CN1479295A - 光记录重放方法和光记录媒体 - Google Patents

光记录重放方法和光记录媒体 Download PDF

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CN1479295A
CN1479295A CNA031370438A CN03137043A CN1479295A CN 1479295 A CN1479295 A CN 1479295A CN A031370438 A CNA031370438 A CN A031370438A CN 03137043 A CN03137043 A CN 03137043A CN 1479295 A CN1479295 A CN 1479295A
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optical recording
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�Ѝ뿵��
井上弘康
三岛康儿
青岛正贵
平田秀树
宇都宫肇
���֪��
新井均
田中美知
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Abstract

一种光记录重放方法和光记录媒体，在环保型材料构成的记录层中，可以用简单的膜结构进行良好的光记录。光记录媒体10在基板12上有由按照要被记录的信息进行了强度调制的作为能量的激光束而进行状态变化的一对电介质层(14A、14B)，以及被它们夹置的记录辅助层16构成的记录层18。记录辅助层16以Sn、Ti、Bi、Ge、C等中的某一元素作为主要成分，而作为电介质层(14A、14B)中母材的电介质材料由包含ZnS、SiO2、AlN、Ta2O5等中至少一种材料来构成。

Description

光记录重放方法和光记录媒体
技术领域
本发明涉及光记录媒体和使用它的光记录重放方法。
背景技术
以往，作为用于记录数字数据的记录媒体，广泛使用以CD(CompactDisc)和DVD(Digital Versatile Disc)为代表的光记录媒体。这些光记录媒体大致分为CD-ROM(Read Only Memory)和DVD-ROM那样的不能进行数据追记和重写类型的光记录媒体(ROM型光记录媒体)、如CD-R(Recordable)和DVD-R那样的可以进行数据追记但不能进行数据重写类型的光记录媒体(追记型光记录媒体)、以及如CD-RW(Rewritable)和DVD-RW那样的可进行数据重写类型的光记录媒体(重写型光记录媒体)。
众所周知，在ROM型光记录媒体中，一般是通过制造阶段基板上形成的预置坑来记录数据，在重写型光记录媒体中，例如使用相变化材料作为记录层的材料，一般利用基于其相状态变化的光学特性变化来记录数据。
相反，在追记型光记录媒体中，作为记录层的材料，一般使用花青系色素、酞花青系色素、偶氮色素等有机色素，利用基于其化学变化(根据情况施加化学变化并伴随物理性变形)的光学特性变化来记录数据。
但是，有机色素因日光等照射而恶化，所以在使用有机色素作为记录层的材料时，难以提高长期保存的可靠性。在追记型光记录媒体中，为了提高长期保存的可靠性，最好由有机色素以外的材料来构成记录层。作为由有机色素以外的材料来构成记录层的例子，如(日本)特开昭62-204442号公报记载的那样，已知叠层两层反应层并将其用作记录层的技术。
另一方面，近年来，提出了使数据的记录密度提高，并且可实现非常高的数据传输速率的下一代光记录媒体。在这种下一代光记录媒体中，为了实现大容量-高数据传输速率，必然将用于数据记录-重放的激光束的束点直径压缩得非常小。这里，为了缩小束点直径，需要使用于将激光束进行聚焦的物镜的数值孔径(NA)在0.7以上，例如增大到0.85左右，同时使激光束的波长λ在450nm以下，例如缩短到400nm左右。
但是，如果将用于聚焦激光束的物镜高NA化，则产生光记录媒体的弯曲和倾斜的容许度、即倾斜余量非常小的问题。设用于记录-重放的激光束的波长为λ，作为激光束光路的透光层(透明基体)的厚度为a，则倾斜余量T可用以下的式(1)表示。
T＝λ/d·NA3                                        (1)
从式(1)可知，物镜的NA越大，倾斜余量会越小。此外，设产生波面像差(慧形像差)的透光层(透明基体)的折射率为n，倾角为θ，则波面像差系数W可用以下的式(2)表示。
W＝{d·(n2-1)·n2·sinθ·cosθ·(NA)2}/{2λ(n2-sin2θ)3/2}  (2)
从式(1)和式(2)可知，为了增大倾斜余量，并且抑制慧形像差的产生，减小记录-重放中使用的激光束入射的透光层(透明基体)的厚度d是非常有效的。
根据这样的理由，在下一代的光记录媒体中，为了确保充分的倾斜余量，并且抑制慧形像差的产生，需要使透光层(透明基体)的厚度薄到100μm左右。因此，在下一代的光记录媒体中，难以在如现行的光记录媒体那样的透光层(透明基体)上形成记录层，正在研究在基体上形成的记录层等上根据旋转涂敷法等形成薄的树脂层来作为透光层(透明基体)的方法。因此，在下一代的光记录媒体的制作中，与从光入射侧依次进行成膜的现行的光记录媒体不同，从光入射面的相反侧依次进行成膜。
但是，将由两层反应层来构成如下一代光记录媒体那样形成在基体上的记录层的情况，与通过两层反应层来构成如CD和DVD等现行的光记录媒体那样形成在透光层(透明基体)上的记录层的情况相比，信号重放时产生的噪声电平容易增大(C/N比容易变小)的问题明显。
另一方面，因近年来对地球环境关注的提高，所以作为光记录媒体的记录层的材料，也期望选择环境负担更小的材料。而且，为了提高长期保存的可靠性，作为光记录媒体的记录层材料，期望选择对腐蚀-变质等具有充分抗性的材料。
发明内容
本发明的目的在于提供在下一代光记录媒体的记录重放系统中特别有用的新的光记录重放方法和光记录媒体。
本发明人深入研究的结果，发现使用Sn和ZnS等环保型材料，可用简单的膜结构进行良好的光记录-重放。
即，根据以下的本发明，可实现上述目的。
(1)一种光记录重放方法，其特征在于，在基板上，对于至少使记录辅助层和电介质层相邻存在所形成的记录层，从外部照射按照要被记录的信息进行了强度调制的激光束，通过使所述电介质层的至少一部分产生状态变化来改变光学特性而记录信息，并且读取伴随该光学特性变化的反射率的变化，重放所述信息。
(2)如(1)的光记录重放方法，其特征在于，所述电介质层的状态变化是结晶生长。
(3)一种光记录重放方法，包括基板、以及至少包含在基板上相邻设置的记录辅助层和电介质层的记录层，其特征在于，所述电介质层包含引起状态变化的母材，所述记录辅助层包含状态变化促进材料，通过从外部向其照射按照要被记录的信息进行了强度调制的激光束，使该母材产生状态变化，由激光束使反射率产生可读取的变化，可进行所述信息的重放。
(4)一种光记录媒体，包括：基板；以及至少包含在所述基板上相邻设置的记录辅助层和电介质层的记录层；其特征在于，所述记录辅助层包含从Sn、Ti、Si、Bi、Ge、C、V、W、Zr、Zn、Mg、Mn、Ag中选择的至少一种元素，且将其作为主要成分。
(5)如(3)或(4)的光记录媒体，其特征在于，所述电介质层将从Al2O3、AlN、ZnO、ZnS、GeN、GeCrN、CeO2、SiO、SiO2、Si3N4、Ta2O5及SiC构成的组中选择的至少一种电介质材料作为主要成分。
(6)一种光记录媒体，包括：基板；以及记录层，至少相邻设置在所述基板上，包含记录辅助材料和电介质材料；其特征在于，所述记录辅助层包含将从Sn、Ti、Si、Bi、Ge、C、V、W、Zr、Zn、Mg、Ag中选择的至少一种元素作为主要成分。
(7)如(6)的光记录媒体，其特征在于，所述电介质层将包含从Al2O3、AlN、ZnO、ZnS、GeN、GeCrN、CeO2、SiO、SiO2、Ta2O5及SiC构成的组中选择的至少一种电介质材料作为主要成分。
附图说明
图1表示本发明实施方式第1例的光记录媒体的模式图。
图2表示本发明实施方式第2例的光记录媒体的模式图。
图3表示本发明实施方式第3例的光记录媒体的模式图。
图4A表示例1的光记录媒体中的未记录部分的X射线衍射结果的曲线图。
图4B表示记录部分的X射线衍射结果的曲线图。
图5A表示例4的光记录媒体中的未记录部分的X射线衍射结果的曲线图。
图5B表示例4的光存储媒体中的记录部分的X射线衍射结果的曲线图。
具体实施方式
以下参照附图来详细说明本发明的实施例。
实施例的光记录重放方法中使用的光记录媒体10为追记型，如图1所示，由基板12、在基板12上设置的记录层18、以及在记录层18上设置的透光层20构成，其中，记录层18具有记录辅助层14和相邻于其两侧的电介质层16A、16B。此外，在光存储媒体10的中央部分设置孔。对于具有这样结构的光记录媒体10，通过从透光层20侧照射激光束LB来进行数据的记录/重放。再有，也可以仅在记录辅助层14一方上设置电介质层16A或16B。
基板12具有作为确保光记录媒体10所需要的机械强度的基体的作用，在其表面上设置沟22和/或岛24。这些沟22和岛24具有进行数据的记录和重放情况下的激光束的导向轨迹作用。
基板12的厚度被设定为约1.1mm，作为其材料，可使用各种材料，例如，可使用玻璃、陶瓷、或树脂。其中，从成形容易性的观点来看，树脂最好。作为这样的树脂，可列举出聚碳酸酯树脂、丙烯树脂、环氧树脂、聚苯乙烯树脂、聚乙烯树脂、聚丙烯树脂、硅酮树脂、氟系树脂、ABD树脂、聚氨酯树脂等。其中，从加工性等方面来看，最好是聚碳酸酯树脂。
所述电介质层16A、16B作为母材，由包含状态变化材料构成，这种材料通过激光束照射等的能量，使光反射率等光学特性变化。
作为所述母材的电介质材料，只要是产生状态变化的材料即可，并无特别限定，例如可将氧化物、硫化物、氮化物或它们的组合用作主要成分。更具体地说，最好是将从Al2O3、AlN、ZnO、ZnS、GeN、GeCrN、CeO2、SiO、SiO2、Si3N4、Ta2O5、SiC构成的组中选择的至少一种电介质材料作为主要成分，以ZnS-SiO2构成的电介质作为主要成分更好。
再有，‘以电介质材料作为主要成分’是指所述电介质材料的含有率最大。而‘ZnS-SiO2’指ZnS和SiO2的混合物。
此外，电介质材料的层厚度没有特别限定，但最好为5～200nm。如果其层厚度低于5nm，则即使是母材的充分的状态变化，除了不能获得作为层整体的光反射率等光学特性的充分变化以外，作为信号的C/N也不充分。另一方面，如果层厚度超过200nm，则成膜时间变长，有生产率下降的危险，而且，因电介质层16A、16B具有的应力，有发生破裂的危险。此外，也有可能剩下不受所述记录辅助层14影响的部分。
所述记录辅助层14是促进母材反应的层，如上所述，至少在其一方中相邻于电介质层16A、16B，但如果照射具有规定以上功率的激光束，则通过其热量，构成记录辅助层14的元素对电介质层16A、16B产生影响，通过构成电介质层16A、16B的层局部或整体地产生状态变化(例如，非晶体向晶体转移)而成为记录标记。此时，在记录层18中形成了记录标记的部分和其以外的部分对于重放光的光学特性极大不同，可以利用它进行数据的记录-重放。
此外，还可以伴有记录辅助层中含有的记录辅助材料自身的状态变化(例如结晶生长)。这种情况下，通过该变化，可以期待C/N的提高。
所述记录辅助层14将从Sn、Ti、Si、Bi、Ge、C、V、W、Zr、Zn、Mg、Mn、Ag中选择的至少一个元素作为主要成分。
这里所说的主要成分最好占有构成记录辅助层14的元素的50％以上，更好是80原子％。
如果在50原子％以下，则使电介质材料变化的效果不充分，C/N会减小。而且，记录灵敏度变差，需要用大的激光功率进行记录，所以容易引起膜自身的损坏等，保存可靠性恶化。
而且，为了将用于良好地进行电介质层的状态变化所需的激光束的功率抑制到某一程度以下，最好是在80原子％以上。
所述记录辅助层14的层厚度有充分的层厚度，以便通过被照射激光束的束点而使电介质层16A、16B变化，并且如果层积在必要层厚度以上，则最好为1～50nm，以便需要更多的热量，而2～30nm更好。
透光层20是构成激光束的入射面并且成为激光束的光路的层，作为其厚度，最好设定为10～300μm，设定为50～150μm更好。作为透光层20的材料，没有特别限定，但最好使用丙烯系或环氧系等紫外线固化型树脂。此外，也可以使用透光性树脂构成的透光性片和各种粘接剂或粘结剂来形成透光层20，取代使紫外线型固化树脂的膜。
下面，说明上述光记录媒体10的制造方法的一例。
首先，在形成了沟22和岛24的基板12上形成第2(从光入射侧起为第2号)电介质层16B。在形成第2电介质层16B时，例如可以采用包含第2电介质层16B的构成元素的化学种子的汽相生长法。作为这样的汽相生长法，例如可列举出真空镀敷法、溅射法等。
接着，在第2电介质层16B上形成记录辅助层14。该记录辅助层14也与第2电介质层16B同样，可以采用包含记录辅助层14的构成元素的化学种子的汽相生成法来形成。而且，在记录辅助层14上形成第1(从光入射侧起为第1号)电介质层16A。该第1电介质层16A也可采用包含第1电介质层16A的构成元素的化学种子的汽相生长法来形成。
最后，在第1电介质层16A上形成透光层20。透光层20例如通过旋转涂敷法等来覆盖粘度调整后的丙烯系或环氧系的紫外线固化型树脂，可以通过照射紫外线进行固化等方法来形成。由此，完成光记录媒体的制造。
再有，上述光记录媒体的制造方法不限定于上述制造方法，也可以使用在公知的光记录媒体的制造中采用的制造技术。
下面，说明使用上述光记录媒体10的光记录重放方法。
对于光记录媒体10，从透光层20侧入射具有规定输出的激光束LB并照射到记录辅助层14。此时，最好是用于聚焦激光束LB的物镜26的数值孔径(NA)在0.7以上，在0.85左右更好，激光束LB的波长λ最好在450nm以下，在405nm左右更好。这样，可以使λ/NA＜640nm。
通过照射这样的激光束LB，构成记录辅助层14的元素被激光束LB加热，对相邻这些元素的电介质层16A、16B产生影响，局部或整体地产生状态变化(例如从非结晶向结晶的转移)，形成记录标记。形成了记录标记的部分的光学特性与其以外的部分(未记录区域)的光学特性十分不同。因此，通过照射用于读取的激光束时的记录标记部分和其以外部分的反射率不同，可以进行数据的重放。即，利用光学特性的调制，可以进行数据的记录-重放。
本发明不限定于以上的实施方式，可在记述在权利要求范围中的发明范围内进行各种变更，不用说，这些变更也被包含在本发明的范围内。
例如，在上述实施方式的光记录媒体10中，记录辅助层14被夹置在第1和第2电介质层16A、16B间，但如图2所示的实施方式的第2例的光记录媒体30那样，也可以省略电介质层16A或16B的一方来构成记录层32。
此外，在上述实施方式的光记录媒体10、30中，记录辅助层14由单层构成，但本发明的光记录媒体不限定于此，只要是具有相同的效果，也可以由两层以上的层来构成。
而且，在上述实施方式中使用的光记录媒体10、30、40中，在基板12上未配有反射层，但也可以如图4所示的光记录媒体50那样，设置反射层52，以便充分增大形成了记录标记的区域中的反射光电平和未记录区域中的反射光电平。
反射层52具有反射从透光层20侧入射的激光束，并再次从透光层20射出的作用，作为其厚度，最好设定为5～300nm，设定为10～200nm更好。反射层52的材料只要是可反射激光束就没有特别限制，例如，可以使用Mg、Al、Ti、Cr、Fe、Co、Ni、Zn、Ge、Ag、Pt、Au等。在它们当中，从具有高反射率来看，最好使用Al、Au、Ag、Cu或它们的合金(Ag和Cu的合金等)等金属材料。通过设置反射层52，在光记录后，通过多重干涉效应，可容易获得大的重放信号(C/N比)。
【例和比较例】
以下，使用例子更具体地说明本发明，但本发明不限于这些例子。
[光记录媒体的准备]
(例1～3)
根据以下所示的步骤，制作光记录媒体。
首先，将厚度1.1mm、直径120mm的聚碳酸酯基板放置在溅射装置中，在该聚碳酸酯基板的光反射层(仅例2)上，按照溅射法依次形成ZnS和SiO2的混合物构成的第2电介质层、Sn构成的状态变化促进层、ZnS和SiO2的混合物构成的第1电介质层(仅例1、2)。
接着，在第1电介质层上，通过旋转涂敷法来涂敷丙烯系紫外线固化型树脂，照射紫外线并形成透光层(层厚度：100μm)。
再有，在第1电介质层和第2电介质层中ZnS和SiO2的摩尔比为ZnS∶SiO2＝80∶20。
(例4～14)
电介质层、基板、透光层与实施例1相同，将记录辅助层作为Sn以外的各种金属或半金属制作光记录媒体。
(比较例1～3)
对于例4～14，仅改变记录辅助层的材料，其他为同一条件制作光记录媒体。
(例15～18)
状态变化促进材料为Sn，改变电介质层材料来制作光记录媒体。
[记录-重放]
分别制作上述光记录媒体，并将其分别放置在光盘评价装置(商品名：DDU1000，パ ルステツク社制)。然后，对于各光记录媒体，在用于记录的激光束的波长为蓝色波长区域(405nm)，物镜的NA(数值孔径)为0.85时，将该激光束用记录头内的聚焦透镜从透光层侧聚焦在光记录媒体上，进行光记录。
此时的记录信号条件设为：调制方式：(1，7)RLL；信道位长度：0.12μm；记录线速度：5.3m/s；信道时钟：66MHz；记录信号：8T。
接着，对于各例和各比较例中制作的状态变化促进材料的材料和层厚度及电介质层的材料和层厚度不同的光记录媒体，使用上述光盘评价装置来重放记录的信息，测定此时的重放信号的C/N比的值。这里，在重放装置中，用于重放的激光束的波长为405nm，物镜的NA(数值孔径)为0.85，激光束输出为0.3mW。
表1～表4表示其结果。
【表1】
  例1   例2   例3
    膜结构第1介质层辅助记录层第2介质层反射层 80∶20(96nm)Sn(3.5nm)80∶20(78nm) 80∶20(30nm)Sn(3nm)80∶20(30nm)APC(100nm) Sn(6nm)80∶20(60nm)
    8TC/N(dB)   54   53.6   53.2
    ‘80∶20’表示ZnS+SiO2中的ZnS∶SiO2的摩尔比这里，省略了ZnS∶SiO2的记述。()内的数值表示记录层整体的厚度。
【表2】
  例4   例5   例6   例7   例8   例9   例10
    膜结构第1介质层记录辅助层第2介质层反射层 80∶20(20nm)Ti(10nm)80∶20(20nm) 80∶20(20nm)Bi(6nm)80∶20(20nm) 80∶20(60nm)Ge(12nm)80∶20(60nm) 80∶20(20nm)Si(10nm)80∶20(60nm) 80∶20(60nm)C(12nm)80∶20(60nm) 80∶20(20nm)V(10nm)80∶20(20nm) 80∶20(20nm)W(10nm)80∶20(20nm)
    8TC/N(dB)   61.3   47.1   48.1   40.1   38.2   45.6   31
    ‘80∶20’表示ZnS+SiO2中的ZnS∶SiO2的摩尔比。这里，省略了ZnS∶SiO2的记述。()内的数值表示记录层整体的厚度。
【表3】
  例11   例12   例13   例14   比较例1   比较例2   比较例3
    膜结构第1介质层记录辅助层第2介质层反射层 80∶20(20nm)Zr(10nm)80∶20(20nm) 80∶20(20nm)Zn(10nm)80∶20(20nm) 80∶20(20nm)Mg(10nm)80∶20(20nm) 80∶20(20nm)Mn(10nm)80∶20(20nm) 80∶20(20nm)Al(10nm)80∶20(20nm) 80∶20(60nm)Cu(10nm)80∶20(60nm) 80∶20(60nm)Au(12nm)80∶20(60nm)
    8TC/N(dB)   51.7   37.8   48.3   55.1   1.6   2.4   -
    ‘80∶20’表示ZnS+SiO2中的ZnS∶SiO2的摩尔比。这里，省略了ZnS∶SiO2的记述。()内的数值表示记录层整体的厚度。
【表4】
 例15   例16  例17   例18
  膜结构第1介质层记录辅助层第2介质层反射层 Ta2O5(60nm)Sn(6nm)Ta2O5(60nm) AlN(60nm)Sn(6nm)AlN(60nm) ZnS(60nm)Sn(6nm)ZnS(60nm) SiO2(60nm)Sn(12nm)SiO2(60nm)
  8TC/N(dB)  48.8   40.1  49.2   49.2
  ()内的数值表示记录层整体的厚度。
从这些表所示的结果可知，在例1～18中，可获得C/N比为35dB以上的良好结构，使用这些光记录媒体，可获得可充分进行光记录-重放的结果。
在用透过型电子显微镜观察例1的光存储媒体的记录-未记录部分时，在记录部分中可看到ZnS和Sn的结晶化。此外，即使在X射线衍射中，也可以确认在记录后ZnS和Sn的结晶化。
在该X射线衍射中，X射线使用Cu-Kα，阴极管电压＝50kV，阴极管电流＝300mA。衍射峰值的鉴定是与JCPD卡进行核对。例如，β-Sn是04-0673号的材料，通过于其核对，可知β-Sn的衍射位置。
通过X射线衍射来对例1(ZnS-SiO2(80∶20)/Sn/ZnS-SiO2(80∶20)叠层型)的结构中记录部分和未记录部分进行解析(参照图4A、图4B)。
在未记录时(图4A)，可看到β-Sn的衍射峰值和ZnS的宽大的衍射峰值，由此可知Sn为晶体，ZnS是非晶体。记录后(图4B)，可明显看到ZnS的尖锐的衍射峰值，可知产生了结晶。此外，对于Sn，也观察β-Sn的衍射峰值，未观察到SnO2、SnS的衍射峰值。
通过X射线衍射来对例4(80∶20/Ti/80∶20叠层型)结构中记录部分和未记录部分进行解析(参照图5A、5B)。
在未记录时(图5A)，可稍稍看到ZnS的宽大的衍射峰值，而对于Ti，则看不到衍射峰值。由此可知，ZnS为非结晶。记录后(图5B)可看到多个ZnS的衍射峰值，可知引起结晶化。此外，出现了Zn的衍射峰值，通过记录可知，在进行ZnS和Zn的结晶化。
如以上说明，根据本发明的光记录重放方法和光记录媒体，以减小对环境产生的负荷并且简单的结构，可以通过至今还没有的新的方法来进行数据的记录-重放。

Claims (5)

1.一种光记录重放方法，其特征在于，在基板上，对于至少使记录辅助层和电介质层相邻存在所形成的记录层，从外部照射按照要被记录的信息进行了强度调制的激光束，通过使所述电介质层的至少一部分产生状态变化来改变光学特性而记录信息，并且读取伴随该光学特性变化的反射率的变化，重放所述信息。
2.如权利要求1的光记录重放方法，其特征在于，所述电介质层的状态变化是结晶生长。
3.一种光记录媒体，包括基板、以及至少包含在所述基板上相邻设置的记录辅助层和电介质层的记录层，其特征在于，所述电介质层包含引起状态变化的母材，所述记录辅助层包含状态变化促进材料，通过从外部向其照射按照要被记录的信息进行了强度调制的激光束，使该母材产生状态变化，由激光束使反射率产生可读取的变化，可进行所述信息的重放。
4.一种光记录媒体，包括：基板；以及至少包含在所述基板上相邻设置的记录辅助层和电介质层的记录层；其特征在于，所述记录辅助层包含从Sn、Ti、Si、Bi、Ge、C、V、W、Zr、Zn、Mg、Mn、Ag中选择的至少一种元素，且将其作为主要成分。
5.如权利要求4的光记录媒体，其特征在于，所述电介质层将从Al2O3、AlN、ZnO、ZnS、GeN、GeCrN、CeO2、SiO、SiO2、Si3N4、Ta2O5及SiC构成的组中选择的至少一种电介质材料作为主要成分。
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