt and Au. 6. A medium according to claim 2, in which the metal of the first layer is selected from the group consisting of Pd, Pt, Cr, Ta, Rh, V and Co. 7. A medium accordIng to claim 2, in which the metal of the first layer can be locally combined or reacted with silicon by local heating to produce silicide which is an optimally distinguishable mark and which is stable. 8. A medium according to claim 7, in which the material is not normally combinable or reachable with silicon without local heating. 9. A medium. according to claim 7 or 8, in which the local heating is applicable by laser. 10. An optical storage medium according to claim 1, in which said metals are selected from the group comprising Al, Au, Pb and Sn and said semiconductors are selected from the group comprising Ge and Si. 11. An optIcal storage medium according to claim 1, in which said materIals, upon marking with the energy beam, endothermically form the marked area which comprIses an alloy or mixture of said materials. 12. An optical storage medium according to claim lr in which the material of said first layer is selected from the group comprising Al, Au, Pb, Sn and the material of said second layer is selected from the group comprising Al, Au, Pb, Sn, Ge and Si. 13. A method of recording data for subsequent optical readout, in which an energy beam is used to apply local heating to first and second adjacent layers, one of which layers is of metal and the other of which layers is of metal or semiconductor which can be locally combined or reacted with the metal of the first layer by local heating, to produce an optically distinguishable mark and which is stable. 14. A method according to claim 13, in which the metal of the first layer and the metal or semiconductor of the second layer are endothermically reacted or combined together to form the optically distinguishable mark.

Inventors: AHN, KIE YEUNG, HERD, SIGRID RENEE, LEE, MICHAEL HEINO, ONTON, AARE, TU, KING NING, WIEDER, HAROLD
Applicants: INTERNATIONAL BUSINESS MACHINES CORPORATION
Application year: 1982
Main classification: B41M5
IPC codes: G11B7, G11C17, B41M5, G11C13