CN1311739A - Information recording medium and method - Google Patents
Information recording medium and method Download PDFInfo
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- CN1311739A CN1311739A CN99809145A CN99809145A CN1311739A CN 1311739 A CN1311739 A CN 1311739A CN 99809145 A CN99809145 A CN 99809145A CN 99809145 A CN99809145 A CN 99809145A CN 1311739 A CN1311739 A CN 1311739A
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 129
- 239000001301 oxygen Substances 0.000 claims abstract description 129
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- 238000010438 heat treatment Methods 0.000 claims description 9
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- 229910052745 lead Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
- G11B7/0045—Recording
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
- G11B2007/24302—Metals or metalloids
- G11B2007/24312—Metals or metalloids group 14 elements (e.g. Si, Ge, Sn)
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
- G11B2007/24302—Metals or metalloids
- G11B2007/24314—Metals or metalloids group 15 elements (e.g. Sb, Bi)
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
- G11B2007/24302—Metals or metalloids
- G11B2007/24316—Metals or metalloids group 16 elements (i.e. chalcogenides, Se, Te)
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
- G11B2007/24318—Non-metallic elements
- G11B2007/2432—Oxygen
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
An information recording medium has a substrate and a recording layer on the substrate, the recording layer is partially transformable between a crystalline state and an amorphous state by being partially heated and cooled so that a signal is recorded in the recording layer by the partial transformation, and the recording layer includes oxygen.
Description
The present invention relates to a kind of information recording carrier and method for recording information in information recording carrier, by heating and cooling, the recording layer of this information recording carrier can be between crystalline state and non-attitude part change, thereby utilize the part distortion of recording layer, signal record in recording layer.
JP-A-61-2594 discloses and has utilized electron beam evaporation plating or sputter, depositing on the recording medium matrix as tellurium that contains the oxygen recording layer and tellurium oxide potpourri.
JP-A-2-252577 discloses in the gaseous mixture of argon gas and oxygen, by sputter, deposits on the recording medium matrix containing tellurium compound, thereby forms oxygen containing recording layer.
JP-A-63-58636 discloses and has utilized electron beam evaporation plating, depositing on the recording medium matrix as the compound that comprises tellurium oxide and tellurium that contains the oxygen recording layer, and in the gaseous mixture of argon gas and oxygen, by sputter, deposit on the recording medium matrix containing tellurium compound, contain the oxygen recording layer thereby form.
The purpose of this invention is to provide a kind of information recording carrier and a kind of information recording method, by this medium and this method, the information that can suppress to write down as time goes by and the change that takes place and/or can be known the information of playback record reliably.Specifically, the purpose of this invention is to provide a kind of information recording carrier and a kind of information recording method, with regard to this medium and this method, can prevent from partly to be epitaxially grown in the amorphous portion of recording layer around the recording layer crystalline state of recording layer amorphous portion, and/or the amorphous portion of recording layer and clear and level and smooth around the separatrix between its recording layer crystalline state part.
In recent years, in the wide spread of so-called CD, under worse condition, use and preserve CD.So, the necessary reliability that improves CD.By the various persistence experiments that relate to above-mentioned material of considering that this point carries out, find that under high temperature high-temperature severe environment long preservation has after the CD of information of record, the signal quality such as swinging of signal is qualitative is worsened.By this is scrutinized, find the crystalline state part epitaxial growth of contact amorphous sign (mark), thereby changed the shape of crystalline state part.Also find in addition in the central area of amorphous state sign, promptly do not contact the amorphous portion of crystalline state part, any change does not take place.In order to overcome this problem, changed the material and the constituent of recording layer, so that increase the activation evergy of recording layer, thereby improve amorphous stability, but similar phenomenon has still taken place.These situations show and can not solve this phenomenon thereby improve amorphous thermal stability by improving amorphous activation evergy, must propose the improvement based on a kind of neodoxy.The inventor is from order to find the various researchs that address the above problem, in the recording layer between amorphous state sign and the crystalline state part interfacial improvement extremely important, can address the above problem by adjusting the content of oxygen in the recording layer.
In the information recording carrier of the recording layer on comprising matrix and matrix, by spot heating and cooling, recording layer can change the part between crystalline state and amorphous state, thereby change by this part, signal record in recording layer, contained oxygen has limited the change that changes part in the recording layer, especially changes the crystallization again of amorphous recording layer part into from crystalline state, thereby has limited recorded information as time goes by and the variation that takes place.Can be the GE-Sb-Te class, the In-Sb-Te class, the Ag-In-Sb-Te class, (MA comprises Au to the MA-Ge-Sb-Te class, Cu, Pd, Ta, W, Ir, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Ag, Tl, S, among Se and the Pt one of at least), Sn-Sb-Te class, In-Se-Tl class, (MB comprises Au to the In-Se-Tl-MB class, Cu, Pd, Ta, W, Ir, Sc, Y, Ii, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Ag, Tl, S, among Te and the Pt one of at least), materials such as Sn-Sb-Se class are as recording layer.
If the content of oxygen is lower than 2% (atomic percent) of atom total amount in the recording layer in the recording layer, then be difficult to obtain to change the stability of the record mark that forms by the part of recording layer.If the content of oxygen is higher than 20% (atomic percent) in the recording layer, then be not easy to realize the transformation between crystalline state and the amorphous state.In order to improve the stability of record mark, oxygen content is preferably 3～15% (atomic percents), is preferably 8～14% (atomic percents).
Oxygen is included in the recording layer with the form of oxide, make can stably hold the record oxygen in the layer of recording layer, and the restriction ingredient is diffused into the crystalline state part from amorphous portion in recording layer, perhaps partly be diffused into the amorphous portion, and/or partly enter the crystal growth of amorphous portion from crystalline state from crystalline state.
If recording layer comprises Ge, Sb and Te, then best at least a portion Ge is included in the recording layer with the form of oxide.Be in the recording layer among the content a and recording layer of at least a portion Ge of oxide form, remove the relation between the content b of another part Ge outside at least a portion Ge that is oxide form, be preferably in the scope of determining by (0.02≤a/ (a+b)≤0.5).
If recording layer comprises Ge, Sb and Te, preferably at least a portion Sb is included in the recording layer with the form of oxide.Be in the recording layer among the content c and recording layer of at least a portion Sb of oxide form, remove the relation between the content d of another part Sb outside at least a portion Sb that is oxide form, be preferably in the scope of determining by (0.01≤c/ (c+d)≤0.2).
When recording layer comprises Ge, Sb and Te, and corresponding atom content is Ge:10～30% (atomic percent), Sb:10～30% (atomic percent), Te:40～80% (atomic percent), perhaps Ge:35～65% (atomic percent), Sb:10～30% (atomic percent), during Te:35～65% (atomic percent), can easily realize the phase transformation between amorphous phase and the crystalline phase, thereby the rewriting of information is easier to.By adding another atom of 1～10% (atomic percent), for example, 1～10% (atomic percent) be selected from Au, Cu, Pd, Ta, W, Ir, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Ag, Tl, S, Se, at least a atom among Pt and the N can improve amorphous Tc, can improve activation evergy in other words.
When recording layer comprises Ag, In, when Sb and Te, preferably at least a portion In is included in the recording layer with the form of oxide.Be in the recording layer among the content e and recording layer of at least a portion In of oxide form, remove the relation between the content f of another part In outside at least a portion In that is oxide form, be preferably in the scope of determining by (0.01≤e/ (e+f)≤0.5).
When recording layer comprises Ag, In, when Sb and Te, preferably at least a portion Sb is included in the recording layer with the form of oxide.Be in the recording layer in the content g and recording layer of at least a portion Sb of oxide form, remove the relation between the content h of another part Sb outside at least a portion Sb that is oxide form, be preferably in the scope of determining by (0.01≤g/ (g+h)≤0.2).
When recording layer comprises Ag, In, Sb and Te, and corresponding atom content is Ag:1～15% (atomic percent), In:1～15% (atomic percent), Sb:45～80% (atomic percent) is during Te:20～40% (atomic percent), the phase transformation between amorphous phase and the crystalline phase can be easily realized, thereby the rewriting of information can be carried out.By adding another atom of 1～10% (atomic percent), for example, 1～10% (atomic percent) be selected from Au, Cu, Pd, Ta, W, Ir, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Ag, Tl, S, Se, at least a atom among Pt and the N can improve amorphous Tc, can improve activation evergy in other words.
Utilize light beam or electron beam partial heating recording layer.
By making recording layer contain oxygen, the local at least direct contact that prevents between amorphous phase and the crystalline phase of oxygen or oxide, thus prevent the epitaxial crystal growth, thereby improved the stability of amorphous state sign.
If oxygen is present in the recording layer with the form of oxide in the recording layer, and when heating with fusing part of records layer, because the oxide that comprises in this partial record layer, this partial record layer keeps higher viscosity, thereby this partial record layer keeps higher surface tension, so that this partial record layer that fusing and being cooled is subsequently solidified and be smooth arc around at least a portion separatrix between another part recording layer of this partial record layer, when tracer signal on recording layer, one of " 0 " of signal and one state are clear to be determined by at least a portion separatrix that is smooth arc (round) reliably, when from the recording layer read output signal, can be smooth arc. clear " 0 " of identifying signal reliably, at least a portion separatrix place and one of one state.This partial record layer behind the cooling curing can be amorphous state, and another part recording layer can be crystalline state, and perhaps, this partial record layer behind the cooling curing is a crystalline state, and another part recording layer is an amorphous state.
Top method is very effective, and is especially more effective when improving recording density.
When by a spiral groove of formation or a plurality of concentric grooves on matrix, matrix comprises a plurality of annular grooves radially arranged side by side, and annular extension basically between groove, and a plurality of convex regions radially arranged side by side, in a plurality of grooves radially arranged side by side and a plurality of convex regions radially arranged side by side at least one constitutes track record, signal is recorded on this track, and the radial distance between the track record is more little, and recording density is just big more.If the radial distance between the track record is not more than 1 micron, can increase the effect of said method, if the radial distance between the track record is not more than 0.7 micron, then can enlarge markedly the effect of said method.
In addition, fusing and the minimum length of the recording layer part of cooling curing is more little subsequently, promptly record mark is more little, and recording density is just big more.Because when the minimum length of record mark on the circumferencial direction is not more than 0.7 micron, compare with the size of record mark, the amplitude of deformation of the record mark shape that the epitaxial crystal growth of being located by the record mark separatrix causes increases, and the distortion of record mark shape also increases the influence of signal quality, so the effect of said method is increased.When the minimum length of record mark was not more than 0.5 micron in the radial direction, the effect of said method was further increased.
If recording medium also comprises the protective seam that contacts with recording layer, and protective seam can limit and discharge oxygen from recording layer, thereby stably oxygen be remained in the recording layer when comprising one of oxygen and nitrogen at least.When protective seam contains aerobic,, can limit oxygen and diffuse into recording layer from protective seam because recording layer contains aerobic.When protective seam contains nitrogen, can limit recording layer and change crystalline state into from amorphous state, that is, can limit a part of crystalline state recording layer and be epitaxially grown in a part of amorphous state recording layer.
Nitrogen content in the protective seam is preferably 1～50% (atomic percent) of the total content of protective seam all components.Protective seam preferably includes ZnS and SiO
2If protective seam comprises chromium oxide, tantalum oxide, at least a in aluminium oxide and the germanium nitride, then the diffusion of component is limited between protective seam and the recording layer, and each component of recording layer is stable.When protective seam comprised nitrogen, its content was preferably 1～50% (atomic percent).In addition, in recording layer and protective seam zone adjacent one another are, on the bed thickness direction, the gradient of nitrogen content is preferably 1～50 (atom) %/nm.Under this condition; when recording layer being heated to the high temperature that is not higher than its fusing point, being easy to generate nucleus, thereby being easy to take place the phase transformation of amorphous phase to crystalline phase at recording layer and protective seam zone adjacent one another are by the energy beam such as laser beam; that is the deletion of record mark.Like this,, reach the splendid deletion performance of amorphous state sign under the high temperature, therefore can obtain good rewritable media owing to, can obtain the maintenance stability of amorphous state sign under the room temperature by the oxygen content of controlling recording layer and the nitrogen content of protective seam.Preferred ZnS of protective layer material and SiO
2Potpourri because it has low thermal conductivity and good record sensitivity.But after being no less than 100000 times repeatedly rewriting, the S in this material may diffuse in the recording layer, changes the optical coefficient of recording layer, thereby reflection coefficient is reduced.In addition, chromium oxide, tantalum oxide, aluminium oxide and germanium nitride can be used as the material of protective seam.In these materials, the advantage of chromium oxide is that optical coefficient is big, thereby by multiple interference effect, increases the difference of reflection coefficient between amorphous phase and the crystalline phase, and defective is that stress is bigger according to the protective seam mode of deposition.The advantage of tantalum oxide is that its thermal capacity is bigger, has increased heating and fusing recording layer cooling effect afterwards, and defective is to be easy to lose oxygen, thereby the tantalum oxide absorbing light reduces reflection coefficient.The advantage of aluminium oxide is very stable, and defective is less with the adhesion of recording layer.The advantage of germanium nitride is bigger with the adhesion of recording layer, and defective is that most of germanium nitrides are frangible, thereby is difficult to by formation one deck germanium nitrides such as sputters.These protective layer materials have merits and demerits respectively, but their potpourri has remedied shortcoming, thereby only have advantage.For example, the composition of chromium oxide and germanium nitride, the composition of chromium oxide and germanium nitride, the composition of tantalum oxide and aluminium oxide, composition of aluminium oxide and germanium nitride or the like are required potpourris.In addition, except above-described material, also can in above-mentioned protective layer material, add another material.Another material as removing outside the above-mentioned material can use CeO
2, La
2O
3, SiO, In
2O
3, GeO, GeO
2, PbO, SnO, SnO
2, Bi
2O
3, TeO
2, Sc
2O
3, Y
2O
3, TiO
2, ZrO
2, V
2O
5, Nb
2O
5, WO
2, WO
3, CdS, CdSe, ZnSe, In
2S
3, In
2Se
3, Sb
2S
3, Sb
2Se
3, Ga
2S
3, Ga
2Se
3, GeS, GeSe, GeSe
2, SnS, SnS
2, SnSe, SnSe
2, PbS, PbSe, Bi
2Se
3, Bi
2S
3, MgF
2, CeF
3, CaF
2, TaN, Si
3N
4, AlN, CrN, BN, Si, TiB
2, B
4C, SiC, B, C or the like.
When oxygen concentration is the ratio of oxygen atomicity and total atom number in the unit volume, and when the oxygen concentration in the recording layer changes along the thickness direction of recording layer, the composition diffusion property between the thin layer of setting recording laminar surface and contact history layer desirably, and the desirably variation of viscosity and reflection coefficient direction between setting recording laminar surface and the recording layer inside.After the formation recording layer, in comprising the gas of oxygen, recording layer is carried out oxidation processes, perhaps by in the deposition process of recording layer, regulate the oxygen concentration of environmental gas, the oxygen concentration in the scalable recording layer.
When the thickness direction of oxygen concentration along recording layer, when the mid point of recording layer at least one surface towards relative two surfaces of recording layer increases, can limit the composition diffusion between the thin layer of this surface of recording layer and contact history layer, and under the amorphous phase condition, make the reflection coefficient of the midpoint of recording layer keep higher level.
When the thickness direction of oxygen concentration along recording layer, when the mid point of recording layer each surface towards relative two surfaces of recording layer increases, the composition that can limit between each thin layer of recording layer surface and contact history layer spreads, and under the amorphous phase condition, make the reflection coefficient of recording layer midpoint keep higher level.
Preferably make the thickness direction of oxygen concentration along recording layer, at least one surface from the mid point of recording layer to relative two surfaces of recording layer increases to the twice at least of recording layer midpoint oxygen concentration.
When recording medium also comprises the reflection horizon that is used for reflection ray, recording layer is disposed between reflection horizon and the matrix, along the recording layer thickness direction, recording layer has more near the first surface of matrix with more near the second surface in reflection horizon, oxygen concentration on the first surface oxygen concentration of first degree of depth place of first surface (perhaps apart from) is lower than oxygen concentration on the second surface (perhaps apart from the oxygen concentration at second degree of depth place of second surface, second degree of depth basically with first deep equality), oxidation by the first surface of realizing by the oxygen of resin matrix, oxygen concentration on the first surface is increased towards the oxygen concentration on the second surface, thereby make relative two lip-deep oxygen concentrations on the recording layer thickness direction identical.The reflection horizon is metallic reflector normally, and its oxygen permeability is lower than the oxygen permeability of the matrix that is formed from a resin.
As the material that is used for the reflection horizon, preferred Au, Ag, Cu, Al or comprise at least a material as major component in them is because their reflection coefficient is quite high.When only using a kind of in them, its reflection coefficient is very high, but because its thermal conductivity is quite big, therefore writes down sensitivity and be lowered.On the other hand, comprise Ti, Cr, Co, Ni, Sb, Bi, In, Te, Se, Si, Ge, Pb, Ga, As, Zn, Cd, Sc, V, Mn, Fe, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, Os, Ir, Pt, at least a material as its major component in lanthanide series and the radioelement has low reflection coefficient, but has lower thermal conductivity preferably for the record sensitivity.Element in the above mentioned element set, Au and for example below with the element in the element set of mentioning, for example the potpourri of Ti makes the reflection horizon have high reflection coefficient and low thermal conductivity.Concrete example has Au-Co, Au-Cr, Au-Ti, Au-Ni, Ag-Cr, Ag-Ti, Ag-Ru, Ag-Pd, Ag-Cu-Pd, Al-Ti, Al-Cr, Al-Co, Al-Ni, Al-Nb etc.Au-Ag and Au-Cu also can form the reflection horizon of high reflectance and lower thermal conductivity.
When the oxygen concentration on the first surface oxygen concentration of first degree of depth place of first surface (perhaps apart from) is higher than oxygen concentration on the second surface (perhaps apart from the oxygen concentration at second degree of depth place of second surface; second degree of depth is substantially equal to first degree of depth) time; a pair of recording layer is included in the information recording carrier; compare with the matrix in the information recording carrier; the reflection horizon is positioned at relative inner; and by record and/or reproduction; make the temperature of relative inner position in the information recording carrier be higher than the temperature at relative outer fix place; by the oxygen diffusion that begins from protective seam; utilize the carrying out of the oxidation of second surface; oxygen concentration on the second surface is increased towards the oxygen concentration on the first surface, thereby make along relative two lip-deep oxygen concentrations on the recording layer thickness direction identical.
When the thickness direction of oxygen concentration, when first surface increases, can prevent to arrive the point midway of recording layer by the oxygen of matrix from the mid point of recording layer along recording layer.
When the thickness direction of oxygen concentration along recording layer, from the point midway of recording layer when second surface increases, this is comprised in the information recording carrier recording layer, compare with the matrix in the information recording carrier, the reflection horizon is positioned at relative inner, and by record and/or reproduce, make the temperature of relative inner position in the information recording carrier be higher than the temperature at relative outer fix place, being restricted of the oxidation at recording layer point midway place.
When but recording layer comprised the second area of the first area of recorded information and the information that can only reproduce precedence record, the difference of oxygen content preferably was not more than 18% (atomic percent) between first area and the second area.On the first area, repeatedly carry out deletion record signal and recording signal, so that after the transformation of at least a portion recording layer between crystalline state and amorphous state repeatedly repeated on the first area, the difference of oxygen content preferably was not more than 18% (atomic percent) between first area and the second area.
When the first area of recorded information as mentioned above and the difference of reproducing oxygen content between the second area of information of precedence record only are higher than 18%, it is big that the difference of the reflection coefficient between them becomes, so that be difficult to utilize similar method, reproduce the information on first area and the second area.Usually, after on information recording carrier, forming the recording layer that comprises aforesaid first area and second area by modes such as sputters, the oxygen content of first area and second area is identical substantially each other, thereby the reflection coefficient of first area and second area is identical substantially each other, can not produce and reproduce relevant problem, but when being recorded in information on the second area by concavo-convex hole, because with respect to the difference of first area at vpg connection, on the first area, can form the zone line that is used to write down between groove and the groove, can cause as time goes by, the difference of oxygen diffusion aspect, and from outside difference of infiltrating the oxygen aspect.In addition, owing to when at least once writing down, the change of atomic configuration only takes place on the first area of recording layer, therefore compare with the second area of recording layer, the discharge of oxidation or oxide is accelerated.When recording layer comprises oxygen in advance, be difficult to occur the problems referred to above, and after writing down for a long time or repeatedly, can be the difference limit of oxygen content aspect between first area and the second area for not being higher than 18%.
Just by the local recording layer that changes between crystalline state and amorphous state, the information recording method of tracer signal, it comprises the steps: to heat the part of records layer that will melt, and the heated recording layer part of cooling curing, thereby form by remove outside this partial record layer another part recording layer around marker, tracer signal comprises " 0 " state and one state, by definite " 0 " state that will write down at least a portion separatrix between this partial record layer and the described another part recording layer and a kind of state in the one state, and a kind of state that in place, described at least a portion separatrix identification " 0 " state and one state, writes down.
When recording layer comprises oxygen with the form of oxide, heat this partial record layer with box lunch, when making it to melt, the oxide that comprises by this partial record layer, make the viscosity and the surface tension of this partial record layer keep higher level, thereby at least a portion separatrix that is cooled between this partial record layer that solidifies after described another part recording layer and the fusing is smooth arc, by at least a portion separatrix that is smooth arc between this partial record layer and the described another part recording layer, in the recording process of signal, can be on recording medium the clear reliable recording of a kind of state in " 0 " state and the one state, and in the reproduction process of signal, clear this state of discerning reliably from information recording carrier.This partial record layer behind the cooling curing can be amorphous state, and another part recording layer can be crystalline state, and on the other hand, this partial record layer behind the cooling curing can be crystalline state, and another part recording layer can be amorphous state.Preferably by beam irradiation, this partial record layer of heat fused.
Recording layer can comprise first recording layer (4b) and second recording layer (4a), between first recording layer and second recording layer, oxygen concentration can sharply be changed (comparing with the oxygen concentration variation in first recording layer and second recording layer), first recording layer can not can be greater than the thickness of second recording layer along the thickness of 1/3rd, first recording layer of the mean value of the oxygen concentration of thickness direction greater than second recording layer along the mean value of the oxygen concentration of thickness direction.Recording layer can comprise a plurality of second recording layers, and first recording layer can be disposed between second recording layer.
Fig. 1 is the schematic cross section of the structure of phase transformation (transformation) type information recording carrier;
Fig. 2 a is expression according to the radial cross-section figure of the structure in the convex region that has groove and raise with respect to groove on the recording layer of the present invention;
Fig. 2 b is the front view (constitute the concentric surface shape in a plurality of annular concentric grooves radially arranged side by side and convex region and constitute a plurality of annular grooves radially arranged side by side and the helical surface shape in convex region) of two embodiment of expression recording layer according to the present invention recording medium matrix placed thereon;
Fig. 3 be the expression record mark with one of the one state of the signal that will read from record mark or write down by record mark and " 0 " state between the synoptic diagram of relation.When the level of tracer signal was changed, one of the one state of signal and " 0 " state were read or are recorded;
Fig. 4 is that expression can be made of multilayer coating, so that oxygen concentration is along the local schematic section of the recording layer of thickness direction variation;
Fig. 5 has represented after the accelerated test, the relation between oxygen concentration and record mark and the signal jitter;
Fig. 6 has represented after the accelerated test, oxygen concentration, the relation between track pitch and the signal jitter.
To utilize embodiment below, describe the present invention in detail.
[embodiment 1]
Preparation have as shown in Figure 2 annular groove 1 radially arranged side by side ' and convex region 1 " (promptly with one heart or spirality) by diameter 120mm, the matrix 1a of the transparent material of thickness 0.6mm (for example, polycarbonate resin, glass or the like) formation.In one embodiment, groove 1 ' center and adjacent land 1 " the center between radial distance be 0.74 micron.This matrix 1a put into have a plurality of sputtering chambers and provide good bed thickness homogeneity and first sputtering chamber of the sputtering equipment of reproducibility.By utilizing ZnS and SiO
2Potpourri as target, sputter in argon gas, forming thickness on matrix 1a is (ZnS) of 90 nanometers
80(SiO
2)
20(80 and 20 expression molar percentage) first overlayer 2.Subsequently, after this matrix is moved into second sputtering chamber, by utilizing Cr
2O
3As target, the Cr of sputtering sedimentation thickness 20 nanometers in argon gas
2O
3First protective seam 3.After this, after this matrix is moved into the 3rd sputtering chamber, by utilizing the Ag of sintering
2.5Ge
20Sb
22.5Te
55(2.5,20,22.5 and 55 expression atomic percent) as target, the recording layer 4 of sputtering sedimentation thickness 16 nanometers in argon gas.Subsequently, making oxygen partial pressure is 10% the argon gas and the mixed gas of oxygen, flows into the 3rd sputtering chamber with the flow velocity of 200SCCM, continues the regular hour, so that the surface of oxidation recording layer 4.Subsequently, matrix is moved into the 4th sputtering chamber, and be similar to the first tectal formation, (ZnS) of sputtering sedimentation thickness 18 nanometers
80(SiO
2)
20(80 and 20 expression molar percentage) second protective seam 5.Subsequently, in the 5th sputtering chamber, utilize the AlCr alloy as target, sputtering sedimentation thickness is the Al of 35 nanometers
94Cr
6(94 and 6 expression atomic percent) first reflection horizon 6.At last, in the 6th sputtering chamber, utilize the AlTi alloy as target, sputtering sedimentation thickness is the Al of 35 nanometers
99Ti
1(99 and 1 expression percentage by weight) second reflection horizon 7.From sputtering equipment, take out it and deposit protective seam, reflection horizon and tectal matrix, and by the rotation coating, the resin protective layer 8 of coating ultraviolet curing on top layer.
In a comparable manner, deposition (ZnS) on another kind of seemingly matrix 1b
80(SiO
2)
20(80 and 20 expression molar percentage) first overlayer 2 ', Cr
2O
3Protective seam 3 ', Ag
2.5Ge
20Sb
22.5Te
55Recording layer 4 ', (ZnS)
80(SiO
2)
20(80 and 20 expression molar percentage) second protective seam 5 ', Al
94Cr
6(94 and 6 expression atomic percent) first reflection horizon 6 ', Al
99Ti
1(99 and 1 expression percentage by weight) second reflection horizon 7 ' and the resin protective layer 8 of ultraviolet curing '; and by utilizing tack coat 9; with aspectant mode stacked this two matrix 1a and 1b, make the resin protective layer 8,8 of ultraviolet curing ' in the inside of stacked matrix.At this moment, when the diameter of tack coat is not less than 118 millimeters, the more impossible separation that causes owing to the impact that causes by reason such as falling in the generation of tack coat place.Be similar to recording layer 4, to recording layer 4 ' carry out oxidation processes.
Forming recording layer 4,4 ' afterwards, by using wavelength 810 nanometers, 75 millimeters of beam lengths, the oval-shaped laser light beam that width of light beam is 1 millimeter carries out irradiation, initialization formed by the time that changes the mixed gas that applies argon gas and oxygen on recording layer, the dish sample of the several types that oxygen content in the recording layer or concentration are different separately.Subsequently, rotating disc so that obtain the linear velocity of about 6 meter per seconds, utilizes the object lens of NA 0.6 to assemble the semiconductor laser beam of wavelength 660 nanometers, and makes it by matrix irradiation to recording layer, thereby realizes record and reproduction.For record, the use laser power is adjusted to the waveform between 5 milliwatts and 11 milliwatts, thus 8-16 modulated random signal of record.Utilize the power of n milliwatt to form record mark, and utilize the power of 5 milliwatts to be used to realize the direct rewriting of deleting.But, used the multiple-pulse wave recording that the recording impulse except that the shortest sign is divided into two or more recording impulses.The not only enterprising line item on groove but also in the convex region.
After the shake of measuring the signal of record as mentioned above, carrying out in temperature is 90 ℃, 100 hours accelerated test of preservation dish under the environment of relative humidity 80%, and the instability of measuring-signal once more subsequently.Following table has represented that in recording layer under the oxygen content and the different separately situation of concentration, the swinging of signal before and after the accelerated test is qualitative.In addition, Auger electronic analysis method is used to the oxygen content in the survey record layer.
[table 1]
| Mixed gas flow velocity (SCCM) | The gas stream angle of incidence (second) | Oxygen content (atomic percent) | Swinging of signal qualitative (%) | ||
| Before the accelerated test | After the accelerated | ||||
| Sample | |||||
| 1 | ????200 | ????40 | ????25 | ?10.0 | ?10.0 |
| | ????200 | ????30 | ????20 | ?8.5 | ?8.5 |
| | ????200 | ????22 | ????15 | ?8.3 | ?8.5 |
| Sample 4 | ????200 | ????20 | ????14 | ?8.0 | ?8.3 |
| Sample 5 | ????200 | ????10 | ????8 | ?8.0 | ?8.3 |
| | ????200 | ????3 | ????3 | ?7.5 | ?8.5 |
| Sample 7 | ????200 | ????2 | ????2 | ?7.0 | ?8.5 |
| | There is not inflow gas | ????1 | ?7.0 | ?18.5 | |
1-7 compares with sample, and after accelerated test, recording layer is not by qualitative the enlarging markedly of swinging of signal of the sample 8 of abundant oxidation.In addition, before and after the accelerated test, adopt that the swinging of signal of sample 1 of the longest gas stream angle of incidence is qualitative not to show any variation, but its initialize signal instability is qualitative more very different than the swinging of signal of sample 2-8.In addition, in above-mentioned sample 1-7, after forming recording layer, supply with the mixed gas that comprises oxygen, so that the oxidation recording layer, but also can in the mixed-gas environment of argon gas and oxygen, form recording layer, this recording layer of oxidation by sputter.
In addition, with regard to above-mentioned condition, using Ge content in 10～30% (atomic percent) scope, to change, Sb content changes in 10～30% (atomic percent) scope, and under the situation of the recording layer that in 40～80% (atomic percent) scope, changes of Te content, perhaps using Ge content in 35～65% (atomic percent) scope, to change, Sb content changes in 10～30% (atomic percent) scope, under the situation of the recording layer that Te content changes, obtain similar result with above-described result in 35～65% (atomic percent) scope.
In addition, under the situation of using the recording layer that does not comprise Ag, perhaps under the situation of the recording layer that Ag content changes, obtain similar result in 1～10% (atomic percent) scope.
In addition, be replaced in all or part A g, and add 1～10% (atomic percent) be selected from Au, Cu, Pd, Ta, W, Ir, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Ag, Tl, S, Se under the situation of at least a element of Pt and N, obtains similar result.
In addition, in the forming process of recording layer 4, mixed gas by utilizing argon gas and oxygen is as sputter gas, form the second recording layer 4a of thickness 2 nanometers, subsequently by sputter gas is changed into argon gas, form the first recording layer 4b of thickness 16 nanometers, and by once more sputter gas being changed into the mixed gas of argon gas and oxygen, form the second recording layer 4a of thickness 2 nanometers once more, simultaneously after forming recording layer, do not carry out obtaining to increase the effect of reflection coefficient under the situation by the oxidation processes that flows into argon gas-oxygen mixed gas realization.When changing the partial pressure of oxygen that forms in the second recording layer process, so that when 2% (atomic percent) of first recording layer changed into 20% (atomic percent), the qualitative increase of swinging of signal that obtains by accelerated test showed the similar result with result shown in the table 1 the oxygen average content of second recording layer.Be that the reflection coefficient of dish increases 2% under 1/3 or the situation less than the oxygen content of second recording layer of oxygen content of second recording layer in the oxygen content of first recording layer.When only when the side of the first recording layer 4b forms the second recording layer 4a, the performance the when performance of acquisition is very similar to and all forms the second recording layer 4a in the both sides of the first recording layer 4b.In addition, when in the scope of 1～10 nanometer, changing the thickness of the second recording layer 4a, obtains closely similar performance, but when thickness be 5 nanometers or when bigger, write down the sensitivity reduction, and write down required power and increase about 1 milliwatt.
[embodiment 2]
Have a plurality of sputtering chambers and provide good bed thickness homogeneity and first sputtering chamber of the sputtering equipment of reproducibility putting into embodiment 1 identical matrix 1a.Utilize ZnS and SiO
2Potpourri as target, in argon gas, by sputtering sedimentation, on matrix 1a, form (ZnS) of thickness 90 nanometers
80(SiO
2)
20(80 and 20 expression molar percentage) first overlayer 2.Subsequently, after this matrix is moved into second sputtering chamber, utilize Cr
2O
3As target, the Cr of sputtering sedimentation thickness 20 nanometers in argon gas
2O
3First protective seam 3.After this, after this matrix is moved into the 3rd sputtering chamber, by utilizing the Ag of sintering
2.5Ge
20Sb
22.5Te
55(2.5,20,22.5 and 55 expression atomic percent) as target, the recording layer 4 of sputtering sedimentation thickness 16 nanometers in argon gas.Subsequently, matrix is moved into oxide form the chamber, and make it to stay the regular hour in the oxygen atmosphere, so that oxidation recording layer 4.Subsequently, matrix is moved into the 4th sputtering chamber, and be similar to the first tectal formation, (ZnS) of sputtering sedimentation thickness 18 nanometers
80(SiO
2)
20(80 and 20 expression molar percentage) second protective seam 5.Subsequently, in the 5th sputtering chamber, utilize the AlCr alloy as target, sputtering sedimentation thickness is the Al of 35 nanometers
94Cr
6(94 and 6 expression atomic percent) first reflection horizon 6.At last, in the 6th sputtering chamber, utilize the AlTi alloy as target, sputtering sedimentation thickness is the Al of 35 nanometers
99Ti
1(99 and 1 expression percentage by weight) second reflection horizon 7.From sputtering equipment, take out overlayer with deposition, protective seam, the matrix in recording layer and reflection horizon, and, on second reflection horizon 7, form the resin protective layer 8 of ultraviolet curing by the rotation coating.
In a comparable manner, pile up (ZnS) another kind of continuously like on the matrix 1b
80(SiO
2)
20(80 and 20 expression molar percentage) first overlayer 2 ', Cr
2O
3Protective seam 3 ', recording layer 4 ', (ZnS)
80(SiO
2)
20(80 and 20 expression molar percentage) second protective seam 5 ', Al
94Cr
6(94 and 6 expression atomic percent) first reflection horizon 6 ', Al
99Ti
1(99 and 1 expression percentage by weight) second reflection horizon 7 ' and the resin protective layer 8 of ultraviolet curing ', and by tack coat 9,, make the resin protective layer 8,8 of ultraviolet curing ' in the inside of stacked matrix with aspectant mode stacked this two matrix 1a and 1b.At this moment, when the diameter of tack coat is 118 millimeters or when bigger, more impossible the separation that causes owing to the impact that is caused by reason such as falling takes place at the tack coat place.Be similar to recording layer 4, recording layer 4 ' on carry out oxidation processes.
Forming recording layer 4,4 ' afterwards, prepare a plurality of dish samples, according to different oxygen partial pressures and processing time, change the Ge oxide of two or more types in the recording layer and each content of Sb oxide content, utilize method initialization each dish sample identical,, on the dish sample, write down 8-16 modulated random signal subsequently by driver with embodiment 1.Afterwards, carrying out in temperature is 70 ℃, and the environment of relative humidity 90% is preserved 40 days accelerated test of these dishes down, after accelerated test, in driver, reproduce test, studied with accelerated test before compare, error rate increases and is twice or a plurality of dishes of more times.In addition, utilize driver, the constant position on each the dish sample after the initialization writes down 8-16 modulated random signal repeatedly, has studied many reproductions or misregistration.When having represented the content of Ge oxide in changing recording layer and Sb oxide in the table 2, error rate increases and is twice or some dishes of more times.When having represented the content of Ge oxide in changing recording layer and Sb oxide in the table 2, the number of times of duplicate record.Utilize the content of XPS device measuring Ge oxide and Sb oxide, and, determine the content of Ge oxide and Sb oxide by the peak separation of the XPS spectrum of Ge and Sb.In addition, in table 2, a, b, c and d represent the content of the germanium of oxidation respectively, the content of the not oxidized germanium of metal or alloy, the content of the not oxidized antimony of the content of the antimony of oxidation and metal and alloy.
[table 2]
| Oxygen partial pressure (10 -5pa) | Retention time (minute) | ????a/ ???(a+b) | ????c/ ???(c+d) | After the accelerated test, error rate increases and is twice or more times dish number | The number of times of | |
| Sample | ||||||
| 1 | ????10.0 | ????60 | ????0.6 | ???0.26 | ????0/10 | ?30000 |
| | ????5.0 | ????10 | ????0.5 | ???0.2 | ????0/10 | ?100000 |
| Sample 3 | ????3.0 | ????10 | ????0.4 | ???0.14 | ????0/10 | ?110000 |
| Sample 4 | ????1.0 | ????10 | ????0.2 | ???0.07 | ????1/10 | ?130000 |
| | ????1.0 | ????2 | ???0.04 | ???0.02 | ????2/10 | ?150000 |
| | ????1.0 | ????1 | ???0.02 | ???0.01 | ????3/10 | ?200000 |
| Sample 7 | Not oxidized | ???0.01 | ???0.005 | ????8/10 | ?200000 | |
1-6 compares with sample, after accelerated test, recording layer is not enlarged markedly by the abundant error rate of the sample 7 of oxidation, and not only in 10 samples the error rate of 8 samples increase and be twice or more times, and with regard to 4 samples wherein, reproduce the very difficulty that becomes.
In addition, with regard to above-mentioned condition, using Ge content in 10～30% (atomic percent) scope, to change, Sb content changes in 10～30% (atomic percent) scope, and under the situation of the recording layer that in 40～80% (atomic percent) scope, changes of Te content, perhaps using Ge content in 35～65% (atomic percent) scope, to change, Sb content changes in 10～30% (atomic percent) scope, under the situation of the recording layer that Te content changes, obtain similar result with above-described result in 35～65% (atomic percent) scope.
In addition, under the situation of using the recording layer that does not comprise Ag, perhaps under the situation of the recording layer that Ag content changes, obtain similar result in 1～10% (atomic percent) scope.
In addition, be replaced in all or part A g, and add 1～10% (atomic percent) be selected from Au, Cu, Pd, Ta, W, Ir, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Ag, Tl, S, Se under the situation of at least a element of Pt and N, obtains similar result.
[embodiment 3]
Except that groove 1 ' the center and the radial distance between the center of adjacent grooves be 0.75 micron, other technical limitation is identical with embodiment 1, matrix 1a is put into have a plurality of sputtering chambers and provide good bed thickness homogeneity and first sputtering chamber of the sputtering equipment of reproducibility.Utilize ZnS and SiO
2Potpourri as target, in argon gas, by sputtering sedimentation, on matrix 1a, form (ZnS) of thickness 90 nanometers
80(SiO
2)
20(80 and 20 expression molar percentage) first protective seam 2.Subsequently, after this matrix is moved into second sputtering chamber, utilize the Ag of sintering
4In
7Sb
62Te
27(4,7,62 and 27 expression atomic percent) as target, the recording layer 4 of sputtering sedimentation thickness 20 nanometers in argon gas.Subsequently, matrix is moved into oxide form the chamber, and make it to stay the regular hour in the oxygen atmosphere, so that oxidation recording layer 4.Subsequently, matrix is moved into the 3rd sputtering chamber, and be similar to the formation of first protective seam, form (ZnS) of thickness 20 nanometers
80(SiO
2)
20(80 and 20 expression molar percentage) second protective seam 5.Subsequently, in the 4th sputtering chamber, utilize the AlTi alloy, the Al of deposit thickness 100 nanometers as target
99Ti
1(99 and 1 expression percentage by weight) reflection horizon 7.From sputtering equipment, take out it and deposit protective seam, the matrix in recording layer and reflection horizon, and by the rotation coating, the resin protective layer 8 of coating ultraviolet curing on its top layer.
In a comparable manner, pile up (ZnS) another kind of continuously like on the matrix 1b
80(SiO
2)
20(80 and 20 expression molar percentage) first protective seam 2 ', recording layer 4 ', (ZnS)
80(SiO
2)
20(80 and 20 expression molar percentage) second protective seam 5 ', Al
99Ti
1(99 and 1 expression percentage by weight) reflection horizon 6 ' and the resin protective layer 8 of ultraviolet curing '; and by tack coat 9; in aspectant mode these two matrix 1a and 1b are bondd mutually, make the resin protective layer 8,8 of ultraviolet curing ' in the inside of stacked matrix.At this moment, when the diameter of tack coat is 118 millimeters or when bigger, more impossible the separation that causes owing to the impact that is caused by reason such as falling takes place at the tack coat place.Be similar to recording layer 4, to recording layer 4 ' carry out oxidation processes.
Except that only the enterprising line item of groove, under the identical situation of other technical limitation and embodiment 1, measure the instability of the signal of record as mentioned above, subsequently, carrying out in temperature is 80 ℃, the environment of relative humidity 90% is preserved 200 hours accelerated test of these dishes down, and after accelerated test, the instability of measuring-signal.Represented below that in different partials pressure of oxygen under the situation of the different content of In oxide and Sb oxide, the swinging of signal that records before and after the accelerated test is qualitative in retention time and the recording layer.Utilize the content of In oxide and Sb oxide in the XPS device measuring recording layer, and, determine the content of In oxide and Sb oxide by the peak separation of the XPS spectrum of In and Sb.In addition, in table 3, e, f, g and h represent the content of the indium of oxidation respectively, the content of the not oxidized indium of metal or alloy, the content of the not oxidized antimony of the content of the antimony of oxidation and metal and alloy.
[table 3]
| Oxygen partial pressure (10 -5Pa) | Retention time (minute) | ??e/ ?(e+f) | ???G/ ?(g+h) | Swinging of signal qualitative (%) | ||
| Before the accelerated test | After the accelerated | |||||
| Sample | ||||||
| 1 | ????10.0 | ????60 | ??0.6 | ??0.26 | ?10.0 | ????10.0 |
| | ????5.0 | ????10 | ??0.5 | ???0.2 | ??8.0 | ????8.0 |
| | ????3.0 | ????10 | ??0.4 | ??0.15 | ??7.0 | ????7.9 |
| Sample 4 | ????1.0 | ????10 | ??0.2 | ??0.07 | ??7.5 | ????7.9 |
| | ????1.0 | ????2 | ??0.04 | ??0.02 | ??7.3 | ????7.9 |
| | ????1.0 | ????1 | ??0.01 | ??0.01 | ??7.0 | ????8.0 |
| | Not oxidized | ?0.005 | ??0.005 | ??6.7 | ????15.0 | |
1-6 compares with sample, after accelerated test, recording layer not by the sample 7 of fully oxidation in, swinging of signal is qualitative to enlarge markedly.In addition, in the longest sample 1 of the retention time in oxygen atmosphere, the swinging of signal before and after the accelerated test is qualitative mutually the same, but its initialize signal instability is far longer than the initialize signal instability of sample 2-7.
In addition, in above-mentioned sample 1-6, recording layer is maintained at the regular hour in the oxygen atmosphere, so that the oxidation recording layer, but also can be by in the environment of the mixed gas of argon gas and oxygen, forming recording layer, the oxidation recording layer.
In addition, in the above under the condition of Miao Shuing, using Ag content in 1～15% (atomic percent) scope, to change, In content changes in 1～15% (atomic percent) scope, Sb content changes in 45～80% (atomic percent) scope, and under the situation of the recording layer that in 20～40% (atomic percent) scope, changes of Te content, obtain similar result with above-described result.
In addition, adding the Au that is selected from of 1～10% (atomic percent), Cu, Pd, Ta, W, Ir, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Tl, S, Se under the situation of at least a element of Pt and N, obtains similar result.
[embodiment 4]
Have a plurality of sputtering chambers putting into and provide good bed thickness homogeneity and first sputtering chamber of the sputtering equipment of reproducibility as the matrix 1a that uses among the embodiment 1.Utilize ZnS and SiO
2Potpourri as target, in argon gas, form (ZnS) of thickness 90 nanometers
80(SiO
2)
20(80 and 20 expression molar percentage) first overlayer 2.Subsequently, after this matrix is moved into second sputtering chamber, utilize Cr
2O
3As target, in argon gas, form the Cr of thickness 20 nanometers
2O
3First protective seam 3.Afterwards, after this matrix is moved into the 3rd sputtering chamber, utilize the Ag of sintering
2.5Ge
20Sb
22.5Te
55(2.5,20,22.5 and 55 expression atomic percent) as target, forms the recording layer 4 of thickness 16 nanometers in argon gas.Subsequently, making oxygen partial pressure is that the mixed gas of 10% argon gas and oxygen flows into the 3rd sputtering chamber with the flow velocity of 200SCCM, continues the regular hour, so that the surface of oxidation recording layer 4.Subsequently, matrix is moved into the 4th sputtering chamber, in the mixed gas of argon gas and nitrogen, form the ZnS-SiO of thickness 18 nanometers
2-N second protective seam 5.Subsequently, in the 5th sputtering chamber, utilize the AlCr alloy, form the Al of thickness 35 nanometers as target
94Cr
6(94 and 6 expression atomic percent) first reflection horizon 6.At last, in the 6th sputtering chamber, utilize the AlTi alloy, form the Al of thickness 35 nanometers as target
99Ti
1(99 and 1 expression percentage by weight) second reflection horizon 7.From sputtering equipment, take out matrix, and apply, on top layer, form the resin protective layer 8 of ultraviolet curing by rotation with each layer that piles up.In a comparable manner, form (ZnS) like another kind of on the matrix 1b
80(SiO
2)
20(80 and 20 expression molar percentage) first overlayer 2 ', Cr
2O
3Protective seam 3 ', recording layer 4 ', ZnS-SiO
2-N second protective seam 5 ', Al
94Cr
6(94 and 6 expression atomic percent) first reflection horizon 6 ', Al
99Ti
1(99 and 1 expression percentage by weight) second reflection horizon 7 ' and the resin protective layer 8 of ultraviolet curing ', and, adhere to this two matrix 1a and 1b in aspectant mode by tack coat 9, make the resin protective layer 8,8 of ultraviolet curing ' in the inside of stacked matrix.At this moment, when the diameter of tack coat is 118 millimeters or when bigger, more impossible the separation that causes owing to the impact that is caused by reason such as falling takes place at the tack coat place.
The dish for preparing aforesaid several types, utilize drive records 8-16 modulated random signal, so that measurement error rate, subsequently, carrying out in temperature is 90 ℃, and the environment of relative humidity 80% is preserved 100 hours accelerated test of these dishes down, after accelerated test, measure the error rate (reproduction error rate) of same position, and rewrite random signal, so that measure error rate (rewriting error rate) at same position.Following table has represented that the oxygen content in the layer of holding the record is constant, i.e. 8% (atomic percent), and at ZnS-SiO
2In the forming process of-N second protective seam, different nitrogen gas concn in the mixed gas of setting argon gas and nitrogen is so that change ZnS-SiO
2During nitrogen content in-N second protective seam, after accelerated test, error rate increases and is twice or a plurality of dishes of more times.In addition, use the oxygen content in the Auger electronic energy spectrum method survey record layer, and the nitrogen content in second protective seam.
[table 4]
| Nitrogen content in second protective seam | After the accelerated test, under the rewriting condition, error rate increases and is twice or more times dish number (10 number in dish) | After the accelerated test, under the reproducing condition, error rate increases and is twice or more times dish number (10 number in dish) |
| ????0％ | ?????10/10 | ?????0/10 |
| ????1％ | ?????1/10 | ?????0/10 |
| ????2％ | ?????0/10 | ?????0/10 |
| ????15％ | ?????0/10 | ?????0/10 |
| ????25％ | ?????0/10 | ?????1/10 |
| ????50％ | ?????0/10 | ?????2/10 |
| ????60％ | ?????0/10 | ?????9/10 |
Nitrogen content in second protective seam is set under the situation of 60% (atomic percent), and not only the reproduction error rate of 9 dishes in 10 dishes increases and is twice or more times, and 8 dish carts in 10 dishes reveal and self reproduce the very phenomenon of difficulty.In addition, be under the situation of 50% (atomic percent) and 25% (atomic percent) at nitrogen content, the reproduction error rate of some dishes increases and is twice or more times, but in these dishes, the phenomenon of difficulty occurs reproducing.
[embodiment 5]
Changing under the long situation of the shortest sign, after on the sign of the shortest various sign length being recorded in the dish that is similar to embodiment 1 formation, carrying out in temperature is 90 ℃, the environment of relative humidity 80% is preserved down 100 hours accelerated test of these dishes, and after accelerated test the instability of measuring-signal.Groove 1 ' center and adjacent land 1 " the center between radial distance be set to 0.74 micron, at the enterprising line item of groove and convex region.Checkmark position system and sign limbic system, in the system of mark position, set one state information at the sign place, set " 0 " status information in the part of removing outside the sign, in the sign limbic system, edge sets one state information at sign, sets " 0 " status information in the part of removing outside the sign edge.After the accelerated test, the qualitative situation of change of the swinging of signal of the dish that oxygen content is different separately in the recording layer as shown in Figure 5.
[embodiment 6]
Prepare several matrix 1a, these matrixes are by 120 millimeters of diameters, the transparent material that thickness is 0.6 millimeter (for example, polycarbonate resin, glass etc.) constitute, and comprise by the annular groove 1 radially arranged side by side shown in Fig. 2 ' and 1 " (that is, in shape), their differences each other in concentric or helical surface be groove 1 ' center and adjacent land 1 " the center between radial distance.Be similar to embodiment 1, the shortest sign length of the disc recording that forms on these matrixes is after 0.7 micron the sign, carrying out in temperature is 90 ℃, and the environment of relative humidity 80% is preserved down 100 hours accelerated test of these dishes, and after accelerated test the instability of measuring-signal.Checkmark position system and sign limbic system, in the system of mark position, set one state information at the sign place, set " 0 " status information in the part of removing outside the sign, in the sign limbic system, edge sets one state information at sign, sets " 0 " status information in the part of removing outside the sign edge.After the accelerated test, the qualitative situation of change of the swinging of signal of the dish that oxygen content is different separately in the recording layer as shown in Figure 6.
[embodiment 7]
[table 5]
| Holding time | Oxygen content on the first area | Oxygen content on the second area | The difference of oxygen content between first area and the second area | The difference of reflection coefficient between first area and the |
| 0 hour | ????4％ | ????2％ | ????2％ | ????0％ |
| 50 hours | ????8％ | ????2％ | ????6％ | ????0-1％ |
| 100 hours | ????10％ | ????2％ | ????8％ | ????1％ |
| 200 hours | ????15％ | ????2％ | ????13％ | ????2％ |
| 300 hours | ????20％ | ????3％ | ????17％ | ????4％ |
| 500 hours | ????22％ | ????4％ | ????18％ | ????5％ |
| 1000 hours | ????25％ | ????5％ | ????20％ | ????8％ |
Claims (42)
1. information recording carrier, it comprises the recording layer on matrix and the matrix, by spot heating and cooling, recording layer can be between crystalline state and amorphous state local the transformation, thereby change signal record in recording layer by the part, wherein recording layer contains aerobic.
2. according to the described information recording carrier of claim 1, wherein recording layer comprises at least a principal ingredient as recording layer among Te and the Se.
3. according to claim 1 or 2 described information recording carriers, wherein the oxygen content in the recording layer is 2～20% (atomic percents) of the total content of all atoms in the recording layer.
4. according to the arbitrary described information recording carrier of claim 1-3, wherein recording layer contains aerobic with the form of oxide.
5. according to the arbitrary described information recording carrier of claim 1-4, wherein recording layer comprises Ge, and at least a portion Ge is present in the recording layer with the form of oxide.
6. according to the described information recording carrier of claim 5, wherein be in the recording layer among the content a and recording layer of at least a portion Ge of oxide form, remove the relation between the content b of another part Ge outside at least a portion Ge that is oxide form, be preferably in the scope of determining by (0.02≤a/ (a+b)≤0.5).
7. according to the arbitrary described information recording carrier of claim 1-4, wherein recording layer comprises Sb, and at least a portion Sb is present in the recording layer with the form of oxide.
8. according to the described information recording carrier of claim 7, wherein be in the recording layer among the content c and recording layer of at least a portion Sb of oxide form, remove the relation between the content d of another part Sb outside at least a portion Sb that is oxide form, be preferably in the scope of determining by (0.01≤c/ (c+d)≤0.2).
9. according to the arbitrary described information recording carrier of claim 1-4, wherein recording layer contains Ag, In, and Sb and Te, and at least a portion In is present in the recording layer with the form of oxide.
10. according to the described information recording carrier of claim 9, wherein be in the recording layer among the content e and recording layer of at least a portion In of oxide form, remove the relation between the content f of another part In outside at least a portion In that is oxide form, be preferably in the scope of determining by (0.01≤e/ (e+f)≤0.5).
11. according to the arbitrary described information recording carrier of claim 1-4, wherein recording layer comprises Ag, In, and Sb and Te, and at least a portion Sb is present in the recording layer with the form of oxide.
12. according to the described information recording carrier of claim 11, wherein be in the recording layer in the content g and recording layer of at least a portion Sb of oxide form, remove the relation between the content h of another part Sb outside at least a portion Sb that is oxide form, be preferably in the scope of determining by (0.01≤g/ (g+h)≤0.2).
13. according to the described information recording carrier of claim 1, wherein can be by light beam spot heating recording layer.
14. according to the described information recording carrier of claim 1, wherein oxygen is present in the recording layer with the form of oxide in the recording layer, and when heating with fusing part of records layer, because the oxide that comprises in this partial record layer, this partial record layer keeps higher viscosity, thereby this partial record layer keeps higher surface tension, so that this partial record layer of solidifying of fusing and being cooled subsequently and be smooth arc around at least a portion separatrix between another part recording layer of this partial record layer.
15. according to claim 13 or 14 described information recording carriers, wherein tracer signal has " 0 " state and one state, a state in " 0 " state and the one state is determined by described at least a portion separatrix, and is identified at place, described at least a portion separatrix.
16. according to claim 13 or 14 described information recording carriers, wherein this partial record layer behind the cooling curing is an amorphous state, another part recording layer is a crystalline state.
17. according to claim 13 or 14 described information recording carriers, wherein this partial record layer behind the cooling curing is a crystalline state, another part recording layer is an amorphous state.
18. according to the described information recording carrier of claim 1, wherein matrix comprises a plurality of annular grooves radially arranged side by side, and annular is extended between groove, and a plurality of convex regions radially arranged side by side, in described a plurality of grooves radially arranged side by side and the described a plurality of convex regions radially arranged side by side at least one constitutes track record, and signal is recorded on the track record.
19. according to the described information recording carrier of claim 18, wherein the radial distance between the track record is not more than 1 micron.
20. according to the described information recording carrier of claim 18, wherein the radial distance between the track record is not more than 0.7 micron.
21. according to the described information recording carrier of claim 18, wherein in a circumferential direction, fusing and subsequently the minimum length of the recording layer part of cooling curing be not more than 0.7 micron.
22. according to the described information recording carrier of claim 18, wherein in a circumferential direction, fusing and subsequently the minimum length of the recording layer part of cooling curing be not more than 0.5 micron.
23. according to the described information recording carrier of claim 1, also comprise the protective seam of contact history layer, wherein protective seam comprises one of oxygen and nitrogen at least.
24. according to the described information recording carrier of claim 23, wherein nitrogen content is 1～50% (atomic percent) of the total content of all the components in the protective seam in the protective seam.
25. according to the described information recording carrier of claim 23, wherein protective seam comprises ZnS and SiO
2
26. according to the described information recording carrier of claim 23, wherein protective seam comprises chromium oxide at least, tantalum oxide, one of aluminium oxide and germanium nitride.
27. according to the described information recording carrier of claim 1, wherein oxygen concentration is the ratio of oxygen atomicity and total atom number in the unit volume, and the oxygen concentration in the recording layer changes along the thickness direction of recording layer.
28. according to the described information recording carrier of claim 27, wherein oxygen concentration is along the thickness direction of recording layer, from mid point at least one surface increase towards relative two surfaces of recording layer of recording layer.
29. according to the described information recording carrier of claim 27, wherein oxygen concentration is along the thickness direction of recording layer, from mid point each surface increase towards relative two surfaces of recording layer of recording layer.
30. according to the described information recording carrier of claim 27, wherein oxygen concentration is along the thickness direction of recording layer, at least one surface from the mid point of recording layer to relative two surfaces of recording layer increases the twice at least for recording layer midpoint oxygen concentration.
31. according to the described information recording carrier of claim 27, also comprise the reflection horizon that is used for reflection ray, wherein recording layer is disposed between reflection horizon and the matrix, along the recording layer thickness direction, recording layer has more near the first surface of matrix with more near the second surface in reflection horizon, and the oxygen concentration on the first surface is lower than the oxygen concentration on the second surface.
32. according to the described information recording carrier of claim 27, also comprise the reflection horizon that is used for reflection ray, wherein recording layer is disposed between reflection horizon and the matrix, along the recording layer thickness direction, recording layer has more near the first surface of matrix with more near the second surface in reflection horizon, and the oxygen concentration on the first surface is higher than the oxygen concentration on the second surface.
33. according to the described dwelling of claim 27 recording medium, also comprise the reflection horizon that is used for reflection ray, wherein recording layer is disposed between reflection horizon and the matrix, along the recording layer thickness direction, recording layer has more near the first surface of matrix with more near the second surface in reflection horizon, and oxygen concentration is along the thickness direction of recording layer, increases towards first surface from the mid point of recording layer.
34. according to the described dwelling of claim 27 recording medium, also comprise the reflection horizon that is used for reflection ray, wherein recording layer is disposed between reflection horizon and the matrix, along the recording layer thickness direction, recording layer has more near the first surface of matrix with more near the second surface in reflection horizon, oxygen concentration is along the thickness direction of recording layer, increases towards second surface from the mid point of recording layer.
35. according to the described information recording carrier of claim 1, wherein but recording layer comprises the first area and the second area that can only reproduce the information of precedence record of recorded information, and the difference of oxygen content is not more than 18% (atomic percent) between first area and the second area.
36. according to the described information recording carrier of claim 35, wherein on the first area, repeatedly carry out deletion record signal and recording signal, so that after the transformation of at least a portion recording layer between crystalline state and amorphous state repeatedly repeated on the first area, the difference of oxygen content was not more than 18% (atomic percent) between first area and the second area.
37. one kind is passed through the local recording layer that changes between crystalline state and amorphous state, the information recording method of tracer signal, and this method comprises the steps:
Heating will be melted the part of records layer,
Heated this partial record layer of cooling curing, thereby form by remove outside this partial record layer another part recording layer around marker, tracer signal comprises " 0 " state and one state, a state that will write down in " 0 " state and the one state is determined by at least a portion separatrix between described part of records layer and the described another part recording layer, and the state that in place, described at least a portion separatrix identification " 0 " state and one state, is recorded
Wherein recording layer comprises the oxygen that is oxide form, during with convenient heat fused part of records layer, because the oxide that comprises in this partial record layer, this partial record layer keeps higher viscosity and surface tension, thereby be cooled after the fusing this partial record layer of solidifying and at least a portion separatrix between another part recording layer are smooth arcs.
38. according to the described information recording method of claim 37, wherein this partial record layer behind the cooling curing is an amorphous state, another part recording layer is a crystalline state.
39. according to the described information recording method of claim 37, wherein this partial record layer behind the cooling curing is a crystalline state, another part recording layer is an amorphous state.
40. according to the described information recording method of claim 37, wherein by the irradiation of light beam, the described part of records layer of heat fused.
41. according to the described information recording method of claim 37, wherein recording layer comprises first recording layer and second recording layer, between first recording layer and second recording layer, oxygen concentration takes place sharply to change, the mean value of the oxygen concentration on the first recording layer thickness direction be not more than the oxygen concentration on the second recording layer thickness direction mean value 1/3rd, and the thickness of first recording layer is greater than the thickness of second recording layer.
42. according to the described information recording method of claim 41, wherein recording layer comprises a plurality of second recording layers, and first recording layer is disposed between second recording layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22953598 | 1998-07-31 | ||
| JP229535/1998 | 1998-07-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1311739A true CN1311739A (en) | 2001-09-05 |
| CN1180942C CN1180942C (en) | 2004-12-22 |
Family
ID=16893702
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998091456A Expired - Fee Related CN1180942C (en) | 1998-07-31 | 1999-07-30 | Information recording medium and method |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1180942C (en) |
| AU (1) | AU4931399A (en) |
| TW (1) | TW518588B (en) |
| WO (1) | WO2000006391A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7027382B2 (en) | 2001-06-26 | 2006-04-11 | Ricoh Company, Ltd. | Optical recording medium having relation between reflection layer and pit lengths |
| JP2007141417A (en) | 2005-11-22 | 2007-06-07 | Sony Corp | Write-once type optical recording medium and its manufacturing method |
| JP2007293949A (en) * | 2006-04-21 | 2007-11-08 | Toshiba Corp | Optical recording medium, information recording and reproducing apparatus and method |
| JP2008217858A (en) * | 2007-02-28 | 2008-09-18 | Toshiba Corp | Phase change recording medium and information recording and reproducing apparatus using this medium |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6042095A (en) * | 1983-08-19 | 1985-03-06 | Hitachi Ltd | Information recording member |
| JPS63173240A (en) * | 1987-01-12 | 1988-07-16 | Matsushita Electric Ind Co Ltd | Optical information recording medium |
| JP2827201B2 (en) * | 1987-03-18 | 1998-11-25 | 東レ株式会社 | Optical recording medium |
| JPH01303645A (en) * | 1988-05-31 | 1989-12-07 | Matsushita Electric Ind Co Ltd | Optical recording carrier and its production |
| JPH04119885A (en) * | 1990-09-11 | 1992-04-21 | Matsushita Electric Ind Co Ltd | Optical recording medium and preparation thereof |
| JP2512237B2 (en) * | 1991-02-07 | 1996-07-03 | 三菱化学株式会社 | Optical information recording medium |
| JPH04316887A (en) * | 1991-04-16 | 1992-11-09 | Matsushita Electric Ind Co Ltd | Optical recording medium and sputtering target, and manufacture thereof |
| JP3151848B2 (en) * | 1991-04-25 | 2001-04-03 | 松下電器産業株式会社 | Optical information recording medium |
| JPH05124353A (en) * | 1991-11-07 | 1993-05-21 | Toray Ind Inc | Photorecording medium |
| CN1278325C (en) * | 1996-03-11 | 2006-10-04 | 松下电器产业株式会社 | Optical information recording medium and its manufacturing method |
| JPH09306029A (en) * | 1996-05-09 | 1997-11-28 | Matsushita Electric Ind Co Ltd | Optical information medium and its production |
| JPH10324063A (en) * | 1997-05-27 | 1998-12-08 | Teijin Ltd | Phase change type optical recording medium and manufacture thereof |
| JPH10326438A (en) * | 1997-05-26 | 1998-12-08 | Tdk Corp | Production of optical recording medium, and optical recording medium |
| JP3761287B2 (en) * | 1997-05-29 | 2006-03-29 | Ｔｄｋ株式会社 | Optical recording medium and manufacturing method thereof |
| JPH11115315A (en) * | 1997-08-12 | 1999-04-27 | Matsushita Electric Ind Co Ltd | Optical information recording medium, manufacture thereof, and recording/reproducing method of information using the same |
-
1999
- 1999-07-30 WO PCT/JP1999/004110 patent/WO2000006391A1/en active Application Filing
- 1999-07-30 CN CNB998091456A patent/CN1180942C/en not_active Expired - Fee Related
- 1999-07-30 AU AU49313/99A patent/AU4931399A/en not_active Abandoned
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|---|---|
| TW518588B (en) | 2003-01-21 |
| WO2000006391A1 (en) | 2000-02-10 |
| CN1180942C (en) | 2004-12-22 |
| AU4931399A (en) | 2000-02-21 |
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