CN1014009B - 光学记录介质和其制造方法 - Google Patents
光学记录介质和其制造方法Info
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Abstract
本发明所揭示的是包括基体、在基体上形成的记录层和在记录层上形成的保护层的光学记录介质及其制造方法,其中记录层由一束能量照射,由此造成记录层上受照射部分的相变,以此来记录信息其中所述记录层是包含Te和N的薄膜,如果必要所述记录层还可进一步包含Pd。
Description
本发明涉及光学记录介质和其制造方法,更具体地说,涉及设计成在安装在基体上的记录层上投射一束能量诸如光线或热量而由此改变在被照射部分上的光学性能以记录信息的光学记录介质及其制造方法。
光学记录介质可被分成两类:一类被设计成在记录层的部分形成物理变形部分(凹坑),包括孔和凹面,另一类被设计成在记录层部分产生相变并形成光学性能(折射率、反射率、透射率和其他性能)改变的部分。在目前,主要采用在记录层部分形成物理变形部分诸如孔(凹坑形成方法)的光学记录介质。
然而,凹坑形成型光学记录介质存在下列问题:(1)当在记录层部分形成凹坑时,需要相当大的光能用以记录,(2)记录凹坑的形状很难控制,(3)高密度下的记录困难,以及(4)不能将两种光学记录介质相互间紧密地粘附和叠合。相反,通过记录层部分的相变来改变光学性能的光学记录介质(相变型)可以解决上述凹坑形成型光学记录介质的问题。
作为相变型光学记录介质,例如具有由Te、Ge和Sb构成的合金化记录层(日本专利公报第62-196181号)和具有由Te、Sn、Zn和S构成的记录层(日本专利公报第62-167632)的光学记录介质是众所周知的。然而,在这种具有由合金构成的记录层的光学记录介质中,当在基体上形成记录层时,较难控制合金的组成,这造成了低的再现性,并且不可能以高的生产率生产出具有所希恒定的运转性能的光学记录介质。
作为相变型光学记录介质,具有包含TeOx的记录层的记录介质(日本专利公报第50-46317号)也是已知的,该光学记录介质存在下列问题:(1)非晶态时的稳定性低,即由于记录层的结晶温度低而使其服役寿命短,(2)当在氧气氛中实现反应性溅射时,由于氧促进了燃烧,因而不能保证形成所述记录层过程中的安全性。
本发明的发明者在具有包含Te作为其主要成分的相变型记录层的光学记录介质上作了很大努力,从而发现,在基体和保护层之间具有除Te之外还含有N和如果必要还可包含Pd的记录层的光学记录介质具有改进的记录层非晶态稳定性(保持非晶态稳定的性能)和提高的耐氧化性,并且光学记录介质的寿命可以延长。发明者也已发现,通过将记录层的厚度设置在一定的范围内,可以减少信息的读出误差。
本发明是基于这样的新知识完成的,因此本发明的一个目的是为了以相变方法提供光学记录介质,所述介质能够增加记录层的非晶态稳定性,并提高耐氧化性,延长光学记录介质的寿命,并且减少读信息时的误差。
为了达到上述目的,本发明的第一种光学记录介质包括基体、在基体上形成的记录层和在记录层上形成的保护层,其中记录层是由一束能量照射,由此使记录层上受照射的部分发生相变,并形成了光学性能改变的部分,从而记录信息。上述记录层是一层含有Te和N的薄膜。
本发明的第二种光学记录介质包括基体、在基体上形成的记录层和在记录层上形成的保护层,其中记录层由一束能量照射,由此造成记录层上受照射部分的相变,并且形成光学性能改变的部分,从而记录信息,上述记录层是包含Te、Pd和N的薄膜。
本发明的第一种方法是制造一种包括基体、在基体上形成一层包含Te和N的记录层和在记录层上形成的一层保护层的光学记录介质,其中记录层由一束能量照射,由此造成记录层上受照射部分的相变,并形成光学性能变化的部分,从而记录下信息,
其中当在基体上形成记录层时,反应性溅射是在Ar和N2气的气氛中完成的,并且N2对Ar和N2总流动的流量比〔N2/(Ar+N2)〕系设置在5至50%的范围内。
本发明的第二种方法是制造一种包括基体、在基体上形成一层包含Te、Pd和N的记录层和在记录层的上面形成一层保护层的光学记录介质,其中记录层由一束能量照射,由此造成记录层上受照射部分的相变,并形成光学性能改变的部分,从而记录信息,其中当在基体上形成记录层时,反应性溅射是通过采用包括Te和Pd的靶子和在Ar和N2气的气氛中完成的,并且N2对Ar和N2总流动的流量比〔N2/(Ar+N2)〕在1至80%的范围内。
根据本发明的上述光学记录介质和其制造方法,通过将N和Pd(如果必要)结合入主要由Te构成的记录层,并通过将记录层安置在基体层和保护层之间,可以改变记录层的非晶态稳定性和耐氧化性能,并可延长光学记录介质的使用寿命。另外,通过将记录层的厚度调节在一特定值,可以减少信息的读出误差。
图1是本发明一个例子中的光学记录介质的剖视图;
图2和图3是本发明的例子中光学记录介质的记录层厚度与反射率的关系图。
10-光学记录介质
11-基体
12-记录层
13-保护层
下面将详细描述本发明的光学记录介质及其制造方法。
如图1所示,本发明的光学记录介质10是由基体11、在基体表面上形成的记录层12和在记录层12表面上形成的保护层13构成的。
作为基体11,除了无机材料诸如玻璃和铝外,还可采用有机材料,包括聚甲基丙烯酸甲酯、聚碳酸酯、聚碳酸酯和聚苯乙烯的聚合物合金、在美国专利第4614778号的说明书中揭示的非晶态聚烯烃、聚4-甲基-1-戊烯、环氧树脂、聚醚砜、聚砜、聚醚酰亚胺、乙烯和四环十二碳烯的共聚物。该基体11的厚度应足够能使整个记录介质10的刚度适中,该厚度较佳为0.5至2.5mm,更好为1至1.5mm。
在本发明的第一种光学记录介质中,所述记录层12是包含Te和N的薄膜,并且它可包含除Te之外的低熔点元素或其他元素。以记录层中的总原子数计,N在第一种记录层中的含量较佳在0.1至60原子%范围内,更佳在0.3至50原子%的范围内,最佳在0.5至30原子%的范围内。这些值是Surface Science Instruments公司制造的ESCA(X线光电子谱)Model SSX-100测量,测量条件如下:
基底压力:5×10-10乇
X线斑点尺寸:0.6mmφ
附加积分:6倍
激光源:AlK-α-线(1487eV)
通过将这样含量范围内的N结合入记录层,可提高记录层的非晶态稳定性和耐氧化性。
除了Te之外的低熔点元素或其他元素包括Ti、Mn、Ni、Zr、Nb、Ta、Al、Pt、Sm、Bi、In、Se、Pb、Co、Si、Sn、Zn、Ge、Sb等。以记录层中的总原子数计,这些元素的含量可为0至60原子%,更佳为0至40原子%。
在本发明的第二种光学记录介质中,所述记录层12是包含作为其主要成分的Te、Pb和N的薄膜,它可包含除了Te和Pd之外的低熔点元素或其他元素。可包含在记录层12中的除了Te之外的元素包括Ti、Mn、Ni、Zr、Nb、Ta、Al、Pt、Sm、Bi、In、Se、Pb、Co、Si、Pd、Sn、Zn、Ge、Sb等。
Pd在第二种记录层12中的含量(以记录层的总原子数为基准)在1至80原子%范围内,较佳在2至60原子%范围内,更好在3至40原子%范围内。通过将如此含量范围内的Pd结合入记录层,可提高记录层的记录敏感性和C/N比,另外,记录能量范围可以扩大,并可改善薄膜形成性能。
N在第二种记录层12中的含量(以记录层中的总原子数计)较佳在0.1至60原子%范围内,更佳在0.3至50原子%范围内,最佳在0.5至30原子%范围内。通过将如此含量范围内的N结合入记录层,可提高记录层12的非晶态稳定性和耐氧化性。
金属元素(Te、Pd和其他)在记录层12中的含量是由ICP发射分析(感应耦合型等离子体发射分析)测量的,N在记录层12中的含量是由ESCAC(线光电子谱)测量的。
本发明第一种光学记录介质中的第一种记录层12可以下列方式在基体11的表面上形成。
首先,在N2和Ar混合气体中采用Te靶完成反应
性溅射,由此在基体11上形成由包含N2的Te薄层构成的第一种记录层12。在该反应性溅射中,通过控制N2气和Ar气的流量比〔N2/(Ar+N2)〕,可控制N在第一种记录层12中的含量。N气和Ar气的流量比〔N2/(Ar+N2)〕在5至50%范围内,最佳为10至30%。通过在这种气氛中溅射形成第一种记录层12可赋予记录层12以高的非晶态稳定性和良好的耐氧化性。通过将等离子体状态的Te蒸气和氮化碲(Te nitride)蒸气沉积在一起的共沉积方法,而不是溅射方法,在基体上形成记录层12也是可能的。通过蒸气相生长方法或等离子体蒸气相生长方法,也可形成类似的记录层12。将一部分或全部Te和N原子离子化并将它们以束形在基体上汇集也是可能的。
本发明第二种光学记录介质中的记录层12例如可以下列方式在基体11的表面上形成。首先,通过采用Te和Pd合金靶或具有排列好的Pd屑的Te靶,在N气和Ar气的混合气体中完成反应性溅射,由此在基体11上形成由包含Pd和N的Te薄层构成的第二种记录层12。在该反应性溅射中,通过控制N2气和Ar气的流量比〔N2/(Ar+N2)〕,可以控制N在记录层12中的含量。N2气和Ar气的流量比〔N2/(Ar+N2)〕为1至80%范围内,最好为10至40%。在这样的气氛中通过溅射形成第二种记录层12能够赋予第二种记录层12以高的非晶态稳定性和基本上良好的耐氧化性。通过将等离子体状态的Te蒸气、Pd蒸气氮化碲蒸气沉积在一起的共沉积方法而不是溅射方法,在基体上形成第二种记录层12也是可能的。由蒸气相生长方法或等离子体蒸气相生长方法,也可形成类似的记录层12,将一部分或全部Te、N和Pd原子离子化并将它们以束形在基体上汇集也是可能的。
保护层13是在这样成形的记录层12上形成的,希望用具有低导热性(较佳为1.0w/cmdeg或更低)的材料来形成保护层13,从而在将信息记录到记录层12时,防止热量逃失并改善记录灵敏度。例如,保护层13是由有机材料诸如紫外线处理的树脂、无机材料诸如Ti、Al、Ni和Cr或其组合材料所构成的,保护层的厚度为50
至1mm,较好为100
至0.1mm。
通过反应性溅射方法,蒸气相生长方法、等离子体蒸气相生长方法、蒸气沉积方法或自旋涂覆方法或其他方法,可以与形成记录层12所述方法相同的方式在记录层12的表面上形成这样一层保护层13。
例如,为了将信息写到上述记录层12上,可将根据所记录信息而调节(上/下)的一束能量诸如激光束从基体11的一侧照射到记录层12,由此将受照射部分的记录层12的相由非晶态改变为晶态,这样,相应于照射部分,形成了光学性能得到变化的部分。在光学性能变化和没有变化的部分之间存在着读出激光束照射反射率R的差别,通过利用这种反射率R的差别,就可读出信息。
根据所述光学记录介质和其制造方法,由于N包含于主要包括Te的记录层中,并且记录层被设置在基体和保护层之间,从而提高了记录层的非晶态稳定性和耐氧化性,并可延长光学记录介质的工作寿命。当记录层进一步包含Pd时,即使增加N的含量,记录层也不可能是脆性的,因此提高了薄膜的成膜性能。另外,根据本发明,不仅读出信息时的C/N比提高了,而且扩大了记录能量范围。
〔实施例〕
参考下列例子,将对本发明进行详细的描述,但毫无疑问,本发明不应局限于这些例子。
例1
在具有如图1所示结构的光学记录介质10中,在图2中显示了读出光从基体一侧的反射率变化与在包括作为基体11的非晶态聚烯烃树脂板和作为记录层12的Te85N15层(溅射条件:〔N2/(Ar+N2)〕=20(流量比%)的光学记录介质上测得的记录厚度之间的关系。N在记录层中的含量为15原子%,由ESCA测得。所述值是通过采用波长λ为830nm的读出光和假定光学记录介质设置于空气中而计算得到的。
在图中,R表明了在记录光照射之前,光学记录介质的反射率与记录层厚度之间的关系,R′表明了照射后的这种关系。
例2
以与例1相同的条件获得反射率的改变并表示在图3中,不同之处在于溅射条件改变为〔N2/(Ar+N2)〕=40(流量%)。在这种情况下,发现如果记录层的厚度在950至1300
范围内,可减少信息的读出误差。
例3
光学记录介质是通过采用一由非晶态聚烯烃树脂制成的圆盘基体、在〔N2/(Ar+N2)〕=20(流量%)的
条件下由反应性溅射使在其上形成厚度为900
的作为记录层12的Te85N15层、并进一步通过自旋涂覆方法形成经紫外线处理的树脂而制得的。该光学记录介质的C/N比是在下列条件下测量的:圆盘旋转速率为1800rpm,评价位置为半径50mm,记录频率1MHz,效率=50%,结果可获得40dB或更高的C/N比。
对照例1
在与例3相同的条件下制得光学记录介质、仅将溅射条件改变到Ar=100流量%。
以与例3相同的方式测量光学记录介质的C/N比,从而获得C/N比为最大只有13dB。我们认为这是因为,当记录层仅仅是由Te制成时,在刚刚形成记录层以后,就已在某些部分使记录层结晶,用激光束照射的部分与非照射部分之间的光学性能差异就很小。
例4
采用由非晶态聚烯烃树脂制成的圆盘基体作为基体11,通过由其中负载有Pd屑的Te靶进行的反应性溅射(〔N2/(Ar+N2)〕=20(流量%)而在该基体上形成Te85N8Pd7层作为记录层12。N在记录层中的含量为8原子%(由ESCA测量),Pd的含量为7原子%(由ICP测量),ICP是指感应耦合等离子体光谱测定法。通过自旋涂覆方法,由经紫外线处理的树脂进一步形成保护层13,由此产生了光学记录介质。
该光学记录介质的C/N比是在下列条件下测得的:圆盘旋转速率为900rpm,评价位置为半径50mm,记录频率为1MHz,效率=50%,发现可达到50dB或更高的C/N(信噪)比。
例5
在与例4相同的条件下完成溅射,仅将〔N2/(Ar+N2)〕改变为50(流量%),证实可形成所述层。
Claims (3)
1、一种光学记录介质,它包括基体、在基体上形成的记录层以及在记录层上形成的保护层,其中记录层由一束能量照射,由此引起记录层上受照射部分的相变,从而记录信息,其中所述记录层是包含Te和N的薄膜,N在记录层中的含量为0.1至60原子%(以记录层中包含的总原子数为基准)。
2、一种制造包含基体、在基体上形成的含有Te和N的记录层和在所述记录层上形成的保护层的光学记录介质的方法,其中记录层由一束能量照射,由此引起记录层上受照射部分的相变,从而记录下信息,在该方法中,所述记录层是在Ar和N2气氛中采用Te靶由反应性溅射方法在基体上形成的,并且所述N2相对于Ar+N2总流动的流量比〔N2/(Ar+N2)〕在5至50%范围内。
3、如权利要求2所述的方法,其特征在于所述流量比〔N2/(Ar+N2)〕在10至30%范围内。
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US5194363A (en) * | 1990-04-27 | 1993-03-16 | Matsushita Electric Industrial Co., Ltd. | Optical recording medium and production process for the medium |
US5234803A (en) * | 1992-05-21 | 1993-08-10 | Eastman Kodak Company | Optical recording media |
US5328813A (en) * | 1992-06-30 | 1994-07-12 | The Dow Chemical Company | Method for the preparation of optical recording media containing overcoat |
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