1236672 A7 ___B7 五、發明説明（”） 〔本發明所屬之技術領域〕 (請先閲讀背面之注意事項再填寫本頁) 本發明係有關一種耐硫化性甚至是對碟片基板（聚碳 酸酯基板等）及構成碟片的其他薄膜之密著性（以下有「 針對基板等之密著性」爲代表的場合）亦優之光資訊記錄 媒體用反射層（光碟用反射層）、光資訊記錄媒體及光資 訊記錄媒體之反射層用濺鍍靶。由於本發明的反射層也有 很高的反射率，故適用於CD - RW、DVD - RAM、 DVD - RW、DVD + RW等之相變化型光碟（可重複 記錄、再生的光碟）、CD-R、DVD-R等之追加型 光碟。 〔習知技術〕 光碟有好幾種，但以具備能直接記錄在碟片的可記 錄區域之光記錄媒體代表例，舉例有：相變化型光碟及追 加型光碟。 經濟部智慧財產局員工消費合作社印製 其中相變化型的光碟是控制雷射光的功率和照射時間 ，於記錄薄膜層形成結晶相和非晶質相之2相狀態藉此來 記錄資料，並檢測2相的反射率變化藉此執行資料的檢測 (再生）。以此記錄再生方式就可重複記錄、再生，採用 相關方式的光碟，試舉有：CD - RW、DVD — RAM 、DVDRW、DVD + RW 等。 上述相變化型的光碟是指以基板、和在該基板上積層 電介體薄膜層、記錄薄膜層、反射薄膜層、及保護膜層等 各種薄膜層形成的。其中反射薄膜層因兼具散熱薄膜層之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） "~ _ 4 - 1236672 A7 ____B7 五、發明説明（2 ) (請先閲讀背面之注意事項再填寫本頁) 效’故要求該反射薄膜層用材料對反射率、熱傳導率、熱 衝撃之耐久性、耐蝕性以及對基板等的密著性等之諸特性 要十分的良好。尤其就高密度記錄方面，由提高記錄密度 的觀點來看，反射散熱層的熱傳導率爲大的條件是不可或 缺的。可是實際上滿足相關要求特性的反射層用材料並未 被提及。 例如廣泛應用作反射薄膜層材料的A 1合金，對使用 於記錄再生的雷射波長（780nm、65〇nm)而言 ’是具有較高的反射率及耐蝕性（化學上的耐蝕性），但 就反射率這點來看還不夠充分，還有熱傳導率低的缺點。 因而A 1合金用於反射薄膜層要具備該反射層所要求的諸 特性是很困難的，其結果對碟片的構造、設計上產生限制 很不恰當。 於是提案一取代A1合金，使用以Au，Ag，Cu 經濟部智慧財產局員工消費合作社印製 作爲反射薄膜用材料，但卻有各種以下所掲示的問題。例 如純A u或者以A u爲主成份的合金，雖可達到高反射率 、高耐蝕性及高熱傳導率，但A u是極昂貴的，很不實用 。一方面，純A g、純C u，或者以A g、C u爲主成份 的合金雖很便宜，但無論那一者均有耐蝕性差的缺點。而 純C u或者以C u爲主成份的合金會有耐蝕性尤其是耐氧 化性差的問題，其結果招致碟片可靠性（耐久性）降低之 虞。甚至純A g或者以A g爲主成份的合金就算沒有耐蝕 性差還是會有耐硫化性差的問題。 其中最後所掲示的耐硫化性，無論是相變化型、追 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1236672 A7 _B7_ 五、發明説明（3) (請先閲讀背面之注意事項再填寫本頁) 加型（容於後述）之任一種光碟均要求的特性。上述相變 化型的光碟，電介體薄膜層和反射薄膜層是直接接觸的方 式。其中電介體薄膜一般是用ZnS — S i〇2膜，若於反 射薄膜層使用純A g或以A g爲主成份的合金，經長期間 使用，該電介體薄膜中的S與反射薄膜中的A g會在界面 產生反應而生成A g S。其結果反射薄膜層所要求的種種 特性變差，最後碟片的記錄再生特性明顯的受到損傷。 而用上述A u、A g、C u之各材料時，相對於任一 種基板等的密著性都有變差的問題。光碟之反射散熱層隨 重複記錄，因熱循環引起的熱效應衝撃，會使得與該反射 散熱層的界面接合的其他薄膜之附著力降低。其結果實效 上會發生熱傳導降低、熱傳導斑紋，最後顫動等增加，碟 片的記錄再生特性明顯變差。 經濟部智慧財產局員工消費合作社印製 一方面，追加型光碟會因雷射光的功率引起記錄薄膜 層（有機染料層）的染料發熱、變質，使凹軌（預刻在基 板的溝槽）變形，藉此記錄資料，檢測變形處的反射率和 未變形處的反射率之差，藉此執行資料的檢測（再生）。 此記錄再生方式特徵爲，記錄一次資料且不能重寫（記錄 和重複再生僅限一次），採用相關方式的光碟，試舉有： CDR、DVD — R 等。 而於前述相變化型光碟所發現的問題，同樣也會發生 在追加型光碟的反射薄膜層中。 上述追加型光碟所用的反射薄膜層用材料，廣泛應用 A u或以A u爲主成份的合金。該些材料對於使用在記錄 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ' '-- 1236672 A7 ___ B7_ 五、發明説明（4 ) 再生的雷射波長（780nm、650nm)，存在有機 染料層中還是可達到7 0%以上的高反射率。但是a u是 極昂貴的，爲成本上昇的主因。 於是提案一取代上述材料，採用Ag、Cu、A 1作 爲反射薄膜材料。可是以純A g、純C u爲主成份的合金 ’耐蝕性有如前述般變差的缺點。而以純A g或以A g爲 主成份的合金，會有耐鈾性尤其是耐硫化性的問題。追加 型光碟與相變化型光碟不同，不具有以Z n S - S i〇2爲 主成份的電介體薄膜層但有於有機染料層中使用S添加材 料的情形。相關情形，因記錄薄膜層和反射薄膜層是直接 接合，該反射薄膜中的A g會與S —起反應而硫化，其結 果反射率降低，最後碟片的記錄再生特性恐有顯著劣化之 虞。而以純A 1或以A 1爲主成份的合金，反射率低，若 具有有機染料層的話，也有無法達到7 0 %以上的高反射 率之問題。 按此無論是相變化型、追加型，雖然光碟的反射薄膜 層要求相對於反射率、熱傳導率、熱衝撃的耐久性、耐蝕 性、以及相對於基板等的密著性之諸特性優，但卻未提供 得以滿足所有該些之要求特性的金屬薄膜層。 〔發明欲解決之課題〕 本發明係有鑑於上述情形之發明，其目的在於提供一 當然具有高反射率，尤以耐硫化性優，甚至相對於碟片基 板（聚碳酸酯基板等）以及構成碟片之其他薄膜的密著性 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） I—一---1------ (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 1236672 A7 _______B7 五、發明説明（5) 亦很良好的新式光資訊記錄媒體用反射層，光資訊記錄媒 體及光資訊記錄媒體的反射層用濺鍍靶。 (請先閲讀背面之注意事項再填寫本頁) 〔用以解決課題之手段〕 解決上述課題所獲得的本發明之光資訊記錄媒體用反 射層主旨係爲具有含Znl . 5%以上的Ag基合金所構 成。此例中，上述Ag基合金更由以cu、T i 、Nd、 W、Mo、S η及Ge所組成的群中至少選擇一種元素之 合計含有0 . 5〜5 %，對基板等最好是密著性高的，而 上述Ag基合金更由以Cu、Ni 、Au、Y及Nd所組 成的群中至少選擇一種元素，最好合計含有〇 . 5〜3% 之反射特性及耐氧化性高的。 而具備上述光資訊記錄媒體用反射層的光資訊記錄媒 體、以及用上述A g基合金所構成的光資訊記錄媒體的反 射層用濺鍍靶也包括在本發明範圍內。 〔發明之實施形態〕 經濟部智慧財產局員工消費合作社印製 本發明人等專心檢討光資訊記錄媒體用反射層所要求 的諸特性中，尤以耐硫化性，甚至也提高針對碟片基板（ 聚碳酸酯基板等）及構成碟片的其他薄膜之密著性。如前 所述，習知的反射層材料，以提高相變化型光碟的耐鈾性 (尤其是耐硫化性）爲目的則使用A 1合金，以提高追加 型光碟的反射率及耐蝕性（尤其是化學上的安定性）爲目 的則使用純A u或者純A g，但未獲得所希望的特性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -8- 1236672 A7 __________B7 五、發明説明（6 ) (請先閲讀背面之注意事項再填寫本頁) 具體而a ’本發明人等應用於a g中添加各種元素所 製作的A g基合金濺鍍靶，利用濺鍍法形成由各種成份組 成所製成的A g基合金薄膜，評估作爲反射薄膜層的特性 。其結果含有特定量的Ζ η之A g基合金薄膜，其耐硫化 性極優，更發現於上述A g - Ζ η合金中，添加由C u、 N i 、Au、Υ及Nd所組成的群中至少選擇一種元素的 話，會進一步提高反射特性及耐蝕性（尤其是耐氧化性） ，添加由W、Mo、Sn及Ge所組成的群中至少選擇一 種元素的話’密著性顯著提高，至完成本發明。 一般反射率在A g中添加合金元素的情形會比只用純 A g的情形更爲減少之傾向。但如本發明般適當地調整合 金的成份組成、添加量，不但可將減少的反射率控制在容 許範圍內，比起習知來更可以高水準來達成耐硫化性、密 著性等諸特性。 以下針對構成本發明之光資訊記錄媒體用反射層的要 件做說明。 經濟部智慧財產局員工消費合作社印製 首先，本發明之反射層是用含有Znl.5%以上的 A g基合金所構成。亦即本發明重點在於，於A g基合金 中添加1 · 5 %以上的Ζ η，即知耐硫化性顯著提昇。 根據本發明人等的檢討結果，首先，即知A g - Ζ η 合金薄膜中，Ζ η添加量愈多耐硫化性就愈提昇。詳細情 形爲，Ζ η添加量在0〜1 . 5%的範圍中，Ζ η量愈多 耐硫化性也愈爲提昇，因添加Ζ η而發現耐硫化性上昇效 果極爲顯著，上述效果若Ζη添加量超過1.5%會開始 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐1 ~ " '~ 1236672 A7 B7 ___ 五、發明説明（7) (請先閲讀背面之注意事項再填寫本頁) 鈍化，超過5 %幾乎是飽和的關係，所以就算添加5 %以 上對節約而言還是不合理的。但考慮與反射特性的關係， 其上限定爲5% (更好爲3%)較佳。檢查Ag - Zn合 金薄膜之反射率時，則有Ζ η添加量愈多反射率愈小的傾 向（參照後述之實施例）。因而要維持高反射率，耐硫化 性也要確實更優的關係，Ζ η的添加量最好控制在1 . 5 〜5 %的範圍。 且連習知之光資訊記錄媒體用反射層也是應用A g -Ζ η基合金的實例。但如本發明般添加特定量的ζ η，藉 此提高耐硫化性的認識，經仔細調查所有內容均完全沒有 提及。 經濟部智慧財產局員工消費合作社印製 例如於日本特開平第1 0 - 1 1 7 9 9號公報中所揭 示之以A g爲主成份作爲光反射層的光記錄媒體。但即使 仔紐調查該公報，未意識到Ζ η爲雜質，不過是基於「降 低反射率」的大原則來決定添加量。並於特開平第1 1 -1 5 4 3 5 4號公報中乃揭示一於反射散熱層添加Ag及 C u，更得以添加Ζ η之光記錄媒體。上述公報所記載的 是以藉由添加Ζ η來改善A g - C u基反射散熱層的耐蝕 性爲主旨，但更進一步深入，並不如本發明般有啓發Ζ η 能有效改善耐硫化性的認識。 按此’就光資訊記錄媒體分野而言，提升耐硫化性目 的而添加Ζ η是很有效的知見，習知並不知道，經本發明 人等首先發現，此點具有本發明技術上的意義。 再者’本發明目的在於更加提高光資訊記錄媒體用反 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ~ ~ ~ 1236672 A7 ______B7 五、發明説明（8 ) 射層所要求的基本特性〔即反射率及耐鈾性（耐氧化性） (請先閲讀背面之注意事項再填寫本頁) 〕，更由以C u、N i 、A u、Y、N d所組成的群中至 少選擇一種元素，合計含有〇 . 5〜3% (更好爲〇 . 5 〜2%)爲佳。該些元素的合計添加量未滿〇 · 5%，上 述作用無法充分發揮，一方面，上述元素的合計添加量超 過3 %的話，反之該作用降低，作爲光資訊記錄媒體用反 射層的性能變差。 而各元素較佳的添加量，由於在上述元素間，效果發 現區不同，故略有不同。具體是維持控制在Cu : 〇. 5 〜2%、Ni : 0 · 5 〜2%、Au : 〇 · 5 〜1 . 5% 、Y: 1〜3%、Nd: 1〜3%的範圍內。上述範圍內 能維持於與應用純A g薄膜同程度的高反射率。 而上述元素可單獨一種或倂用兩種以上，但至少維持 添加A u。隨A u添加量增多，尤其無法經由實驗證明耐 硫化性提高。但A u很貴，若考慮到多量添加會招致成本 上昇，最好如前所述控制在0 · 5〜1 · 5 %的範圍內， 藉此就能以最小限度的費用來發揮所希望的特性。 經濟部智慧財產局員工消費合作社印製 進而本發明係以提高相對於基板等之密著性爲目的， 在上述Ag — Zn基合金之中，更將由以Cu、T i 、1236672 A7 ___B7 V. Description of the invention (") [Technical field to which the present invention belongs] (Please read the precautions on the back before filling out this page) The present invention is related to a kind of vulcanization resistance, even for disc substrates (polycarbonate substrates) Etc.) and the adhesiveness of other films constituting the disc (in the case of "adhesion against substrates" below), it is also a good reflective layer for optical information recording media (reflective layer for optical discs) and optical information recording. Sputter targets for reflective layers of media and optical information recording media. Since the reflective layer of the present invention also has a high reflectance, it is suitable for phase-change optical discs (reproducible recording and reproducing discs), CD-R, such as CD-RW, DVD-RAM, DVD-RW, DVD + RW, etc. , DVD-R, etc. [Known technology] There are several types of optical discs, but representative examples of optical recording media that can be directly recorded on the recordable area of the disc include, for example, phase change discs and write-once discs. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a phase-change optical disc in which the power and irradiation time of the laser light are controlled, and a two-phase state of a crystalline phase and an amorphous phase is formed on the recording film layer to record data and detect The change of the reflectance of the two phases thereby performs data detection (reproduction). In this recording and reproduction mode, you can repeat recording and reproduction. Discs using related methods include CD-RW, DVD-RAM, DVDRW, DVD + RW, etc. The phase change type optical disc is formed by a substrate and various thin film layers such as a dielectric thin film layer, a recording thin film layer, a reflective thin film layer, and a protective film layer laminated on the substrate. Among them, the reflective film layer is compatible with the Chinese paper standard (CNS) A4 specification (210X297 mm) due to the paper size that also has a heat-dissipating film layer. 5. _ 4-1236672 A7 ____B7 V. Description of the invention (2) (Please read the Please fill in this page again for more details.) Therefore, it is required that the material for the reflective film layer has excellent properties such as reflectance, thermal conductivity, thermal shock resistance, corrosion resistance, and adhesion to substrates. In particular, in terms of high-density recording, from the viewpoint of increasing the recording density, the condition that the thermal conductivity of the reflective heat dissipation layer is large is indispensable. However, the material for the reflective layer which actually satisfies the required characteristics is not mentioned. For example, the A 1 alloy, which is widely used as a material for reflective thin film layers, has a high reflectivity and corrosion resistance (chemical corrosion resistance) for laser wavelengths (780 nm, 65 nm) used for recording and reproduction. However, it is not sufficient in terms of reflectance, and has the disadvantage of low thermal conductivity. Therefore, it is very difficult for the A 1 alloy to be used in the reflective thin film layer to have the characteristics required by the reflective layer, and as a result, the structure and design of the disc are very restricted. Therefore, the first proposal replaced the A1 alloy and used Au, Ag, Cu printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy as the material for the reflective film, but it had various problems as described below. For example, pure Au or alloys with Au as the main component can achieve high reflectivity, high corrosion resistance, and high thermal conductivity, but Au is extremely expensive and very impractical. On the one hand, although pure Ag, pure Cu, or alloys mainly composed of Ag and Cu, are cheap, no matter which one has the disadvantage of poor corrosion resistance. On the other hand, pure Cu or alloys containing Cu as the main component have the problem of poor corrosion resistance, especially poor oxidation resistance. As a result, the reliability (durability) of the disc may be reduced. Even pure Ag or alloys containing Ag as the main component have poor corrosion resistance, even if they do not have poor corrosion resistance. Among them, the vulcanization resistance shown at the end, whether it is a phase-change type, or the size of the paper, applies the Chinese National Standard (CNS) A4 (210X 297 mm) 1236672 A7 _B7_ V. Description of the invention (3) (Please read the back Note: Please fill in this page again.) Features required for any type of discs (described later). In the phase change optical disc, the dielectric thin film layer and the reflective thin film layer are in direct contact with each other. The dielectric thin film is generally a ZnS-Si 102 film. If pure Ag or an alloy containing Ag is used as the reflective thin film layer, S and reflection in the dielectric thin film are used for a long period of time. Ag in the film will react at the interface to form Ag S. As a result, various characteristics required for the reflective film layer are deteriorated, and the recording and reproduction characteristics of the disc are significantly damaged in the end. On the other hand, when each of the above-mentioned materials Au, Ag, and Cu is used, there is a problem that the adhesion to any substrate or the like is deteriorated. The reflective heat dissipation layer of the optical disc is repeatedly recorded, and the thermal effect caused by thermal cycling will reduce the adhesion of other films bonded to the interface of the reflective heat dissipation layer. As a result, a decrease in heat conduction, a heat conduction streak, and an increase in tremors and the like eventually occur, and the recording and reproduction characteristics of the disc are significantly deteriorated. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy , So as to record the data, detect the difference between the reflectance at the deformed position and the reflectance at the undeformed position, thereby performing the detection (regeneration) of the data. This recording and reproduction method is characterized in that the data is recorded once and cannot be rewritten (recording and repeated reproduction are limited to one time). The discs using related methods include CDR, DVD — R, etc. The problems found in the aforementioned phase change optical discs also occur in the reflective film layer of the additional type optical discs. As the material for the reflective film layer used in the above-mentioned supplementary optical disc, Au or an alloy containing Au as a main component is widely used. For these materials, the Chinese National Standard (CNS) A4 specification (210X297 mm) is used for the recording ^ paper size. '-1236672 A7 ___ B7_ V. Description of the invention (4) Regenerated laser wavelength (780nm, 650nm), In the presence of organic dye layers, a high reflectance of more than 70% can still be achieved. But a u is extremely expensive, which is the main cause of rising costs. Therefore, proposal 1 replaces the above-mentioned materials and uses Ag, Cu, A 1 as the reflective film material. However, alloys containing pure Ag and pure Cu as their main components have the disadvantage that the corrosion resistance deteriorates as described above. On the other hand, alloys containing pure Ag or Ag as the main component have problems with uranium resistance, especially sulfur resistance. Unlike a phase change optical disc, a supplemental optical disc does not have a dielectric thin film layer containing Z n S-S i02 as a main component, but may use an S additive material in an organic dye layer. In a related case, since the recording film layer and the reflective film layer are directly bonded, Ag in the reflective film reacts with S and vulcanizes. As a result, the reflectance is reduced, and the recording and reproduction characteristics of the final disc may be significantly deteriorated. . On the other hand, pure A 1 or an alloy containing A 1 as a main component has a low reflectance. If an organic dye layer is provided, there is a problem that a high reflectance of 70% or more cannot be achieved. Regardless of whether it is a phase change type or an additional type, although the reflective film layer of the optical disc is required to have excellent characteristics with respect to reflectance, thermal conductivity, thermal shock resistance, corrosion resistance, and adhesion to a substrate, etc., No metal thin film layer is provided to satisfy all of these required characteristics. [Problems to be Solved by the Invention] The present invention is an invention in view of the above-mentioned circumstances, and its object is to provide a high reflectivity, of course, particularly excellent vulcanization resistance, even for a disc substrate (polycarbonate substrate, etc.) and composition. Adhesion of other films on the disc This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) I— 一 --- 1 ------ (Please read the precautions on the back before filling (This page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperative, printed 1236672 A7 _______B7 V. Description of the invention (5) The reflective layer for the new-type optical information recording medium, the optical information recording medium and the reflective layer for the optical information recording medium Sputter target. (Please read the precautions on the back before filling in this page) [Means to solve the problem] The reflection layer for the optical information recording medium of the present invention obtained by solving the above problem is to have an Ag group containing Znl. 5% or more Made of alloy. In this example, the Ag-based alloy is further composed of at least one element selected from the group consisting of cu, T i, Nd, W, Mo, S η, and Ge. The total content of the element is 0.5 to 5%. It is highly adhesive, and the Ag-based alloy is further composed of at least one element selected from the group consisting of Cu, Ni, Au, Y, and Nd, and preferably contains a total of 0.5 to 3% of reflection characteristics and oxidation resistance. Sexually high. An optical information recording medium having the above-mentioned reflective layer for an optical information recording medium and a sputtering target for a reflective layer of the optical information recording medium made of the Ag-based alloy are also included in the scope of the present invention. [Implementation form of the invention] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the inventors and others focused on reviewing the various characteristics required for the reflective layer for optical information recording media. Especially, the resistance to vulcanization is improved, and even the disc substrate ( Polycarbonate substrates, etc.) and other films that make up the disc. As mentioned above, the conventional reflective layer material uses the A 1 alloy for the purpose of improving the uranium resistance (especially sulfur resistance) of phase change optical discs, in order to improve the reflectance and corrosion resistance of additional optical discs (especially For chemical stability), pure Au or pure Ag is used for the purpose, but the desired characteristics are not obtained. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -8- 1236672 A7 __________B7 V. Description of the invention (6) (Please read the precautions on the back before filling this page) Specific and a 'This invention People have applied Ag-based alloy sputtering targets made by adding various elements to ag, and formed Ag-based alloy films made of various components by a sputtering method, and evaluated the characteristics as reflective film layers. As a result, the Ag-based alloy thin film containing a certain amount of Z η has excellent vulcanization resistance. It is more found in the above-mentioned A g-Z η alloy, which is composed of Cu, Ni, Au, rhenium, and Nd. When at least one element is selected from the group, the reflection characteristics and corrosion resistance (especially oxidation resistance) are further improved. When at least one element is selected from the group consisting of W, Mo, Sn, and Ge, the adhesion is significantly improved. To complete the present invention. The general reflectance tends to decrease more when alloying elements are added to Ag than when only pure Ag is used. However, by appropriately adjusting the composition and addition amount of the alloy as in the present invention, not only the reduced reflectance can be controlled within the allowable range, but also various properties such as vulcanization resistance and adhesion can be achieved at a higher level than conventional ones . The following describes the elements constituting the reflective layer for the optical information recording medium of the present invention. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs First, the reflective layer of the present invention is composed of an Ag-based alloy containing Znl.5% or more. That is, the present invention focuses on adding Z η of more than 1.5% to the Ag-based alloy, which means that the vulcanization resistance is significantly improved. According to the results of the review by the present inventors, first, it is known that as the amount of added Z η in the Ag-Z η alloy thin film increases, the vulcanization resistance increases. In detail, the addition amount of Z η is in the range of 0 to 1.5%. The more the amount of Z η is, the more the vulcanization resistance is improved. It is found that the effect of increasing vulcanization resistance is extremely significant due to the addition of Z η. Adding more than 1.5% will start to apply the Chinese National Standard (CNS) A4 specification (210 × 297 mm 1 ~ " '~ 1236672 A7 B7 ___) 5. The invention description (7) (Please read the notes on the back before filling (This page) Passivation, the relationship of more than 5% is almost saturated, so it is unreasonable to save even if it is more than 5%. However, considering the relationship with reflection characteristics, the upper limit is 5% (better 3%) It is better. When the reflectance of the Ag-Zn alloy thin film is checked, the more the amount of Z η added, the smaller the reflectance (refer to the embodiment described later). Therefore, to maintain a high reflectance, the sulfur resistance must also be more accurate. The optimal relationship is that the addition amount of Z η is preferably controlled in the range of 1.5 to 5%. Moreover, even the conventional reflective layer for optical information recording media is also an example of the application of the Ag-Z η-based alloy. However, as in the present invention, Adding a specific amount of ζ η to improve vulcanization resistance After careful investigation, all contents were not mentioned at all. It is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, as disclosed in Japanese Unexamined Patent Publication No. 10-1 1 79 9 with A g as the main component. It is an optical recording medium for the light reflecting layer. However, even if Zainiu investigated the bulletin, he did not realize that Z η was an impurity, but decided to add the amount based on the general principle of "reducing the reflectance." The publication No. 5 4 3 5 4 discloses an optical recording medium in which Ag and Cu are added to the reflective heat dissipation layer to further add Z η. What is described in the above publication is to improve A g-C u by adding Z η The corrosion resistance of the base reflective heat dissipation layer is the main purpose, but it goes deeper and is not as inspiring as the present invention. Z η can effectively improve the vulcanization resistance. Click here for the purpose of improving the vulcanization resistance of optical information recording media. The addition of Z η is a very effective knowledge, and it is not known to the public. The inventors first discovered that this point has the technical significance of the present invention. Furthermore, the present invention aims to further improve the optical information recording medium. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ~ ~ ~ 1236672 A7 ______B7 V. Description of the invention (8) Basic characteristics required for the radiation layer [ie reflectance and uranium resistance (oxidation resistance) ( Please read the notes on the back before filling this page)]], and at least one element is selected from the group consisting of Cu, Ni, Au, Y, Nd, which contains a total of 0.5 to 3% (more It is preferably 0.5 to 2%). The total addition amount of these elements is less than 0.5%, and the above effects cannot be fully exerted. On the one hand, if the total addition amount of the above elements exceeds 3%, the effect is reduced. As a reflective layer for optical information recording media, the performance deteriorates. The preferred amount of each element is slightly different because the effect discovery area is different among the above elements. Specifically, it is maintained within a range of Cu: 0.5 to 2%, Ni: 0.5 to 2%, Au: 0.5 to 1.5%, Y: 1 to 3%, and Nd: 1 to 3%. . Within the above range, high reflectance can be maintained at the same level as the application of pure Ag film. The above elements may be used singly or in combination of two or more, but at least the addition of Au may be maintained. With the increase of the amount of Au added, the improvement of vulcanization resistance cannot be proved by experiments. However, Au is very expensive. If you consider that a large amount of addition will cause cost increase, it is best to control it in the range of 0.5 to 1.5% as described above, so that you can achieve the desired cost with the minimum cost. characteristic. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, the present invention aims to improve the adhesion to substrates. Among the Ag-Zn-based alloys mentioned above, Cu, T i,
Nd、W、Mo、Sn及Ge所組成的群中至少選擇一種 元素，合計添加0 . 5〜3% (更好爲0 · 5〜2%)的 範圍爲佳。該些元素的合計添加量未滿0 . 5 %，上述作 用無法充分發揮，一方面，上述元素的合計添加量超過3 %的話，反之該作用會降低，作爲光資訊記錄媒體用反射 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - A7 1236672 B7 五、發明説明（9) 層的性能變差。 而各元素的較佳添加量，在上述元素間由於效果發現 區域不同，會略不相同。具體是維持控制在Cu : 0 . 5 〜3%、Ti :0·5 〜2.0%、Nd:l.〇 〜 3.0%、W:0_5〜1.0%、Mo:〇.5〜 1 . 0%、Sn : 0. 5 〜2 · 0%、Ge ·· 〇 . 5 〜 3 . Ο %的範圍內。 本發明之光資訊記錄媒體用反射層係含有上述成份， 剩餘部爲A g，但更不損及本發明作用的範圍，也可添加 上述成份以外的其他成份。例如目的在獲得提高硬度等的 特性，也可積極地添加P d、P t等貴金屬和過渡元素（ 除前述以外的）。而且也可包括◦ 2，N 2等氣體成份和預 先包含在屬於溶解原料的A g - Ζ η基合金之雜質。 本發明推薦利用濺鍍法形成由上述成份組成所構成的 A g基合金。本發明所應用的元素〔提高耐硫化性元素（ Zn)、提高密著性元素（Cu、Ti 、Nd、W、Mo 、S η、G e )、提高反射特性及耐氧化性元素（C u、 N i 、Y、N d )〕是以平衡狀態對a g之固溶度極小的 (再者A u爲全率固溶），但利用濺鍍法形成的薄膜則因 濺鍍法固有氣相急冷而成爲非平衡固溶的緣故，相較於以 其他薄膜形成法形成A g基合金薄膜的場合，上述合金元 素會均勻地存在A g矩陣中，其結果耐硫化性、密著性顯 著的提昇。 而濃鍍時’濺鍍靶材最好是使用以熔解、鑄造法所製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公董） 丨卜——#! (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -12- A7 1236672 _____B7 五、發明説明（1〇) 作的A g基合金（以下稱「熔製A g基合金靶材料」）。 相關熔製A g基合金靶材料是組織均勻的材料，而濃射率 及出射角度均勻的緣故，會得到成份組成均勻的A g基合 金薄膜（反射金屬層）很安定的結果，製作更高性能的光 碟。再者’上述熔製A g基合金靶材料的氧含有量控制在 1 0 0 p pm以下’膜形成速度很容易保持一定，Ag基 合金薄膜膜的氧重也很低的關係，該A g基合金薄膜的反 射率及耐餓性（特別是耐硫化性）即顯著的提高。 根據以下實施例詳述本發明。但下述實施例並未使本 發明受到限制’只要在不脫離前、後所述之主旨的範圍做 變更實施，就全包括在本發明之技術範圍內。 〔實施例〕 實施例1 本實施例是硏究各種A g二元基合金薄膜的反射率及 高溫高試驗前後的反射率變化量。 先採用由表1所示之各種成份組成所製成的A g二元 基合金靶（含有2.0%各種合金元素），利用DC磁控 管濺鍍，於透明聚碳酸酯樹脂基板（基板尺寸：直徑5 0 mm、厚度1mm)上，製作形成厚度1 〇〇〇 的各種 A g二元基合金薄膜（反射薄膜層）之試料。其次，就上 述試料來看，是測定測定波長：8 0 0〜2 0 0 n m之範 圍內的反射率（分光反射率）。反射率是由反射薄膜層側 所測定。於表1倂記各種A g基合金薄膜之中之波長 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） IT (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -13- 1236672 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（M) 8 0 0 nm的反射率及波長3 9 0 nm的反射率。 〔表1〕 No. 合金系 反射率（％ ) 測定波：λ = 800ηιη 測定波長：λ = 390η 1 Ag-2.0% Zn 91.9 73.9 2 Ag-2.0% Ti 93.7 84.7 3 Ag-2.0% W 92.9 82.6 4 Ag-2.0% Mo 93.1 85:2 5 Ag-2.0% Sn 96.6 92.7 6 Ag-2.0% Ge 92.0 82.8 Ag-2.0% Cu 98.6 77.9 8 Ag-2.0% Ni 97.8 90.5 9 Ag-2.0% Au 99.7 92.3 10 Ag-2.0% Y 98.8 84.2 11 Ag-2.0% Nd 97.5 85.9 12 純Ag 98.3 88.3 13 Ag-2.0% A1 96.4 71.4 14 Ag-2.0% Ga 94.9 97.6 15 Ag-2.0% In 94.7 95.3 16 Ag-2.,0% Pd 95.7 86.9 17 Ag-2.00/〇 Pt 92.8 81.3 由表即知，No . 1〜1 1的Ag二元基合金，反正 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1236672 A7 B7 五、發明説明（12) 就是波長8 0 0 nm爲9 0%以上、波長3 9 0 nm爲 70%以上的高反射率示之，據知具有與No·12〜 1 7之A g二元基合金同程度之優異的反射率。當中添加 Sn、Cu、Ni 、Au、Y、Nd各元素的Ag二元基 合金’尤其初期反射率（以濺鍍成膜之後的薄膜反射率） 是很高的。 其次，使用上述試料作環境加速（負荷）試驗，來執 行高溫高濕試驗（用溫度8 0 °C、濕度9 0 % R Η實施 4 8小時），評估反射薄膜層的耐蝕性（耐氧化性）。具 體而言，針對完成高溫高濕試驗後的各試料，來測定反射 薄膜層的反射率（分光反射率），算出試驗前後的反射率 差（亦即完成試驗後的反射率減少量），藉此評估耐蝕性 (耐氧化性）。於表2表示各種A g基合金薄膜附加高溫 高濕試驗時的波長8 0 0 n m的反射率變化量及波長 3 9 0 nm的反射率變化量。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15- 1236672 A7 B7 五、發明説明（13) 經濟部智慧財產局員工消費合作社印製 〔表2〕 No. 合金系 反射率變化（□ V ) 測定波長：λ = 800ηιη 測定波長 :A = 390nm 1 A g - 2.0 % Zn + 2.5 -6.0 2 Ag-2.0% Ti + 2.5 -4.0 3 Ag-2.0% W -1.4 -5.8 4 Ag-2.0% Mo -12 -5.6 5 Ag-2.0% Sn -5.8 -15.0 6 Ag-2.0% Ge -16.1 -5.3 7 Ag-2.0% Cu -0.4 -6.7 8 Ag2.0°/〇 Ni -0.4 -5.3 9 Ag-2.0% Au -0.7 -2.6 10 Ag-2.0°/〇 Y + 1.5 -5.0 11 Ag-2.0% Nd + 2.1 + 8.7 12 純Ag -1.0 -9.6 13 Ag-2.00/〇 A1 -3.7 -15.7 14 Ag-2.0% Ga -16.1 -5.3 15 Ag-2.0% In -11.2 -8.9 16 Ag-2.0% Pd -0.7 -2.4 17 Ag-2.00/〇 Pt -0.9 -1.3 供實驗用的試料當中，尤以含有Z η、T i 、C u、 Ni 、Au、Y、Nd的各元素之Ag基合金，據知反射 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -16- A7 1236672 B7 五、發明説明（14) 率減少量少，耐蝕性（耐氧化性）極優。 (請先閱讀背面之注意事項再填寫本頁) 而考慮上述表1及表2的結果，由確保高反射率及高 耐蝕性（高耐氧化性）的觀點來看，得知特別是使用A g 〜Cu 基、Ag— N i 基、Ag— Au 基、Ag— Y 基、 A g - N d基各合金薄膜爲佳。 實施例2 本實施例是調查當A g二元基合金薄膜中的合金添加 量做各種變化時的初期反射率及高溫高濕試驗前後的反射 率變化量。 首先，在實施例1中，特別是反射率及耐蝕性均優的 各種薄膜’亦即Ag — C u基、Ag — N i基、Ag —At least one element is selected from the group consisting of Nd, W, Mo, Sn, and Ge, and a range of 0.5 to 3% (more preferably 0.5 to 2%) is added in total. The total added amount of these elements is less than 0.5%, and the above-mentioned effect cannot be fully exerted. On the one hand, if the total added amount of the above elements exceeds 3%, the effect will be reduced, and it will reflect the paper size as an optical information recording medium. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -11-A7 1236672 B7 V. Description of the invention (9) The performance of the layer is deteriorated. The preferred addition amount of each element will be slightly different due to the effect discovery area among the above elements. Specifically, the control is maintained at Cu: 0.5 to 3%, Ti: 0.5 to 2.0%, Nd: 1.0 to 3.0%, W: 0 to 5 to 1.0%, Mo: 0.5 to 1.0%, Sn: Within a range of 0.5 to 2.0%, and Ge to 0.5%. The reflective layer for an optical information recording medium of the present invention contains the above-mentioned components, and the remaining portion is Ag, but it does not impair the scope of the present invention, and other components may be added. For example, the purpose is to improve the hardness and other properties. It is also possible to actively add precious metals such as P d and P t and transition elements (other than the above). It may also include gaseous components such as ◦ 2, N 2 and impurities previously contained in the Ag-Z η-based alloy which is a dissolved raw material. In the present invention, it is recommended to form an Ag-based alloy composed of the above-mentioned components by a sputtering method. The elements used in the present invention [enhance sulfur-resistant element (Zn), improve adhesion element (Cu, Ti, Nd, W, Mo, S η, Ge), improve reflection characteristics and oxidation resistance element (C u , N i, Y, N d)] is a solution with a very low solid solubility in ag (again, A u is a solid solution at full rate) in equilibrium, but the thin film formed by the sputtering method has an inherent gas phase due to the sputtering method. Because it is rapidly cooled and becomes an unbalanced solid solution, compared with the case where an Ag-based alloy thin film is formed by other thin film forming methods, the above alloy elements are uniformly present in the Ag matrix. As a result, the vulcanization resistance and adhesion are remarkable. Promotion. In the case of thick plating, the sputtering target is best to use the paper made by melting and casting. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297). 丨 —— #! (Please read the precautions on the back first Fill out this page again) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-12- A7 1236672 _____B7 V. Description of the invention (10) A g-based alloy (hereinafter referred to as "melted A g-based alloy target material") . The related molten A g-based alloy target material is a material with uniform structure, and the uniform emissivity and emission angle are uniform. The result is a stable A g-based alloy film (reflective metal layer) with uniform composition and higher production. Performance disc. In addition, 'the oxygen content of the above-mentioned molten A g-based alloy target material is controlled below 100 p pm', the film formation rate is easily maintained constant, and the relationship between the oxygen weight of the Ag-based alloy thin film film is also low, and the A g The reflectance and starvation resistance (especially sulfur resistance) of the base alloy film are significantly improved. The invention is described in detail based on the following examples. However, the following embodiments do not limit the present invention ', as long as they are changed and implemented without departing from the scope of the subject matter described before and after, they are all included in the technical scope of the present invention. [Example] Example 1 This example investigates the reflectance of various Ag binary alloy films and the change in reflectance before and after a high temperature and high test. First, an Ag binary alloy target (containing 2.0% of various alloy elements) made of various components shown in Table 1 was used, and DC magnetron sputtering was applied to a transparent polycarbonate resin substrate (substrate size: A diameter of 50 mm and a thickness of 1 mm) were used to prepare samples of various Ag binary-based alloy films (reflective film layers) having a thickness of 1,000. Next, from the viewpoint of the above sample, the reflectance (spectral reflectance) in the range of 80 to 200 nm is measured. The reflectance is measured from the reflective film layer side. The wavelengths in the various Ag-based alloy films listed in Table 1 are in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). IT (Please read the precautions on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives-13- 1236672 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (M) Reflectance at 800 nm and reflectance at 390 nm. [Table 1] No. Alloy reflectance (%) Measurement wave: λ = 800ηιη Measurement wavelength: λ = 390η 1 Ag-2.0% Zn 91.9 73.9 2 Ag-2.0% Ti 93.7 84.7 3 Ag-2.0% W 92.9 82.6 4 Ag-2.0% Mo 93.1 85: 2 5 Ag-2.0% Sn 96.6 92.7 6 Ag-2.0% Ge 92.0 82.8 Ag-2.0% Cu 98.6 77.9 8 Ag-2.0% Ni 97.8 90.5 9 Ag-2.0% Au 99.7 92.3 10 Ag -2.0% Y 98.8 84.2 11 Ag-2.0% Nd 97.5 85.9 12 Pure Ag 98.3 88.3 13 Ag-2.0% A1 96.4 71.4 14 Ag-2.0% Ga 94.9 97.6 15 Ag-2.0% In 94.7 95.3 16 Ag-2., 0 % Pd 95.7 86.9 17 Ag-2.00 / 〇Pt 92.8 81.3 As you can see from the table, Ag binary base alloy No. 1 ~ 1 1 anyway (please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1236672 A7 B7 V. Description of the invention (12) It shows the high reflectance with a wavelength of 80 0 nm being more than 90% and a wavelength of 3 90 nm being more than 70%. It is known that it has excellent reflectivity to the same degree as the A g binary-based alloy of No. 12 to 17. In particular, the binary binary alloy of Ag, to which Sn, Cu, Ni, Au, Y, and Nd are added, has a particularly high initial reflectance (the reflectance of a thin film after being formed by sputtering). Next, the above samples were used as an environmental acceleration (load) test to perform a high-temperature and high-humidity test (using a temperature of 80 ° C and a humidity of 90% R Η for 48 hours) to evaluate the corrosion resistance (oxidation resistance) of the reflective film layer. ). Specifically, for each sample after the high temperature and high humidity test is completed, the reflectance (spectral reflectance) of the reflective film layer is measured, and the reflectance difference before and after the test (that is, the reflectance reduction after the test is completed) is calculated. This evaluates corrosion resistance (oxidation resistance). Table 2 shows the amount of change in reflectance at a wavelength of 800 nm and the amount of change in reflectance at a wavelength of 390 nm during various high temperature and high humidity tests of various Ag-based alloy films. (Please read the notes on the back before filling this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -15- 1236672 A7 B7 V. Description of the invention (13) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs [Table 2] No. Alloy system reflectance change (□ V) Measurement wavelength: λ = 800ηιη Measurement wavelength: A = 390nm 1 A g-2.0% Zn + 2.5- 6.0 2 Ag-2.0% Ti + 2.5 -4.0 3 Ag-2.0% W -1.4 -5.8 4 Ag-2.0% Mo -12 -5.6 5 Ag-2.0% Sn -5.8 -15.0 6 Ag-2.0% Ge -16.1- 5.3 7 Ag-2.0% Cu -0.4 -6.7 8 Ag2.0 ° / 〇Ni -0.4 -5.3-9 Ag-2.0% Au -0.7 -2.6 10 Ag-2.0 ° / 〇Y + 1.5 -5.0 11 Ag-2.0% Nd + 2.1 + 8.7 12 Pure Ag -1.0 -9.6 13 Ag-2.00 / 〇A1 -3.7 -15.7 14 Ag-2.0% Ga -16.1 -5.3 15 Ag-2.0% In -11.2 -8.9 16 Ag-2.0% Pd- 0.7 -2.4 17 Ag-2.00 / 〇Pt -0.9 -1.3 Among the experimental samples, especially Ag-based alloys containing the elements of Z η, Ti, Cu, Ni, Au, Y, Nd, it is known Reflect this paper standard applicable to China National Standard (CNS) A4 (210X 297mm) (Please read the notes on the back before filling out this page) -16- A7 1236672 B7 V. Description of the invention (14) The reduction rate is small, and the corrosion resistance (oxidation resistance) is excellent. (Please read the precautions on the back before filling in this page.) Considering the results of Tables 1 and 2 above, from the viewpoint of ensuring high reflectance and high corrosion resistance (high oxidation resistance), we know that A is particularly used. g ~ Cu-based, Ag-Ni-based, Ag-Au-based, Ag-Y-based, and Ag-Nd-based alloy thin films are preferred. Example 2 This example investigates the initial reflectance and the change in reflectance before and after a high-temperature and high-humidity test when the alloy addition amount in the Ag binary alloy film is variously changed. First, in Example 1, in particular, various thin films' having excellent reflectance and corrosion resistance, that is, Ag—Cu group, Ag—Ni group, and Ag—
Au基、Ag - Y基、Ag — d基之五種薄膜中，邊改變 合金元素的添加量邊測定測定波長8 0 0〜2 0 0 n m之 範圍中的反射率（分光反射率）。反射率是由反射薄膜層 側進行測定。於第1圖表示合金添加量和波長7 0 0 n m 方面的初期反射率之關係。 經濟部智慧財產局員工消費合作社印製 若自第1圖之任一 A g基合金薄膜中，合金元素添加 量爲0〜1 %的範圍初期反射率約9 9 %以上的話，就具 有與純A g薄膜同程度或以上之極尚的反射率。而合金元 素添加量若超過1 %，初期反射率會慢慢開始降低，但就 算添加5 %，也不過維持在約9 5 %以上的高初期反射率 0 其次，於上述試料中，藉由與實施例1同樣的方法來 氏張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐) " 1236672 A7 __ B7 五、發明説明（15) (請先閲讀背面之注意事項再填寫本頁) 評估反射薄膜層的耐蝕性（耐氧化性），調查耐蝕性和合 金兀素添加量的關係。於第2圖表示，高溫高濕試驗前後 之A g基合金薄膜中，波長7 0 0 nm之反射率和合金元 素添加量的關係。 由第2圖即知，任一 A g基合金薄膜的反射率減少量 都比純A g少，經由合金化即可提高耐鈾性（耐氧化性） 。再者，耐鈾性係合金元素添加量最大爲1 %左右，據知 添加量超過1 %即有降低之傾向，但因合金種類而添加3 %以上，考慮到耐蝕性比純A g低的見解，合金元素添加 量最好控制在0 · 5〜3 %的範圍內。 實施例3 本實施例是針對各種A g二元基合金薄膜於硫化氫（ Η 2 S )氣氛中實施曝露試驗來評估耐硫化性。 經濟部智慧財產局員工消費合作社印製 首先，用表3所示的各種A g二元基合金靶（合金元 素含2 . 0 % )，利用與實施例1同樣的方法形成各種 A g二元基合金薄膜（反射簿膜層），製作爲試料後，測 定測定波長8 0 0〜2 0 0 nm範圍中的反射率（分光反 射率）。其次，針對上述試料實施環境加速試驗即硫化氫 氣氛中曝露試驗〔氣氛··大氣+ H2S (50ppm)、溫 度5 0 °C、濕度9 0 % R Η〕，藉以評估反射薄膜層的耐 硫化性。具體而言是針對試驗結束後的試料測定反射薄膜 層的反射率（分光反射率），算出試驗前後的反射率差（ 亦即試驗結束後的反射率減少量），藉此評估耐硫化性。 I紙張尺度適用中國國家標準（CNS ) Α4規格（210x297公釐1 ~ ~ 1236672 A7 B7 五、發明説明（16) 於表3倂記針對硫化氫氣氛中曝露試驗前後的A g基合金 薄膜之波長8 0 0 nm的反射率變化量及波長3 9 0 nm 的反射率變化量。 〔表3〕Of the five types of Au-based, Ag-Y-based, and Ag-d-based films, the reflectance (spectral reflectance) in the range of 80 to 200 nm was measured while changing the amount of alloying elements added. The reflectance is measured from the side of the reflective film layer. The relationship between the amount of alloy added and the initial reflectance at a wavelength of 7 00 nm is shown in Fig. 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, if any alloy element is added in the range of 0 to 1% in any Ag-based alloy film shown in Figure 1, the initial reflectance will be more than 99%. A g film with extremely high reflectivity of the same level or above. If the amount of alloying elements exceeds 1%, the initial reflectance will gradually begin to decrease, but even if it is added at 5%, it will still maintain a high initial reflectance of about 95%. Secondly, in the above sample, by The same method is used in Example 1 to apply the Chinese National Standard (CNS) A4 specification (210X 297 mm) in the same method. &Quot; 1236672 A7 __ B7 V. Description of the invention (15) (Please read the precautions on the back before filling this page ) Evaluate the corrosion resistance (oxidation resistance) of the reflective film layer and investigate the relationship between the corrosion resistance and the amount of alloy element added. Fig. 2 shows the relationship between the reflectance at a wavelength of 700 nm and the amount of alloying elements in the Ag-based alloy thin film before and after the high temperature and high humidity test. As shown in Fig. 2, the reflectance reduction of any Ag-based alloy thin film is smaller than that of pure Ag, and uranium resistance (oxidation resistance) can be improved by alloying. In addition, the maximum amount of uranium-resistant alloying elements is about 1%. It is known that the amount of addition of more than 1% tends to decrease, but it is added more than 3% due to the type of alloy. Considering that the corrosion resistance is lower than that of pure Ag In the opinion, the addition amount of alloying elements should preferably be controlled in the range of 0.5 to 3%. Example 3 This example evaluates sulfur resistance by performing an exposure test on various Ag binary alloy films in a hydrogen sulfide (（2 S) atmosphere. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs First, various A g binary base alloy targets (alloy elements containing 2.0%) shown in Table 3 were used to form various A g binary using the same method as in Example 1. After the base alloy thin film (reflection film layer) was prepared as a sample, the reflectance (spectral reflectance) in the measurement wavelength range of 800 to 2000 nm was measured. Next, the above samples were subjected to an environmental accelerated test, namely an exposure test in an atmosphere of hydrogen sulfide [atmosphere · air + H2S (50ppm), temperature 50 ° C, humidity 90% R Η], to evaluate the sulfuration resistance of the reflective film layer. . Specifically, the reflectance (spectral reflectance) of the reflective film layer is measured for the sample after the test, and the reflectance difference before and after the test (that is, the reflectance decrease after the test) is calculated to evaluate the vulcanization resistance. I Paper size applies Chinese National Standard (CNS) A4 size (210x297 mm 1 ~ ~ 1236672 A7 B7 V. Description of invention (16) In Table 3, note the wavelength of A g-based alloy film before and after exposure test in hydrogen sulfide atmosphere Change in reflectance at 800 nm and change in reflectance at wavelength 390 nm. [Table 3]
No. 合金系 反射率變化（□% ) 測定波長：A = 800nm 測定波長 :A=390nm 1 Ag-2.0% Zn -22.6 -38.4 2 Ag-2.0% Ti -75.3 -65.8 3 Ag-2.06% Cu -78.1 -64.2 4 Ag-2.0% Ni -84.6 -79.4 5 Ag-2.0% Au -36.7 -54.6 6 純Ag -91.6 -63.2 7 Ag-2.00% A1 -43.2 -73.3 8 Ag-2.0% Mg -49.7 -70.1 9 Ag 2.0% Pd -40.5 -73.7 10 Ag-2.0% Pt -25.6 -46.4 由表3即知，含有Zn的Ag基合金薄膜（No . 1 )反射率減少量相較於其他A g基合金薄膜是最少的， A g - Ζ η基合金是耐硫化性極優的。 實施例4 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） I-----1----- (請先閱讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 -19- 1236672 A7 經濟部智慧財產局員工消費合作社印製 __B7五、發明説明（17) 本實施例係於硫化氫氣氛中曝露試驗附加A g _ 合金薄膜，調查反射率變化量。 首先利用與實施例1同樣的方法，形成使z n添 做各種變化的A g - Ζ η二元基合金薄膜（反射薄膜 ，製成試料後，測定測定波長8 〇 〇〜2 0 0 n m範 反射率（分光反射率）。於第3圖表示ζ η添加量和 7 0 0 n m方面的初期反射率之關係。 由第3圖即知，Ag - Ζ η合金薄膜會有隨2 n 量增加，而初期反射率降低之傾向，但Ζ η添加5 % 8 5 %以上的高反射率。 其次，於上述試料中，利用與實施例3同樣的方 評估反射薄膜層的耐硫化性，調查耐硫化性和Ζ η添 的關係。於第4圖表示，硫化氫氣氛中曝露試驗前後;^ A g - Ζ η合金薄膜與波長7 0 0 nm之反射率減少 Ζ η添加量的關係。 由第4圖即知，隨著Ζ η添加量的增加，反射率 量會慢慢減少，藉由添加Ζ η就能提高耐硫化性。詳 看發現Ζη添加量爲〇〜1·5%之藉由添加Ζη的 化性提昇效果極爲顯著，但該效果一旦Ζ η添加量超過 1 . 5 %就開始鈍化，超過5 %幾乎就飽和。 以上若考慮第3圖〜第4圖的結果，得知只要將 Ζ η合金薄膜中的Ζ η添加量控制在1 . 5〜5 %的 ，即可維持高初期反射率，耐硫化性也會提昇。 Ζ η 加量 層） 圍的 波長 添加 還有 法來 加婕 籩和 減少 細來 耐硫 g — _j---r---参！ (請先閲讀背面之注意事項再填寫本頁；> .訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 20- A7 1236672 B7 _ 五、發明説明（18) 實施例5 本實施例係利用圖案測試來評估各種A g基合金薄_ 的密著性。 首先，利用與實施例1同樣的方法，形成表4所条的 各種A g二元基合金薄膜（反射薄膜層），製作成試料。 其次’將上述試料全面利用微影成像及濕式鈾刻加工成寬 1 〇 // m的條帶形狀，以光學顯微鏡來觀察加工後的條帶 圖案有無剝離，藉此評估密著性。其結果於表4示之。 i丨卜/N——参—丨 〈%先閱讀#5注意事項再填寫本頁)No. Alloy system reflectance change (□%) Measurement wavelength: A = 800nm Measurement wavelength: A = 390nm 1 Ag-2.0% Zn -22.6 -38.4 2 Ag-2.0% Ti -75.3 -65.8 3 Ag-2.06% Cu- 78.1 -64.2 4 Ag-2.0% Ni -84.6 -79.4 5 Ag-2.0% Au -36.7 -54.6 6 Pure Ag -91.6 -63.2 7 Ag-2.00% A1 -43.2 -73.3 8 Ag-2.0% Mg -49.7 -70.1 9 Ag 2.0% Pd -40.5 -73.7 10 Ag-2.0% Pt -25.6 -46.4 As shown in Table 3, the decrease in reflectance of the Ag-based alloy film (No. 1) containing Zn is compared with other Ag-based alloy films It is the least, and the Ag-Zη-based alloy is excellent in sulfur resistance. Example 4 This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) I ----- 1 ----- (Please read the precautions on the back before filling this page), 11 Wisdom of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Property Bureau-19- 1236672 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy The amount of change in reflectivity. First, the same method as in Example 1 was used to form a Ag-Z η binary alloy thin film (reflective film with various changes in zn) (reflective film. After the sample was formed, the measurement wavelength was measured at 800-200 nm. (Spectral reflectance). The relationship between the amount of ζ η added and the initial reflectance at 700 nm is shown in Figure 3. As shown in Figure 3, the Ag-Z η alloy thin film will increase with the amount of 2 n. The initial reflectance tends to decrease, but Z η is added with a high reflectance of 5% to 85%. Next, in the above sample, the sulfur resistance of the reflective film layer was evaluated by the same method as in Example 3, and the sulfur resistance was investigated. Fig. 4 shows the relationship between the addition of Zn-η alloy film and the reflectance at a wavelength of 7 0 nm and the decrease in the amount of Zn addition added before and after the exposure test in a hydrogen sulfide atmosphere. The figure shows that with the increase of the amount of added Z η, the amount of reflectance will gradually decrease, and the vulcanization resistance can be improved by adding Z η. Looking at it in detail, it is found that the amount of added Z η is 0 ~ 1 · 5%. The effect of improving the chemical properties of Zn is extremely significant, but once this effect exceeds Zn 1.5% begins to passivate, and more than 5% is almost saturated. If the results of Figures 3 to 4 are considered above, it is known that as long as the amount of Z η added to the Z η alloy film is controlled to 1.5 to 5% It can maintain a high initial reflectance, and the sulfur resistance will also be improved. Z η Additive layer) There is also a method to add zirconia and reduce fine sulfur resistance in the surrounding wavelength g — _j --- r --- Come on! (Please read the precautions on the back before filling in this page; >. The size of the paper used in the book is applicable to China National Standard (CNS) A4 (210 X 297 mm) 20- A7 1236672 B7 _ V. Description of the invention (18) Implementation Example 5 In this example, a pattern test was used to evaluate the adhesion of various Ag-based alloy thin films. First, the same method as in Example 1 was used to form various Ag-based binary alloy films (reflections) as shown in Table 4. Thin film layer) to make a sample. Secondly, the above sample was processed into a strip shape with a width of 10 // m by using lithography imaging and wet uranium engraving, and an optical microscope was used to observe the strip pattern after processing. This is used to evaluate the adhesion. The results are shown in Table 4. i 丨 卜 / N—— 参 — 丨 <% first read # 5 precautions before filling in this page)
、1T 經濟部智慧財產局員工消費合作社印製 本紙張 -21 - 1236672 A7 B7 五、發明説明（19) 〔表4〕Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, this paper -21-1236672 A7 B7 V. Description of Invention (19) [Table 4]
No. 合金系 評估結果 (剝離狀況） 1 Ag-2.0% Zn 有剝離 2 Ag-2.0% Tj 無剝離 3 Ag-2.0% W 無剝離 4 Ag-2.0% Mo 無剝離 5 Ag-2.0% S π 無剝離 6 Ag-2.0% Ge 無剝離 7 Ag-2.0% Cu 無剝離 8 Ag-2.0% Ni 有剝離 9 Ag-2.0% An 有剝離 10 Ag-2.0% Y 有剝離 11 Ag-2.0% Nd 無剝離 12 純Ag 有剝離 13 Ag-2.0% A1 有剝離 14 Ag-2.0% Ga 有剝離 15 Ag-2.0% In 有剝離 16 Ag-2.0% Pd 有剝離 17 Ag-2.0% Pt 有剝離 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 據知含有表4中之Cu、Ti 、W、Mo、Sn、 G e、N d的各成份之A g二元基合金，就基板全面來看 認爲完全沒有剝離，密著性極優。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 22 1236672 A7 B7 五、發明説明（20) 實施例6 本實施例係利用剝離試驗來評估各種A g基合金薄膜 的密著性。 首先，認爲除實施例5之試料中密著性良好的試料所 使用的樹脂基板大小，基板尺寸變爲：1 2 . 7 X 1 2 · 7mm以外，均與實施例5同樣地形成各種Ag二 元基合金薄膜，製作成試料。其次，針對上述試料實施剝 離試驗，測定剝離時的荷重（拉伸強度），藉此定量性地 評估密著性。具體而言，在試料的基板側和薄膜側分別貼 固金屬製治具，針對兩金屬製治具，利用拉伸試驗機進行 拉伸試驗，測定薄膜和基板剝離界面時的荷重（拉伸強度 )。再者，金屬製治具的貼固通常是使用接著劑，但本實 施例爲避免於接著時產生熱度，接著劑則用常溫硬化型的 2液性環氧樹脂。而爲了比較，就連含有其他元素的a g 二元基合金薄膜也做同樣的試驗。將該些結果於表5示之 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23- 1236672 A7 __ B7 五、發明説明（21) ---- Ν〇. ---—___ 合金系 拉伸強度(kgf/cma2) ._1 Ag-2.0% Ti 170.3 2 Ag-2.0% W 105.4 —3 Ag-2.0% Mo 102.8 4 Ag-2.0% Sn 13 .7 5 Ag-2.0% G e 173.8 6 Ag-2.0% Nd 180.4 7 Ag-2.0% Cu 91.4 8 純Ag 19.0 9 Ag-2.0% A1 76:7 10 Ag-2.0°/〇 Mg 44.7 11 Ag-2.0% Ga 49.6 12 Ag-2.0% In 25.1 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表5中之自前述實施例5即被認爲密著性良好的 No . 1〜7之Ag二元基合金，拉伸強度均表示爲9 k g f / c m 2以上有極高的密著性。對此，其他的A g 元基合金均是拉伸強度低，密著性差的。 如此一來，由剝離試驗的結果亦確認A g - C u基 Ag — T i 基、Ag— W 基、Ag— Mo 基、Ag — S 基、Ag - Ge基、Ag - Nd基的各合金基都是密著 極優的。 本紙張尺度適用中國國家標準（CNS) Α4規格（210x297公釐） ο 二 、η性 -24- 1236672 Α7 Β7 五、發明説明（22) 實施例7 (請先閲讀背面之注意事項再填寫本頁) 應用表6所示的各種Ag四元基合金祀，與實施例6 同樣地形成厚度1 0 〇 〇的A g〜3 . 、z n — 〇 · 85%、Sn — i . 〇%的八11四元基合金薄膜（反 射薄膜層）製成g式料。並在上述A g四元基合金祀使用下 述3種類的靶。 (工）以真空熔解法製作Ag〜3 · 〇%、Zn — Ο . 8 5 %、S n —工· 〇 %的A u四元基合金 (2)以粉末治金法製作Ag〜3 · 〇%、Zn 一 〇.85%、Sn 1.0%的AU四元基合金 (3)薄膜組成調整爲Ag 一 3 · 〇%、Zn_ 0 · 85%、Sn —丄· 〇%的八1[合金之鑲嵌狀靶（在 純A g靶上植入a n、s n、A u的晶片：板狀小片的複 合型靶） ’ 經濟部智慧財產局員工消費合作社印製 針對上述試料，與實施例1同樣地測定初期反射率的 同時’貫施咼溫高濕試驗（溫度8 〇、濕度9 0 % R Η )’算出試驗前後的反射率減少量，藉此評估反射薄膜層 的耐蝕性（耐氧化性）。所得的結果於表6示之。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -25- 1236672 A7 B7 五、發明説明（y 〔表6〕 濺鍍靶 ------- 反射率 -—— 反射率變化（△%) 種類 測定波長： 測定波長： 測定波長： 測定波長： A=800nm A=390nm λ = 8 0 0 π m A=390nm (1) 90.5 71.6 -0.9 -8.4 (2) 88.4 67.5 -2.3 -14.7 (3) 90.1 71.3 -1.1 -8.9 (請先閲讀背面之注意事項再填寫本頁) 由表6½知，使用上述（丄）〜（3)的各種靶所成 膜的A g四兀基合金薄膜，均是初期反射率高，但反射率 變化量小的。尤其上述（i )的靶，其傾向顯而易見，使 用該熔製A g基合金濺鍍靶是最適合的。 而連在Ag — Zn合金中添加Cu、τ丨、Nd、w 、M 〇、S n、G e 之至少—種，以及 c u、N 土 、A u 、Y、N d之至少一種的試料也實施與本實施例同樣的實 驗’其結果確認可獲得與表6同樣的效果。 經濟部智慧財產局員工消費合作社印製 實施例8 本貫施例係調查於A g - ζ η基合金添加第三成份的 一元基合金薄膜之初期反射率、耐蝕性（耐氧化性）及耐 硫化性。 具體而a是利用與貫施例1同樣的方法，形成第$圖 所示的各種Ag三元基合金薄膜（第三成份是在〇〜6% 的範圍來變化並添加C u、Y、N i 、n d、A u的各元 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -26- 1236672 A7 _；__B7 五、發明説明（j 素）製作試料，調查各種合金薄膜和初期反射率的關係。 於第5圖表示第三成份的添加量和波長7 〇 〇 n m的初期 反射率之關係。 由第5圖發現無論那一合金反射率都會因添加第三成 份而慢慢下降之傾向，但連該第三成份添加5 %的場合下 ’也能維持8 5 %以上的高反射率。因而得知添加上述元 素作爲第三成份是很有用的。 其次’針對上述試料利用與實施例1同樣的方法來評 估反射層薄膜的耐蝕性（耐氧化性）。於第6圖表示高溫 咼濕試驗前後之波長7 0 0 m m的反射率變化量和第三成 份的添加量之關係。 由第6圖得知，即使添加上述第三成份，反射率減少 量並無變化，或變化非常小，耐蝕性（耐氧化性）因添加 第三成份而提昇。 更針對上述試料，利用與實施例3同樣的方法來評估 反射薄膜層的耐硫化性。於第7圖表示硫化氫氣氛中曝露 試驗前後的波長7 0 〇 m m之反射率減少量和第三成份的 添加量之關係。 由第7圖得知，隨著添加第三成份，A g三元基合金 的反射率減少量則慢慢地減少，耐蝕性（耐氧化性）則比 上述三元基合金和A g - 3 % Ζ η的二元基合金更爲提昇 。而其效果則因元素種類而異，發現第二成份爲A u時， 耐硫化性提昇效果最爲顯著，其次認爲依Y ' N d、N i 、C u的順序提昇效果。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ——#! (請先閲讀背面之注意事項再填寫本頁) 訂 線· 經濟部智慧財產局員工消費合作社印製 -27- 1236672 A7 _____ B7 五、發明説明（^ 實施例9 本實施例係評估A g三元基合金薄膜的密著性。 具體而言乃利用與實施例1同樣的方法，形成表7所 示的各種A g三元基合金薄膜製作試料後，利用與實施例 5同樣的方法，藉由圖案測試實施密著性試驗。於表7倂 s己相對於上述a g三元基合金薄膜的條帶圖案之剝離狀況 11K---^-----— (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28- 1236672 A7 B7 五、發明説明（2〇) 〔表7〕No. Evaluation results of alloy system (peeling status) 1 Ag-2.0% Zn with peeling 2 Ag-2.0% Tj without peeling 3 Ag-2.0% W without peeling 4 Ag-2.0% Mo without peeling 5 Ag-2.0% S π None Peel 6 Ag-2.0% Ge No peel 7 Ag-2.0% Cu No peel 8 Ag-2.0% Ni Yes peel 9 Ag-2.0% An Yes peel 10 Ag-2.0% Y Yes peel 11 Ag-2.0% Nd No peel 12 Pure Ag with peeling 13 Ag-2.0% A1 with peeling 14 Ag-2.0% Ga with peeling 15 Ag-2.0% In with peeling 16 Ag-2.0% Pd with peeling 17 Ag-2.0% Pt with peeling (please read the back Please fill in this page again) The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed an A g binary base alloy that is known to contain the components of Cu, Ti, W, Mo, Sn, G e, and N d in Table 4, From the overall perspective of the substrate, it is considered that there is no peeling at all, and the adhesion is excellent. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 22 1236672 A7 B7 V. Description of invention (20) Example 6 This example uses a peel test to evaluate the adhesion of various Ag-based alloy films. . First, it is considered that various Ags were formed in the same manner as in Example 5 except that the size of the resin substrate used in the sample with good adhesion among the samples in Example 5 and the substrate size were: 12.7 x 1 2 · 7mm. A binary base alloy film was made into a sample. Next, a peel test was performed on the above sample, and the load (tensile strength) at the time of peel was measured to thereby quantitatively evaluate the adhesion. Specifically, a metal jig was attached to the substrate side and the film side of the sample, and the two metal jigs were subjected to a tensile test using a tensile tester to measure the load (tensile strength) at the peeling interface between the film and the substrate. ). In addition, an adhesive is usually used for attaching a metal jig, but in this embodiment, in order to avoid generation of heat during the adhesion, a two-liquid epoxy resin of room temperature curing type is used for the adhesive. For comparison, the same test was performed on ag binary alloy films containing other elements. These results are shown in Table 5 (please read the precautions on the back before filling this page). The paper printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm)- 23- 1236672 A7 __ B7 V. Description of the invention (21) ---- No. -----___ Alloy system tensile strength (kgf / cma2) ._1 Ag-2.0% Ti 170.3 2 Ag-2.0% W 105.4 —3 Ag-2.0% Mo 102.8 4 Ag-2.0% Sn 13 .7 5 Ag-2.0% G e 173.8 6 Ag-2.0% Nd 180.4 7 Ag-2.0% Cu 91.4 8 pure Ag 19.0 9 Ag-2.0% A1 76 : 7 10 Ag-2.0 ° / 〇Mg 44.7 11 Ag-2.0% Ga 49.6 12 Ag-2.0% In 25.1 (Please read the precautions on the back before filling this page) Printed by the Employee Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5 Among the Ag binary alloys No. 1 to 7 which are considered to have good adhesion from Example 5 above, the tensile strengths are all shown to be 9 kgf / cm 2 or more and have extremely high adhesion. For this reason, other Ag element-based alloys have low tensile strength and poor adhesion. In this way, the results of the peel test also confirmed that each of the Ag-Cu-based Ag—Ti-based, Ag-W-based, Ag-Mo-based, Ag-S-based, Ag-Ge-based, and Ag-Nd-based alloys. The bases are dense and excellent. This paper size applies to Chinese National Standard (CNS) Α4 size (210x297 mm) ο η-24-1236672 Α7 Β7 V. Description of the invention (22) Example 7 (Please read the precautions on the back before filling this page ) Applying various Ag quaternary alloys shown in Table 6 to form A g ~ 3 with a thickness of 100%, zn — 0.85%, Sn — i. 8%, as in Example 6. Quaternary alloy film (reflective film layer) is made into g-type material. The following three types of targets are used for the above-mentioned Ag quaternary alloy. (Work) Production of Ag ~ 3 · 〇%, Zn—O. 85%, Sn—Work · 0% by vacuum melting method (2) Production of Ag ~ 3 · by powder metallurgy method The composition of the AU quaternary alloy (3) thin film of 〇%, Zn-10.85%, and Sn 1.0% was adjusted to Ag-3.0%, Zn_0 · 85%, and Sn— 丄 · 〇% of the 8-1 [alloy Mosaic target (chips with an, sn, and Au implanted on pure Ag targets: composite targets with plate-like small pieces) '' Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for the above samples, the same as in Example 1 The initial reflectance was measured at the same time, and the "reduced temperature and high humidity test (temperature 80, humidity 90% R ')" was used to calculate the decrease in reflectance before and after the test to evaluate the corrosion resistance (oxidation resistance of the reflective film layer). ). The results obtained are shown in Table 6. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -25- 1236672 A7 B7 V. Description of the invention (y [Table 6] Sputtering target ------- Reflectivity --- Reflectivity Variation (△%) Kind of measurement wavelength: Measurement wavelength: Measurement wavelength: Measurement wavelength: A = 800nm A = 390nm λ = 8 0 0 π m A = 390nm (1) 90.5 71.6 -0.9 -8.4 (2) 88.4 67.5 -2.3 -14.7 (3) 90.1 71.3 -1.1 -8.9 (Please read the precautions on the back before filling in this page) As shown in Table 6½, the A g tetramethyl group formed by using the various targets of the above (丄) ~ (3) All alloy thin films have high initial reflectance, but the change in reflectance is small. In particular, the target (i) above has a clear tendency, and the molten Ag-based alloy sputtering target is most suitable. It is connected to Ag — At least one of Cu, τ 丨, Nd, w, M0, Sn, and Ge added to the Zn alloy, and at least one of cu, N soil, Au, Y, and N d are also implemented. The results of the same experiment were confirmed as in Table 6. The results are confirmed to be the same as those in Table 6. Example 8 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This example is to investigate the initial reflectance, corrosion resistance (oxidation resistance) and sulfuration resistance of a mono-based alloy thin film with a third component added to the A g-ζ η-based alloy. Specifically, a is the use and implementation of Example 1 In the same way, various Ag ternary alloy thin films as shown in Fig. (The third component is changed in the range of 0 to 6% and each element of Cu, Y, Ni, nd, and Au are added. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -26- 1236672 A7 _; __B7 V. Description of the invention (j) Production samples, investigate the relationship between various alloy films and the initial reflectance. The figure shows the relationship between the added amount of the third component and the initial reflectance at a wavelength of 700 nm. From Figure 5, it is found that the reflectance of any alloy tends to gradually decrease due to the addition of the third component. When the component is added at 5%, it can also maintain a high reflectance of more than 85%. Therefore, it is useful to know that the above element is added as the third component. Secondly, the same method as in Example 1 was used to evaluate the above sample. Corrosion resistance of reflective film ( Oxidation). Figure 6 shows the relationship between the change in reflectance at a wavelength of 700 mm before and after the high-temperature humidity test and the addition of the third component. From Figure 6, it can be seen that even if the third component is added, the reflection There is no change in the rate of decrease, or the change is very small, and the corrosion resistance (oxidation resistance) is improved by adding a third component. For the above samples, the same method as in Example 3 was used to evaluate the vulcanization resistance of the reflective film layer. Fig. 7 shows the relationship between the decrease in reflectance at a wavelength of 700 mm before and after the exposure test in a hydrogen sulfide atmosphere and the addition amount of the third component. From Figure 7, it can be seen that with the addition of the third component, the reflectance reduction of the A ternary alloy gradually decreases, and the corrosion resistance (oxidation resistance) is higher than that of the above ternary alloy and A g-3 The% Zn η binary-based alloy is even higher. The effect varies according to the type of element. It is found that when the second component is Au, the effect of improving the vulcanization resistance is the most significant. Secondly, it is considered that the effect is improved in the order of Y'Nd, Ni, and Cu. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) —— #! (Please read the precautions on the back before filling this page). 1236672 A7 _____ B7 V. Description of the Invention (^ Example 9 This example evaluates the adhesion of the A g ternary alloy film. Specifically, various methods shown in Table 7 were formed using the same method as in Example 1. After the sample of the Ag ternary alloy film was prepared, the adhesion test was performed by a pattern test using the same method as in Example 5. Table 7 倂 s has been compared with the strip pattern of the ag ternary alloy film. Peeling status 11K --- ^ -----— (Please read the precautions on the back before filling this page) Order the paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to apply the Chinese National Standard (CNS) A4 specifications ( 210X297 mm) -28- 1236672 A7 B7 V. Description of the invention (20) [Table 7]
No. 含金系 評估結果（剝離狀況） 1 Ag-3.0% Zn-2.0% Ti 無剝離 2 Ag-3.0% Zn-2.0% W 無剝離 3 Ag-3.0°/〇 Zn-2.0% Mo 無剝離 4 Ag-3.0% Zn-2.0% Sn 無剝離 5 Ag-3.0% Zn-2*0% Ge 無剝離 6 Ag3.0% Zn-2.0% Cu 無剝離 7 Ag-3.0% Zn-2.0% Ni 有剝離 8 Ag-3.0% Zn-2.0% Au 有剝離 9 Ag-3.0% Zn-2.0% Y 有剝離 10 Ag-3.0% Zn-2.0% Nd 無剝離 11 純Ag 有剝離 12 Ag-3.0% Zn-2.00/〇 A1 有剝離 13 Ag-3.0% Zn-2.0% Ga 有剝離 14 Ag-3.0% Zn-2.0% In 有剝離 15 Ag-3.0% Zn-2.00/〇 Pd 有剝離 16 Ag-3.0% Zn-2.0% Pt 有剝離 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 由表7即知，添加Cu、Ti 、W、Mo、Sn、 G e之各元素的A g基合金薄膜，認爲於基板全面完全沒 有剝離，密著性極優。 實施例1 0 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1236672 A7 B7 五、發明説明（2) 本實施例乃利用與實施例9有別的評估方法，來評估 A g三元基合金薄膜的密著性。 (請先閲讀背面之注意事項再填寫本頁) 具體而言乃利用與實施例1同樣的方法，形成第8圖 所示的各種Ag - ZnX的三元基合金薄膜（XgTi 、 W、Μ 〇、S η、G e、N d之各元素）製作試料後，利 用與實施例6同樣的方法實施剝離試驗（去皮試驗），定 量地評估密著性。其結果倂記於第8圖。 由第8圖即知，隨著添加第三元素，a g基合金的密 著強度（剝離之際的拉伸強度）增加，密著性比A g — Ζ η二元基合金及純A g更爲提昇。密著性上昇作用以 T i爲最大，其次發現依序爲w、Sn、Nd、M〇、 G e 〇 〔發明效果〕 經濟部智慧財產局員工消費合作社印製 本發明之光資訊記錄媒體用反射層係如上述所構成， 當然具有高反射率，尤以耐硫化性優，進而對於碟片基板 (聚碳酸酯基板等）及構成碟片的其他薄膜的密著性也很 良好’光資訊記錄媒體（相變化型及追加型光碟）的性能 、可靠性均格外地提高。而本發明的濺鍍靶適於利用濺鍍 形成上述光資訊記錄媒體用反射層時使用，所形成的反射 薄膜層之成份組成很易安定的優點外，也可達到有效獲得 耐硫化性、反射率、密著性等之諸特性亦優之反射薄膜層 的優點。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -30- 1236672 Α7 Β7 五、發明説明（ 〔圖面之簡單說明〕 第1圖係表示實施例2之A g基合金反射薄膜層中的 合金元素添加量和初期反射率的關係之座標圖。 第2圖係表示實施例2之A g基合金反射薄膜層中的 合金元素添加量和反射率減少量的關係之座標圖。 第3圖係表示實施例4之A g基合金反射薄膜層中的 Ζ η添加量和初期反射率的關係之座標圖。 第4圖係表示實施例4之A g基合金反射薄膜層中的 Ζ η添加量和反射率減少量的關係之座標圖。 第5圖係表示實施例8之A g - Ζ η合金反射薄膜層 中的第三成份之添加量和初期反射率的關係之座標圖。 第6圖係表示實施例8之A g - Ζ η合金反射薄膜層 中的第三成份之添加量和反射率減少量的關係之座標圖。 第7圖係表示實施例8之A g - Ζ η合金反射薄膜層 中的第三成份之添加量和反射率減少量的關係之座標圖。 第8圖係表示實施例1〇之Ag-η合金反射薄膜層 中的第三成份之添加量和拉伸強度的關係之座標圖。 — IK——r---参------1T------% (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -31 -No. Result of gold-containing evaluation (peeling status) 1 Ag-3.0% Zn-2.0% Ti No peeling 2 Ag-3.0% Zn-2.0% W No peeling 3 Ag-3.0 ° / 〇Zn-2.0% Mo No peeling 4 Ag-3.0% Zn-2.0% Sn without peeling 5 Ag-3.0% Zn-2 * 0% Ge without peeling 6 Ag3.0% Zn-2.0% Cu without peeling 7 Ag-3.0% Zn-2.0% Ni with peeling 8 Ag-3.0% Zn-2.0% Au with peeling 9 Ag-3.0% Zn-2.0% Y with peeling 10 Ag-3.0% Zn-2.0% Nd without peeling 11 pure Ag with peeling 12 Ag-3.0% Zn-2.00 / 〇 A1 With peeling 13 Ag-3.0% Zn-2.0% Ga With peeling 14 Ag-3.0% Zn-2.0% In With peeling 15 Ag-3.0% Zn-2.00 / 〇Pd With peeling 16 Ag-3.0% Zn-2.0% Pt There is peeling (please read the precautions on the back before filling this page). The printing of employee co-operatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is shown in Table 7. Add A, G of each element of Cu, Ti, W, Mo, Sn, G e It is considered that the base alloy film has no peeling at all on the entire substrate and has excellent adhesion. Example 1 0 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1236672 A7 B7 V. Description of the invention (2) This example uses a different evaluation method from Example 9 to evaluate A g Adhesion of ternary-based alloy films. (Please read the precautions on the back before filling this page.) Specifically, the same method as in Example 1 was used to form various Ag-ZnX ternary alloy thin films (XgTi, W, Μ shown in Figure 8). (S, η, G e, N d) after preparing a sample, a peel test (peel test) was performed by the same method as in Example 6 to quantitatively evaluate adhesion. The results are shown in FIG. 8. As can be seen from Fig. 8, with the addition of the third element, the adhesion strength (tensile strength at the time of peeling) of the ag-based alloy increases, and the adhesion is more than that of the Ag-Z η binary-based alloy and pure Ag. For promotion. T i is the largest increase in adhesion, followed by w, Sn, Nd, M0, G e 〇 [Inventive effect] The Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs printed the optical information recording medium of the present invention. The reflective layer is composed as described above, of course, it has a high reflectance, and it is particularly excellent in vulcanization resistance. Furthermore, it has good adhesion to the disc substrate (polycarbonate substrate, etc.) and other films constituting the disc. The performance and reliability of recording media (phase change and add-on discs) have been significantly improved. The sputtering target of the present invention is suitable for forming the above-mentioned reflective layer for an optical information recording medium by sputtering. The composition of the formed reflective thin film layer is easy to stabilize, and it can also effectively obtain sulfur resistance and reflection. The various characteristics such as efficiency, adhesion, etc. are also superior to the advantages of the reflective film layer. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -30- 1236672 A7 B7 V. Description of the invention ([Simplified description of the drawing] Figure 1 shows the reflection of the Ag-based alloy of Example 2 A graph showing the relationship between the amount of alloying elements added to the thin film layer and the initial reflectance. Figure 2 is a graph showing the relationship between the amount of alloying elements and the amount of reflectance reduction in the Ag-based alloy reflective thin film layer of Example 2. Fig. 3 is a graph showing the relationship between the amount of added Z η and the initial reflectance in the Ag-based alloy reflective film layer of Example 4; Coordinate diagram of the relationship between the amount of Z η added and the amount of reflectance reduction. Figure 5 is a graph showing the relationship between the amount of the third component in the A g-Zn alloy reflective film layer of Example 8 and the initial reflectance. Fig. 6 is a graph showing the relationship between the added amount of the third component and the reflectance reduction amount in the Ag-Z η alloy reflective film layer of Example 8. Fig. 7 is a graph showing A g of Example 8 -The third component in the Zn alloy reflective film layer The graph of the relationship between the amount of addition and the amount of reflectance reduction. Figure 8 is a graph showing the relationship between the amount of the third component in the Ag-η alloy reflective film layer of Example 10 and the tensile strength. — IK——r --------- 1T ------% (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperatives Paper size applies to China National Standard (CNS) A4 Specification (210X297 mm) -31-