CN1647178A - 光记录介质 - Google Patents
光记录介质 Download PDFInfo
- Publication number
- CN1647178A CN1647178A CNA038086522A CN03808652A CN1647178A CN 1647178 A CN1647178 A CN 1647178A CN A038086522 A CNA038086522 A CN A038086522A CN 03808652 A CN03808652 A CN 03808652A CN 1647178 A CN1647178 A CN 1647178A
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- China
- Prior art keywords
- layer
- optical recording
- recording media
- dielectric layer
- record
- Prior art date
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- 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
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Abstract
一种光记录介质,其特征在于:被构成为从记录用的光或重放用的光的入射侧按顺序形成有记录层、第1吸收层和散热层,同时上述第1吸收层的消光系数k在上述记录用或重放用的光的波长中满足0.06≤k≤1.0。如上所述,按照该光记录介质,通过以在记录用或重放用的光的波长中使其消光系数k大于等于0.06小于等于1.0的方式构成第1吸收层,即使在以高密度进行了记录时,也可充分地提高重放耐久性,同时可充分地降低交叉擦除。由此,实现了能进行高密度记录而且重放耐久性高、难以发生交叉擦除的光记录介质。
Description
技术领域
本发明涉及被构成为能通过照射记录用的光或重放用的光来进行记录信息的记录或重放的光记录介质。
背景技术
近年来,能进行高密度记录而且能擦除记录信息并再次进行写入的光记录介质(以下也称为「改写型光记录介质」)越来越引人注目。该改写型光记录介质中的相变型光记录介质通过照射激光使记录层的结晶状态变化来进行记录信息的记录,通过检测伴随这种状态变化的记录层的反射率变化来进行记录信息的重放。该相变型光记录介质与光磁记录介质用的光学***比较,在能用单纯的结构的光学***记录重放记录信息这一点上是引人注目的。此时,在相变型光记录介质中,因为结晶质状态和非晶质状态的反射率之差大而且非晶质状态的稳定度比较高等,故作为该记录层用的光学材料,一般使用Ge-Sb-Te类等硫属化合物类材料。
在该相变型光记录介质中,在记录信息的记录时,照射能将记录层升温到熔点以上的高功率(记录功率)的激光(记录用激光束)。此时,对于被照射了记录功率的激光的部位来说,因在记录层被熔融了之后进行急剧冷却而形成非晶质的记录标记。此外,在记录标记的擦除时,照射能将记录层升温到记录层的结晶化温度以上而不到熔点的比较低的功率(擦除功率)的激光。此时,对于被照射了擦除功率的激光的部位来说,因记录层被加热到结晶化温度以上之后逐渐地被冷却而使记录标记(非晶质部分)复归到结晶质(记录标记的擦除)。这样,在相变型光记录介质中,通过使单一的激光的强度(照射功率)变化而能进行记录数据的重写。
另一方面,为了实现高密度记录,近年来的光记录介质处于其光道间距被缩小的趋势。此外,对于记录重放时对光记录介质照射的激光来说,为了能进行更小的记录标记的记录/重放,其波长的缩短或射出激光的记录重放光学***中的物镜的数值孔径的提高正在不断得到进展。因而,能增大对于1片光记录介质能记录的记录信息量(高密度记录的实现)。此时,在将激光的波长定为λ、将物镜的数值孔径定为NA时,用λ/NA来表示在记录层表面上照射的记录用激光束的光点直径,该λ/NA越小,就越能进行更小的记录标记的记录/重放,同时能对更窄的光道间距的光记录介质进行记录重放。
发明者研究了上述的现有的光记录介质的结果,发现了以下那样的应改善的课题。即,在该现有的光记录介质中,为了能进行记录数据的重写,将记录层构成为能利用擦除功率的激光的照射使非晶质部分(记录标记)复归到结晶质(记录标记的擦除)。因此,对于这种光记录介质来说,一般使用对记录标记的结晶状态没有影响的低功率的激光,以免记录标记因记录信息的重放时照射的重放用激光束而消失。但是,即使使用了例如低功率的激光作为重放用的光(重放用激光束),在进行了多次的记录信息的重放时,在记录标记的形成部位中也起因于某种主要原因而产生再结晶化(复归到结晶质)。因此,起因于该再结晶化而存在抖动(jitter)的增大、即重放耐久性较大地下降的课题。此时,本发明者在针对该再结晶化的主要原因而使用具有数值孔径大的物镜的光学***并照射了短波长的激光时,即上述的(λ/NA)小时,发现了起因于激光光束点内的能量密度变高而产生再结晶化的情况。因而,可认为通过使用(λ/NA)大的激光可减少抖动,但在这样的情况下,发生难以进行高密度记录的问题。
此外,在现有的光记录介质中,发生在与记录对象邻接的光道(以下,也称为「邻接光道」)中形成的记录标记(非晶质部分)再结晶化那样的所谓交叉擦除,起因于该交叉擦除的发生而存在C/N下降的课题。具体地说,在记录信息的记录时,在对光记录介质照射了记录功率的激光时,与照射了激光的记录对象的光道一起,邻接光道的温度上升。此时,邻接光道中形成的记录标记发生再结晶化。在该情况下,已知记录对象的光道间距相对于激光束的光点直径越窄就越容易发生交叉擦除的情况。因而,可认为通过减小激光束的光点直径能避免交叉擦除的发生,但本发明者发现了,即使在记录对象的光道间距与光束点直径的关系为相同时,光束点内的能量密度越高,例如在缩短由记录重放光学***射出的激光束的波长时,就越容易发生交叉擦除。因此,可认为通过使激光束的光点直径变化来避免交叉擦除的发生一般来说是困难的。
发明内容
本发明是为了解决上述那样的问题而进行的,其主要目的在于提供可进行高密度记录、而且能谋求重放耐久性的提高和交叉擦除的减少的光记录介质。
关于与本发明有关的光记录介质,被构成为从记录用的光或重放用的光的入射侧按顺序形成记录层、第1吸收层和散热层,同时上述第1吸收层的消光系数k在上述记录用或重放用的光的波长中满足0.06≤k≤1.0。
在该光记录介质中,通过在记录用或重放用的光的波长中将第1吸收层构成为其消光系数k大于等于0.06小于等于1.0,在以高密度进行了记录时,可充分地提高重放耐久性,同时可充分地减少交叉擦除。
此时,在上述记录层中的上述光的入射侧面上形成第2吸收层,最好被构成为上述第2吸收层的消光系数k在上述记录用或重放用的光的波长中满足0.06≤k≤1.0。通过以这种方式来构成,可进一步提高重放耐久性,而且可进一步减少交叉擦除。此时,在缩短最短标记长度来记录时(以高密度记录记录信息时),可进一步降低抖动。
此外,最好被构成为在上述记录用或重放用的光的波长λ与该记录用或重放用的光的照射光学***中的数值孔径NA的关系满足λ/NA≤680nm的条件下能进行记录或重放。通过以这种方式来构成,与被构成为在满足λ/NA>680nm的条件下能进行记录或重放的光记录介质相比,能充分地以高密度来记录记录信息。
再者,最好用小于等于0.35μm的间距形成记录光道间距。通过以这种方式来构成,能以更高密度来记录记录信息。
此外,最好被构成为能将最短的标记长度规定为小于等于0.17μm来记录信息。通过以这种方式来构成,能以更高密度来记录记录信息。
再有,本公开与作为在2002年4月19日申请的日本专利申请的特愿2002-117508中包含的主题相关联,这些公开的全部在此作为参照事项来引入。
附图说明
图1是示意性地示出了本发明的第1形态中的光记录介质的层结构的剖面图。
图2是示意性地示出了本发明的第2形态中的光记录介质的层结构的剖面图。
图3是采用本发明的第2形态中的光记录介质的层结构制作的光记录介质1的剖面图。
图4是采用本发明的第2形态中的光记录介质的层结构制作的光记录介质1A的剖面图。
图5是在记录层4上形成了第1电介质层3(第1吸收层A1)的状态的剖面图。
图6是示出作为第1实施例制作的各光记录介质的结构以及关于交叉擦除和重放耐久性的评价结果的图。
图7是示出作为第2实施例制作的各光记录介质的结构以及关于交叉擦除和重放耐久性的评价结果的图。
图8是示出作为第3实施例制作的各光记录介质的结构以及关于抖动的评价结果的图。
图9是用曲线表示关于第3实施例中的实施例10、11和比较例6、7的最短标记长度Ms与抖动的发生率的关系的图。
图10是示出作为第4实施例制作的各光记录介质的结构以及关于重放信号的C/N的评价结果的图。
图11是示出作为第5实施例制作的各光记录介质的结构以及关于重放信号的C/N的评价结果的图。
图12是示出作为第6实施例制作的各光记录介质的结构以及关于交叉擦除和重放耐久性的评价结果的图。
具体实施方式
以下,参照附图说明与本发明有关的光记录介质的合适的发明的实施形态。
最初,参照附图说明本发明的特征部分。
在与本发明有关的光记录介质的第1形态中,如图1中所示,从激光L(本发明中的「记录用的光或重放用的光」)的入射侧看,按下述顺序形成记录层4、第2电介质层5和散热层6。此外,在与本发明有关的光记录介质的第2形态中,如图2中所示,从激光L的入射侧看,按下述顺序形成第1电介质层3、记录层4、第2电介质层5和散热层6。此时,第2电介质层5相当于本发明中的第1吸收层,第1电介质层3相当于本发明中的第2吸收层。在此,考虑层叠顺序而容易理解起见,也将第1电介质层3称为第1吸收层A1、将第2电介质层5称为第2吸收层A2。在用(n+ik(n是折射率))表示复折射率时,将该第1吸收层A1和第2吸收层A2(以下在不加区别时,也称为「吸收层A」)形成为激光L的波长中的消光系数k大于等于0.06小于等于1.0。与此不同,如后述那样,在将吸收层A形成为其消光系数k为0时,不能实现本发明的效果,在将吸收层A形成为其消光系数k为超过1.0的较大数值时,该吸收层A中的激光L的吸收率过高,在记录信息的记录和重放中产生了障碍。
此时,对于吸收层A的消光系数k来说,可根据关于吸收层A的反射率和透射率来计算。具体地说。作为一例,可按以下的程序来计算。首先,通过在滑动玻璃上形成厚度20nm的吸收层A来制作测定用样品A-1。其次,通过在滑动玻璃上按顺序形成厚度20nm的吸收层A和厚度100nm的反射层来制作测定用样品A-2。再有,作为测定用样品A-2的反射层,使用复折射率(n+ik)为已知的光学材料。其次,对于测定用样品A-1、A-2分别实测激光L的波长中的反射率和透射率。在该反射率和透射率的实测时,作为一例,使用岛津制作所制的分光光度计(MPS-2000)用45°绝对镜面反射率测定附属装置(RTA-2000特形)。接着,根据关于测定用样品A-1、A-2实测了的反射率和透射率,利用矩阵法求出复折射率。利用该复折射率来确定消光系数k。再有,关于复折射率,不限定于上述的计算方法,也可使用椭圆计等来求出。
在第1形态中的光记录介质中,激光L在透过记录层4和第2电介质层5(第2吸收层A2)被散热层6反射了后,再次透过第2电介质层5到达记录层4。此时,由于第2电介质层5吸收激光L的一部分而发热,故与不存在第2电介质层5的现有的光记录介质相比,可抑制记录层4的发热量。在该情况下,由于在散热性良好的散热层6与记录层4之间存在第2电介质层5,故在该第2电介质层5中产生的热被传递到散热层6中而迅速地散热。因此,第2电介质层5的发热几乎不对记录层4产生影响。因而,在第1形态中的光记录介质中,减少了抖动,提高了重放耐久性。此外,在第1形态中的光记录介质中,由于在该第2电介质层5中产生的热被传递到散热层6中而迅速地散热,故因激光L的照射而升温到比较高的温度的区域限于光束点及其附近。因而,在该第1形态中的光记录介质中,可避免交叉擦除的发生。
在该第1形态中的光记录介质中,在激光L(记录/重放光)的波长λ与激光L的照射光学***的数值孔径NA的关系为λ/NA≤680nm的情况下,最好在λ/NA≤630nm的情况下,可充分地得到上述的效果。
在该情况下,λ/NA与激光L的光束点直径相关,λ/NA越小,激光L的光束点直径就越小,作为结果,光束点内的能量密度提高了。此外,如上所述,一般来说,如果光束点内的能量密度提高,则重放耐久性降低,同时容易发生交叉擦除。另一方面,在该第1形态中的光记录介质中,即使在λ/NA如上述那样比较小的情况下,也可提高重放耐久性,而且可减少交叉擦除。在该情况下,现实地说,在可使用的激光波长和数值孔径方面存在限制,难以规定为显著地短的波长和显著地大的数值孔径。因此,规定为250nm≤λ/NA,最好规定为350nm≤λ/NA。
此外,在记录光道间距窄时容易发生交叉擦除。因此,在λ/NA为上述范围内且将记录光道间距Pt定为Pt≤0.35μm时、特别是Pt≤0.33μm时,与本发明有关的层结构是有效的。再有,记录光道间距Pt的下限值不作特别的限制,但如上所述,由于在可使用的激光波长和数值孔径方面存在限制,故显著地减小与λ/NA相关的光束点直径在实际上是困难的。因而,通常规定为0.14μm≤Pt,最好规定为0.15μm≤Pt。
另一方面,在第2形态中的光记录介质中,除了第1形态中的光记录介质外,从激光L的入射侧看,通过在记录层4的跟前侧表面上形成第1电介质层3(第1吸收层A1),既可谋求因第2电介质层5产生的重放耐久性的提高,又可利用第1电介质层3谋求抖动的进一步的降低。此时,在该第2形态中的光记录介质中,在将记录标记的最短标记长度Ms定为Ms≤0.17μm时,与其它的光记录介质相比,可充分地降低抖动。此外,在Ms≤0.165μm时,特别是在Ms≤0.16μm时,进而在Ms≤0.155μm时,与其它的光记录介质相比,降低抖动的效果特别好。这样,由于在缩短了最短标记长度Ms时可降低抖动,故第2形态中的光记录介质作为高密度记录用的光记录介质是特别有效的。再有,在将最短标记长度Ms定为上述的值时降低抖动的原因尚未搞清楚。
在上述的第1和第2形态中的光记录介质的制作时,最好利用溅射法来形成吸收层A。再有,吸收层A也可由组成不同的多个层来构成。关于该吸收层A的厚度,在能谋求重放耐久性的提高和抖动的降低的范围内,以使作为光记录介质整体的光学设计和热设计变得容易的方式适当地决定即可。作为一例,将吸收层A的厚度规定为大于等于5nm小于等于50nm,更为理想的是规定为大于等于5nm小于等于40nm。此时,如果吸收层A过薄,则重放耐久性的提高和抖动的降低变得困难。另一方面,如果吸收层A过厚,则由于激光L的照射时的来自光记录介质的反射光量变少,难以得到充分的重放输出,记录信息的重放变得困难。此外,使用于吸收层A的光学材料不作特别限定,以使作为光记录介质整体的光学设计和热设计变得容易的方式适当地决定即可。作为一例,最好使用氧化铈或氧化锌,也可使用含有这些材料的至少一种的电介质。
此时,如在后述的实施例中说明的那样,通过设置由ZnO(消光系数k=0.1)构成的吸收层A,实现了本发明的效果,但设置了使用ZnO靶在含有氧气的气氛中由反应性溅射形成的吸收层A(消光系数k=0)的情况下,未实现本发明的效果。即,即使吸收层A的构成元素相同,只是通过利用构成元素的比率的变化使消光系数k从0.1稍微地向0变化,就不能实现本发明的效果。因而,为了稳定地实现本发明的效果,在吸收层A的形成时必须严格地进行控制以使消光系数k成为目标值。具体地说,例如在利用溅射法形成吸收层A时,利用靶组成或反应性溅射时的反应性气体的流量等来控制消光系数k。
此外,为了充分地发挥本发明的效果,最好与记录层4密接地形成吸收层A。但是,根据需要也可在记录层4与吸收层A之间设置另外的层(例如,第1电介质层3和第2电介质层5以外的电介质层)。但是,如果在记录层4与吸收层A之间形成的层过厚,则存在损害本发明的效果的可能性,因此,将该层的厚度规定为小于等于30nm,最好小于等于20nm。再者,本发明对于相变型光记录介质特别有效,但也可应用于进行热模式记录的类型的光记录介质(例如,光磁记录介质)。在该光磁记录介质中,一般来说,在λ/NA小时,容易因重复重放而产生磁化反转,此外,容易产生交叉擦除。但是,通过采用与本发明有关的光记录介质的层结构,可有效地避免这些问题。
在特开昭63-217542号公报中,公开了以夹住记录层的方式形成了透明的耐热保护层、而且在记录层与透明的耐热保护层之间形成了在记录和擦除中使用的激光L的波长中显示出吸收的第2耐热保护层的光学信息记录构件。该公报中的第2耐热保护层在激光L的波长中显示出吸收这一点上与本发明中的吸收层A近似。但是,在以下说明的方面中,本发明与该公报记载的发明有很大的不同。在该公报的作用的一栏中记载了如下的要旨:由于通过使用具有光吸收性的保护层、光吸收层(记录层+保护层)的厚度比以往厚、从而热容量变大,故能使记录光道的沟内的光道宽度方向的温度分布变得均匀。即,在该公报记载的发明中,如在其图2中作为曲线10示出的那样,利用记录光照射而升温的区域在记录光道宽度方向上扩展,而且,在记录光道中央的峰值温度降低了。因而,根据该公报的记载,在设置了具有光吸收的保护层的情况下,可预期交叉擦除不会减少,而是恶化了。但是,本发明者门在按照该公报中记载的内容进行了实验时,与预期的情况相反,确认了减少交叉擦除的效果。
此时,该公报记载的发明在未设置散热性良好的散热层这一点上与本发明的第1形态不同。因而,在该公报记载的发明中,起因于未设置散热层这一点,在光吸收性的保护层中发生的热滞留于该处,作为结果,可认为记录层的升温区域在记录光道宽度方向上扩展而发生交叉擦除。但是,在该公报记载的发明中,利用波长830nm的激光进行了记录,与本发明的第1形态相比,由于光束点直径大,故光束点内的能量密度比较低。因此,在该公报记载的发明中,可认为关于交叉擦除和重放耐久性没有特别产生问题。因而,在与使用波长短的激光并用短的记录标记记录的本发明的第2形态为同一条件下,可认为关于交叉擦除和重放耐久性会产生大的问题。
再者,在该公报记载的发明中,使用了波长为830nm的显著地长的激光。因此,在该公报中,虽然没有关于最短标记长度的记载,但可预期该公报记载的发明中的最短标记长度比用与本发明的第2形态有关的光记录介质记录的最短标记长度显著地长。因而,在该公报记载的发明中,在与使用波长短的激光并用短的记录标记记录的本发明的第2形态为同一条件下,难以实现抖动的降低。
其次,参照附图说明根据上述的本发明的第2形态制作的光记录介质。
如图3中所示,对于光记录介质1来说,在支撑基体7上按顺序层叠了由金属或半金属构成的散热层6、第2电介质层5(第2吸收层A2)、相变型的记录层4、第1电介质层3和透光性基体2。在该光记录介质1中,从透光性基体2的形成面一侧入射激光L(记录/重放光)。再有,在支撑基体7与散热层6之间也可设置由电介质材料构成的中间层。支撑基体7是用来维持光记录介质1的刚性的,在其表面上形成了沟(groove)和岸(land)(未图示)。该支撑基体7的厚度通常定为0.2~1.2mm、最好是0.4~1.2mm即可,可以是透明的、也可以是不透明的。此时,关于支撑基体7,可以与通常的光记录介质同样地用聚碳酸酯等的树脂来形成,也可使用玻璃来形成。
散热层6是夺取在第2电介质层5中产生的热并迅速地传递到支撑基体7上用的层,由溅射法或蒸镀法等的汽相生长法在支撑基体7的表面上形成。该散热层6的形成材料不作特别限定,但作为一例,用Al、Au、Ag、Pt、Cu、Ni、Cr、Ti、Si等的金属或半金属或包含这些金属中的1种或1种以上的合金等形成即可。但是,由于在以单体使用Ag或Al的情况下,不能得到充分的耐蚀性,故最好添加提高耐蚀性用的元素。此外,在光记录介质1中,由于在散热层6的形成时的结晶生长的缘故,激光L的入射侧的表面粗糙度容易变大,起因于此,存在重放噪声增大的可能性。因而,在散热层6的形成时,最好减小其结晶粒径,不以单体使用Ag或Al,为了减小散热层6的结晶粒径或为了将散热层6作为非晶质层来形成,最好添加元素。
但是,在该散热层6的形成时添加了其它元素的情况下,散热层6本身的热传导率下降。因而,为了谋求交叉擦除的降低和重放耐久性的提高,通过将热传导率高的Ag作为主成分元素来形成散热层6,在激光L的照射时使记录层4和第2电介质层5迅速地冷却,这是较为理想的。此时,作为在Ag中添加的副成分元素,例如可举出Mg、Pd、Ce、Cu、Ge、La、S、Sb、Si、Te和Zr等。使用至少1种这些副成分元素、最好2种或2种以上这些副成分元素。再有,在散热层6中的副成分元素的含有量在添加的元素单体中为0.05~2.0原子%、最好为0.2~1.0原子%,作为副成分整体,规定为0.2~5原子%、最好为0.5~3原子%。此时,如果副成分元素的含有量过少,则因含有这些元素得到的效果(表面粗糙度的减少等)不充分。另一方面,如果副成分元素的含有量过多,则热传导率变小。
此外,存在下述的趋势:结晶粒径越小,由金属或半金属构成的散热层6的热传导率越低。因此,在散热层6为非晶质的情况下,由于在记录时难以得到充分的冷却速度,故首先在作为非晶质层形成了散热层6后最好对该散热层6进行热处理使其结晶化。通过先作为非晶质层形成了后利用热处理使其结晶化,可维持非晶质时的表面粗糙度(平滑度),而且可谋求因结晶化导致的热传导率的提高。对于该散热层6来说,在其厚度不够时,难以得到充分的反射率,而即使过分地加厚,反射率也不那么增加,而且成本因所消耗的材料而提高。因此,通常最好规定为大于等于10nm小于等于300nm。
再有,在本发明的实施形态中,说明用金属或半金属形成散热层6的例子,但也可用其它的材料来形成散热层6。例如,在具有多个记录层4、4的所谓的多层光记录介质中,由于经表面一侧的记录层4照射激光L,故在该表面一侧的记录层4上设置了散热层6的情况下,由于该散热层6的存在,激光L的透射率显著地下降。因而,在多层光记录介质中,为了降低记录层4、4相互间的串扰,大多在记录层4、4间设置比较厚的树脂层。此时,由于具有某种程度的厚度的树脂层的热容量比较大,故在将本发明应用于多层记录介质时,将上述树脂层作为本发明中的散热层来利用。
通过利用溅射法等以夹住记录层4的方式形成第1电介质层3和第2电介质层5,防止记录层4的氧化和变质,同时通过隔断在激光L的照射时从记录层4传递的热或在平面方向上传递热来保护支撑基体7或透光性基体2。此外,通过设置第1电介质层3和第2电介质层5,可提高激光L的调制度。此时,第2电介质层5相当于本发明中的第1吸收层,利用后述的光学材料而被形成为薄膜状。再有,在本发明的实施形态中,将第2电介质层5的厚度方向的整体形成为起到第2吸收层A2的功能,但本发明不限定于此,也可象第1电介质层3那样用多个单位电介质层的层叠体构成第2电介质层5,将各单位电介质层的至少1层定为第2吸收层A2,在该情况下,作为第2吸收层A2以外的单位电介质层,其热传导率最好与第2吸收层A2为同等或比其高。
关于第1电介质层3,层叠了组成不同的单位电介质层3a~3c而构成。此时,在记录层4上形成的单位电介质层3c(第1吸收层A1)起到本发明中的第2吸收层的功能。再有,在本发明的实施形态中,说明在记录层4上形成了由多个单位电介质层3a~3c的层叠体构成的第1电介质层3的例子,但该第1电介质层3也可象上述的第2电介质层5那样,将其厚度方向上的整体形成为单一的膜状以便能作为第1吸收层A1来利用。在该结构中,在作为第1吸收层A1的第1电介质层3过厚的情况下,由于激光L的反射光量变少,难以得到充分的重放输出,故最好将第1电介质层3整体的厚度形成为小于等于50nm。因而,通常如图3中所示,最好用多个单位电介质层3a~3c等的层叠体构成第1电介质层3,将这些层中的1个单位电介质层定为第1吸收层A1。
作为在这些第2电介质层5和单位电介质层3a~3c(第1电介质层3)中使用的电介质(光学材料),作为一例,最好是包含从Si、Ge、Zn、Al、稀土类元素等中选择的至少1种金属成分的各种化合物。此外,作为化合物,最好是氧化物、氮化物或硫化物,也可使用含有这些化合物的2种以上的混合物。再者,关于第1电介质层3和第2电介质层5的各自的厚度,以能充分地得到上述的保护效果或提高调制度的效果的方式适当地决定即可,但通常将第1电介质层3的厚度规定为大于等于30nm小于等于300nm,最好规定为大于等于50nm小于等于250nm,将第2电介质层5的厚度规定为大于等于5nm小于等于50nm。但是,为了作成急剧冷却的结构,将第2电介质层5的厚度规定为小于等于30nm,最好规定为小于等于25nm。
用相变材料利用溅射法形成记录层4,通过照射记录功率的激光L形成记录标记,记录各种记录信息。该记录层4的组成不作特别限定,但最好至少含有Sb和Te。此时,由于只由Sb和Te构成的记录层4的结晶化温度约为130℃,非常低,记录信息的保存可靠性不充分,故为了提高结晶化温度,最好添加其它的元素。作为该添加元素,作为一例,可举出Mn、In、Ag、Au、Bi、Se、Al、P、Ge、H、Si、C、V、W、Ta、Zn、Ti、Sn、Pb、Pd和稀土类元素(Sc、Y和镧族元素)等。在这些元素中,因为提高保存可靠性的效果特别好,故最好是从稀土类元素、Ag、In和Ge中选择的至少1种材料。
具体地说,作为含有Sb和Te的组成,在用M表示分别除了Sb和Te的元素、用下述的(1)式表示记录层构成元素的原子比时,最好满足以下的条件。
(SbxTe1-x)1-yMy...(1)式
较为理想的是,规定为满足:
0.2≤x≤0.9
0≤y≤0.4
更为理想的是,规定为满足:
0.5≤x≤0.85
0.01≤y≤0.2
在上述(1)式中表示Sb的含有量的x过小的情况下,由于结晶化速度慢,故以比较快的线速度的记录标记的擦除变得困难,同时记录层4的结晶质区域中的反射率下降,重放信号输出下降。此外,在x过小的情况下,记录信息的记录(记录标记的形成)变得困难,在x过大的情况下,由于在结晶状态与非晶质状态之间的反射率差变小,故重放信号输出下降。另一方面,元素M不作特别限定,但最好从显示出提高保存可靠性的效果的上述元素中选择至少1种。在表示元素M的含有量的y过大的情况下,重放输出容易下降。因而,关于记录层4的厚度,较为理想的是规定为大于等于4nm小于等于50nm,更为理想的是规定为大于等于5nm小于等于30nm。此时,如果记录层4过薄,则由于结晶相的生长变得困难,故结晶化变得困难。另一方面,如果记录层4过厚,则由于记录层的热容量变大,故记录信息的记录变得困难,同时重放信号输出也下降。
利用与支撑基体7为相同程度厚度的树脂板或玻璃板将透光性基体2形成为能透过激光L。再有,为了实现因高NA化导致的高记录密度,最好使透光性基体2实现薄型化。此外,最好将透光性基体2的厚度规定为大于等于30μm小于等于300μm。此时,如果透光性基体2过薄,则因附着于其表面上的尘埃导致的光学的影响变大。相反,如果透光性基体2过厚,则难以实现因高NA化导致的高记录密度。此外,为了使透光性基体2实现薄型化,例如可利用各种粘接剂或粘合剂将由透光性树脂构成的光透过性薄片粘贴在第1电介质层3上而作成透光性基体2,或可通过以薄膜状涂敷树脂在第1电介质层3上直接形成透光性树脂层(透光性基体2)来作成透光性基体2。
在该光记录介质1中,在记录信息的记录时所照射的激光L透过透光性基体2、第1电介质层3、记录层4和第2电介质层5被散热层6反射了后,再次透过第2电介质层5到达记录层4。此时,由于单位电介质层3c和第2电介质层5分别吸收激光L的一部分而发热,故与不设置单位电介质层3c和第2电介质层5的情况相比,可抑制记录层4的发热量。在该情况下,由于在透光性基体2与记录层4之间存在单位电介质层3c(第1电介质层3),而且在散热性良好的散热层6与记录层4之间存在第2电介质层5,故在单位电介质层3c中产生的热传递给透光性基体2而迅速地被散热,在第2电介质层5中产生的热传递给散热层6而迅速地被散热。因此,单位电介质层3c和第2电介质层5的发热几乎不对记录层4产生影响。因而,按照该光记录介质1,可降低抖动,进而可提高重放耐久性。此外,在该光记录介质1中,由于在第2电介质层5中产生的热传递给散热层6而迅速地被散热,故对记录层4照射激光L时升温到比较高的温度的区域就限于光束点及其附近。因而,按照该光记录介质1,可避免交叉擦除的发生。
其次,说明图4中示出的光记录介质1A。关于该光记录介质1A,在支撑基体7上按顺序形成了第1电介质层3、记录层4、第2电介质层5、散热层6和保护层2A,通过从支撑基体7一侧照射激光L来进行记录信息的记录重放。在该情况下,与上述的光记录介质1同样地形成支撑基体7即可,但为了能透过激光L,必须用透光性材料来形成。此外,保护层2A是为了提高耐擦伤性或耐蚀性而设置的。该保护层最好由各种有机类的物质来构成,但用由电子线、紫外线等放射线使放射线硬化型化合物或其组成物硬化的物质来构成特别理想。保护层2A的厚度通常大于等于0.1μm小于等于100μm,利用旋转涂敷、凹印涂敷、喷射涂敷、浸渍等通常的方法来形成即可。再有,关于其它的各层,对于与对应的光记录介质1的构成要素为同一的部分附以同一符号,省略重复的说明。
在该光记录介质1A中,在记录信息的记录时所照射的激光L透过支撑基体7、第1电介质层3、记录层4和第2电介质层5被散热层6反射了后,再次透过第2电介质层5到达记录层4。此时,由于单位电介质层3c和第2电介质层5分别吸收激光L的一部分而发热,故与上述的光记录介质1同样,与不设置单位电介质层3c(第1电介质层3)和第2电介质层5的情况相比,可抑制记录层4的发热量。在该情况下,由于在支撑基体7与记录层4之间存在第1电介质层3,而且在散热性良好的散热层6与记录层4之间存在第2电介质层5,故在单位电介质层3c中产生的热传递给支撑基体7而迅速地被散热,在第2电介质层5中产生的热传递给散热层6而迅速地被散热到保护层2A中。因此,单位电介质层3c和第2电介质层5的发热几乎不对记录层4产生影响。因而,按照该光记录介质1A,可降低抖动,进而可提高重放耐久性。此外,在该光记录介质1A中,由于在第2电介质层5中产生的热传递给散热层6而迅速地被散热,故对记录层4照射激光L时升温到比较高的温度的区域就限于光束点及其附近。因而,即使是该光记录介质1A,也可避免交叉擦除的发生。
再有,在上述的实施形态中,在记录层4的一个面上形成了第2电介质层5(第2吸收层A2)、同时在另一个面上形成了单位电介质层3c(第1吸收层A1)的例子,但如图5中所示,也可只在记录层4的一个面上形成作为本发明的第2吸收层的单位电介质层3c(第1吸收层A1)。即使是这样的层结构(不存在第2电介质层5的结构),也由本发明者确认了能提高重放耐久性而且能降低交叉擦除的发生率。但是,在只在记录层4的入射方向跟前形成了第1电介质层3的光记录介质中,与象与本发明有关的光记录介质那样从激光L的入射方向起按顺序形成了记录层4、第2电介质层5和散热层6的光记录介质1、1A相比,不能较大地提高重放耐久性,而且交叉擦除的发生率也稍微大一些。因而,最好在记录层4的入射方向的内部一侧形成本发明中的第1吸收层。
(实施例)
其次,一边参照附图,一边利用实施例更详细地说明与本发明有关的光记录介质。
(第1实施例)
如以下那样来制作图6中示出的实施例1、2和比较例1的光记录介质,评价了关于这些实施例和比较例的交叉擦除的发生和重放耐久性。再有,假定各光记录介质具有与图3中示出的光记录介质1为同一的结构。
<制作方法>
使用了在射出成型时形成了沟的直径120mm、厚度1.2mm的盘状聚碳酸酯作为支撑基体7。在该情况下,将沟深度在光路中定为λ/6(波长λ=405nm)。此外,将岸沟记录方式中的记录光道间距定为0.3μm。在Ar气氛中利用溅射法以厚度100nm形成了散热层6。在该情况下,使用了AgPdCu(Ag∶Pd∶Cu=98∶1∶1)作为靶。
利用溅射法以厚度12nm形成了第2电介质层5。在图6中示出该第2电介质层5的组成和消光系数k。k为0.1的第2电介质层5(实施例1、2)起到第2吸收层A2(本发明中的第1吸收层)的功能。再有,图6中示出的复折射率为:
CeO2:2.7+0.1i
ZnO:2.3+0.1i
Al2O3:1.76+0i
此外,各吸收层的复折射率如上所述,是使用岛津制作所制的分光光度计(MPS-2000)用45°绝对镜面反射率测定附属装置(RTA-2000特形)来测定的。
使用合金靶并在Ar气氛中利用溅射法以厚度12nm形成了记录层4。记录层的组成(原子比)在上述的(1)式中规定为:
x=0.796
y=0.07
M=In、Ge
In∶Ge=1∶6
使用ZnS(80mol%)-SiO2(20mol%)靶在Ar气氛中利用溅射法以厚度50nm形成了第1电介质层3。在第1电介质层3的表面上对紫外线硬化型树脂进行旋转涂敷并硬化形成了透光性基体2。
<评价>
利用整体擦除装置对上述实施例1、2和比较例1的光记录介质中的记录层4进行了初始化(结晶化)后放置在光记录介质评价装置上,在下述的条件下:
激光波长λ:405nm
数值孔径NA:0.85
记录线速度V:6.5m/s
记录信号:(1-7)RLL(最短标记长度0.173μm)
按下述程序测定了交叉擦除。在上述条件下,将λ/NA规定为476nm。
首先,在测定对象光道上重写10次8T信号,将其载体输出定为C1。其次,在与上述测定对象光道邻接的两侧的光道上分别重写100次7T信号。其次,对于最初在测定对象光道上记录了的8T信号再次测定输出,将其定为C2。该C2-C1为交叉擦除。再有,将在测定对象光道上重写时的记录功率和擦除功率定为实施例1、2和比较例1中的最佳值(抖动最小的值)。另一方面,将在与上述测定对象光道邻接的两侧的光道上重写时的记录功率和擦除功率定为提高实施例1、2和比较例1中的最佳值30%的值。在图6中示出该测定条件下的交叉擦除(XE+30)。在上述测定条件下,与将记录功率和擦除功率定为最佳值时相比,交叉擦除变大。再有,在图6中示出将沟(G)定为测定对象光道时的交叉擦除和将岸(L)定为测定对象光道时的交叉擦除。
其次,对于实施例1、2和比较例1,评价了重放耐久性。在该重放耐久性的评价时,在与交叉擦除测定为同样的条件下在测定对象光道(沟)上用最佳记录功率记录了混合信号后,用0.5mW的功率进行了反复重放,研究了抖动不恶化的最大重放次数。在图6中示出其结果。
如该图中所示,在将第2电介质层5(第2吸收层A2)的消光系数k定为0.1的实施例1、2中,交叉擦除小,此外,重放耐久性为良好。与此不同,在消光系数k为0的比较例1中,交叉擦除大,此外,重放耐久性也较大地下降。因而,通过将本发明中的第1吸收层(在该情况下,是第2电介质层5)的消光系数k规定为大于等于0.06(在该情况下,是0.1),可制造抖动小且重放耐久性良好的光记录介质。
(第2实施例)
与上述第1实施例同样地制作图7中示出的实施例3~9和比较例2~4,与第1实施例同样地评价了关于这些例的交叉擦除的发生和重放耐久性。再有,在该第2实施例中,使用了沟记录用基板(光道间距0.32μm、沟深度22nm)作为支撑基体7。此外,利用Ar和N2的反应性溅射形成实施例8、9和比较例2、4中的第2电介质层5的AIN,此时,通过使Ar和N2的比率变化制作了消光系数k不同的光记录介质。此时,一般来说,在交叉擦除超过-1.0dB时,对该光记录介质的记录特性产生影响。
如图7中所示,在将第2电介质层5(第2吸收层A2)的消光系数k定为大于等于0.06小于等于1.0的实施例3~9中,交叉擦除小,此外,重放耐久性为良好。与此不同,在消光系数k为0的比较例2和消光系数k为0.01的比较例3中,交叉擦除大,此外,重放耐久性也较大地下降。此外,在消光系数k为1.2的比较例4中,由于重放输出小,重放是困难的,故连交叉擦除的发生和关于重放耐久性的评价变得困难。因而,通过将本发明中的第1吸收层(在该情况下,是第2电介质层5)的消光系数k规定为大于等于0.06小于等于1.0,可制造抖动小且重放耐久性良好的光记录介质。
(第3实施例)
如下述那样来制作图8中示出的实施例10、11和比较例5~7的光记录介质,评价了关于这些例的交叉擦除的发生。再有,关于各光记录介质,用与图3中示出的光记录介质1为同一的结构进行了制作。
<制作方法>
与第1实施例同样地形成了支撑基体7、散热层6、记录层4和透光性基体2。此外,利用溅射法以厚度12nm形成了第2电介质层5(第2吸收层A2)。在图8中示出该第2电介质层5的组成和消光系数k。消光系数k为0.1的第2电介质层5(实施例10、11)起到第2吸收层A2(本发明中的第1吸收层)的功能。再有,使用ZnO靶在Ar气体气氛中利用溅射法形成了由ZnO构成的第2电介质层5(实施例11)。此外,通过在含有氧气的Ar气体气氛中使用ZnO靶进行反应性溅射形成了由ZnO+O构成的第2电介质层5(比较例7)。在该情况下,ZnO+O的复折射率规定为
ZnO+O:2.2+0i
以厚度为10nm的方式形成第1电介质层3中的单位电介质层3c(第1吸收层A1)。在图8中示出该单位电介质层3c的组成和消光系数k。再有,在比较例6、7中,形成了消光系数k为0的电介质层以代替单位电介质层3c。第1电介质层3中的单位电介质层3b的厚度为25nm,由ZnS(80mol%)-SiO2(20mol%)构成。第1电介质层3中的单位电介质层3a的厚度为60nm,由Al2O3构成。
<评价>
利用整体擦除装置对上述实施例10、11和比较例5~7的光记录介质中的记录层4进行了初始化(结晶化)后放置在光记录介质评价装置上,在下述的条件下:
激光波长λ:405nm
数值孔径NA:0.85
记录线速度V:6.5m/s
记录信号:(1-7)RLL测定了抖动。再有,在测定时,控制了时钟频率,使得最短标记长度为图8中示出的值。该抖动是所谓的时钟抖动,是利用时间间隔分析器测定重放信号以求出「信号的摆动(σ)」并使用检测窗口宽度Tw根据σ/Tw(%)计算的值。在图8中示出其结果。此外,在图9中示出一部分样品的结果。此时,如果抖动小于等于12%,则误差在容许范围内,可重放记录信息。此外,为了充分地确保各种容限,该抖动最好小于等于10%。
如图8、9中所示,如果最短标记长度Ms大于等于0.160μm,则在实施例10、11和比较例5~7的全部中抖动不到10%。另一方面,在将最短标记长度Ms定为0.147μm时,在将单位电介质层3c(第1吸收层A1)的消光系数k定为0.1的实施例10、11中,抖动不到12%,而在将消光系数k定为0的比较例6、7中,抖动超过了13%。因而,通过将本发明中的第2吸收层(在该情况下,是单位电介质层3c)的消光系数k规定为大于等于0.06,可制造抖动小的光记录介质。此时,即使单位电介质层3c的消光系数k为0.1,在将第2电介质层5的消光系数k定为0时(比较例5),将最短标记长度Ms定为0.147μm时的抖动也为12.9%。因而,通过将本发明中的第1和第2吸收层的各消光系数k分别规定为大于等于0.06,可制造抖动更小的光记录介质。再有,在设置了由ZnO构成的吸收层的实施例11中,实现了本发明的效果,而在ZnO中过度地添加了氧以使消光系数k下降的比较例7中,未能实现本发明的效果。根据这一点,本发明的效果不是依赖于吸收层的构成要素而产生的,而是依赖于消光系数k。
(第4实施例)
与上述第3实施例同样地制作图10中示出的实施例12~20和比较例8~11的光记录介质,同时测定了这些例的C/N比。再有,在该第4实施例中,使用了沟记录用基板(光道间距0.32μm、沟深度22nm)作为支撑基体7。此外,将单位电介质层3c的厚度定为30nm。在该情况下,一般来说,只要C/N大于等于35dB,就可利用目前的信号处理技术进行记录信息的重放(记录标记的读取),可作为光记录介质来使用。
如图10中所示,在第2电介质层5和单位电介质层3c这两者的消光系数k大于等于0.06小于等于1.0的实施例12~20中,即使最短标记长度Ms为任何的值,C/N比都高达35dB或以上,可正常地重放记录信息。另一方面,在第2电介质层5和单位电介质层3c的某一个的消光系数k为1.2的比较例8、11中,重放输出变小,重放变得困难,其结果,连C/N比的测定都变得困难。此外,在第2电介质层5和单位电介质层3c这两者的消光系数k为0的比较例9中,在最短标记长度Ms大于等于0.147μm时,C/N比大于等于35dB,但在最短标记长度Ms为0.138μm时,C/N比为30.5dB,记录信息的正常的重放变得困难。再者,在第2电介质层5的消光系数k为0.06、单位电介质层3c的消光系数k为0.01的比较例10中,在最短标记长度Ms大于等于0.147μm时,C/N比大于等于35dB,但在最短标记长度Ms为0.138μm时,C/N比为30.8dB,与比较例9同样,记录信息的正常的重放变得困难。因而,通过将本发明中的第1和第2吸收层的各消光系数k分别规定为大于等于0.06小于等于1.0,可制造在高密度记录时的C/N比大(可进行正常的重放)的光记录介质。
(第5实施例)
与上述第4实施例同样地制作图11中示出的实施例21和比较例12的光记录介质,同时测定了这些例的C/N比。再有,利用Ar和N2的反应性溅射形成该第5实施例中的单位电介质层3c的AIN,此时,通过使Ar和N2的比率变化制作了消光系数k不同的光记录介质。
如图11中所示,在第2电介质层5和单位电介质层3c这两者的消光系数k为0.1的实施例21中,在全部的最短标记长度Ms中C/N比大于等于35dB,可正常地重放记录信息。另一方面,单位电介质层3c的消光系数k为0的比较例12中,在将最短标记长度Ms定为0.138μm时,C/N比为31.2dB,记录信息的正常的重放变得困难。即,即使在使用了同一材料的情况下,只要没有成为其消光系数k满足本发明的条件的状态,就不能得到本发明的效果。因而,通过将本发明中的第1和第2吸收层的各消光系数k分别规定为大于等于0.06小于等于1.0,可制造在高密度记录时的C/N比大(可进行正常的重放)的光记录介质。
(第6实施例)
与第1实施例同样地对于在上述的第3实施例中制作的光记录介质(实施例10和比较例6)评价了交叉擦除的发生和重放耐久性。在图12中示出其结果。
如该图中所示,在将第2电介质层5(第2吸收层A2)和单位电介质层3c(第1吸收层A1)的消光系数k分别定为0.1的实施例10中,交叉擦除小,此外,重放耐久性为良好。与此不同,在消光系数k分别为0的比较例6中,交叉擦除大,此外,重放耐久性也较大地下降。因而,通过将本发明中的第1吸收层(此时,是第2电介质层5)和单位电介质层3c(第1吸收层A1)的消光系数k分别规定为大于等于0.06,可制造抖动小且重放耐久性良好的的光记录介质。
产业上利用的可能性
如上所述,按照该光记录介质,通过以在记录用或重放用的光的波长中使其消光系数k大于等于0.06小于等于1.0的方式构成第1吸收层,即使在以高密度进行了记录时,也可充分地提高重放耐久性,同时可充分地降低交叉擦除。由此,实现了能进行高密度记录而且重放耐久性高、难以发生交叉擦除的光记录介质。
Claims (11)
1.一种光记录介质,其特征在于:
被构成为从记录用的光或重放用的光的入射侧按顺序形成有记录层、第1吸收层和散热层,同时上述第1吸收层的消光系数k在上述记录用或重放用的光的波长中满足0.06≤k≤1.0。
2.如权利要求1中所述的光记录介质,其特征在于:
在上述记录层中的上述光的入射侧表面上形成有第2吸收层,被构成为上述第2吸收层的消光系数k在上述记录用或重放用的光的波长中满足0.06≤k≤1.0。
3.如权利要求1中所述的光记录介质,其特征在于:
被构成为在上述记录用或重放用的光的波长λ与该记录用或重放用的光的照射光学***中的数值孔径NA的关系满足λ/NA≤680nm的条件下可进行记录或重放。
4.如权利要求2中所述的光记录介质,其特征在于:
被构成为在上述记录用或重放用的光的波长λ与该记录用或重放用的光的照射光学***中的数值孔径NA的关系满足λ/NA≤680nm的条件下可进行记录或重放。
5.如权利要求1中所述的光记录介质,其特征在于:
记录光道间距被形成为小于等于0.35μm。
6.如权利要求2中所述的光记录介质,其特征在于:
记录光道间距被形成为小于等于0.35μm。
7.如权利要求3中所述的光记录介质,其特征在于:
记录光道间距被形成为小于等于0.35μm。
8.如权利要求1中所述的光记录介质,其特征在于:
被构成为可将最短的标记长度规定为小于等于0.17μm来记录信息。
9.如权利要求2中所述的光记录介质,其特征在于:
被构成为可将最短的标记长度规定为小于等于0.17μm来记录信息。
10.如权利要求3中所述的光记录介质,其特征在于:
被构成为可将最短的标记长度规定为小于等于0.17μm来记录信息。
11.如权利要求5中所述的光记录介质,其特征在于:
被构成为可将最短的标记长度规定为小于等于0.17μm来记录信息。
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EP (1) | EP1577888A2 (zh) |
JP (1) | JP2003317315A (zh) |
KR (1) | KR20040105242A (zh) |
CN (1) | CN1647178A (zh) |
AU (1) | AU2003236266A1 (zh) |
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JP2005190642A (ja) * | 2003-12-03 | 2005-07-14 | Ricoh Co Ltd | 光記録媒体 |
JP2005209247A (ja) * | 2004-01-20 | 2005-08-04 | Tdk Corp | 光記録媒体 |
JP4327691B2 (ja) * | 2004-09-30 | 2009-09-09 | 株式会社東芝 | 光記録媒体 |
WO2008013168A1 (fr) * | 2006-07-27 | 2008-01-31 | Sharp Kabushiki Kaisha | Support d'enregistrement d'informations optiques, dispositif de reproduction pour support d'enregistrement d'informations optiques, et procédé de reproduction pour support d'enregistrement d'informations optiques |
US8576515B2 (en) | 2007-02-16 | 2013-11-05 | Seagate Technology Llc | Thin film structure with controlled lateral thermal spreading in the thin film |
US7869162B2 (en) * | 2007-02-16 | 2011-01-11 | Seagate Technology Llc | Thin film structure with controlled lateral thermal spreading in the thin film |
US20130100135A1 (en) * | 2010-07-01 | 2013-04-25 | Thomson Licensing | Method of estimating diffusion of light |
US9263076B1 (en) | 2012-12-21 | 2016-02-16 | Seagate Technology Llc | Heatsink for heat assisted magnetic recording media |
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FR2818422B1 (fr) * | 2000-12-19 | 2003-01-17 | Commissariat Energie Atomique | Support d'enregistrement optique a plusieurs niveaux de lecture/ecriture par faisceau laser |
JPWO2003028022A1 (ja) * | 2001-09-26 | 2005-01-13 | Tdk株式会社 | 光記録媒体 |
JP2003276342A (ja) * | 2002-03-26 | 2003-09-30 | Tdk Corp | 光記録媒体 |
JP2007157314A (ja) * | 2005-11-10 | 2007-06-21 | Canon Inc | 追記型光ディスク及び光記録方法 |
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- 2003-04-14 EP EP03746893A patent/EP1577888A2/en not_active Withdrawn
- 2003-04-14 CN CNA038086522A patent/CN1647178A/zh active Pending
- 2003-04-14 AU AU2003236266A patent/AU2003236266A1/en not_active Abandoned
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Cited By (2)
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CN102629479A (zh) * | 2011-02-03 | 2012-08-08 | 索尼公司 | 光信息记录介质 |
CN102629479B (zh) * | 2011-02-03 | 2016-11-02 | 索尼公司 | 光信息记录介质 |
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EP1577888A2 (en) | 2005-09-21 |
KR20040105242A (ko) | 2004-12-14 |
TW200405320A (en) | 2004-04-01 |
TWI260619B (en) | 2006-08-21 |
US20050221049A1 (en) | 2005-10-06 |
WO2003090218A2 (fr) | 2003-10-30 |
AU2003236266A1 (en) | 2003-11-03 |
JP2003317315A (ja) | 2003-11-07 |
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