201232533 六、發明說明： 【發明所屬之技術領域】 本發明涉及光資訊記錄媒體用記錄層和光資訊記 體。 【先前技術】 光資訊記錄媒體（光碟）由CD、DVD、BD這樣 碟代表，根據記錄再生方式，被大致區分爲唯讀型、 寫入型、重寫型三類。其中，單次寫入型的光碟的記 式，主要被大致區分爲如下方式：使記錄層產生相變 變方式；使多個記錄層產生反應的層間反應方式；使 記錄層的化合物產生分解的分解方式；使記錄層上局 地形成孔和凹坑等的記錄標記的開孔方式。 在前述相變方式中，作爲記錄層的材料提出的是 用了基於記錄層的結晶化造成光學特性變化的材料。 在專利文獻1中，提出了含有Te-O-M ( Μ爲從金屬 、半金屬元素和半導體元素中選出的至少一種元素） 錄層’在專利文獻2中，提出了含有Sb和Te的記錄 作爲前述層間反應方式的光資訊記錄媒體的記錄 例如在專利文獻3中提出有一種記錄層，其使第一記 由含有In-O- ( Ni、Mn、Mo)的合金構成，並且使第 錄層由含有Se和/或Te元素、〇(氧）、以及從Ti、 Zr之中選出的一個元素的合金構成。另外在專利文獻 提出’第一記錄層含有以In爲主成分的金屬，第二 錄媒 的光 單次 錄方 的相 構成 部性 ，利 例如 元素 的記 層。 層， 錄層 二記 Pd、 4中 記錄 -5- 201232533 層含有屬於5B或6B族元素的至少一種元素，層疊氧化物 以外的金屬或非金屬，通過加熱帶來的反應或合金化進行 記錄。 作爲分解構成前述記錄層的化合物的分解方式的記錄 層，例如在專利文獻5中，公開了以氮化物爲主成分的記 錄層，其硏究的是，通過加熱來分解該氮化物，從而進行 記錄的材料和有機色素材料。 作爲前述開孔方式的記錄層，硏究了由低熔點金屬材 料構成的記錄層。例如在專利文獻6中，提出有一種由在 Sn合金中添加有3B族、4B族、5B族的元素的合金構成 的記錄層。另外在專利文獻7中，提出有一種由Sn基合 金構成的記錄層，該Sn基合金在1〜50原子％的範圍內含 有Ni和/或Co。此外在專利文獻8中公開有一種由In合 金構成的記錄層，該In合金含有2 0〜65原子％的Co，其 中還含有從Sn、Bi、Ge、Si中選出的一種以上的元素19 原子％以下。另外在專利文獻9中公開有一種記錄層，其 由Pd、Ag、Ο構成，該Pd、Ag、Ο的原子數的比率被控 制在規定範圍內。 〔專利文獻1〕特開2005-135568號公報 〔專利文獻2〕特開2003-331461號公報 〔專利文獻3〕特開2 0 0 3 - 3 2 6 8 4 8號公報 〔專利文獻4〕日本專利第3499724號公報 〔專利文獻5〕國際公開第2003/101750號手冊 〔專利文獻6〕特開2002-225433號公報 201232533 〔專利文獻7〕特開2007-196683號公報 〔專利文獻8〕日本專利第4 1 1 0 1 94號公報 〔專利文獻9〕特開2005-238516號公報 在光資訊記錄媒體所要求的需求特性中，要求的有： 通過寫入鐳射的入射，具有可充分再生記錄訊號的訊號振 幅（高調變度）：訊號強度高（高C/N比）；難以產生劣 化和環境劣化的高耐久性。C/N比是載波雜訊比（Carrier to Noise ratio)的意思，讀取時的訊號和背景的噪音輸出 級別的比。 作爲上述現有技術所公開的記錄材料，以記錄材料單 體難以滿足這些要求。 在相變方式中，記錄層單獨的反射率低，所以應該提 高光碟狀態下的反射率，需要反射膜’並且爲了增加調製 度，需要在記錄層的上下設置ZnS-Si02等介電體層（介 電質膜），構成光碟的層數增多’生產率差。由於層間反 應方式也需要多層記錄層’因此構成光碟的層數增多’生 產率差。 在分解方式中’作爲記錄層’使用有機色素材料的光 資訊記錄媒體被廣泛使用’但是’因爲難以吸收藍色鐳射 和藍紫色鐳射這樣短波長（4 00nm附近）的可見光線，所 以得不到良好的記錄資訊’不能提高記錄密度。另外’使 用了有機色素材料的光資訊記錄媒體’抑制日光等的光造 成的劣化和長期保存造成的劣化有困難。 相對於此’前述開孔方式’因爲記錄層自身的反射率 201232533 高，並且也能夠確保大的調變度，所以能夠降低構成光碟 的層數，但要達成更高的記錄靈敏度時’還需要進—步硏 究。 【發明內容】 本發明鑒於這種情況而做，其目的在於’提供一種既 能夠降低光碟的層數，又滿足上述要求特性’能夠提高光 資訊記錄媒體的生產率的光資訊記錄媒體用記錄層’和具 有該記錄層的光資訊記錄媒體。 能夠解決上述課題的本發明，是光資訊記錄媒體用記 錄層，即通過鐳射的照射而進行記錄的記錄層，其具有如 下要旨：含有Μη氧化物，在構成前述記錄層中所含氧化 物的全部金屬元素中所占的Μη的原子比爲80原子％以下 ，並且不含金屬Μη。 此外，也優選的實施方式是，還含有從In氧化物、 Zn氧化物、Sii氧化物和Cu氧化物構成的群中選出的至少 一種氧化物。 本發明還包括光資訊記錄媒體，其特徵在於，具有前 述光資訊記錄媒體用記錄層。 此外，本發明的優選實施方式，是一種光資訊記錄媒 體，其在前述光資訊記錄媒體用記錄層之上和/或之下， 層疊有介電體層。 本發明的前述光記錄資訊媒體，優選不含金屬層。 另外優選的實施方式爲，前述光資訊記錄媒體，具有 -8- 201232533 多層前述光資訊記錄媒體用記錄層，並在多層 媒體用記錄層的層間具有透明中間層。 根據本發明，能夠提高實用性的記錄鐳射 錄靈敏度優異的光資訊記錄媒體用記錄層（特 入型光資訊記錄媒體用記錄層），和具有該記 訊記錄媒體（特別是單次寫入型光資訊記錄媒彳 還有，在本說明書中，所謂“記錄靈敏度 後述的實施例一欄中所詳述的，意思是，通過 射鐳射（寫入鐳射），即使是比較低的記錄鐳 致5〜15mW，也能夠實現高C/Ν比和高調變度 【實施方式】 本發明者們，爲了實現通過寫入鐳射的照 敏度優異的單次寫入型光資訊記錄媒體用記錄 銳意硏究。其結果發現，如果使用的記錄層， 有的記錄層不同的材料，即，其是含有Μη氧 層，或是優選含有Μη氧化物，和從In氧化;f 物、Sn氧化物和Cu氧化物構成的群中選出的 化物的記錄層，則能夠達成預期的目的。若對 照射鐳射’則Μη氧化物被鐳射加熱分解，放 )，在被鐳射照射的部分生成氣泡。其結果是 化，標記形成。如果採用這樣的伴隨著鐳射照 泡生成的不可逆的記錄方式，則發現記錄靈敏 高，從而完成了本發明。 光資訊記錄 功率下的記 別是單次寫 錄層的光資 豊）= 優異”，如 對記錄層照 射功率，大 射，記錄靈 層而進行了 其含有與現 化物的記錄 2?、Ζη氧化 至少一種氧 上述記錄層 Β氧（〇2氣 ，膜形狀變 射而來的氣 度比以往提 -9- 201232533 在本發明的記錄層進行的記錄方式中’鐳射照射前的 記錄層的構造爲非晶質’在鐳射照射後也是非晶質’這一 點與相變方式不同，相變方式利用的是’非晶質通過鐳射 照射而變成結晶。 作爲本發明的記錄層記錄靈敏度優異的理由被認爲是 ，在通過鐳射照射而發生氣泡’進行標記形成的部分’與 沒有發生氣泡的部分（即’未形成標記的部分）相比，透 射率增加（即反射率降低），從而能夠增大調變度。 另外，如本發明通過在記錄層中含有Μη氧化物，與 不含Μ η氧化物的記錄層相比，能夠加大膜的光吸收率， 因此能夠將寫入光的鐳射的能量高效率地轉換成熱能。此 外在本發明中，在構成記錄層所含的氧化物的全部金屬元 素（優選爲Μη和從In、Zn、Sn和Cu構成的群中選出的 至少一種元素）中，因爲適當控制著其中所占的Μη量的 比（原子比），所以能夠控制記錄所需要的鐳射功率。其 結果是，根據本發明，在實用的記錄鐳射的功率（大致5 〜1 5mW )，上述氧化Μη的分解被促進，能夠使記錄靈感 度提高。 還有，本發明的記錄層不含金屬Μη。這是由於，若 金屬Μη包含在記錄層中，則金屬Μη的氧化和分解進行 ’耐久性降低。因此，本發明的記錄層不含金屬Μη，從 而能夠抑制記錄層因環境劣化造成的長期可靠性降低。根 據本發明者們的硏究結果’因爲適當控制了上述Μη量的 比（原子比），所以如後述的實施例所示，能夠得到良好 -10- 201232533 的特性。 以下，詳細說明本發明的記錄層的結構。在本說明書 中，爲了說明的方便，有將從In、Zn、Sn和Cu構成群出 選出的至少一種元素稱爲X群元素的情況。 如前述，本發明的記錄層，是通過鐘射的照射進彳了 §己 錄的記錄層’其特徵在於’含有Μη氧化物。優選的本發 明的記錄層’含有Μη氧化物’和從In氧化物、Ζη氧化 物、Sn氧化物和Cu氧化物構成的群中選出的至少一種氧 化物。如上述在記錄層中，不含金屬Mn。 本發明的記錄層含有Μη氧化物，只要Μη氧化物的 形態是通常存在的形態，則沒有特別限定。作爲Μη氧化 物，除了 ΜηΟ、Μη304、Μη203、Μη02等這樣由Μη和氧 (〇 )構成的氧化物以外，還可以列舉與上述記錄層中所 含的其他元素（X群元素= In、Zn、Sn和Cu的至少一種 )的複合氧化物（X-Mnx-Oy)。 在本發明的記錄層中，含有上述Μη氧化物，並且需 要Μη在構成記錄層所含的氧化物的全部金屬元素中所占 的原子比爲80原子％以下。若Μη被含有超過80原子％ ’ 則通過鐳射照射無法良好地形成氣泡’得不到記錄信號。 本發明的記錄層，除了 Μ η氧化物以外，也可以含有 從Iri氧化物、Ζη氧化物、Sn氧化物和Cu氧化物構成的 群中選出的至少一種氧化物。這些氧化物在膜折射率的控 制和記錄靈敏度（調製度和C/N比）的控制上有用。In氧 化物、Ζη氧化物、Sn氧化物和Cu氧化物的形態也是通常 -11 - 201232533 存在的形態，沒有特別限定，例如對於In氧化物來說， 可例示In2〇3等，Zn氧化物可例示ZnO等，Sn氧化物可 例示SnO或Sn02等，Cu氧化物可例示CuO、Cu20等。 在本發明中，含有上述氧化物的至少一種即可，可以分別 單獨含有In氧化物、Zn氧化物、Sn氧化物和Cu氧化物 ，也可以含有兩種以上的氧化物。其中優選的氧化物是In 氧化物。 還有，記錄層中含有上述選擇氧化物，即In氧化物 、Zn氧化物、Sn氧化物和Cu氧化物時，優選不含它們的 金屬元素（即，金屬In、金屬Zn、金屬Sn、金屬Cu)。 這是因爲，這些金屬元素會從其他氧化物奪取氧而發生氧 化，在這樣的情況下，會對記錄層的特性造成影響。 爲了得到記錄靈敏度優異的記錄層，優選在構成形成 本發明的記錄層的氧化物（Μη氧化物，和優選從In氧化 物、Zn氧化物、Sn氧化物和Cu氧化物構成的群中選出的 至少一種氧化物）的金屬元素（Μη和X群元素）中所占 的Μη量的原子比（由下式表示’以下有簡稱爲“Μη比” 的情況）爲1 〇原子％以上。 Μη 量（原子％) = {[Mn]/ ( [Mn]+[In]+[Zn]+[Sn]+[Cu] ) }χ100 式中，[Μη]、[In]、[Zn]、[Sn]和[Cu]意思分別是，在 本發明的記錄層中所含的Mn量（原子％) 、In量（原子 % )、乙11量（原子°/。）、311量（原子％) 、〇11量（原子％ )° 遼有，記錄層中不含In、Zn、Sn、Cu時，分別作爲 -12- 201232533 〇原子％計算。 在此，若Μη低於1 0原子％，則鐳射照射時分解的氧 化Μη少，因此放出的氧量不充分，生成的氣泡變少，結 果是訊號強度（C/N比）變小。另外在記錄層存在2層以 上的多層光碟中，距鐳射入射面最遠的記錄層要求有一定 程度的透射率。若Μη比低於1 0原子％，則記錄層的光吸 收率也變小，因此記錄所需要的鐳射功率變大，不爲優選 。Μη比優選爲1 0原子％以上，更優選爲1 2原子％以上， 進一步優選爲15原子％以上。 可是，若氧化Μη多，則調變度變小，因此Μη比爲 80原子％以下，優選爲70原子％以下，更優選爲60原子 %以下。 本發明的記錄層，如上述含有Μη氧化物，並可含有 在製作時不可避免混入的不可避免的雜質。另外優選本發 明的記錄層含有Μη氧化物，和從In氧化物、Ζη氧化物 、Sn氧化物和Cu氧化物構成的群中選出的至少一種氧化 物，並可含有在製作時不可避免混入的不可避免的雜質。 上述記錄層的優選的膜厚，在記錄層之上和/或之下 插入介電體層等其他層的情況，和沒有這些其他層的情況 是不同的。雖然根據光資訊記錄媒體的構造也有所不同， 但主要在單層使用記錄層時（不設介電體層時），優選使 記錄層的膜厚爲10〜60nm。若記錄層的膜厚過薄，則分 解的Μη量變少，因此難以獲得記錄帶來的充分的反射率 變化。更優選爲20nm以上，特別優選爲3 0nm以上。另 -13- 201232533 一方面，若記錄層的膜厚過厚，則膜的形成花費時間，生 產率降低，並且記錄所需要的鐳射功率變大。更優選爲 5 Onm以下，進—步優選爲45 nm以下。另外，在記錄層之 上和/或之下設置介電體層時，優選使記錄層的膜厚爲2〜 50nm’更優選爲3nm以上，進—步優選爲5nm以上，再 更進一步優選爲l〇nm以上，更優選爲40nm以下，進一 步優選爲1 5nm以下。 本發明的記錄層如上述，含有Μη氧化物（特定的比 例的Μη )，優選含有Μη氧化物，和從In氧化物、Ζη氧 化物、Sn氧化物和Cu氧化物構成的群中選出的至少一種 氧化物，但爲了得到這樣的形態的記錄層，優選以濺射法 形成記錄層。根據濺射法，還能夠確保碟片面內的膜厚分 佈均勻性，因此優選。 爲了以濺射法形成含有上述氧化物的記錄層，進行反 應性濺射，作爲濺射條件，優選調整氣體流量而進行。特 別是優選使氧流量對於Ar (氬）流量的比爲0.5倍以上， 更優選爲1 . 〇倍以上。另外，氧流量對於Ar流量的比優 選爲5 · 0倍以下。濺射法的其他條件沒有特別限定，能夠 採用通用的方法，將氣壓控制在例如0. 1〜1 .OPa的範圍， 將濺射電子控制在例如0.5〜20 W/cm2的範圍。 作爲前述濺射法中使用的濺射靶材（以下僅稱爲“靶 材”），可列舉含有Μη氧化物，餘量是不可避免的雜質 的耙材。 優選的靶材爲，（A )含有Μη氧化物，和從In氧化 -14- 201232533 物、Zn氧化物、Sn氧化物和Cu氧化物構成的群中選出的 至少一種氧化物，餘量爲不可避免的雜質。或者也可以使 用（B )含有Μη金屬靶材’和從In、Zn、Sn和Cu構成 的群中選出的至少一種元素的金屬靶材來替代上述（A) 的靶材，使它們同時放電而進行多元濺射。此外也可以使 用（C)金屬和氧化物混合靶材。金屬元素通過導入氧而 成爲氧化物。 也能夠使用如下濺射靶材，即，相對於上述（A )〜 (C )的濺射靶材所含的Μη原子，和從ln原子、Zn原子 、Sn原子和Cu原子構成的群中選出的至少一種原子（實 際含有的原子）的合計，Μη原子的比率爲1〇〜80原子％ 〇 還有，作爲上述（Α)和（C)的濺射靶材，特別是將 Μη的金屬粉末或Μη氧化物的粉末，和從In氧化物、Zn 氧化物、Sn氧化物和Cu氧化物構成的群中選出的至少一 種氧化物或金屬的粉末進行混合，使之燒結，使用這樣的 濺射靶材，在生產率和所形成的薄膜的組成的面內均勻性 和厚度控制的點上優選。在上述濺射靶材的製造時，儘管 微量，但還是有雜質混入濺射靶材中。但是，本發明的濺 射靶材的成分組成，沒有規定至這些不可避免混入的微量 成分，只要不阻礙本發明的上述特性，這些不可避免的雜 質的微量混入是被允許的。 本發明的光資訊記錄媒體，具有的特徵是具備上述記 錄層這一點，利用Μη的氧化物分解而發生的〇2氣體的效 -15- 201232533 果來形成標記。 在本發明中，上述記錄層以外的構成沒有特別限 能夠採用光資訊記錄媒體的領域中公知的構成。 本發明的光資訊記錄媒體，具有上述記錄層，還 錄層之上和/或之下（至少單面）層疊有介電體層， ，能夠省略以往爲了提高反射率所需要的金屬層（ Au、Cu、A1、Ni、Cr、Ti等的金屬層和其合金層） 成。如上述本發明的記錄層，具有高反射率、變化率 此即使不特別設置反射層，也可以充分地進行訊號再: 另外，通過在記錄層之上和/或之下設置介電體 能夠提高訊號強度，能夠進一步改善訊號特性。這是 ，防止了因鐳射照射導致記錄層分解而發生的氧的逃 從而能夠降低反射率的降低，能夠確保作爲記錄層所 的反射率。 作爲上述介電體層的種類可列舉公知的，可例示 Si、Al、In、Zn、Zr、Ti、Nb、Ta、Cr、Sn 等的氧化 Si、Al、In、Ge、Cr、Nb、Mo、Ti 等的氮化物；Zn 物；Cr、Si、Al、Ti、Zr、Ta 等的碳化物；Mg、Ca 等的氟化物；或其混合物等。若考慮生產率和記錄靈 的提筒等，則優選使用Ill2〇3。 上述介電體層的膜厚，優選大致爲2〜30nm。若 體層的膜厚過薄，則發生的02氣體的覆蓋性不充分 錄靈敏度降低。另一方面，若介電體層的膜厚過厚， 於光的干涉，導致作爲層疊膜（記錄層+介電體層） 定， 在記 由此 Ag、 的形 ，因 生。 層， 由於 散， 需要 例如 物； 硫化 、La 敏度 介電 ，記 則由 整體 -16- 201232533 吸收降低，因此需要的寫入鐳射功率變高，並且標 時的形態變化（氣泡的生成）難以發生，因此記錄 降低。若考慮這樣的情況，則將介電體層設於記錄 層（鐳射非入射側）時的優選的膜厚爲3〜1 5nm， 錄層的上層（鐳射入射側）時的優選的膜厚大致: 3 Onm 〇 另外，作爲光資訊記錄媒體（光碟），其構造 爲，在刻有鐳射的引導用的凹槽的基板上層疊記錄 在其上層疊透光層。 例如，作爲前述基板的原材，可列舉聚碳酸酯 降冰片烯系樹脂、環烯烴系共聚物、非晶聚烯烴等 ’作爲前述光透過層可以使用聚碳酸酯或紫外線硬 。作爲透光層的材質，優選對於進行記錄再生的鐳 高透射率，光吸收率小。前述基板的厚度可列舉例 〜1.2mm。另外前述透光層的厚度可列舉例如0.1〜 9 本發明的記錄層記錄特性優異，但爲了記錄層 性提高或記錄特性的進一步提高，也可以在記錄層 和/或下層，設置氧化物層、氮化物層、硫化物層; 過層疊這些層，能夠改善記錄層的耐久性，並且能 步提高記錄特性。 還有，上述顯示的是記錄層和透光層分別各形戶 的1層光碟，但並不限定於此，也可以是記錄層和 多層層疊的2層以上的光碟。 記形成 靈敏度 層的下 設於記 爲2〜 可列舉 層，再 樹脂、 。另外 化樹脂 射具有 如0.5 1.2mm 的耐久 的上層 等。通 夠進一 1層 透光層 -17- 201232533 前述2層以上的光碟的情況下，由記錄層和根據需要 層疊的光學調節層以及介電體層所構成的記錄層群與其他 記錄層群之間，也可以具有例如由紫外線硬化樹脂或聚碳 酸酯等透明樹脂等構成的透明中間層。通過設置透明中間 層，能夠爲了多層記錄而在縱深方向會聚鐳射的焦點。 本發明的特徵在於，採用前述的記錄層，優選的記錄 層之上和/或之下設置有介電體層的層疊膜這一點，所述 記錄層以外的基板和透光層，還有透明中間層等的形成方 法沒有特別限定，以通常進行的方法形成來製造光資訊記 錄媒體即可。 作爲光資訊記錄媒體，可列舉CD、DVD或BD，作爲 具體例，例如可列舉BD_R，其可以將波長約3 80nm至 45 0nm，優選約405 nm的藍色鐳射照射到記錄層上，進行 資料的記錄和再生。 〔實施例〕 以下，列舉實施例更具體地說明本發明，但本發明當 然不受下述實施例限制，在不脫離前後述的宗旨的範圍內 也可以適宜加以變更實施，這些均包含在本發明的技術範 圍內。 在本實施例中，使用的記錄層由如下構成：Μη氧化 物，和從In氧化物、Ζη氧化物、Sn氧化物和Cu氧化物 構成的群中選出的至少一種，調查記錄層所含的Μη元素 的比率和X群元素的組合對記錄特性等造成的影響。 -18- 201232533 (1 )光碟的製作 本實施例中使用的光碟的構成槪略模式圖顯示在圖1 中。如圖1所示，光碟具有在聚碳酸酯基板1之上按順序 層疊如下層的構造：介電體層2;含Μη氧化物的記錄層3 :介電體層4;透光層5。 上述光碟的製作方法如下。 作爲碟片基板，使用聚碳酸酯基板1 (厚度：1.1mm ，直徑：120mm，磁軌間距：〇.32μπι，凹槽深度：約 25 nm)，在基板1上，通過DC磁控管濺射法，依次形成 表1記述的下側介電體層2、如表1所示Μη比不同的記 錄層3、表1記述的上側介電體層4。記錄層3的膜厚爲 40nm，記錄層之上/之下分別層疊的介電體層2、4的厚度 ，上/下均爲1 〇nm。 用於記錄層形成的濺射，以如下方式進行。這時的濺 射條件爲，Ar流量：lOsccm，並且氧流量：lOsccm，氣 壓：0.2Pa，DC濺射功率：100〜200W，基板溫度：室溫 〇 表1的No. 1、2中使用純Μη靶材。 表1的Νο.3〜7中，利用純Μη和純Cu這兩種元素 的靶材，通過多元濺射成膜，由此使Μη比變化。同樣在 表1的No.8〜12、15、16中，利用純Μη和純In這兩種 元素的靶材，No. 1 3中利用純Μη和純Sn這兩種元素的靶 材，No . 1 4中利用純Μη和純Zn這兩種元素的靶材。 201232533 在介電體層2、4中，使用濺射靶材’Ar seem，並且氧流量：lOsccm，氣壓：〇.2Pa’ DC :100〜200W，基板溫度：室溫，形成表1的成 介電體層（濺射靶材是表1的成分組成的公知的 ，N 〇. 2、4 〜1 4 是 I η 2 Ο 3，N 〇 . 1 5 是 S η Ο 2，N 〇. 1 < )° 接著，在介電體層4上旋塗紫外線硬化性樹 化藥社制“ BRD-864” ）後，照射紫外線而形 0.1mm的透光層，得到光碟。 記錄層的成分組成，以上述同樣的條件形成 單層膜（沒有介電體層），使用ICP發光分析法 錄層單層膜進行分析。 (XPS分析） 對於表1的各試料，通過XPS法，分析記錄 的Μη和In、Zn、Sn、Cu等的狀態。具體來 physical Electronics社製X射線光電子能譜儀 SXM，實施基於最表面的廣域光電子能譜的定性 後，通過Ar濺射從表面向深度方向進行蝕刻， 定深度測量膜的構成元素和在最表面檢測到的元 光電子能譜。根據在各深度得到的狹域光電子能 強度比和相對靈敏度係數，計算深度方向組成分 % )。另外，根據各元素的混合能譜（montage )的峰値位置推定結合狀態。其結果是，在No. 流量：1 〇 濺射功率 分組成的 濺射靶材 5 是 Ζ η Ο 2 脂（曰本 成膜厚約 記錄層的 對於該記 層中所含 說，使用 Quantera 分析。其 在每個固 素的狹域 譜的面積 佈（原子 spectrum 3〜1 6的 -20- 201232533 各試料中’未確認到記錄層中有Μη和X群原子作爲金屬 存在（記錄層3除了 No.l、2全部含有Μη氧化物，不含 金屬Μη，此外Νο·3〜16含有X群元素的氧化物）。 對於介電體層2、4也進行上述同樣的分析。 (2 )光碟的評價 以如下方式評價製作的光碟的初期記錄特性（記錄鐳 射的功率、C/N比、調變度）。 首先，使用PULSTEC工業社製“ ODU- 1 000”的光碟 評價裝置（記錄鐳射中心波長：4〇5nm、ΝΑ (數値孔徑） ：0.85)，照射再生/記錄鐳射，進行光碟的讀取、記錄。 線速度作爲4.92m/s進行評價。 關於調變度（C/N比成爲最大的點的調變度），使用 橫河電機株式會社製數字示波器"DL1 640” ，測量記錄部 分的最大反射率和最小反射率，基於下式進行計算。 調變度（比）=(最大反射率一最小反射率）/(最大反射率） 關於C/N比，使用ADVANTEST社製R3131A譜線分 析器，測量能夠得到最高C/N比的記錄功率。詳細地說’ 就是反復記錄〇.6〇μιη的標記（相當於Blu-ray Disk的8T )，測量再生鐳射功率〇.3mW下的訊號讀取時的4.12MHz 頻率成分的信號強度（載波C/dB )，和其前後的頻率成 分的訊號強度（噪音N/dB ) ’計算C/N比。 這些結果量並顯示在表1中。表1中記述了能夠得到 最高C/N比時的記錄鐳射的功率（記錄功率）和該最高 -21 - 201232533 C/Ν 比。 在本實施例中，調變度（比）爲〇·4以上，C/N比爲 43以上的爲記錄靈敏度優異。 【表1】 下側介電體層2 記錄層3 上側介電體層4 C/N比 調變度(比） 記錄功率[mW] 1 4nt m Μη 無 不能記錄 - ·β 2 In2〇3 Μη In2〇3 不能記錄 » - 3 無 Cu70Mn30 無 51 0.18 5 4 In2〇3 Cu90Mnl0 In2〇3 55 0.66 8 5 Ιη2〇3 Cu70Mn30 In2〇3 58 0.77 6 6 In2〇3 Cu40Mn60 In2〇3 59 0.8 5.5 7 Ιη2〇3 Cu20Mn80 Ιιΐ2〇3 58 0.65 5.5 8 Ιπ2〇3 In90Mnl0 In2〇3 56 0.4 13 9 Ιη2〇3 In80Mn20 In2〇3 60 0.46 9.5 10 Ιη2〇3 In60Mn40 In2〇3 63 0.74 7.5 11 Ιη2〇3 In40Mn60 In2〇3 63 0.68 6 12 Ιη2〇3 In2〇Mn80 In2〇3 62 0.66 5 13 Ιη2〇3 Sn60Mn40 In2〇3 61 0.69 7 14 Ιη2〇3 Zn60Mn40 In2〇3 57 0.75 8 15 Sn〇2 ln60Mn40 Sn〇2 59 0.61 6 16 Ζη〇2 In60Mn40 Zn〇2 58 0.61 6 ※記錄層的數字是原子％。（各金屣相對於除去氧原子的全部金屬原子的原子比）。 ※記錄層3、和介電體暦2、4出表中成分(氧化物)構成’餘S是不可避免的雜質。 由表1能夠進行如下考察。首先，滿足本發明的規定 No.4〜16的記錄層，調變度和C/Ν比這兩方面均良好。 即，確認到發揮出良好的記錄特性。201232533 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a recording layer for optical information recording media and an optical information recording. [Prior Art] The optical information recording medium (disc) is represented by a disc such as a CD, a DVD, or a BD, and is roughly classified into a read-only type, a write type, and a rewrite type according to the recording and reproducing method. Among them, the recording mode of the single-write type optical disc is mainly roughly classified into a mode in which a phase change is caused in the recording layer, an interlayer reaction mode in which a plurality of recording layers are caused to react, and a compound in the recording layer is decomposed. Decomposition method; a method of opening a recording mark such as a hole or a pit on the recording layer. In the above-described phase change mode, as a material of the recording layer, a material which changes optical characteristics due to crystallization by a recording layer is used. Patent Document 1 proposes a recording layer containing Te-OM (an at least one element selected from a metal, a semimetal element, and a semiconductor element). In Patent Document 2, a recording containing Sb and Te is proposed as the foregoing. Recording of an optical information recording medium in the interlayer reaction mode is proposed, for example, in Patent Document 3, in which a recording layer is formed of an alloy containing In-O- (Ni, Mn, Mo), and the recording layer is made of It is composed of an alloy containing Se and/or Te elements, cerium (oxygen), and one element selected from Ti and Zr. Further, it has been proposed in the patent literature that the first recording layer contains a metal containing In as a main component, and the phase of the second recording of the second recording medium constitutes a partiality, for example, a layer of an element. Layer, recording layer Two records Pd, 4 Record -5- 201232533 The layer contains at least one element belonging to the 5B or 6B group element, and a metal or a non-metal other than the laminated oxide is recorded by heating reaction or alloying. As a recording layer which decomposes the compound which comprises the said recording layer, for example, the patent document 5 discloses the recording layer which has a nitride as a main component, and it is set as the decomposition of the nitride by heating, and is performed. Recorded materials and organic pigment materials. As the recording layer of the above-described opening method, a recording layer composed of a low melting point metal material was examined. For example, Patent Document 6 proposes a recording layer composed of an alloy in which an element of Group 3B, Group 4B, and Group 5B is added to a Sn alloy. Further, Patent Document 7 proposes a recording layer composed of a Sn-based alloy containing Ni and/or Co in a range of 1 to 50% by atom. Further, Patent Document 8 discloses a recording layer composed of an In alloy containing 20 to 65 atom% of Co, which further contains one or more elements selected from the group consisting of Sn, Bi, Ge, and Si. %the following. Further, Patent Document 9 discloses a recording layer composed of Pd, Ag, and ytterbium, and the ratio of the number of atoms of Pd, Ag, and ytterbium is controlled within a predetermined range. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-331461 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2003-331461 (Patent Document 3) Japanese Patent Laid-Open Publication No. Hei 2 0 0 3 - 3 2 6 8 4 8 (Patent Document 4) Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the demand characteristics required for an optical information recording medium, it is required to have a sufficiently reproducible recording signal by writing the incident of laser light, as disclosed in Japanese Laid-Open Patent Publication No. 2005-238516. Signal amplitude (high-modulus variation): high signal strength (high C/N ratio); high durability that is difficult to cause deterioration and environmental degradation. The C/N ratio is the carrier-to-noise ratio, the ratio of the signal at the time of reading to the noise output level of the background. As the recording material disclosed in the above prior art, it is difficult to satisfy these requirements with a recording material unit. In the phase change mode, the recording layer has a low reflectance alone, so the reflectance in the state of the optical disc should be increased, and the reflective film is required. In order to increase the degree of modulation, it is necessary to provide a dielectric layer such as ZnS-SiO 2 on the upper and lower sides of the recording layer. The electric film), the number of layers constituting the optical disc is increased, and the productivity is poor. Since the interlayer reaction mode also requires a multilayer recording layer 'thereby increasing the number of layers constituting the optical disk', the productivity is poor. In the decomposition method, an optical information recording medium using an organic dye material as a recording layer is widely used 'but' because it is difficult to absorb visible light rays of a short wavelength (near 400 nm) such as blue laser and blue-violet laser, and thus cannot be obtained. Good record information 'can't increase record density. Further, the optical information recording medium using the organic dye material has difficulty in suppressing deterioration due to light such as sunlight and deterioration due to long-term storage. In contrast to the 'opening method', since the reflectance of the recording layer itself is high 201232533 and a large degree of modulation can be ensured, the number of layers constituting the optical disk can be reduced, but when a higher recording sensitivity is to be achieved, Step into the study. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a recording layer for an optical information recording medium that can reduce the number of layers of a optical disk and satisfy the above-mentioned required characteristics. And an optical information recording medium having the recording layer. The present invention which is capable of solving the above-mentioned problems is a recording layer for an optical information recording medium, that is, a recording layer which is recorded by irradiation of laser light, and has a purpose of containing an oxide of Mn and constituting an oxide contained in the recording layer. The atomic ratio of Μη in all the metal elements is 80 atom% or less, and does not contain metal Μn. Further, a preferred embodiment further contains at least one oxide selected from the group consisting of In oxide, Zn oxide, Sii oxide, and Cu oxide. The present invention also includes an optical information recording medium comprising the above-described recording layer for an optical information recording medium. Further, a preferred embodiment of the present invention is an optical information recording medium in which a dielectric layer is laminated on and/or under the recording layer for an optical information recording medium. The optical recording information medium of the present invention preferably does not contain a metal layer. In a preferred embodiment, the optical information recording medium has a recording layer for the optical information recording medium of -8 to 201232533, and has a transparent intermediate layer between the layers of the recording layer for the multilayer medium. According to the present invention, it is possible to improve the practical recording layer for an optical information recording medium (recording layer for a special optical information recording medium) excellent in recording laser recording sensitivity, and to have the recording recording medium (especially a single write type) In the present specification, the "recording sensitivity" will be described in detail in the column of the first embodiment, which means that by laser (writing laser), even a relatively low recording radium 5 In order to realize the recording of the write-once optical recording medium having excellent illuminance by writing laser, the inventors of the present invention have made an effort to achieve high C/Ν ratio and high modulating change. As a result, it has been found that if the recording layer is used, some of the recording layers have different materials, that is, they contain a Μη oxygen layer, or preferably contain Μη oxide, and are oxidized from In; f, Sn oxide, and Cu oxide. The recording layer of the selected compound in the group can achieve the intended purpose. If the laser is irradiated, the Μ 氧化物 oxide is decomposed and decomposed by the laser, and is generated in the portion irradiated by the laser. As a result, the formation is marked, and if such an irreversible recording method accompanying the generation of the laser bulb is employed, it is found that the recording sensitivity is high, and the present invention has been completed. The recording under the optical information recording power is a single write. Recording layer of light 豊) = excellent", such as the recording layer irradiation power, large shot, recording the layer of the layer and its record containing the present material 2?, Ζ η oxidation of at least one oxygen of the above recording layer Β oxygen (〇2 In the recording method of the recording layer of the present invention, 'the structure of the recording layer before the laser irradiation is amorphous' is also amorphous after the laser irradiation. 'This is different from the phase change method, and the phase change method uses 'amorphous crystals to be crystallized by laser irradiation. The reason why the recording layer of the present invention is excellent in recording sensitivity is considered to be that bubbles are generated by laser irradiation'. The portion where the mark is formed 'the transmittance is increased (ie, the reflectance is lowered) as compared with the portion where the bubble does not occur (ie, the portion where the mark is not formed), thereby Further, according to the present invention, by containing the Mn oxide in the recording layer, the light absorption rate of the film can be increased as compared with the recording layer containing no η η oxide, so that the writing light can be written. The laser energy is efficiently converted into thermal energy. Further, in the present invention, at least all of the metal elements constituting the oxide contained in the recording layer (preferably Μη and at least one selected from the group consisting of In, Zn, Sn, and Cu) are selected. In one element), since the ratio (atomic ratio) of the amount of Μn occupied therein is appropriately controlled, it is possible to control the laser power required for recording. As a result, according to the present invention, the power of the laser is practically recorded (approximately 5). 〜1 5mW), the decomposition of the above-mentioned cerium oxide η is promoted, and the recording inspiration can be improved. Further, the recording layer of the present invention does not contain metal Μη, because if the metal Μn is contained in the recording layer, the metal Μ Oxidation and decomposition proceed to 'deterioration. Therefore, the recording layer of the present invention does not contain metal Μn, so that long-term reliability reduction of the recording layer due to environmental deterioration can be suppressed. According to the results of the investigation by the inventors of the present invention, since the ratio (atomic ratio) of the amount of Μη is appropriately controlled, the characteristics of the -10-201232533 can be obtained as shown in the examples to be described later. Hereinafter, the structure of the recording layer of the present invention will be described in detail. In the present specification, for convenience of explanation, at least one element selected from the group consisting of In, Zn, Sn, and Cu is referred to as an X group element. As described above, the recording layer of the present invention is a recording layer which has been recorded by the irradiation of a clock, and is characterized by the fact that it contains Μη oxide. The preferred recording layer 'of the present invention contains Μη oxide' and at least one oxide selected from the group consisting of In oxide, Ζ η oxide, Sn oxide and Cu oxide. As described above, in the recording layer, metal Mn is not contained. The recording layer of the present invention contains an Μ η oxide, and is not particularly limited as long as the form of the Μ η oxide is a form which is usually present. Examples of the Μη oxide include an oxide composed of Μη and oxygen (〇), such as ΜηΟ, Μη304, Μη203, Μη02, and the like, and other elements contained in the recording layer (X group element = In, Zn, A composite oxide (X-Mnx-Oy) of at least one of Sn and Cu. In the recording layer of the present invention, the above-mentioned Μη oxide is contained, and the atomic ratio of Μη in all the metal elements constituting the oxide contained in the recording layer is required to be 80 atom% or less. If Μη is contained in an amount of more than 80 at%, the bubbles cannot be formed well by laser irradiation. A recording signal is not obtained. The recording layer of the present invention may contain, in addition to the η η oxide, at least one oxide selected from the group consisting of Iri oxide, Ζ η oxide, Sn oxide, and Cu oxide. These oxides are useful in controlling the refractive index of the film and controlling the recording sensitivity (modulation degree and C/N ratio). The form of the In oxide, the cerium oxide, the Sn oxide, and the Cu oxide is also a form which is usually in the range of -11 to 201232533, and is not particularly limited. For example, for the In oxide, In2〇3 or the like can be exemplified, and the Zn oxide can be exemplified. ZnO or the like is exemplified, and examples of the Sn oxide include SnO or Sn02, and examples of the Cu oxide include CuO and Cu20. In the present invention, at least one of the above oxides may be contained, and the In oxide, the Zn oxide, the Sn oxide, and the Cu oxide may be separately contained, or two or more kinds of oxides may be contained. Among the preferred oxides are In oxides. Further, when the recording layer contains the above-mentioned selective oxides, that is, In oxide, Zn oxide, Sn oxide, and Cu oxide, metal elements not containing them (i.e., metal In, metal Zn, metal Sn, metal) are preferable. Cu). This is because these metal elements oxidize by taking oxygen from other oxides, and in such a case, the characteristics of the recording layer are affected. In order to obtain a recording layer excellent in recording sensitivity, it is preferable to select an oxide (Μη oxide, and preferably a group composed of In oxide, Zn oxide, Sn oxide, and Cu oxide) constituting the recording layer of the present invention. The atomic ratio of the amount of Μ η in the metal element (Μη and the X group element) of at least one oxide (the case where the following formula is abbreviated as "Μη ratio") is 1 〇 atom% or more. Μη amount (atomic %) = {[Mn]/ ( [Mn]+[In]+[Zn]+[Sn]+[Cu] ) }χ100 where [Μη], [In], [Zn], [Sn] and [Cu] mean the amount of Mn (atomic %), the amount of In (atomic %), the amount of B (atomic ° / /), and the amount of 311 (atomic %) contained in the recording layer of the present invention, respectively. ), 〇11 amount (atomic %) ° Liao, when the recording layer does not contain In, Zn, Sn, Cu, respectively, as -12- 201232533 〇 atomic % calculated. When Μη is less than 10 atom%, the amount of oxidized enthalpy decomposed during laser irradiation is small, so that the amount of oxygen released is insufficient, and the generated bubbles are reduced, and as a result, the signal intensity (C/N ratio) becomes small. Further, in a multilayer optical disc having more than two layers in the recording layer, the recording layer farthest from the laser incident surface is required to have a certain degree of transmittance. When the Μn ratio is less than 10 atom%, the light absorption rate of the recording layer is also small, so that the laser power required for recording becomes large, which is not preferable. The Μn ratio is preferably 10% by atom or more, more preferably 12% by atom or more, and still more preferably 15% by atom or more. However, when the amount of cerium oxide η is large, the degree of modulation becomes small, so the Μn ratio is 80 atom% or less, preferably 70 atom% or less, and more preferably 60 atom% or less. The recording layer of the present invention contains Μη oxide as described above and may contain unavoidable impurities which are inevitably mixed during production. Further preferably, the recording layer of the present invention contains Μη oxide, and at least one oxide selected from the group consisting of In oxide, Ζ η oxide, Sn oxide, and Cu oxide, and may contain inevitably mixed in at the time of production. Inevitable impurities. The preferred film thickness of the above recording layer is different from the case where other layers such as a dielectric layer are inserted on and/or under the recording layer. The structure of the optical information recording medium differs depending on the structure of the optical information recording medium. However, when the recording layer is used in a single layer (when the dielectric layer is not provided), the thickness of the recording layer is preferably 10 to 60 nm. When the film thickness of the recording layer is too small, the amount of enthalpy of decomposition is small, so that it is difficult to obtain a sufficient change in reflectance due to recording. It is more preferably 20 nm or more, and particularly preferably 30 nm or more. Further, on the one hand, if the film thickness of the recording layer is too thick, the formation of the film takes time, the productivity is lowered, and the laser power required for recording becomes large. More preferably, it is 5 Onm or less, and the further step is preferably 45 nm or less. Further, when a dielectric layer is provided on and/or under the recording layer, the thickness of the recording layer is preferably 2 to 50 nm', more preferably 3 nm or more, further preferably 5 nm or more, and still more preferably 1 〇 nm or more, more preferably 40 nm or less, further preferably 15 nm or less. The recording layer of the present invention contains Μη oxide (specific ratio of Μη) as described above, preferably contains Μη oxide, and at least selected from the group consisting of In oxide, Ζ η oxide, Sn oxide, and Cu oxide. An oxide, but in order to obtain a recording layer of such a form, it is preferred to form a recording layer by a sputtering method. According to the sputtering method, it is also possible to ensure uniformity in film thickness distribution in the surface of the disk. In order to form a recording layer containing the above oxide by a sputtering method, reactive sputtering is performed, and it is preferable to adjust the gas flow rate as sputtering conditions. In particular, it is preferable that the ratio of the oxygen flow rate to the Ar (argon) flow rate is 0.5 times or more, and more preferably 1. times or more. Further, the ratio of the oxygen flow rate to the Ar flow rate is preferably 5 · 0 times or less. The other conditions of the sputtering method are not particularly limited, and the gas pressure can be controlled in a range of, for example, 0.1 to 1 .OPa by a general method, and the sputtering electrons can be controlled, for example, in the range of 0.5 to 20 W/cm 2 . As the sputtering target used in the sputtering method (hereinafter simply referred to as "target"), a tantalum material containing an indium oxide and the balance being an unavoidable impurity can be cited. A preferred target is (A) at least one oxide selected from the group consisting of ITO and oxidized from In-oxidation-14-201232533, Zn oxide, Sn oxide and Cu oxide, and the balance is not Avoid impurities. Alternatively, (B) a metal target containing at least one element selected from the group consisting of a Mn metal target 'and a group consisting of In, Zn, Sn, and Cu may be used instead of the target of the above (A) to cause them to simultaneously discharge. Multi-component sputtering was performed. It is also possible to use (C) a metal and oxide mixed target. The metal element becomes an oxide by introducing oxygen. It is also possible to use a sputtering target which is selected from the group consisting of ηη atoms contained in the sputtering targets of the above (A) to (C), and a group consisting of ln atoms, Zn atoms, Sn atoms and Cu atoms. The total of at least one atom (actually contained atoms), the ratio of Μη atoms is from 1 80 to 80 at%. 〇 Also, as the sputtering targets of the above (Α) and (C), especially the metal powder of Μη Or a powder of Μ 氧化物 oxide, and a powder of at least one oxide or metal selected from the group consisting of In oxide, Zn oxide, Sn oxide, and Cu oxide, is mixed, and sintered, using such sputtering The target is preferred in terms of productivity and in-plane uniformity and thickness control of the composition of the formed film. At the time of manufacture of the above sputtering target, although a trace amount is present, impurities are mixed into the sputtering target. However, the component composition of the sputtering target of the present invention is not limited to such a minute component which is inevitably mixed, and as long as the above characteristics of the present invention are not inhibited, a trace amount of these unavoidable impurities is allowed. The optical information recording medium of the present invention is characterized in that it has the above-described recording layer, and the mark is formed by the effect of the 〇2 gas generated by the decomposition of the oxide of Μη. In the present invention, the configuration other than the recording layer is not particularly limited to a configuration known in the art of using an optical information recording medium. The optical information recording medium of the present invention has the above-mentioned recording layer, and a dielectric layer is laminated on the upper and/or lower (at least one side) of the recording layer, and the metal layer ( Au, which is conventionally required for improving the reflectance, can be omitted. A metal layer of Cu, Al, Ni, Cr, Ti, or the like, and an alloy layer thereof are formed. The recording layer of the present invention as described above has a high reflectance and a rate of change, so that the signal can be sufficiently regenerated even if a reflective layer is not particularly provided: In addition, by providing a dielectric body on and/or under the recording layer, the dielectric layer can be improved. Signal strength can further improve signal characteristics. This prevents the escape of oxygen generated by the decomposition of the recording layer by the laser irradiation, thereby reducing the decrease in reflectance and ensuring the reflectance as the recording layer. The type of the dielectric layer is known, and examples thereof include Si, Al, In, Zn, Zr, Ti, Nb, Ta, Cr, Sn, and the like, Si, Al, In, Ge, Cr, Nb, and Mo. a nitride such as Ti; a Zn material; a carbide such as Cr, Si, Al, Ti, Zr, or Ta; a fluoride such as Mg or Ca; or a mixture thereof. It is preferable to use Ill2〇3 in consideration of productivity and a cartridge for recording. The film thickness of the dielectric layer is preferably approximately 2 to 30 nm. If the film thickness of the bulk layer is too small, the coverage of the 02 gas which is generated is insufficient, and the recording sensitivity is lowered. On the other hand, if the film thickness of the dielectric layer is too thick, interference with light causes the film to be laminated (recording layer + dielectric layer), and the shape of Ag is formed. Layer, due to scattering, needs for example; vulcanization, La susceptibility dielectric, and the absorption is reduced by the overall -16 - 201232533, so the required writing laser power becomes high, and the morphological change of the standard (bubble generation) is difficult Occurs, so the record is reduced. In consideration of such a case, a preferable film thickness when the dielectric layer is provided on the recording layer (laser non-incident side) is 3 to 15 nm, and a preferable film thickness at the upper layer (laser incident side) of the recording layer is substantially: In addition, as an optical information recording medium (disc), it is configured such that a light-transmitting layer is laminated thereon on a substrate on which a groove for guiding laser is engraved. For example, a polycarbonate norbornene-based resin, a cycloolefin-based copolymer, an amorphous polyolefin or the like can be used as the raw material of the substrate. As the light-transmitting layer, polycarbonate or ultraviolet light can be used. As a material of the light-transmitting layer, radium having high transmittance for recording and reproduction is preferable, and the light absorptivity is small. The thickness of the substrate is exemplified by an example of 1.2 mm. Further, the thickness of the light-transmitting layer is, for example, 0.1 to 9 . The recording layer of the present invention is excellent in recording characteristics. However, in order to improve recording layer properties or to further improve recording characteristics, an oxide layer may be provided on the recording layer and/or the lower layer. The nitride layer and the sulfide layer; by laminating these layers, the durability of the recording layer can be improved, and the recording characteristics can be improved step by step. Further, the above description shows a single-layer optical disc of each of the recording layer and the light-transmitting layer. However, the present invention is not limited thereto, and may be a recording layer and two or more layers of optical discs stacked in multiple layers. The formation of the sensitivity layer is set as 2 to be exemplified, and then resin. The additional resin has a durable upper layer such as 0.5 1.2 mm. Passing through a layer of light-transmitting layer -17-201232533 In the case of the above-mentioned two or more layers of optical discs, a recording layer group composed of a recording layer and an optical adjustment layer and a dielectric layer laminated as needed, and other recording layer groups Further, for example, a transparent intermediate layer made of a transparent resin such as an ultraviolet curable resin or polycarbonate may be used. By providing a transparent intermediate layer, the focus of the laser can be concentrated in the depth direction for multi-layer recording. The present invention is characterized in that the above recording layer is used, and a laminated film of a dielectric layer is provided on and/or under a preferred recording layer, a substrate other than the recording layer and a light transmissive layer, and a transparent intermediate The method of forming the layer or the like is not particularly limited, and it may be formed by a usual method to produce an optical information recording medium. Examples of the optical information recording medium include a CD, a DVD, and a BD. Specific examples include, for example, BD_R, which can irradiate a blue laser having a wavelength of about 3 80 nm to 45 0 nm, preferably about 405 nm, onto a recording layer to perform data. Recording and regeneration. [Examples] The present invention is not limited by the following examples, but the present invention is not limited to the following examples, and may be appropriately modified and implemented without departing from the spirit and scope of the above-described embodiments. Within the technical scope of the invention. In the present embodiment, the recording layer used is composed of at least one selected from the group consisting of In oxide, Ζ η oxide, Sn oxide, and Cu oxide, and is included in the investigation recording layer. The effect of the ratio of the Μn element and the combination of the X group elements on the recording characteristics and the like. -18-201232533 (1) Production of optical disc A schematic diagram of the configuration of the optical disc used in the present embodiment is shown in Fig. 1. As shown in Fig. 1, the optical disk has a structure in which a layer of the following layers is laminated on the polycarbonate substrate 1 in order: a dielectric layer 2; a recording layer 3 containing Mn oxide: a dielectric layer 4; and a light-transmitting layer 5. The above optical disc is produced as follows. As the disc substrate, a polycarbonate substrate 1 (thickness: 1.1 mm, diameter: 120 mm, track pitch: 32.32 μm, groove depth: about 25 nm) was used, and DC magnetron sputtering was performed on the substrate 1. In the method, the lower dielectric layer 2 described in Table 1 and the recording layer 3 having different Μn ratios and the upper dielectric layer 4 described in Table 1 are formed in this order. The film thickness of the recording layer 3 was 40 nm, and the thickness of the dielectric layers 2, 4 laminated on the upper/lower side of the recording layer was 1 〇 nm up/down. Sputtering for recording layer formation was carried out in the following manner. The sputtering conditions at this time were Ar flow rate: 10 sccm, and oxygen flow rate: 10 sccm, gas pressure: 0.2 Pa, DC sputtering power: 100 to 200 W, substrate temperature: room temperature, and No. 1 and 2 in Table 1 were used in pure Μη. Target. In Νο. 3 to 7 of Table 1, a target of two elements of pure Μη and pure Cu was used to form a film by multi-equivalent sputtering, thereby changing the Μn ratio. Similarly, in No. 8 to 12, 15, and 16 of Table 1, a target of two elements of pure Μη and pure In was used, and a target of two elements of pure Μη and pure Sn was used in No.13, No. A target using pure Μη and pure Zn as elements in 1 4 . 201232533 In the dielectric layers 2, 4, the sputtering target 'Ar seem, and the oxygen flow rate: lOsccm, gas pressure: 〇. 2Pa' DC: 100~200W, substrate temperature: room temperature, forming the dielectric of Table 1 The bulk layer (the sputtering target is well known in the composition of Table 1, N 〇. 2, 4 〜 1 4 is I η 2 Ο 3, N 〇. 1 5 is S η Ο 2, N 〇. 1 < ) Then, "BRD-864" manufactured by UV-curable Shuhua Chemical Co., Ltd. was spin-coated on the dielectric layer 4, and then a light-transmitting layer of 0.1 mm was irradiated with ultraviolet rays to obtain an optical disk. The composition of the recording layer was formed into a single layer film (without a dielectric layer) under the same conditions as above, and analyzed by an ICP luminescence recording single layer film. (XPS analysis) With respect to each sample of Table 1, the state of Μη and In, Zn, Sn, Cu, and the like recorded were analyzed by the XPS method. Specifically, the X-ray photoelectron spectrometer SXM manufactured by Physical Electronics Co., Ltd. is characterized by the wide-area photoelectron spectroscopy based on the outermost surface, and then etched from the surface to the depth direction by Ar sputtering, and the constituent elements of the film are measured at the depth. Surface photoelectron spectroscopy. The depth direction component is calculated based on the narrow-area photoelectron energy intensity ratio and the relative sensitivity coefficient obtained at each depth. Further, the bonding state is estimated based on the peak position of the mixed energy spectrum (montage) of each element. As a result, in the No. flow rate: 1 〇 sputtering power component of the sputtering target 5 is Ζ Ο Ο 2 grease (the thickness of the film is about the recording layer, which is included in the layer, using the Quantera analysis) In the area of the narrow-spectrum spectrum of each solid element (atomic spectrum 3 to 16-20-201232533 in each sample], it is not confirmed that there are Μη and X group atoms in the recording layer as metal (record layer 3 except No) .l and 2 all contain Μη oxide, and do not contain metal Μη, and Νο·3~16 contains oxides of group X elements.) The same analysis was performed for dielectric layers 2 and 4. (2) Evaluation of optical discs The initial recording characteristics (recording laser power, C/N ratio, and modulation degree) of the produced optical disk were evaluated as follows. First, an optical disk evaluation device "ODU-1 000" manufactured by PULSTEC Industrial Co., Ltd. (recording laser center wavelength: 4 〇 5 nm, ΝΑ (number 値 aperture): 0.85), irradiation reproduction/recording of laser, reading and recording of the optical disk. The linear velocity was evaluated as 4.92 m/s. About the modulation degree (the C/N ratio becomes the largest) Point modulation), using Yokogawa Digital oscilloscope "DL1 640", which measures the maximum reflectivity and minimum reflectance of the recorded portion, and is calculated based on the following formula: Modulation (ratio) = (maximum reflectance - minimum reflectance) / (maximum reflectance) For the C/N ratio, the R3131A line analyzer manufactured by ADVANTEST is used to measure the recording power that can obtain the highest C/N ratio. In detail, it is the mark of 〇.6〇μιη that is repeatedly recorded (equivalent to Blu-ray Disk). 8T), measuring the signal intensity (carrier C/dB) of the 4.12MHz frequency component when the signal is read at 3mW, and the signal strength (noise N/dB) of the frequency components before and after it is calculated. The ratio of these results is shown in Table 1. Table 1 shows the power (recording power) of the recorded laser when the highest C/N ratio is obtained and the highest ratio of 21 - 201232533 C/Ν. In the examples, the modulation degree (ratio) is 〇·4 or more, and the C/N ratio is 43 or more, which is excellent in recording sensitivity. [Table 1] Lower dielectric layer 2 Recording layer 3 Upper dielectric layer 4 C/N Specific modulation (ratio) recording power [mW] 1 4nt m Μη - · β 2 In2〇3 Μη In2〇3 Cannot record » - 3 No Cu70Mn30 No 51 0.18 5 4 In2〇3 Cu90Mnl0 In2〇3 55 0.66 8 5 Ιη2〇3 Cu70Mn30 In2〇3 58 0.77 6 6 In2〇3 Cu40Mn60 In2 〇3 59 0.8 5.5 7 Ιη2〇3 Cu20Mn80 Ιιΐ2〇3 58 0.65 5.5 8 Ιπ2〇3 In90Mnl0 In2〇3 56 0.4 13 9 Ιη2〇3 In80Mn20 In2〇3 60 0.46 9.5 10 Ιη2〇3 In60Mn40 In2〇3 63 0.74 7.5 11 Ιη2〇3 In40Mn60 In2〇3 63 0.68 6 12 Ιη2〇3 In2〇Mn80 In2〇3 62 0.66 5 13 Ιη2〇3 Sn60Mn40 In2〇3 61 0.69 7 14 Ιη2〇3 Zn60Mn40 In2〇3 57 0.75 8 15 Sn〇2 ln60Mn40 Sn〇2 59 0.61 6 16 Ζη〇2 In60Mn40 Zn〇2 58 0.61 6 * The number of the recording layer is atomic %. (Atomic ratio of each metal ruthenium to all metal atoms from which oxygen atoms are removed). * The recording layer 3 and the components (oxides) in the surface of the dielectric layers 2 and 4 are formed. The remaining S is an unavoidable impurity. Table 1 can be examined as follows. First, the recording layers satisfying the regulations No. 4 to 16 of the present invention are excellent in both the degree of modulation and the C/Ν ratio. That is, it was confirmed that good recording characteristics were exhibited.
No.l、2是記錄層只由金屬Μη ( 100% )構成的比較 例，Νο·2是在記錄的上下設有介電體層的例子。於是 No. 1、2均不能進行記錄，因此不能對於C/Ν比、調變度 進行測量。 -22- 201232533 另外，Νο·3是沒有形成介電體層的例子，另 No .4〜16是在記錄層的上下形成介電體層的例子。 Νο·3，形成介電體層的No.5中，C/N比提高，I 提高4倍左右。因此可知，透過在記錄層上下設a 層，能夠得到更高的調變度。其理由被認爲是由方 鐳射輸入，Μη氧化物被分解時，通過使介電體开 發生的〇2，形態變化帶來的標記形成變得容易。 另外，記錄層的組成不是Μη氧化物和In氧{· 是使用Μη氧化物和Sn或Zn的氧化物的記錄層 、14 )時，與含有Μη氧化物和In氧化物的f No. 10)也同樣，能夠得到良好的調變度和C/N {： ，使用Sn氧化物、Zn氧化物的介電體層（No.l 時，也與No.l〇(In氧化物的介電體層）同樣，食 良好的調變度和C/N比。 【圖式簡單說明】 圖1是表示實施例1製作的光資訊記錄媒體 模式圖。 【主要元件符號說明】 1 :基板 2、4 :介電體層 3 :記錄層 5 :透光層 -方面， 相對於 !變度也 ί介電體 t，記錄 f中嵌入 S物，而 (No. 1 3 ，錄層（ :。另外 5、16 ) i夠得到 槪略的 -23-Nos. 1 and 2 are comparative examples in which the recording layer is composed only of metal Μ (100%), and Νο·2 is an example in which a dielectric layer is provided on the upper and lower sides of the recording. Therefore, No. 1 and 2 cannot be recorded, so the C/Ν ratio and the modulation degree cannot be measured. -22-201232533 Further, Νο·3 is an example in which a dielectric layer is not formed, and Nos. 4 to 16 are examples in which a dielectric layer is formed on the upper and lower sides of the recording layer. Νο·3, in No. 5 in which the dielectric layer was formed, the C/N ratio was increased, and I was increased by about 4 times. Therefore, it can be seen that a higher degree of modulation can be obtained by providing the a layer on the upper and lower sides of the recording layer. The reason for this is considered to be that it is input by a square laser, and when the Μη oxide is decomposed, it is easy to form a mark by morphological change by causing 介2 to occur in the dielectric opening. Further, the composition of the recording layer is not Μη oxide and In oxygen {· is a recording layer using 14 Μ 氧化物 oxide and an oxide of Sn or Zn, 14 ), and f No. 10) containing Μ 氧化物 oxide and In oxide. Similarly, a good modulation degree and C/N {:, a dielectric layer using Sn oxide or Zn oxide (in the case of No. 1, also with No. 1 ( dielectric layer of In oxide)) Similarly, a good modulation degree and a C/N ratio are shown. Fig. 1 is a schematic view showing an optical information recording medium produced in the first embodiment. [Description of main component symbols] 1 : Substrate 2, 4: The electric layer 3: the recording layer 5: the light transmissive layer - the surface is also the dielectric t, and the S is embedded in the f, and (No. 1 3 , the recording layer (:. 5, 16) i is enough to get a strategic -23-