CN100540325C

CN100540325C - Optical record medium

Info

Publication number: CN100540325C
Application number: CNB2005800306641A
Authority: CN
Inventors: 让原肇; 花冈克成; 柴田清人; 金子裕治郎; 岩佐博之
Original assignee: Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2004-07-16
Filing date: 2005-07-14
Publication date: 2009-09-16
Anticipated expiration: 2025-07-14
Also published as: CN101018672A

Abstract

A kind of optical record medium, it comprise utilize with amorphous phase that causes by bombardment with laser beams and crystalline phase between the relevant optical constant of reversible transition layer.This phase change recording layers comprises Ge, Sb, Sn, Mn and X.The X representative is selected from least a element among In, Bi, Te, Ag, Al, Zn, Co, Ni and the Cu.When the relation of its each content is represented by Ge α Sb β Sn γ Mn δ X ε and the element of α, β, γ, δ and the ε mathematic(al) representation below satisfying respectively: during alpha+beta+γ+δ+ε=100,5≤α≤25,45≤β≤75,10≤γ≤30, ≤ δ≤20 and 0≤ε≤15 0.5 (atom %), and the total content of Ge, Sb, Sn, Mn and X is at least 95 atom % of this phase-change recording stratum total.

Description

Optical record medium

Technical field

The present invention relates to phase-change optical recording medium.

Background technology

Optical record medium has been put in the practical application, and it comprises the so-called phase-change optical recording medium of the reversible transition principle of utilizing between crystalline phase and the amorphous phase.The recording materials of phase-change optical recording medium comprise AgInSbTe and AgInSbTeGe material, and wherein Ag, In, Ge etc. join in the matrix (matrix) that Sb, Te make.These materials can be used for CD-RW, DVD-RW, DVD+RW medium.Every kind of this phase-change optical recording medium has stepped construction; wherein first protective layer, recording layer, second protective layer and refracting layer are as basic layer; on the stepped construction plastic base that is formed with spiral or concentric grooves disposed thereon, and carry out the two-value recording of information and duplicate.For satisfying the record of higher number and high power capacity, change into laser diode to the laser beam of 660nm by the wavelength 650nm that will be used for DVD with royal purple zone 405nm wavelength, perhaps, can obtain 20GB or bigger recording capacity at the one-sided of dish by using the lens of large-numerical aperture (NA) 0.85.

On the other hand, for the information that allows to use the DVD record and duplicate, can consider setting recording and duplicate 0.65 the method for numerical aperture for using traditionally.But, because the lens numerical aperture is the recording capacity of 0.65 DVD is the recording capacity of 0.85 DVD less than the lens numerical aperture, the present patent application people has provided a kind of method of recording multi-value information, and its difference by near the amount of the crystalline portion the record mark of non-crystalline state realizes (non-patent literature 1, patent documentation 1 and patent documentation 2) 20GB or bigger recording capacity.

Below, the technology that non-patent literature 1 is disclosed provides description.

Fig. 1 shows the schematic diagram that concerns between record labelled amount and radio frequency (Rf) signal.The record token-based originally is positioned at the center of each unit.Relation similarly is presented at mutually in the hole (phase pit), wherein writes down mark and is recorded on the substrate with the phase state of rewritable phase change material or concavo-convex or irregular status.Be recorded in the situation in hole mutually on the substrate at the record mark with concavo-convex or irregular form, the optical depth of the inside groove that this is cheated mutually need be set to λ/4, so that the signal gain of RF signal maximization.Sign of lambda is represented the recording/copying Wavelength of Laser.Value when the RF signal value focuses on the center of unit with the laser beam that is used to write down and duplicate is by assignment, and changes according to the amount size of the record mark in the unit.The RF signal is generally not maximum when writing down mark in the unit and exist, and when record labelled amount maximum RF signal minimum.

When carrying out many-valued record, for example, be 6 according to above-mentioned zone modulator approach record indicia patterns number or many-valued number of levels, the signal of RF as a result of each record mark shows as distribution shown in Figure 2.These RF signal values are respectively by normalized numeric representation, and this normalization numerical value is that dynamic range or DR are defined as 1 and obtain by the width with maximum RF signal value and minimum RF signal value.Write down and duplicate for about 0.6um by the girth of setting each unit, this length back will be referred to as element length, it is represented with 12 in Fig. 1, use λ=650nm, lens numerical aperture (NA)=0.65, and the optical system of focused beam diameter pact=0.8um is represented with 11 in Fig. 1.Among Fig. 1,14 represent groove, and 15 represent the track record width, and 17 represent the amorphous state record mark of the crystallization of antiradar reflectivity, and 19 represent the non-recording section of high reflectance.This many-valued record mark can be by modulation ratio such as recording power Pw, erase power Pe, lowest power Pb laser power and form as time started of the parameter of recording method shown in Figure 3.In Fig. 3,11 represent the copying beam diameter, 12 representative unit length, and 13 representative units, the many-valued record mark of 17 representatives, 19 represent crystalline portion, and 20 represent pulse start time.

In above-mentioned many-valued recording method, along with the increase of record linear density, the lasing beam diameter that element length focuses on relatively reduces gradually, and when object element was replicated, the laser beam of focusing was run out of outside this unit to adjacent cells.Therefore, even adjacent cells has the labelled amount identical with object element, the RF signal value that duplicates of object element is affected according to the combination of the labelled amount of adjacent cells.Therefore, there is the interactive signal influence between target record mark and the adjacent cells mark.As shown in Figure 2, because this influence, the RF signal value in each pattern distributes and has deviation.Therefore, be applied to which record indicia patterns in order to determine object element, what need to keep respectively to write down mark duplicates interval between the RF signal value greater than the interval of deviation.As shown in Figure 2, the interval of each RF signal value of the record of each pattern numbers equals this deviation substantially, and this STA representation the limit determined of executive logging indicia patterns reluctantly.

The technology that proposes to break through this limit is for using the many-valued detection technique (multivalue-detection technique) of continuous 3 data cells (consecutive three-datacells), and it discloses in non-patent literature 1.This technology comprises that the research multi-valued signal distributes, and for example comprises, when using 8 values, 8 ³During=512 pattern recordings, the pattern of the combination of continuous 3 data cells generating pattern table, and calculates the pattern of continuous 3 data cells according to the result of the reproducing signals of unknown data, and then determines to remain the many-valued unknown signaling that duplicates with reference to pattern table.This technology makes in determining multi-valued signal, in addition under traditional cell density or signal message take place when duplicating can reduce error rate under the SDR value condition that interactive signal disturbs.(multivalue tones) is defined as " n " when many-valued tone, the dynamic range that defines many-valued RF signal is during for " DR ", the SDR value is by ratio ∑ σ i/ (n * DR) expression, be the mean value of the standard deviation of each multi-valued signal " σ i ", and represented the signal quality of shaking in corresponding two value records.Usually, when setting many-valued number of tones " n " when being set to particular value, " σ i " is more little for the standard deviation of multi-valued signal, and dynamic range " DR " is big more, and the SDR value is more little.As a result, error rate is owing to the raising of the detection performance of multi-valued signal reduces.On the contrary, along with the increase of many-valued number of tones, SDR value and error rate will increase respectively.

When using many-valued detection technique, for example shown in Figure 4ly go out, many-valued detection can be with 8 value realizations, and wherein many-valued number of tones is increased to 8, and the distribution of each RF signal value overlaps mutually.

Above-mentioned phase-change optical recording material can also use in many-valued recording method.Yet, can rewrite or the once recordable medium in, as DVD-R/RW, DVD+R/R, by using in the phase change medium and multi-value phase change medium that blue laser diode (blue laser diode) or blue line standard (Blu-ray standard) write down and duplicate, require high-speed record and duplicate.For reaching this requirement, be necessary to challenge the raising of realization crystalline rate and the balance between the record mark longer-term storage stability.For with therein as the Sb of matrix ₇₀Te ₃₀There is restriction in the AgInSbTe material that forms eutectic composition, and this material is using till now always.In fact, at 8X or more in the record under the high linear speed, because the longer-term storage stability problem of record mark, it can not use DVD.Therefore seek by using other to contain the Sb material, rather than use the material that contains Sb and Te to realize the raising of crystalline rate and the balance between the record mark longer-term storage reliability as matrix.Its preferable material is GaSb and GeSb.For example, patent documentation 3 has disclosed the material that adds In in GeSb, also discloses Sn, Bi, Zn, Ga etc. and is added into GeSb as adding element to be preferably 10 atom % or amount still less.Its preferable material is GaSb and GeSb.In addition, what the example of preferred material comprised that GeSbSnIn that patent documentation 4 discloses, GeMnSb, patent documentation 6 that patent documentation 5 discloses disclose adds Te, In and Ga to GeSbSn, but above-mentioned material but can't solve the challenge that proposes among the present invention.

Patent documentation 1, TOHKEMY communique (JP-A) 2003-218700 number

Patent documentation 2, TOHKEMY communique (JP-A) 2004-152416 number

Patent documentation 3, TOHKEMY communique (JP-A) 2001-39301 number

Patent documentation 4, TOHKEMY communique (JP-A) 2002-11958 number

Patent documentation 5, TOHKEMY communique (JP-A) 2004-341240 number

Patent documentation 6, TOHKEMY communique (JP-A) 2004-203011 number

Non-patent literature 7, use the Data Detection of pattern identification, 2001 optical storage international symposiums, technical brief 2001, Pg-27 (Data Detection using Pattern Recognition, InternationalSymposium on Optical Memory 2001, Technical Digest 2001, Pg-27).

Summary of the invention

Along with at a high speed and the increase that requires of huge storage capacity recording, need a kind of phase-change material, this phase-change material can high-speed record, effective arbitrarily definite length of control record mark, and longer-term storage stability is splendid.Especially, along with the increase of record amount, higher to the high-speed record and the requirement of duplicating.Record keep the mark lengths about 0.1um under non-crystalline state, and control mark is the basis of two value records and many-valued record effectively near 0.1um.Particularly, in many-valued record, the difference of the shortest mark and longest mark is little, and must fine control the mark lengths of the two.

In addition, in many-valued record, because marked region can change in the groove of recorded information, and the reflected signal voltage that duplicates from the marked region that changes with rule at interval separately to read information thus, so increased the quantity of reproducing signals mistake, thereby the loss of the record mark under the condition that not only relates to high temperature and high humility and the variation of mark lengths, and relate to when containing the crystalline state of record between mark and changing the reflectance varies that causes, do not allow reading of information.In addition, for two value records and many-valued record, require to use also that the optical constant of amorphous state and crystalline state has the very material of big difference in the royal purple zone of 650nm wavelength region may and 405nm wavelength.Particularly, in many-valued record, the reflectivity of the zero level of no information record is big more, reflected signal voltage difference between signal level is also big more, and for example the maximum horizontal of the 8th value signal and the difference between the zero level are big more, so-called modulation factor is good more, because information reads with the signal level that reflects.

Therefore target of the present invention provides a kind of phase-change optical recording medium, the suitable structure that it comprises the phase-change optical recording material and satisfies this requirement.

A first aspect of the present invention is an optical record medium; it comprises substrate; first protective layer; phase change recording layers; second protective layer and reflecting layer; wherein this phase change recording layers is the layer that utilizes the optical constant relevant with the reversible transition between amorphous phase and crystalline phase that is caused by bombardment with laser beams; and this phase change recording layers comprises Ge; Sb; Sn; Mn and X; wherein the X representative is selected from In; Bi; Te; Ag; Al; Zn; Co; at least a element among Ni and the Cu; wherein work as Ge; Sb; Sn; when the relation of Mn and X is represented by Ge α Sb β Sb γ Mn δ X ε; α; β; γ; mathematic(al) representation below δ and ε satisfy respectively: 5≤α≤25; 45≤β≤75; 10≤γ≤30; 0.5≤δ≤20 and 0≤ε≤15; wherein when alpha+beta+γ+δ+ε=100; α; β; γ; δ and ε represent atom % respectively, and Ge wherein; Sb; Sn; the sum total of the content of Mn and X is at least 95 atom % of phase-change recording stratum total.

A second aspect of the present invention is the optical record medium according to first aspect, the mathematic(al) representation below wherein the ratio of element α satisfies: 10≤α≤25.

A third aspect of the present invention is the optical record medium according to any one aspect in first aspect or the second aspect, the mathematic(al) representation below wherein the ratio of element β satisfies: 50≤β≤70.

A fourth aspect of the present invention is the optical record medium according to any one aspect of first aspect in the third aspect, the mathematic(al) representation below wherein the ratio of element δ satisfies: 1.0≤δ.

A fifth aspect of the present invention is that wherein phase change recording layers also comprises the Ga of 7 atom % or less amount according to the optical record medium of any one aspect of first aspect in the fourth aspect.

A sixth aspect of the present invention is that wherein phase change recording layers also comprises the arbitrary element that is selected among Tb, Dy, Nd, Gd, Ti, Zr, Cr, Fe and the Si according to the optical record medium of any one aspect in first aspect to the five aspects.

A seventh aspect of the present invention is the optical record medium according to any one aspect in first aspect to the six aspects; wherein first protective layer, phase change recording layers, second protective layer and reflecting layer are successively set on the substrate with stepped construction, and perhaps reflecting layer, second protective layer, phase change recording layers, first protective layer are successively set on the substrate with stepped construction.

A eighth aspect of the present invention is the optical record medium according to the 7th aspect; wherein optical record medium also comprises adhesive phase and covered substrate, and reflecting layer, second protective layer, phase change recording layers, first protective layer, adhesive phase and covered substrate layer are arranged on the substrate with stepped construction.

A ninth aspect of the present invention is the optical record medium according to any one aspect in the 7th aspect or the eight aspect, and wherein the reflecting layer comprises one of any in Ag and the Ag alloy.

A tenth aspect of the present invention is the optical record medium according to the 7th aspect, and wherein second protective layer comprises ZnS and SiO ₂Mixture.

A eleventh aspect of the present invention is the optical record medium according to the 7th aspect, and wherein reflecting layer, second protective layer, phase change recording layers and first protective layer are successively set on the substrate with stepped construction, and second protective layer comprises and is selected from ZrO ₂, Y ₂O ₃And TiO ₂Mixture, SiO ₂, Nb ₂O ₅Mixture and SiO ₂, Ta ₂O ₅Any one mixture in the mixture.

A twelveth aspect of the present invention is the optical record medium according to the tenth aspect, and wherein optical recording layer also is included in the anti-sulfuric horizon between the reflecting layer and second protective layer.

A thirteenth aspect of the present invention is the optical record medium according to the 7th aspect, and wherein first protective layer comprises ZnS and SiO ₂Mixture.

A fourteenth aspect of the present invention is the optical record medium according to any one aspect in 13 aspects, the 7th aspect to the; wherein this optical record medium also is included in the boundary layer between first protective layer and the phase change recording layers; wherein the thickness of this boundary layer be 1nm to 10nm, and comprise ZrO ₂, Y ₂O ₃And TiO ₂Mixture, SiO ₂And Nb ₂O ₅Mixture and SiO ₂And Ta ₂O ₅One of any in the mixture.

A fifteenth aspect of the present invention is that wherein this optical record medium also is included in the boundary layer between the phase change recording layers and second protective layer according to the optical record medium of any one aspect in 14 aspects, the 7th aspect to the.

A sixteenth aspect of the present invention is the optical record medium according to any one aspect in first aspect to the 15 aspects, and wherein this first protective layer comprises ZnS and SiO ₂, and ZnS: SiO ₂Composition than for 60mol% to 85mol%: 40mol% to 15mol%, and second protective layer comprises ZnS and SiO ₂, and ZnS: SiO ₂Composition than for 30mol% to 85mol%: 70mol% to 15mol%.

Description of drawings

Fig. 1 shows the schematic diagram that concerns between record labelled amount and radio frequency (RF) signal.

Fig. 2 has shown the area modulation method disclosed according to non-patent literature 1, when the quantity of service recorder indicia patterns is many-valued number of levels=6 when carrying out many-valued record, and the figure that distributes from the radiofrequency signal value of each record indicia patterns.

Fig. 3 has shown the figure that carries out the recording method of many-valued record among Fig. 2.

Fig. 4 has shown by increasing many-valued number of tones to 8, the figure of the example that the distribution of each radiofrequency signal value overlaps each other.

Fig. 5 has shown the figure according to the stepped construction example of optical record medium of the present invention.

Fig. 6 has shown the figure according to another example of stepped construction of optical record medium of the present invention.

Fig. 7 has shown according to the stepped construction of the optical record medium of the present invention figure of an example again.

Fig. 8 has shown the figure of bombardment with laser beams impulse waveform.

Fig. 9 has shown the SDR recording power dependence of the optical record medium of example 2 and the figure of dynamic range (DR) according to the present invention.

Figure 10 has shown according to the present invention the figure of the repeat replication performance of the optical record medium of example 2.

Figure 11 has shown that in according to the optical record medium of example 36 data are capped the figure that writes the SDR after (overwrite).

Figure 12 has shown the dependent figure of SDR recording power according to the optical record medium of example 37.

Figure 13 has shown the figure that concerns between the jitter value according to the record number of times of the optical record medium of example 41 and comparative example 11 and gained.

Figure 14 has shown the figure that concerns between the jitter value according to the record number of times of the optical record medium of example 42 and comparative example 12 and gained.

The specific embodiment

Below the present invention is provided detailed description.

Optical record medium according to the present invention allows two value records and many-valued record, and in many-valued record, the many-valued recording method that can use non-patent literature 1 to disclose.

As shown in Figure 5; example according to optical record medium structure of the present invention comprises a kind of structure; wherein first protective layer 3, phase change recording layers 5, second protective layer 7 and reflecting layer 9 are successively set on the transparency carrier 1, phase change recording layers 5 utilize with amorphous phase that causes by bombardment with laser beams and crystalline phase between the relevant optical constant of reversible transition.

This transparency carrier is preferably transparent to the laser beam in the 800nm scope at 400nm for wavelength at least, and has little birefringence and narrow distribution.In the substrate forming process, this substrate its each radial location relatively can have the birefringence distribution.The birefringence of material is preferably narrower, and formed substrate also preferably has narrow birefringence and distributes.In view of there is not birefringence in it, preferably use glass substrate, but because Merlon is more cheap than glass, so use polycarbonate substrate usually.

Usually, substrate have groove depth 20nm to 35nm, groove width 0.2um to 0.3um, slot pitch 0.40um is to the guiding groove of 0.50um.

The first protective layer example comprises oxide, nitride, carbide and their mixture.Near the material that has high-transmission rate the 400nm wavelength is suitable.Carbide such as SiC with high light absorptive are unaccommodated, but can combine with the protective layer of being made by oxide and nitride etc., with the thin layer of several nanometers of being formed for providing extinction.Wherein, preferred zinc sulphide (ZnS) and silica (SiO ₂) mixture (ZnSSiO ₂), its composition is than being ZnS: SiO ₂Be preferably 30mol% to 90mol%: 70mol% to 10mol%, and more preferably 60mol% to 85mol%: 40mol% is to 15mol%.When first protective layer adopts above-mentioned material, repeating to write with below the hot conditions, the crystallization of layer self can be limited, and in the distortion that repeats to write the high recording sensitivity of fashionable maintenance and reduce layer.

In first protective layer that forms, every kind of oxygen ratio of forming oxide components is not limited to the stoichiometric proportion composition, and the oxygen ratio allows oxygen lack.For example, SiO _xThe oxygen ratio be 0＜x≤2.Described second protective layer, boundary layer etc. also are like this later on.

First protective layer 3 can be configured to two-layer or more multi-layered.When duplicate record,, may be diffused into recording layer between

recording layer

5 and 3 elements that constitute protective layer of first protective layer along with the increase of record number of times.Therefore, as shown in Figure 6, boundary layer 4 can be formed between first protective layer 3 and the recording layer 5.And the boundary layer (not shown) can be provided between the recording layer 5 and second protective layer 7.

Another kind of structure is to use on substrate by except ZnSSiO ₂Outside the layer made of oxide, nitride or its mixture, and ZnSSiO ₂Layer and recording layer are successively set on the substrate with stepped construction.The purpose of this structure is the laser beam heat radiation during for duplicate record, promptly before heat arrives substrate, heat is dissipated to the outer peripheral portion of groove.When boundary layer was set, the purpose except improving duplicate record character can provide crystallization to quicken the function of auxiliary layer to this boundary layer according to recording layer material, wipes performance with raising.In the case, boundary layer is in crystalline state or polycrystalline form, and is used for the karyomorphism one-tenth/growth of auxiliary recording layer.The example of boundary layer comprises oxide, carbide and nitride.In order to prevent that boundary layer is compromised its longer-term storage stabilizability or archives storage stability under high temperature or high humidity, this boundary layer preferably has the thickness of several nanometers.

In the present invention, boundary layer is mainly due to the reduction that prevents from respectively to write down character, and at ZnSSiO ₂Thickness be in 30nm in the scope of 100nm the time, use when particularly using royal purple laser.By between first protective layer 3 and recording layer 5 boundary layer being set, first protective layer that the temperature rising is caused in the middle of can preventing to write down worsens and reduces the reflectivity reduction that refractive index causes, and prevents the decline of record performance.

Preferred boundary layer material is transparent, and is the light of 405nm for wavelength, has to be about 2.3 refractive index, and it equals ZnSSiO ₂Refractive index.The raw material example comprises SiO ₂, Al ₂O ₃, ZrO ₂, MgO, ZnO, Nb ₂O ₅, Ta ₂O ₅, Y ₂O ₃, TiO ₂, AlN and SiN.Preferred high-melting-point, refractive index are about 2.3 ZrO ₂And TiO ₂Mixture, Y ₂O ₃Also add the mixture in the said mixture, SiO ₂And Nb ₂O ₅Mixture, and SiO ₂And Ta ₂O ₅Mixture.Forming by sputter when using this material as target material in the boundary layer, by with the Y of 3 atom % to 8 atom % ₂O ₃With ZrO ₂Mix, even when using large area target, can prevent that also target material is destroyed.At ZrO ₂, Y ₂O ₃And TiO ₂Mixture in, when it is defined as [(ZrO ₂) _1-x(Y ₂O ₃) _x] _1-y(TiO ₂) _yThe time, the ratio of every kind of oxide (mol%) is preferably 2≤x≤8 and 10≤y≤70.With regard to the light transmission and the dissipation of heat, also preferred In ₂O ₃Mixture and In with ZnO ₂O ₃Mixture with MgO.

Interfacial layer thickness is preferably 1nm to 10nm.Be difficult to forming thickness is 1nm or thinner layer, and when thickness during greater than 10nm, thermal conductivity will raise, and heat diffusion is to periphery, and this causes the reduction of recording sensitivity and the decline of record performance.And when thickness is that 10nm or bigger boundary layer are in hot conditions following time, the mark of record may diminish owing to the formation/growth of the nuclei of crystallization, and may disappear according to material.

For second protective layer, preferably use and first protective layer identical materials: the ZnSSiO ₂Yet, be enhanced because thermal conductivity is lower than the recording sensitivity of second protective layer of first protective layer, so ZnS: SiO ₂The composition ratio be preferably 30mol% to 85mol%: 70mol% is to 15mol%.For example, first protective layer preferably has ZnS: SiO ₂=70: 30 composition ratio, and second protective layer preferably has ZnS: SiO ₂=80: 20 composition ratio.

Here, first protective layer is arranged on the protective layer of laser emission side, and near the protective layer that is arranged on the reflecting layer is called second protective layer.

For the reflecting layer, Al, Ag, Cu, Pd, Nd, Ni, Ti, Au, Bi, In and its alloy have been used.For carrying out the high linear speed record, be fit to adopt high thermal conductivity material.Wherein, preferred Ag and contain Ag and measure 95 atom % or higher alloy.When adopting the Ag alloy, silver alloy preferably is mixed with and the material of thermal conductivity near Ag.The preferred at least a element that is selected among Nd, Cu, Bi and the In that uses joins among the Ag with 2 atom % or amount still less, more preferably joins among the Ag with 1 atom % or amount still less.When using the weak point laser beam wavelength, because the concavo-convex of surface, reflecting layer causes the minimizing of reflected signal and cause signal noise, so preferably use the Ag alloy.

Work as ZnSSiO ₂Be used for second protective layer; and when on this second protective layer, being provided with the reflecting layer of making by Ag or Ag alloy; because under hot conditions, may form Ag and S compound and write down the character reduction, so need between this second protective layer and this reflecting layer, form the anti-sulfuric horizon of making by oxide, nitride, carbide.For this anti-sulfuric horizon, SiOC, SiC, ZnO, MgO, TiO ₂, TiO ₂Mixture, ZnO with TiC ₂Mixture, Ta with ZrC ₂O ₅Mixture and Nb with TaC ₂O ₅And SiO ₂Mixture be suitable material.Perhaps, can use the material of above-mentioned boundary layer.The thickness of first protective layer is preferably 40nm to 250nm, and the thickness of second protective layer is preferably 5nm to 20nm, and the thickness of anti-sulfuric horizon is preferably 1nm to 5nm, and the thickness in reflecting layer is preferably 100nm to 180nm.

Phase change recording layers according to optical record medium of the present invention comprises Ge, Sb, Sn, Mn and X, wherein the X representative is selected from In, Bi, Te, Ag, Al, Zn, Co, at least a element among Ni and the Cu, and work as Ge, Sb, Sn, when the relation of Mn and each composition of X is represented by Ge α Sb β Sb γ Mn δ X ε, wherein when alpha+beta+γ+δ+ε=100, α, β, γ, δ and ε represent atom % respectively, α, β, γ, mathematic(al) representation below the element of δ and ε satisfies respectively: 5≤α≤25,45≤β≤75,10≤γ≤30,0.5≤δ≤20,0≤ε≤15.The total content of Ge, Sb, Sn, Mn and X is at least 95 atom % of phase change recording layers total content.

Traditionally, the material of recording layer comprises Sb and Te.In this examples of materials based near Sb: Te=70: the eutectic composition of 30 (atom %) has added Ge, Ag, In, Ga, Sn, Zn and rare earth element, this material comprises Ag-In-Sb-Te, Ge-In-Sb-Te, Ge-Sb-Te, Ge-Ag-In-Sb-Te, Ge-Sn-Sb-Te, Ge-Zn-Sb-Te, Ga-Ge-Sb-Te, and Ga-Se-Te.These materials have the composition of 60≤Sb≤80 (atom %) and 10≤Te≤30 (atom %) respectively, and the additional elements amount is that 5 atom % are to 15 atom %.

When hanging down the linear velocity record, use these materials can obtain satisfied performance, still, when carrying out the high linear speed record, even initial record performance is splendid, the storage stability under the hot conditions still can reduce.This phenomenon can occur when DVD writes down with the linear velocity that is higher than 14m/s.It not only is suitable for DVD, and is suitable for using the recording medium of blue laser.

On the other hand, the method that many-valued record is to use the tone of reflection to carry out the information record and duplicate, its difference that requires between low-level reflected signal and the high-level reflected signal is that dynamic range is big.When using blue laser to carry out many-valued record,, need make the bigger material of dynamic range owing to the material of above-mentioned Sb of comprising and Te is less than dynamic range under the red wavelength spectrum in the dynamic range under the blue wavelength spectrum.Therefore, require to improve dynamic range and memory reliability.Basically, bigger in order to make dynamic range, the optical constant in recording materials between crystalline phase and the amorphous phase or the difference of refractive index are big more, and be just good more.As a kind of suitable recording materials, use GaSb, GeSb, InSb, SnSb, ZnSb etc., wherein be matrix with Sb.

Optical constant comprises refractive index " n " and absorption coefficient " k ".Refractive index " n " and absorption coefficient " k " are defined as " nc " and " kc " respectively in crystalline state, and in amorphous state, be defined as " na " and " ka ", for Ga: Sb=14: 86 situation, near the 650nm wavelength optical constant is respectively: nc=3.41, kc=4.67, na=4.36, ka=2.81.This optical constant is respectively near the 405nm wavelength: nc=1.38, kc=3.28, na=2.63, ka=3.12.Therefore, the value of Δ n=(na-nc) is 0.95 near the 650nm wavelength, and the value of Δ n=(na-nc) is 1.25 near the 405nm wavelength, and the difference between " ka " and " kc " is little: 0.16.

As Ga: Sb=50: in the time of 50, near the 650nm wavelength, nc=3.48, kc=4.53, na=4.31, ka=2.61, and near the 405nm wavelength, nc=1.37, kc=3.29, na=2.53, ka=2.98.Δ n is 0.83 near the 650nm wavelength, and Δ n is 1.16 near the 405nm wavelength.

Therefore, when line speed record rose to the most about 35m/s, GaSb and GeSb were suitable material.The preferred compositing range of Sb, Ga and Ge is 50≤Sb≤95 (atom %), Ga≤5 (atom %) or Ge≤50 (atom %).

When the content of Sb is higher than 80 atom %, experience phase transformation and becoming in the process of crystalline state after recording layer carries out initialization step, whole medium is difficult to crystallization equably, promptly form medium after, be uneven mutually, and particularly can not in many-valued record, use this layer.Memory reliability under the hot conditions is impaired, and the end of the mark of write once recording is by crystallization and degeneration.

The GaSb material has Ga: Sb=12: 88 eutectic composition.Recording layer with this composition is folded between first protective layer and second protective layer, and is arranged on second protective layer to form recording medium by the reflecting layer that the Ag alloy is made.When the laser beam of 660nm wavelength recording layer be changed to crystalline phase mutually after when shining panel surface with the power of 15mW, this recording layer begins partly to form amorphous state by the linear velocity near 15m/s.

When further adding the amount of Ga to recording layer, it begins to form amorphous linear velocity and significantly reduces, and this makes initialization be stranded energy more.As a result, only use two kinds of elements of Ga and Sb, can not obtain being enough to the record performance that under low line speed record 10m/s, writes down.

And Ge and Sb have Ge: Sb=16: 84 composition.The line speed record that amorphous state begins to form is 20m/s.But, only use two kinds of elements of Ge and Sb, also can not obtain being enough to the record performance that writes down under the speed up to 10m/s.

Then, tested the material that adds element as the third, it can be allowed to adjust line speed record from low-level to high level, and have high optical constant under crystalline phase and amorphous phase by initialization easily.

Especially, test Sn adds Ge to: Sb=16: 84 (atom %) and Ga: Sb=12: the situation of 88 (atom %).

Definition (Ge ₁₆Sb ₈₄) _100-xSn _x(Ga ₁₂Sb ₈₈) _100-ySn _y, and change " x " and " y ".In the GeSnSb material, when " x " and " y " becomes 0,5,10,15,20 and 25 (atom %) respectively, when the use amount of Sn rises to 15 atom %, the line speed record that amorphous state begins to form only is about 2m/s, and be 20 atom % or when higher, it is faster that speed increases to 5m/s in the use amount of Sn.And in the GeSnSb material, by adding the only Sn of 5 atom % to GaSb, the line speed record that amorphous state begins to form becomes 10m/s or higher.

In addition, recording medium (80 ℃, 85%RH (relative humidity)) under hot conditions keeps the variation with the reflectivity of the non-recording section after the check crystallization in 200 hours.Change the result and show that reflectivity reduces with the increase of Sn amount, especially the reflectivity of GaSnSb material obviously reduces.When adding the Sn of 20 atom % to GaSnSb, about 5% reflectivity takes place reduce.For the GeSnSb material, reflectivity be reduced to 2% or still less.

In many-valued record, because by reflectivity size discrimination information, the variation of reflectivity causes the reduction of record performance, and reflectance varies is preferably little.But, when the GeSnSb material in statu quo uses, when with low linear velocity record,, otherwise can not obtain preferred record performance, although it is suitable for 10m/s or the record under the high linear speed more unless add 25 atom % or more Ge.On the other hand, when adding Sn, the optical constant difference between crystalline phase and the amorphous phase is big, and this is preferred, because it has increased the dynamic range of two-value and many-valued record.

So, based on above discovery, as assay to the method for the record that can under high linear speed, write down and have wide line speed record scope, the present inventor finds by adding Mn and adjust its composition ratio in recording layer material GeSnSb, can address this problem, and this optical record medium has the advantage that covers write performance with high linear speed and high reliability record the time.10m/s or higher linear velocity scope represented in term " high linear speed ".

Particularly, the inventor finds that preferable material is represented by 5≤α≤25,45≤β≤75,10≤γ≤30,0.5≤δ≤20 (atom %) when composition formula is defined as Ge α Sb β Sn γ Mn δ.Such material makes the difference of optical constant become big.Even when adding Mn, reflectivity is equal to or higher than the situation when not adding Mn.The amount of Ge is high more, and crystalline rate is slow more.Therefore, in the situation of low linear velocity record, by increasing Ge content can obtain high reliability under low speed optical record medium.

On the other hand, the content by reducing Ge and increase Sb and the content of Sn can obtain being suitable for optical record medium with the high linear speed record.Sn is higher than Sb to the influence that increases crystalline rate.Therefore, content by reducing Ge and the content that increases Sn can obtain being suitable for the optical record medium with the high linear speed record, but it causes the reduction of reliability and has restriction for the high linear speed record.In reliability, known shelving (Shelf) performance reduces with the minimizing of Ge content and the increase of Sn content.Shelving performance is used to estimate optical record medium and is retained in record performance under the hot conditions.With this understanding, optical record medium is not suitable for the high linear speed record.Therefore, by adding crystalline rate, can obtain having outstanding duplicate record performance and and guaranteeing the material of the optical recording layer of reliability in high writing speed than Sn the 4th kind of element M n faster.Its reflectivity under high temperature and the high humidity is reduced to 1% or littler.

When Ge content is higher than 25 atom % and repeats to cover that to write indegree be for 1000 times or more for a long time, record performance descends, although improved the data storage stability.In addition, the line speed record that can access suitable record performance is low, and this is unsuitable for the high linear speed record.When Ge was added into the amount less than 5 atom %, data storing reliability descended, although be suitable for the high linear speed record.The addition of Ge is preferably 10 atom % or higher.

When adding is less than the Sb of 45 atom %, be unsuitable for high-speed record, and when the Sb that adds more than 75 atom %, the data storage stability reduces.The addition of Sb is preferably 50 atom % to 70 atom %.

When adding is less than the Sn of 10 atom %, be unsuitable for the high linear speed record, the crystalline state reflectivity reduces, and the optical constant difference between crystalline phase and the amorphous phase diminishes, and it causes reproducing signals SN than reducing.When the Sn that adds more than 30 atom %, the fusing point and the crystallization temperature of recording materials are lowered, so that memory reliability descends.

When the Mn that adds more than 20 atom %, be unsuitable for the high linear speed record, and recording sensitivity will descend.The addition of Mn is preferably 5 atom % or lower.When using Mn in the high linear speed that carries out under the linear velocity that the is being higher than 20m/s record, load DeGrain in the addition of Mn during less than 5 atom %, and preferred L n addition is 0.5 atom % or higher.0.5 the Mn addition of atom % in the scope of 1 atom % is significantly to the effect of the linear velocity of about 30m/s, and for DVD, this influence under the 28m/s of corresponding 8X or higher speed also clearly.Even when the atomic weight of Mn changed, the variable quantity of the variable quantity relative atomic weight of crystalline rate was less, and has the composition allowance.Zn has the crystalline rate that causes very greatly with respect to 1 atom % variation to be changed, and has narrow allowance.Bi also is like this.

Optical record medium is mostly by the magnetron sputtering manufacturing, but when material comprised Mn, the used target of equipment had the high density ratio, and promptly 99% or higher theoretical value and the ratio of the density between the actual value that calculates by composition material.This means that the target that has the high density ratio when forming layer by sputter is outstanding on discharge stability, make it possible to quality and the uniformity making meticulous recording layer and improve tracer signal.When not comprising Mn in the material, this density ratio is lower than 95%.That is, the density ratio that comprises the material of GeSbSn is about 94%.When material comprised Te and do not comprise Mn, this density ratio was about 89%.

In addition, in order to improve memory reliability and DOW, the preferred at least a element that is selected among In, Bi, Te, Ag, Al, Zn, Co, Ni and the Cu that adds is as element X.Load ε (atom %) and be preferably 0≤ε≤15.

The preferred thickness of recording layer is that 10nm is to 20nm.

Phase change layer preferably comprises only the material of Ge, Sb, Sn, Mn and X, but can also comprise other elements.The total content of Ge, Sb, Sn, Mn and X should account at least 95% of whole phase change recording layers total content.

Except that Ge, Sb, Sn, Mn and X, preferably use Ga as adding element.Also preferably in constituting the material of forming, add 7 atom % or Ga still less.Adopt this composition, before the manufacture process of carrying out phase change recording medium and the commitment record and the evaluation of duplicating, can reduce crystallization temperature, and obtain the condition that is suitable in initialization step, writing down easily, in initialization step, the recording layer of amorphous phase is changed into crystalline phase.In addition, can add at least a element that is selected among Tb, Dy, Nd, Gd, Ti, Zr, Cr, Fe and the Si.

Another structure according to recording medium of the present invention comprises a kind of structure; wherein as shown in Figure 5 and Figure 6 each layer backward setting; be reflecting layer 9, second protective layer 7, recording layer 5 and first protective layer 3 with stepped construction according to being set in sequence on its substrate that is provided with guide recess of inverted configuration shown in Figure 5; perhaps comprise a kind of structure, wherein reflecting layer 9, second protective layer 7, recording layer 5, boundary layer 4 and first protective layer 3 are successively set on (Fig. 7) on the substrate with stepped construction.When the Ag alloy was used in the reflecting layer, anti-sulfuric horizon can be arranged between second protective layer 7 and this reflecting layer 9.

In this case, as the ZrO of above-mentioned boundary layer material ₂And TiO ₂Mixture, except ZrO ₂And TiO ₂Also comprise Y outside the mixture ₂O ₃Mixture, SiO ₂And Nb ₂O ₅Mixture and SiO ₂And Ta ₂O ₅Mixture can be used for second protective layer.In addition, can use In ₂O ₃And SnO ₂Mixture, In ₂O ₃With ZnO mixture and ZnO and Al ₂O ₃Mixture.Preferably has the ZnSSiO of ratio ₂The mixture of high thermal conductivity.Using numerical aperture of objective is especially effective in the optical record medium of 0.85 optical pickup.These mixtures and ZnSSiO ₂Compare and have high thermal conductivity respectively, work, and improve the formation of record mark and cover write performance improving recrystallization speed.

The preferred thickness of second protective layer be 3nm to 15nm, and more preferably 4nm to 10nm.

According to the present invention, can provide a kind of optical record medium, when using the laser of 405nm wavelength even it still can provide and have than wide dynamic range and improve many-valued record performance and memory reliability.

Have the phase change recording medium of special component by use, can also provide can be with splendid control mode record random length mark, with high linear speed record and optical record medium with splendid longer-term storage stability.Particularly, by adding Ga, can under the prerequisite of not damaging the high-speed record performance, improve recording sensitivity.In addition, by in second protective layer material, using oxide and boundary layer being provided, can improve the record performance under the high-speed record.

In addition, by adopting boundary layer that the optical record medium of the duplicate record performance with improvement can be provided.

By the layer structure that adopts every layer to be provided with, can provide the optical record medium of record performance with raising with traditional optical record medium (layer structural order) reverse order.

In addition, can provide optical record medium, wherein can obtain splendid record performance, and have high memory reliability with two value records with large storage capacity.

Example

Hereinafter, describe the present invention in detail with reference to instantiation; Yet, the invention is not restricted to described example.

(example 1 to 3)

Also be provided with groove depth thereon at thickness with 21nm with 0.6mm, 0.30 the groove width of μ m, 0.45 on the birefringence polycarbonate substrate of the guiding groove of the slot pitch of μ m (ST3000 is made by TEIJIN-Bayer Polytec Ltd.), set gradually by ZnSSiO by sputter ₂(70: 30mol%) make and have the thickness of 41nm first protective layer, by each material of forming of the example in the table 11 to 3 row make and have the recording layer of the thickness of 14nm, by ZnSSiO ₂(80: 20mol%) make and have second protective layer of the thickness of 6nm, by Nb ₂O ₅: SiO ₂=80: 20 (mol%) make and have 4nm thickness anti-sulfuric horizon and by Ag _99.5Bi _0.5(atom %) makes and has the reflecting layer of the thickness of 140nm.

Next; on the reflecting layer; adopt the UV curable resin (SD318 of the thickness of 7 μ m; by DAINIPPON INK AND CHEMICALS, INC makes), to form environmental protective cover by the rotation coating; on environmental protective cover, use the UV curable resin (DVD003 of thickness with 10 μ m; by Nippon Kayaku Co., Ltd. makes) the further stacked not reeded covered substrate of thickness with 0.6mm, to form recording medium according to example 1 to 3.

The recording layer of each these optical record medium carries out crystallization by the initialization apparatus that use has major diameter LD, and the LD wavelength is 800nm, and beam diameter is that radial direction * orbital direction is 200 μ m * 1 μ m.Adopt constant linear velocity (CLV-Constant Linear Velocity) method to carry out crystallization, promptly move the feed point of initialization apparatus with the feed rate of revolution 36 μ m by rotating each these recording medium with the linear velocity of 3.0m/s.

In addition,, prepare a sample, wherein on the upper and lower side of recording layer, form the protective layer of making by ZnSSiO2 in order to determine the optical constant of each these recording medium, and by using initialization apparatus to carry out initialization in an identical manner.The optical constant of employed recording layer before and after initialization step is na=1.09 in the example 1, ka=3.32, nc=2.36, kc=3.19.The value of Δ n is 1.27.

The record of these optical record mediums and duplicate and use LD equipment to carry out, promptly being equipped with the wavelength with 405nm and the numerical aperture (NA) of object lens thereon is 0.65 laser diode and the pick-up head with beam diameter of 0.54 μ m.The recording power (Pw) that is radiated the laser beam on the panel surface of recording medium is set to maximum 10mW, and erase power (Pe1, Pe2) is set to 40% to 60% of recording power.Lowest power (Pb) is set to 0.1mW, and it is lower than the signal replication power of 0.6mW.

Elementary cell length is confirmed as 0.24 μ m, and carries out the many-valued record of eight values in this unit.Line speed record is set to 6m/s.In order to form the record mark, carry out record with following mode, as shown in Figure 8, when the short mark of record promptly was called " level 1 " mark of M1 and similarly is called " level 7 " mark of M7, the bombardment with laser beams of recording power started from the leading delay Tms from elementary cell.The area of mark is controlled by regulating recording power radiated time (Tmp) and lowest power radiated time (Tcl) subsequently.Adopt identical recording power radiated time (Tmp) in each level, but each level is changed lowest power radiated time (Tcl).

Table 2 shows each setting-up time of M1 to M7.Recording power (Pw) is set to 0.62 with the Pe/Pw ratio of erase power (Pe).The clock frequency that writes down is set to 25MHz.Recorded at random is from M1 to the M7 mark with eight values that form of unmarked M0.Fluctuating for the variation of determining reflected signal on each level is SDR, has loaded data for 39 sectors, and one of them sector comprises 1,221 unit.

The filtering reproducing signals eliminating the extensive variation of the reflected signal a few kHz levels or littler that exists around track, and utilizes and carries out AGC from the alphabetic data of the precedence record of M0 to M7 and handle.Carry out AGC and handle, thereby based on the difference of eliminating the amplitude variations of trailer record random signal from the amplitude of M0 to M7 level, it is treated to the signal that each all has the certain level amplitude.

Subsequently, signal is similar to the especially little signal of amplitude of the mark on M1 and the M2 level by bellow expansion joint with amplification.Signal is retrieved, and determines the standard deviation of reflection potential energy on each level, determines their SDR value thus.

Fig. 9 shows and is writing down the signal on three tracks adjacent one another are and be replicated under the situation of the signal that is write down on the intermediate orbit of three tracks the recording power dependence of the SDR value of gained and dynamic range (DR) by the recording layer of utilization according to the optical record medium of example 2.

Stayed 80 ℃ of high temperature and 85%RH (relative humidity) 200 hours according to the optical record medium of example 1 to 3, with the reflectivity that detects non-recording section and the reflectivity of recording section.The result before and after the test all show 1% or still less reflectivity on reduction.Table 1 shows in the situation that is fit to write down under the recording power (filing) and tests (shelving) laggard line item in storage, the variation of SDR and dynamic range (DR), and two kinds of situations have shown that all the decline of record performance is suppressed to minimum.

Table 1

Table 2

	Tms	Tmp	Tcl
	Tms	Tmp	Tcl	M1	14.75	5.00	3.85
M2	14.00	5.00	6.60	M1	14.75	5.00	3.85
M2	14.00	5.00	6.60	M3	12.75	5.00	7.50
M4	10.25	5.00	9.75	M3	12.75	5.00	7.50
M4	10.25	5.00	9.75	M5	8.50	5.00	12.60
M6	8.75	5.00	16.60	M5	8.50	5.00	12.60
M6	8.75	5.00	16.60	M7	3.75	5.00	22.25

Figure 10 has showed the duplicate record performance detection result of each optical record medium in the example 2, even wherein show 0.05% or the decline of record performance still less behind tracer signal repeat replication 100,000 times.

Example 4 to 19 and comparative example 1 to 8

At thickness and be provided with the birefringence polycarbonate substrate (ST3000 of guiding groove of slot pitch of groove width, the 0.32 μ m of groove depth with 22nm, 0.20 μ m thereon with 1.1mm, make by TEIJIN-Bayer Polytec Ltd.) on, set gradually by Ag by sputter _99.5Bi _0.5(atom %) make and have the thickness of 140nm the reflecting layer, by SiC make and have the anti-sulfuric horizon of the thickness of 2nm, by ZnSSiO ₂(80: 20mol%) make and have the thickness of 10nm second protective layer, by the material of the various compositions shown in the row of example in the table 34 to 19 and comparative example 1 to 8 make and have the recording layer of the thickness of 14nm, by ZnSSiO ₂(70: 30mol%) make and have first protective layer of the thickness of 40nm.On first protective layer, use the UV curable of thickness with 25 μ m resin laminated have a pressure sensitivity adhesive sheet of the thickness of 75 μ m, have the light-transmitting layer of the thickness of 0.1mm with preparation, produce optical record medium thus.Then, this optical record medium experiences initialization in the mode identical with example 1.

By using these optical record mediums, the composition of component and the relation between the record performance have been detected.

Under the condition of the reproducing power of the shortest mark lengths of 0.149 μ m, modulating mode (1-7) RLL, 0.30mW, adopt the pick-up head of wavelength 405nm and numerical aperture 0.85, each such optical record medium is write down and duplicates.The line speed record that each such optical record medium adopts is as shown in table 3.Record is to carry out under 5.5mW/3.2mW, 12mW/3mW and the 15mW/2.5mW respectively for the linear velocity of 9.8m/s, 29.5m/s and 39.4m/s at recording power/erase power.The record of a track carries out 11 times in succession, continues the record of three tracks subsequently, duplicates the track of second record then.

On-line velocity is in 20m/s or the higher record, at the bombardment with laser beams of optimizing recording power and lowest power after the time, and by following for the number of combinations between mark lengths nT (n=2 to 8) setting recording power pulses of radiation and the lowest power pulses of radiation: be labeled as one for 2T mark and 3T, be labeled as two for 4T mark and 5T, be labeled as three for 6T mark and 7T, be labeled as four for 8T, thereby carry out record.

The signal that is write down duplicates with the speed of 4.9m/s, determines jitter value.According to optical record medium, behind record, also to stand 80 ℃ of high temperature and 200 hours processing of 85%HR (relative humidity), be removed with assessment afterwards and duplicate the result.As comments, for initial shake, 8.0% or littler jitter value be confirmed as and can accept.Stand shake after the high-temperature process for medium, be 2% or be defined as more for a short time and can accept from the jitter value (Δ shake) that initial jitter value changed.

The result that table 3 is described shows that α, the β of phase-change material Ge α Sb β Sn γ Mn δ X ε of the present invention and γ need satisfy the composition range of the present invention's definition respectively, the mathematic(al) representation below promptly α, β and γ satisfy respectively:

5≤α≤25，45≤β≤75，10≤γ≤30。

For the element of Mn, when adopting 0.5 atom % to 20 atom %, it is no problem to find.

Example 20 to 24 and comparative example 9

Be provided with at thickness and on it on polycarbonate substrate of guiding groove of slot pitch of groove width with 27nm groove depth, 0.25 μ m, 0.74 μ m with 0.6mm, by the sputter setting by ZnSSiO ₂(80: 20mol%) make and have first protective layer of the thickness of 58nm, by the material of each composition shown in the row of example in the table 3 20 to 24 and comparative example 9 make and have the recording layer of the thickness of 14nm, by ZnSSiO ₂(80: 20mol%) make and have second protective layer of the thickness of 16nm, by Nb ₂O ₅: SiO ₂=80: 20 (mol%) make and have the anti-sulfuric horizon of the thickness of 4nm, made and had the reflecting layer of the thickness of 140nm by Ag.On the reflecting layer; use the UV curable resin (SD318 of 7 μ m thickness; by DAINIPPON INK AND CHEMICALS; INC makes); to form environmental protective cover by spin coated, the covered substrate with thickness of 0.6m is also used the UV curable resin of the thickness of 15 μ m, and (DVD003 is by Nippon kayaku Co.; Lrd. make) be laminated on the environmental protective cover, to produce the optical record medium of real root according to example 20 to 24 and comparative example 9.Next, with the identical mode initialization optical record medium of example 1.

Under the condition of the line speed record of the erase power of the recording power of 35mW, 8.3mW, 27.9m/s, come number of combinations between setting recording power pulses of radiation and the lowest power pulses of radiation to optimize the burst length of each optical record medium by following for mark lengths nT (n=3 to 14): to be labeled as one for 3T, be labeled as two for 4T mark and 5T, be labeled as three for 6T mark and 7T, be labeled as four for 8T mark and 9T, be labeled as five for 10T mark and 11T, be labeled as seven for 14T, thereby each such optical record medium is carried out record.The record of a track carries out 11 times, five tracks of recording occurring continuously subsequently, never mark under the linear velocity of the reproducing power of 0.7mW and 3.5m/s then.

Table 3 shows the result of initial jitter value.From found that of example 20 to 21 and comparative example 9, be 0.5 atom % or when bigger, jitter value is 9% or littler when adopting the Mn amount.After writing down 1,000 time, jitter value is 9% or littler.For Ga, example 22 to 24 shows, when the content of Ga is 7% or still less the time, jitter value is 9% or littler.

Table 3

Example 25 to 36

At thickness and be provided with the birefringence polycarbonate substrate (ST3000 of guiding groove of slot pitch of groove width, the 0.32 μ m of groove depth with 22nm, 0.20 μ m thereon with 1.1mm, make by TEIJIN-Bayer Polytec Ltd.) on, set gradually by Ag by sputter _99.5Bi _0.5(atom %) make and have the thickness of 160nm the reflecting layer, by SiC make and have the anti-sulfuric horizon of the thickness of 3nm, by ZnSSiO ₂(80: 20mol%) make and have the thickness of 5nm second protective layer, by the material of the various compositions shown in the row of the example in the table 4 25 to 36 make and have the recording layer of the thickness of 14nm, by ZnSSiO ₂(70: 30mol%) make and have first protective layer of the thickness of 40nm.On first protective layer, use the UV curable of thickness with 25 μ m resin laminated have a pressure sensitivity adhesive sheet of the thickness of 75 μ m, have the light-transmitting layer of the thickness of 0.1mm with preparation, produce optical record medium thus.Then, this optical record medium experiences initialization in the mode identical with example 1.

Under the condition of the erase power of the recording power (Pw) of the reproducing power of the shortest mark lengths of the clock frequency of the line speed record of 19.6m/s, 264MHz, 0.149 μ m, modulating mode (1-7) RLL, 0.35mW, 9mW, 3mW, adopt the pick-up head of 405nm wavelength and 0.85nm numerical aperture (NA), each such optical record medium is carried out record.At the bombardment with laser beams of optimizing recording power and lowest power after the time, and by following for the number of combinations between mark lengths nT (n=2 to 8) setting recording power pulses of radiation and the lowest power pulses of radiation: be labeled as one for 2T mark and 3T, be labeled as two for 4T mark and 5T, be labeled as three for 6T mark and 7T, be labeled as four for 8T.The record of each track carries out 11 times, and three tracks of recording occurring continuously subsequently duplicate the mark of the record of second track then with 4.9m/s, measure initially shake to adopt Limit EQ (limited equilibrium).

Table 4 shows the result, and the initial jitter value of gained all is 8.0% or littler.

Table 4

Example 37

The optical record medium of example 37 uses the mode identical with example 2 to be prepared, as long as by [(ZrO ₂) ₉₇(Y ₂O ₃) ₃] ₈₀(TiO ₂) ₂₀(mol%) make and boundary layer with thickness of 3nm is formed between the recording layer and first protective layer, and carried out initialization step in the mode identical subsequently with example 2.Then, adopt identical record and the copying equipment used, write the record mark with the line speed record of 6m/s, the recording power of 8mW, the erase power covering of 5mW with example 2.The measurement result of SDR as shown in figure 11.

Example 38

At thickness and be provided with the birefringence polycarbonate substrate (ST3000 of guiding groove of slot pitch of groove width, the 0.45 μ m of groove depth with 21nm, 0.30 μ m thereon with 0.6mm, make by TEIJIN-Bayer Polytec Ltd.) on, set gradually by Ag by sputter _99.5Bi _0.5(atom %) make and have the reflecting layer of the thickness of 140nm, by Nb ₂O ₅: SiO ₂(80: 20mol%) make and have the anti-sulfuric horizon of the thickness of 3nm, by ZnSSiO ₂(80: 20mol%) make and have the thickness of 12nm second protective layer, by same material used in the example 2 make and have the recording layer of the thickness of 14nm, by Nb ₂O ₅: SiO ₂(80: 20mol%) make and have 3nm thickness boundary layer and by ZnSSiO ₂(70: 30mol%) make and have first protective layer of the thickness of 40nm.On first protective layer, use UV curable resin (DVD003, by NipponKayaku Co., the Ltd. makes) lamination of thickness not have the same substrate of groove or have the covered substrate of the thickness of 0.6mm, to produce optical record medium with 15 μ m.Next, as in example 1, the initialization optical record medium carries out many-valued record with the line speed record at 6m/s, and carries out the SDR assessment.Figure 12 shows the recording power dependence of SDR.

Example 39

At thickness and be provided with the birefringence polycarbonate substrate (ST3000 of guiding groove of slot pitch of groove width, the 0.32 μ m of groove depth with 22nm, 0.20 μ m thereon with 1.1mm, make by TEIJIN-Bayer Polytec Ltd.) on, set gradually by Ag by sputter _99.5Bi _0.5(atom %) make and have the thickness of 140nm the reflecting layer, by SiC make and have the anti-sulfuric horizon of the thickness of 2nm, by ZnSSiO ₂(80: 20mol%) make and have the thickness of 10nm second protective layer, by with example 1 in used identical materials make and have the recording layer of the thickness of 14nm, by ZnSSiO ₂(70: 30mol%) make and have first protective layer of the thickness of 40nm.On first protective layer, use the UV curable of thickness with 25 μ m resin laminated have a pressure sensitivity adhesive sheet of the thickness of 75 μ m, have the light-transmitting layer of the thickness of 0.1mm with preparation, produce optical record medium thus.Then, this optical record medium experiences initialization in the mode identical with example 1.

Under the condition of the erase power (Pe) of the recording power (Pw) of the reproducing power of the shortest mark lengths of the clock frequency of the line speed record of 4.9m/s, 66MHz, 0.149 μ m, modulating mode (1-7) RLL, 0.35mW, 4.5mW, 3.2mW, adopt the pick-up head of the numerical aperture of 405nm wavelength and 0.85, optical record medium is carried out record.At the bombardment with laser beams of optimizing recording power and lowest power after the time, and the number of combinations of recording power pulses of radiation and lowest power pulses of radiation is set at (n-1), thereby carries out record for mark lengths nT (n=2 to 8).

The signal of duplicated record, and use Limit EQ to measure the jitter value of gained as equalization methods, second track record have 4.5% jitter value, 0.60 modulation degree and 17% reflectivity behind three tracks of recording occurring continuously.Jitter value increases by 5.0% after the mark covering of record writes 1,000 time.

Example 40

At thickness and be provided with the birefringence polycarbonate substrate (ST3000 of guiding groove of slot pitch of groove width, the 0.32 μ m of groove depth with 22nm, 0.20 μ m thereon with 1.1mm, make by TEIJIN-Bayer Polytec Ltd.) on, set gradually by Ag by sputter _99.5Bi _0.5(atom %) make and have the thickness of 140nm the reflecting layer, by SiC make and have the anti-sulfuric horizon of the thickness of 2nm, by ZnSSiO ₂(80: 20mol%) make and have the thickness of 10nm second protective layer, have Ge: Sb: Sn: Mn: Te=8: 63: 22: 5: 2 composition and have the recording layer of the thickness of 14nm, by ZnSSiO ₂(70: 30mol%) make and have first protective layer of the thickness of 40nm.On first protective layer, use the UV curable of thickness with 25 μ m resin laminated have a pressure sensitivity adhesive sheet of the thickness of 75 μ m, have the light-transmitting layer of the thickness of 0.1mm with preparation, produce optical record medium thus.Then, this optical record medium experiences initialization in the mode identical with example 1.

Under the condition of the erase power (Pe) of the recording power (Pw) of the reproducing power of the shortest mark lengths of the clock frequency of the line speed record of 19.6m/s, 264MHz, 0.149 μ m, modulating mode (1-7) RLL, 0.35mW, 9mW, 5mW, adopt the pick-up head of 405nm wavelength and 0.85 numerical aperture, optical record medium is carried out once record.At the bombardment with laser beams of optimizing recording power and lowest power after the time, and the number of combinations of recording power pulses of radiation and lowest power pulses of radiation is set at (n-1), thereby carries out record for mark lengths nT (n=2 to 8).

With the 4.9m/s reproducing signals, and use Limit EQ to measure the jitter value of gained as equalization methods.Second track record has 6.0% jitter value, 0.61 modulation degree and 20% reflectivity behind three tracks of recording occurring continuously.Jitter value increases by 1.5% after the mark covering of record writes 1,000 time.。

Example 41

At thickness and be provided with the birefringence polycarbonate substrate (ST3000 of guiding groove of slot pitch of groove width, the 0.32 μ m of groove depth with 22nm, 0.20 μ m thereon with 1.1mm, make by TEIJIN-Bayer Polytec Ltd.) on, set gradually by Ag by sputter _99.5Bi _0.5(atom %) make and have the thickness of 140nm the reflecting layer, use TiO: TiC=50: the target of 50 (mol%) and have the anti-sulfuric horizon of the thickness of 4nm, by ZnSSiO ₂(80: 20mol%) make and have the thickness of 4nm second protective layer, have Ge: Sb: Sn: Mn=11: 64.5: 18: 6.5 composition and have the recording layer of the thickness of 12nm, by ZnSSiO ₂(80: 20mol%) make and have first protective layer of the thickness of 33nm.On first protective layer, use the UV curable of thickness with 25 μ m resin laminated have a pressure sensitivity adhesive sheet of the thickness of 75 μ m, have the light-transmitting layer of the thickness of 0.1mm with preparation, produce optical record medium thus.Then, this optical record medium experiences initialization in the mode identical with example 1.

Under the condition of the erase power (Pe) of the recording power (Pw) of the reproducing power of the shortest mark lengths of the clock frequency of the line speed record of 19.6m/s, 264MHz, 0.149 μ m, modulating mode (1-7) RLL, 0.35mW, 9mW, 3mW, adopt the pick-up head of the numerical aperture of 405nm wavelength and 0.85, optical record medium is carried out record.

At the bombardment with laser beams of optimizing recording power and lowest power after the time, and for mark lengths nT (n=2 to 8) number of combinations of recording power pulses of radiation and lowest power pulses of radiation is set at: be labeled as 1 for 2T and 3T, be labeled as 2 for 4T and 5T, be labeled as 3 for 6T and 7T, be labeled as 4 for 8T, thereby carry out record.Signal writes down 11 times on per three tracks, and the signal on second track record of continuous recording three tracks is replicated with 4.9m/s, and jitter value is measured with Limit EQ.After the erase power with the recording power of 10.5mW, 3.3mW writes down, detect the record time data/coherency of shake, promptly directly cover write diagnostics.Figure 13 shows the result.

Comparative example 11

Prepare optical record medium with the mode identical, be Ge: Sb: Sn=14.5 as long as the composition of recording layer is changed: 65.5: 20 (atom %) with example 41.

With optical record medium being write down and duplicates, wherein under the erase power of the recording power of 9.0mW, 3.0mW, carry out record with the same mode of example 41.Figure 13 shows the result.

Example 42

At thickness and be provided with the birefringence polycarbonate substrate (ST3000 of guiding groove of slot pitch of groove width, the 0.32 μ m of groove depth with 22nm, 0.20 μ m thereon with 1.1mm, make by TEIJIN-Bayer Polytec Ltd.) on, set gradually by Ag by sputter _99.5Bi _0.5(atom %) make and have the thickness of 140nm the reflecting layer, use TiO: TiC=50: the target of 50 (mol%) and have the anti-sulfuric horizon of the thickness of 4nm, by ZrO ₂: TiO ₂: Y ₂O ₃(77.6: 20: 2.4mol%) make and have the thickness of 8nm second protective layer, have Ge: Sb: Sn: Mn=11: 64.5: 18: 6.5 composition and have the recording layer of the thickness of 12nm, by ZnSSiO ₂(80: 20mol%) make and have first protective layer of the thickness of 33nm.On first protective layer, use the UV curable of thickness with 25 μ m resin laminated have a pressure sensitivity adhesive sheet of the thickness of 75 μ m, have the light-transmitting layer of the thickness of 0.1mm with preparation, produce optical record medium thus.Then, this optical record medium experiences initialization in the mode identical with example 1.

At the bombardment with laser beams of optimizing recording power and lowest power after the time, and for mark lengths nT (n=2 to 8) number of combinations of recording power pulses of radiation and lowest power pulses of radiation is set at: be labeled as 1 for 2T and 3T, be labeled as 2 for 4T and 5T, be labeled as 3 for 6T and 7T, be labeled as 4 for 8T, thereby carry out record.Signal writes down 11 times on per three tracks, and the signal on second track record of continuous recording three tracks is replicated with 4.9m/s, and jitter value is measured with Limit EQ.After the erase power with the recording power of 10.5mW, 3.3mW writes down, detect the record time data/coherency of shake, promptly directly cover write diagnostics.Figure 14 shows the result.

Optical record medium stood hot and humid degree condition under 80 ℃ and 85%HR (relative humidity) 200 hours.The reflectivity of gained and test comparison before.Reflectivity be changed to 0.5% or littler.

Comparative example 12

Prepare optical record medium with the mode identical, as long as the composition of recording layer is changed into Ge: Sb: Sn=14.5: 65.5: 20 (atom %) with example 42.

With the mode identical optical record medium is write down and duplicates, as long as carry out record under the erase power with the recording power of 9.5mW, 2.6mW with example 42.Figure 14 shows the result.

Example 41 to 42 and comparative example 11 and 12 show, cover write diagnostics and be improved by adding Mn, and reflectivity diminishes with respect to the variation of environment temperature.

Example 43

Prepare optical record medium with the mode identical, as long as the composition of recording layer changes over Ge: Sb: Sn: Mn: Ga=11: 64.5: 18: 3.5: 3 (atom %) with example 42.

With the mode identical optical record medium is write down and duplicates, as long as carry out record with the recording power of 8.5mW or than example 42 low 1mW with example 42.Improved record sensitiveness under high-speed record in the material of recording layer by adding Ga.

Claims

1, a kind of optical record medium comprises:

Substrate,

First protective layer,

Phase change recording layers,

Second protective layer and

The reflecting layer,

Wherein this phase change recording layers be utilize with amorphous phase that causes by bombardment with laser beams and crystalline phase between the relevant optical constant of reversible transition layer, and comprise Ge, Sb, Sn, Mn and X,

Wherein the X representative is selected from least a element among In, Bi, Te, Ag, Al, Zn, Co, Ni and the Cu,

Wherein, when the relation of the content separately of described Ge, Sb, Sn, Mn and X is represented by Ge α Sb β Sn γ Mn δ X ε, the mathematic(al) representation below the element of α, β, γ, δ and ε satisfies respectively: 5≤α≤25,45≤β≤75,10≤γ≤30,0.5≤δ≤20 and 0≤ε≤15

Wherein, when alpha+beta+γ+δ+ε=100, α, β, γ, δ and ε represent atom % respectively, and,

Wherein, the content summation of Ge, Sb, Sn, Mn and X is at least 95 atom % of this phase-change recording stratum total.

2, according to the optical record medium of claim 1, the mathematic(al) representation below wherein the content of this element α satisfies: 10≤α≤25.

3, according to the optical record medium of claim 1, the mathematic(al) representation below wherein the content of this element β satisfies: 50≤β≤70.

4, according to the optical record medium of claim 1, the mathematic(al) representation below wherein the content of this element δ satisfies: 1.0≤δ.

5, according to the optical record medium of claim 1, wherein this phase change recording layers also comprises the Ga of 7 atom % or amount still less.

6, according to the optical record medium of claim 1, wherein this phase change recording layers also comprises any element that is selected among Tb, Dy, Nd, Gd, Ti, Zr, Cr, Fe and the Si.

7, according to the optical record medium of claim 1; wherein this first protective layer, this phase change recording layers, this second protective layer and this reflecting layer form stepped construction with this order on substrate, and perhaps this reflecting layer, this second protective layer, this phase change recording layers, this first protective layer form stepped construction with this order on substrate.

8, according to the optical record medium of claim 7; wherein this optical record medium also comprises adhesive phase and covered substrate layer, and this reflecting layer, this second protective layer, this phase change recording layers, this first protective layer, this adhesive phase and this covered substrate layer form stepped construction with this order on substrate.

9, according to the optical record medium of claim 7, wherein this reflecting layer comprises the one of any of Ag and Ag alloy.

10, according to the optical record medium of claim 7, wherein this second protective layer comprises ZnS and SiO ₂Mixture.

11, according to the optical record medium of claim 7, wherein this reflecting layer, this second protective layer, this phase change recording layers and this first protective layer form stepped construction with this order on substrate, and this second protective layer comprises and is selected from ZrO ₂, Y ₂O ₃And TiO ₂Mixture, SiO ₂And Nb ₂O ₅Mixture, and SiO ₂And Ta ₂O ₅Any mixture in these three kinds of mixtures of mixture.

12, according to the optical record medium of claim 10, wherein this optical record medium also is included in the anti-sulfuric horizon between this reflecting layer and this second protective layer.

13, according to the optical record medium of claim 7, wherein this first protective layer comprises ZnS and SiO ₂Mixture.

14, according to the optical record medium of claim 7, wherein this optical record medium also is included in the boundary layer between this first protective layer and this phase change recording layers,

Wherein the thickness of this boundary layer is 1nm to 10nm, and comprises ZrO ₂, Y ₂O ₃And TiO ₂Mixture, SiO ₂And Nb ₂O ₅Mixture, and SiO ₂And Ta ₂O ₅Any mixture in these three kinds of mixtures of mixture.

15, according to the optical record medium of claim 7, wherein this optical record medium also is included in the boundary layer between this phase change recording layers and this second protective layer.

16, according to the optical record medium of claim 1, wherein this first protective layer comprises ZnS and SiO ₂, and ZnS: SiO ₂The composition ratio is 60mol% to 85mol%: 40mol% to 15mol%, and this second protective layer comprises ZnS and SiO ₂, and ZnS: SiO ₂Composition is than being 30mol% to 85mol%: 70mol% to 15mol%.