CN1033893A - 制备光记录体的方法 - Google Patents
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Abstract
一种制备光记录体的方法;包括在一基片上形成
一薄的包括至少一低熔点金属,碳和氢的光记录薄
膜,并在所述的基片上,在70°至300℃温度下加热
这样形成的薄膜至少5秒时间。这样制备的光记录
体具有强化了的记录灵敏度和延长的使用寿命。
Description
本发明涉及一种制备包括基片和载持在所述的基片上的光记录薄膜的光记录体的方法,所述的光记录体通过在所述的薄膜上经由能量束如光或热的辐照使形成改变了物理构造或改变了光学性质的区段而能够记录信息,因此所述的区段的排列可相应于要被记录的信息。特别是,它涉及一种制备这样的光记录体,具有延长使用寿命和增强了(或提高了)记录灵敏度的方法。
有两种光记录体体系,根据一个体系,具有改变了物理构造如孔和凹点的区段经由能量束的辐照而在光记录薄膜上形成,因此所述的区段的排列可相应于要被记录的信息。而根据另一系统,具有改变了光学性质如改变了折射率或反射率的区段则经由能量束的辐照而在光记录薄膜上形成,所述的区段的排列即相应于要被记录的信息。
在该领域中已知记录薄膜最初由用于该两体系的光记录体的低熔点金属如碲(Te)构成(日本专利公开号58-71195和59-9234)。Te薄膜,典型的低熔点金属薄膜,能够在其中形成所希望的改变了物理构造的区段或改变了光学性质(这种区段通常将被认为其中的凹点),且为很有希望的高灵敏度的材料。本文所用的“记录灵敏度,我们是指每单位面积形成凹点所需的能量(毫微焦/微米2)。
当Te可放置在环境气氛中时,则Te被氧或潮气氧化,并且由于透射的增加而变成透明的。当这种Te被用作为光记录薄膜时,该薄膜的厚度很薄仅为几百个 (10-10米)。因此,如果该薄膜的透射由于Te的氧化而增加,则该薄膜的记录灵敏度将显著下降。更进一步讲,当薄的Te薄膜被氧化时,一方面该材料的熔点和汽化温度将提高,而另一方面,由于该薄膜变成透明的这事实,由该薄膜吸收如光的能量将降低,导致形成凹点所需的功率级的提高。结果,该薄膜的记录灵敏度显著下降。例如,当Te薄膜可放置在保持70℃温度的气氛中,且相对的湿度为85%时,该薄膜的记录灵敏度在约5小时中下降约20%,且在约15小时中下降约50%。
为了解决上面所讨论的问题,已作了各种努力以达到抑制Te薄膜的氧化的目的。已知一方法,其中Te薄膜被涂覆一层稳定的无机材料。当这方法对抑制Te薄膜的氧化是有效的时,却由于它降低了该薄膜的记录灵敏度及它花费大而不能商业化。还已知一方法,其中Te薄膜被涂覆一层塑料材料。后面所提到的方法较好,其中由于该塑料材料的低的热导率,它不会严重地影响该薄膜的记录灵敏度。但是,该Te薄膜的氧化由于该塑料材料相对地易于被氧和潮气渗透而没被充分地抑制。
进一步讲,当包括低熔点金属如Te的记录薄膜的记录灵敏度可称高时,它并不足够高,且因此,在该领域中,需要具有进一步提高的记录灵敏度的光记录薄膜。
本发明的一个目的在于提供一种制备高灵敏度的,因此能够降低能量地记录信息且具有延长的使用寿命的光记录体的方法。
一种根据本发明用于制备包括基片和载持在所述基片上的光记录薄膜的光记录体的方法,所述的光记录体通过在所述的薄膜上由能量束的辐照使能形成改变了物理构造或改变了光学性质的区段而能够记录信息,因此所述的区段的排列可相应于要被记录的信息,该方法包括在所述的基片上形成一薄的包括作为基本元素的(1)至少一种低熔点金属元素(2)碳和(3)氢的光记录薄膜,和在从70°至300℃温度下,在至少5秒时间内,在所述的基片上热处理该所形成的薄膜。
根据本发明的方法所制备的光记录体具有延长的使用寿命,且是高灵敏度的,其中每单位面积形成凹点所需的能量由于该经热处理的记录薄膜中具有增强的耐久性而降低。
图1为描述根据本发明的方法制备的光记录体的横截面示意图。
图2为显示实施例4在热处理前的-Te-Se(硒)薄膜的差示扫描量热法的结果的曲线。
图3为显示实施例4在热处理后的-Te-Se薄膜的差示扫描量热法的结果的曲线。
图4为显示在实施例4的一光记录体上热处理前和后的记录和读出性质的示意图。
现在将详细描述本发明。
如图1所示,在根据本发明方法中,一光记录体10通过在基片11的表面上覆以光记录薄膜12而构成。
构成该基片11的一材料实例包括,例如,无机材料如玻璃和铝;以及有机材料如聚甲基丙烯酸甲酯,聚碳酸酯、聚碳酸酯和聚苯乙烯的聚合物合金,如美国专利4,614,778中所揭示的非晶态聚烯烃,聚(4-甲基-1-戊烯),环氧树脂,聚醚聚砜,聚砜和聚醚酰亚胺。该基片11的厚度是这样的,以致它可提供基本上具有合适的刚度的记录体,且较好地为从0.5至2.5毫米,及更好地为从1至1.5毫米。
该光记录薄膜12包括至少一低熔点金属元素,碳(C)和氢(H),且当用一能量束,如一激光束,根据将要被记录的信息被时断时续调制辐照时,在该薄膜受辐照的那些区段形成凹点。该凹点可被改变物理构造如孔或凹下,或可为那儿光学性质如折射率或反射率已被改变的区段。该记录薄膜12的厚度应足够的厚以提供一足够的反射率,且应足够的薄而不削弱该薄膜的记录灵敏度。它通常约为从100 至1微米,较好地为从200至500 。
作为在该记录薄膜12中的低熔点金属元素,碲(Te),铋(Bi),锌(Zn),镉(Cd),铝(Pb)和锡(Sn)可单独或混合应用。其中,碲特别好。
在该记录薄膜12中的低熔点金属如Te的含量以整个薄膜为基准较好地为从40至90%原子。
除了上述该低熔点金属之外,该记录薄膜12还可包括另一金属如锑(Sb),硒(Se)。
在该记录薄膜12中含有如上所述另一金属的Sb的情况下,Sb的含量以整个薄膜为基准通常应不大于60%原子,较好地为不大于40%原子,且更好地为从1至25%原子。已发现将这些含量的Sb混合至该记录薄膜中,基本上消除了该薄膜随着时间而使透射(性)改变,因此该薄膜的耐久性可得到增强,且该薄膜的使用寿命可延长。
在该记录薄膜12中除了Te之外还含有Se的情况下,Se的含量为这样,当在该薄膜中所含有的Te和Se的原子比由式TexSe1-x表示时,X满足0.4<X<0.99,较好地为0.5<X<0.97,且更好地为0.6<X<0.95。已发现将这些含量的Se混合至该记录薄膜中,对抑制该薄膜的氧化是非常有效的。
该记录薄膜12的C的含量以整个薄膜为基准较好地为从5至40%原子。实际上少于5%原子的C,在基本上由一低熔点金属构成的一记录薄膜上将不能实现使用寿命的明显改进(延长)。另一方面,实际上超过40%原子的高含量的C应该避免,或否则该薄膜的记录灵敏度将受不利影响。
该记录薄膜12的H含量以整个薄膜为基准,从使用寿命看,较好地为从5至40%原子。
在该记录薄膜中所含有的金属元素可由ICP(感应耦合等离子体)发射分光分析来测定,同时,在该薄膜中的碳和氢可由有机元素分析来测定。
该记录薄膜12可通过各种以前已知的干法涂层方法在该基片11上形成。
例如,一作为记录薄膜12的含有C和H的Te薄膜可在该基片11上形成,它是通过在氩和一含C和H的有机气体如CH4和C2H2的混合气中,用Te作为对阴极。使用一反应性溅镀方法来制备的。换句话说,含有C和H的Te的薄膜可在该基片11上,采用离子喷镀,化学蒸镀或等离子体汽相外延方法来制备。这些干法涂覆方法也可用于形成一薄的Te和其它金属或多种金属的合金,一除Te之外的低熔点金属或其合金如本文前述含有C和H的薄膜。
其中使用一溅射离子镀层法,将含有C和H的低熔点合金的薄的记录薄膜12溅镀在一基片11上形成,在所形成的薄膜中C和H的含量,可通过选择在该混合气氛中一有机气体如CH4与Ar的比例和所要施加的高频电能来调节。例如,在CH4/Ar比为1,且在一Te对阴极和基片11之间施加一高频(13.56兆赫)电能约0.3瓦/平方厘米的一情况下,可形成一每个Te原子含有0.2个C原子的薄膜。当提供该所形成的薄膜化学上最稳定的最佳的H含量依赖于该特殊的C含量时,该H含量可在本文前述所提供的范围内选择,而在所形成的该薄膜中释出的过多的氢气是不能结合至该薄膜中的。该记录薄膜12的厚度可易于控制,因为与溅镀时间成正比。
如上所述已形成的该记录薄膜12的反射率和消光系数等光学性质取决于该薄膜的C和H含量。当该薄膜用于记录和读出信息时,该薄膜的厚度可根据所需的光学性质来选择。作为一实验的结果,已发现该薄膜12的合适的厚度在从100 至1微米范围内,且较好地如本文上面所述在从200至500 的范围内。在上述条件下所形成的薄膜为非晶形的。当形成改变了物理构造的区段以记录信息于这一含有C和H及低熔点金属的薄膜上时,该所形成的改变了物理构造的界面比在一主要由一低熔点金属构成的薄膜上所形成的界面要光滑,因此一用于读出来自前述的薄膜的记录信息的噪声电平可有利地低。偶然,当形成改变了光学性质的区段以记录信息时,因为凹点的物理构造没有改变,所以不存在由于物理构造的变化而造成用于读出信息的噪声电平升高的问题。
然后,在基片11上所形成的记录薄膜12在一惰性气体,还原性气体或一多少含有一些氧的减压惰性气体的气氛中热处理。该热处理在70℃至300℃一温度范围内,完全低于薄膜12中所含有的低熔点金属的熔点之下进行。一较好的热处理温度为90℃至300℃。该热处理在至少5秒,通常为5秒至1000分钟,且较好地为5至100分钟时间内进行。已发现该记录薄膜的记录灵敏度、根据本发明通过该热处理可得到加强。术语“强化了的记录灵敏度”意味着降低用于记录在该记录薄膜的单位面积中的信息所需的能量束如激光的能量。
该光记录体采用根据本发明的方法来制备,它已经过热处理而具有强化了的记录灵敏度。进一步讲,它具一延长的使用寿命,因为其中所用的记录薄膜含有C和H,且因此具有更好的耐久性。更进一步讲,因为该记录薄膜本身是耐久性的,故潮气或氧可渗透的丙烯酸或其它廉价的塑料基片能安全地利用,提供该对光记录体的大量生产廉价且合适的方法。
本发明将通过下列描述根据本发明的方法的实施例和下列在本发明的范围外的对比实施例来进一步描述。然而这些例子只应该是对本发明的理解,而并不表示对本发明的限制。
实施例1
在基片11上形成一具有厚度250 ,且基本上由60%原子的Te,15%原子的C及25%原子的H构成的记录薄膜12,它是在一CH4和Ar(体积比为1∶4)的混合气体中,使用主要由Te构成的对阴极。通过反应性溅镀法制成的。这样形成的记录薄膜12可放置在保持100℃温度的氮气氛中20分钟时间。这样制备的产物为一光记录体,当信息通过一根据该信息调制的激光束而记录在上面时,它形成一改变了物理构造的图型。
实施例2
对比实施例1
重复实施例1,只是不进行该项热处理。
对比实施例2
重复实施例2,只是不进行该项热处理。
使用一频率1兆赫的激光束测试这样制备的光记录体的记录灵敏度(毫微焦/微米2)。该记录灵敏度为用于形成凹点以记录该薄膜每单位面积的信息所需的激光束的能量,且该能量越低,该记录灵敏度越好。结果如表1中所示。
表1
表1揭示出根据本发明的该热处理提高记录灵敏度大于10%。
实施例3
在一CH4和Ar(体积比为1∶4)的混合气体中,用一Te-Sb合金对阴极,使用反应性溅镀法,在基片11上形成具有厚度为250 ,且主要由55.2%原子的Te,4.8%原子的Sb,15%原子的C及25%原子的H构成的记录薄膜12。这样形成的记录薄膜12可放置在一保持100℃温度的氮气氛中20分钟时间。这样制备的产物为一光记录体,当信息通过一根据该信息调制的激光束而记录在上面时,它形成一改变了物理构造的图型。
对比实施例3
重复实施例3,只是不进行该项热处理。
使用一频率1兆赫的激光束测试这样制备的光记录体的记录灵敏度(毫微焦/微米2),结果如表2中所示。
表2
表2揭示出根据本发明的该热处理提高了灵敏度大于10%。
在实施例3和对比实施例1中所制备的光记录体可放置在70℃温度,且相对湿度为90%的气氛中1000小时时间。该记录薄膜的透射的百分比降低取决于每一测试体。结果如表3中所示。
表3
表3揭示出在根据本发明的实施例3中所制备的该记录体即使经过1000小时记录薄膜的透射率也不会有任何下降。而对比实施例1的记录体其记录薄膜的透射率有明显的降低。后一记录体的薄膜已变得多少有些发暗。这认为是由于Te的氧化。透射率随时间的下降是不利的,因为它需要用于记录和读出的射线束的能量的瞬间调整(节)。
实施例4
一具有厚度250 ,含有C和H的Te-Sb合金的甲烷/氩-等离子体溅镀薄膜,它是通过反应性溅镀法,在的-Ar和CH4的混合气体气氛中,在一保持压力约5毫乇下的真空器中,使用Te-Se合金,Te64Se40(数字表示原子百分数等等)的对阴极,在一基片上溅镀而成的。Ar和CH4至该真空容器的流量比为1∶1。该薄膜的ICP发射分光分析表明该薄膜的金属成分的组成为Te75Se25。这样形成的薄膜进行差示扫描量热(DSC),其结果如图2中所示出。在约100℃温度下,可观察到在这样形成的薄膜的DSC曲线中的放热峰。
这样形成的薄膜在一真空炉中,在85℃温度下热处理约24小时。经热处理的薄膜进行DSC。结果如图3中所示。从图3中揭示出该在100℃附近的放热峰通过热处理而消失了。这认为是因为该薄膜通过该热处理而结晶了。
该薄膜在波长780毫微米时的光学系数(折射率和消光系数)在该热处理前和后(被)测定。该薄膜在该热处理前具有折射率为3.0和消光系数为-0.25,且在热处理后具有折射率为3.4和消光系数为-0.91。已经证实该薄膜的光学系数由于受热处理而改变。
一厚度为250 的相同的薄膜在一具有预制凹槽的非晶态聚烯烃基片上形成,并在该热处理前和后测试记录和读出信息的性质。在测试中,用一具有一线速度为9.4米/秒和辐射时间为50毫微秒的记录频率为5.4兆赫的激光记录信息。图4为显示该测试结果的示意图,其中在该读出时间的信号电平(载体)对记录时间的激光能量进行标绘。在图4的曲线中,它的意思是该载体越是接近于达到0,因记录信息所形成的凹点就越多。从图4中它揭示出在该根据本发明已经热处理的薄膜上,用激光能量约5毫瓦几乎完全形成凹点,同时在该热处理前的对比薄膜需要一激光能量至少约7.5毫瓦以形成同样性质的凹点。该已经热处理的薄膜可放置在70℃和相对湿度为90%的气氛中000小时时间。观察到无反射率和透射的变化。
Claims (8)
1、一种制备包括基片和载持在所述的基片上的光记录薄膜的光记录体的方法,其特征在于所述的光记录体通过在所述的薄膜上由能量束的辐照形成改变了物理构造或光学性质的区段而能记录信息,因此所述的改变了的区段的排列可相应于要被记录的信息,该方法包括在所述的基片上形成一薄的包括作为基本元素的至少一低熔点金属元素,碳和氢的光记录薄膜,及在70°至300℃温度下,在至少5秒时间内,在所述的基片上热处理这样形成的薄膜。
2、根据权利要求1所述的方法,其特征在于其中所述的低熔点金属元素选自碲,铋,锌,镉,铟,铅,锡和至少它们中两种元素的合金。
3、根据权利要求2所述的方法,其特征在于其中所述的低熔点金属元素为碲。
4、根据权利要求1所述的方法,其特征在于其中所述的光记录薄膜还包括了所述的低熔点金属元素碳和氢之外的另一金属。
5、根据权利要求4所述的方法,其特征在于其中所述的另一金属为锑。
6、根据权利要求4所述的方法,其特征在于其中所述的另一金属为硒。
7、根据权利要求1所述的方法,其特征在于其中所述的热处理在一惰性气体气氛中进行。
8、根据权利要求1所述的方法,其特征在于其中所述的热处理在一还原性气体气氛中进行。
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JP62294322A JPH01134739A (ja) | 1987-11-20 | 1987-11-20 | 光記録媒体の製造方法 |
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JP62294323A JPH01137442A (ja) | 1987-11-20 | 1987-11-20 | 光記録媒体の製造方法 |
JP294323/87 | 1987-11-20 | ||
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JP63051307A JPH01224956A (ja) | 1988-03-04 | 1988-03-04 | 光記録媒体の製造方法 |
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US5061597A (en) * | 1989-04-18 | 1991-10-29 | Mitsui Petrochemical Industries, Inc. | Optical recording media and process for preparing same |
US5294518A (en) * | 1992-05-01 | 1994-03-15 | International Business Machines Corporation | Amorphous write-read optical storage memory |
US5729645A (en) * | 1996-08-13 | 1998-03-17 | The Trustees Of The University Of Pennsylvania | Graded index optical fibers |
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JPS6120719A (ja) * | 1984-07-09 | 1986-01-29 | Asahi Chem Ind Co Ltd | 光デイスク用プラスチツク基板の製造方法 |
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DE3671122D1 (de) * | 1985-02-22 | 1990-06-13 | Asahi Chemical Ind | Informationsaufzeichnungsmedium. |
EP0212336B1 (en) * | 1985-08-15 | 1990-11-28 | International Business Machines Corporation | A method of optical recording |
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