TWI246681B - Optical information medium and its use - Google Patents

Optical information medium and its use Download PDF

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Publication number
TWI246681B
TWI246681B TW090126577A TW90126577A TWI246681B TW I246681 B TWI246681 B TW I246681B TW 090126577 A TW090126577 A TW 090126577A TW 90126577 A TW90126577 A TW 90126577A TW I246681 B TWI246681 B TW I246681B
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TW
Taiwan
Prior art keywords
layer
dielectric layer
recording layer
recording
information medium
Prior art date
Application number
TW090126577A
Other languages
English (en)
Inventor
Guo-Fu Zhou
Johannes Cornelis Norb Rijpers
Original Assignee
Koninkl Philips Electronics Nv
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Application granted granted Critical
Publication of TWI246681B publication Critical patent/TWI246681B/zh

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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B7/2433—Metals or elements of Groups 13, 14, 15 or 16 of the Periodic Table, e.g. B, Si, Ge, As, Sb, Bi, Se or Te
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
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    • G11B7/2403—Layers; Shape, structure or physical properties thereof
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    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

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1246681 A7 B7 __ 五、發明説明（1 ) 本發明係關於一種可用雷射光束裝置來抹除記錄的光學 資訊媒體，該雷射光束具有雷射光波長，而該媒體具有一 基板及一堆疊層，而該堆疊包括第一介電層與第二介電層 、能夠在非結晶狀與結晶狀態間改變的記錄層、以及反射 層，而該記錄層配置在第一介電層與第二介電層間。 本發明也與將此類光學媒體使用於高速記錄有關。 由 M. Chen、K. A. Rubin及 R· W· Barton在 Applied Physics Letters 49 (1986) 502所發表的論文，能了解開始段落中所 描述的光學資訊媒體類型。 光學資訊媒體以相位改變原理為基礎是具有吸引力的， -因其可結合直接覆寫（DOW)及具有容易相容性之高密度儲 存的唯讀光學資料儲存系統。相位改變光學記錄於結晶狀 記錄層使用一種聚焦相當高功率的雷射光束，其牽涉到亞 微米大小之非結晶狀的記錄標誌。當記錄資訊時，該媒體 被移動到相關的聚焦雷射光束，並根據記錄的資訊調變。 而於高功率的雷射光束熔化結晶狀記錄層時形成標誌。當 雷射光束關閉和/或隨後移動到相對的記錄層時，該已炼化 之標諸的冷卻發生於記錄層，非結晶狀的資訊標誌留置在 記錄層接觸的區域，而結晶狀記錄層繼續留在未接觸的區 域。因此可藉由用較低位準的-功率來加熱同一雷射光束， 而且不需要溶化該記錄層，即可完成非結晶狀標誌的抹除 。該非結晶狀標諸代表資料位元，能夠被讀取，例如，藉 由相當低的功率聚焦雷射光束通過基板。非結晶狀標誌與 相關結晶狀記錄層的反射差異能引起調變的雷射光束，其 -4- 本紙張尺度適財@國家標準(CNS) A4規格(21G χ 297公董) 1246681 A7 B7 五、發明説明（2 ) 隨後由偵測器根據所記錄的資訊轉換成調變的光流。 相位改變光學記錄最重要的需求之一是高的資料速率， 此意謂著能夠用至少30 Mbits/s的速率將資料寫入及重寫入 該媒體。如此高的資料速率要求記錄層具有高的結晶速度 ，即，短的結晶時間。為確保先前記錄的非結晶狀標誌在 直接覆寫期間能夠被結晶化，該記錄層必須有適當的結晶 速度來配合相對於該媒體之雷射光束的速度。如果結晶速 度對先前所記錄的非結晶狀標誌而言是不夠快的，則所代 表的舊資料在直接覆寫期間，不能被完全抹除，即再結晶 化。上述將導致高干擾位準。而高密度記錄及高資料速率 ，的光學記錄媒體特別需要高的結晶速度，例如，磁碟形的 DVD+RW及DVR-red and blue。DVD+RW為新世代高密度多 樣化數位光碟+RW的縮寫，其中RW稱為此類磁碟的重寫能 力，而DVR為數位視訊記錄光學儲存磁碟，其中red and blue為所使用的雷射波長。對此等磁碟完成抹除的時間 (CET)最多為60 ns。於結晶環境中，完成抹除時間係定義為 抹除已寫非結晶狀標誌之脈衝的最小歷時，其為靜態的測 量。對DVD+RW而言，每120 mm磁盤有4.7 GB記錄密度， 需要的資料速率為33 Mbits/s，但對DVR-red而言，該速率 為35 Mbits/s。而對可重寫4目位改變光學記錄系統例如 DVR-blue而言，所要求的使用者資料速率高吟50 Mbits/s。 相位改變媒體已知的類型包括承載一堆疊層的基板，該 堆疊層連.續包括第一電介質、適合定義相位改變之化合物 GeTe的記錄層、第二介電層、以及反射層。此一堆疊層能 -5- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 裝 訂
1246681 A7 _____B7 五、發明説明（3~-- 夠稱為IPIM結構，其中M代表一反射或反映層，以戈表第一 或第二介電層，而ρ代表一相位改變記錄層。當雷射光的波 長在350-70Ό nm的範圍内時，（^與。合成的記錄層在非結 晶狀與結晶狀相位間有相當高的相對反射差。此外，
Te合成的記錄層因大約180〇C相當高的結晶溫度，而具有很 好的熱穩定性。而高的熱穩定性使得檔案具有長的使用期 ’通常此為儲存媒體的必要條件之一。 而目前已知媒體的缺點，為^與。所合成之記錄層的完 成抹除時間對合成比率非常的敏感。只有精確的5〇:5〇比例 月b產生令人滿意且短的完成抹除時間。而該敏感度的缺點 .將導致差的製造重複能力❶ —… 本發明的目的是使開始段落中所描述的光學資訊媒體， 能適用於高資料速率光學記錄，例如DVR_blue，而所擁有 的完成抹除時間值為50 ns或更短，而且容易製造。 以下列來達到上述的目的 記錄層包括慣用的化合物GexTe1()()_x， 其中·· X是at·%中Ge的分數，而且3〇<x<7〇 , -第一介電層所包含的化合物，係挑選自以與^的氧化物、
Si與A1的氮化物及si的碳化物所組成的群組，於本發明中是 和記錄層相連接。 ， 第一介電層已存在的此等氧化物、氮化物及碳化物大大 地擴大記錄層Ge與Te化合物可用的合成範圍。該可用的合 成範圍是具有低完成抹除時間之^與。的合成範圍。此外 ，對合成範圍30<X<70 ,使用氧化物、氮化物或碳化物時 本纸張尺度_巾國國家標準(CNS) A4規格(210X297公釐) 1246681 五、發明説明（ 4 A7 B7 ，該完成抹除時間出乎意料地變成非常的低，… 或更大的因子。因Α Γ你τ &例如近乎2 且不會增加1技^ 合物的合成非常的多樣化’ 疋成抹除時間，所以對製造而言，一 範圍是有利的。而為了獲得好的效二： 求精確的50:50比例，χ==5〇。 个而冉要 於實施例中’第_介電層及第二介電層包含—種化人物 的=::係挑選自丁_的氧化物，，氮化物二 的石反化物所組成的群組，於本發明中是和記轉層相連接。 士述的優點為該記錄層的兩面與㈣以的氧化物、以與八丨的 亂化物或Si的碳化物的介電層相連接’如此甚至會導致更 =完成抹除時間，例如近乎3的因子，而且連該記錄層 化合物的合成範圍也將更廣泛。 "最好帛-介電層及第二介電層包含一種從丁成及叫队 群組所挑選的化合物。此等原料具有容易製造的優勢，而 且已也月非吊'適合擴大可用的合成範圍並降低完成抹除時 間。 於最佳實施例中，第一介電層及第二介電層的厚度最多 為 15 nm。因 Ta205及 Si3N4的熱傳導性比（ZnS)8〇(si〇2)2〇好， 且為介電層常使用的原料，而對與丁32〇5或以川4所接觸之記 錄層的功率敏感度是較低的。然而，當所使用的Ta2〇5或
ShN4層比15 nm薄，則不會或很難影響該記錄之功率的敏 感度。 於更佳實施例中，第一介電層及第二介電層之厚度的範 圍為2-10 nm。厚度為2-1〇 11111的層對記錄層的功率敏感度沒 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1246681 A7 ____ B7 了3明説明(1 " 有顯著的影響。而比2 nm薄的層確實是難以製造，因為此 類薄層的厚度控制是困難的，而且此類薄層中出現小孔的 可能性是很高的。 因此，最好為40<x<60 ,其中X是記錄層所慣用之化合物 GexTe10“的值。上述x的範圍特別適合獲得較低的完成抹除 時間（CET)，並為高資料速率記錄的要求。而高資料速率記 錄需要高的記錄速度，因為光學記錄媒體上標誌的大小大 體上由記錄點的大小來決定，該記錄點對特定的雷射光波 長及記錄透鏡的數值孔徑而言是相當固定的。應瞭解高速 度記錄意指於上述背景中，該媒體的線性速度相當於至少 _7·2 m/s的雷射光束，而且該媒體的線性速度根據 Disc標準為六倍速。而對應於8倍速的CD_速度，9·6 線 性速度所需的完成抹除時間值最好低於45 ns，但對應於i2 倍速的CD-速度，14·4 m/s線性速度所需的完成抹除時間值 甚至低於35 ns。而媒體的抖動應該位於低的恆定位準。此 外’該媒體應該具有好的熱穩定性。 此外，該記錄層的化合物所包含的0(氧）4N(氮）的總數 能提高到5 at·%。而0*N的增加會導致較短的完成抹除時 間，而提高到1.5的因子。當氧或氮以介於〇 〇1與5間的 微量出現於化合物中，最好是介於15與2〇此％間，能夠大 大地降低完成抹除時間的值。由於在獲得記錄層的處理情 況中，難以獲得氧或氮的值比〇·〇1 at%低，例如，以惰性 氣體氣壓誠，其中氧或氮背景壓力必然會出現。當氧或 氮的濃度超過5 at·% ,該記錄層的完成抹除時間值上升超 :297公釐） 1246681 A7 B7
過50 ns，而且對抖動及直接覆寫有不利的影響。再者，在 直接覆寫a寸，非結晶狀及結晶反射的最大改變變得有點令 人然法接文。此外，因為當氧或氮的含量太高時，容易形 成氧氣或氮氣，使該記錄的非結晶狀標誌變得不穩定。 該反射層至所包含的原料至少有一種挑選自八丨、丁丨、Au 、Ag、Cu、Rh、Pt、Pd、Ni、c〇、Mn、Cr、M〇、％、沿 及Ta所組成的群組，包括其合金。 為了保護該記錄層不受濕氣影響，另加的介電層於本發 明中疋和第一和/或第二介電層相鄰，來熱隔絕記錄層與基 板和/或反射層，並最佳化該光學對比。通常該雷射光到達 ’記錄層之前，先穿透第二介電暑。......... 尤其，第三介電層於本發明中是和第一介電層相鄰，並 ”於第"電層與反射層之間，與該記錄層的一側相隔。 該厚度通常是介於1〇與50 nm間，但最好是介於15與35 nm 間。當該層太薄時，對記錄層/第一介電層與另一介電層即 反射層間的熱隔絕，會有不利的影響。因此，增加該記錄 層的冷卻速度，將導致緩慢的再結晶或抹除處理以及差的 循環能力。而該冷卻速度將因增加第三介電層的厚度而降 低。 第四介電層於本發明中是和第二介電層相鄰，且與記錄 層的一側相隔。 由於抖動的觀點，該介電層或鄰近介電層的總厚度最好 至少為70 nm，且首先由雷射光入射。於結晶環境中，以最 佳光學對比的觀點讀出非結晶狀記錄標誌，此層或這些層 • 9 - 1246681
的厚度取好的設定值是超過70 nm，視所使用之雷射光波長 及介電層或層的反射指標而定。該堆疊相對基板之最外層 的另一選擇，係以如^^从光固化多（甲基）丙烯酸酯保護霞蓋 層的方法來與環境隔開。而於此案例中，基板與覆蓋層可 彼此互換，且雷射光進入堆疊·前，首先需穿透基板。 完成抹除時間值對厚度範圍在20到200 nm間的反射層較 不敏感。但當反射層的厚度比60 nm薄時，由於冷卻率太 低，因此對循環能力有不利的影響。當反射層的厚度為 160 nm或更厚，該循環能力進一步下降，但由於增加熱傳 導，所以記錄及抹除功率必須要高。而該反射層的厚度最 脅介於80 nm與120 nm間。 - 另外的介電層，即第三及第四介電層，可由ZnS& Si〇2 的混合物組成，例如（ZnS)80(SiO2)20。 反射層及介電層皆可由蒸汽沉積或濺鍍來提供。 當該雷射光束最初入射通過該資訊媒體的基板時，該雷 射波長至少可穿透該資訊媒體的基板，而該資訊媒體的基 板是由例如多碳酸酯、多甲基甲基丙烯酸酯（pMMA)、非結 晶狀多烯烴或玻璃所組成。於典型的範例中，該基板為圓 盤形，而其直徑為120 mm，厚度為01、〇 6或丨2 mm。 該圮錄堆疊側邊之基板的表面最好備有能夠被光學掃瞄 的伺服磁軌。該伺服磁軌通常是螺旋形的溝褙，而且在射 入製模或模壓製品期間，由製模裝置形成於基板上。此外 ，此等溝槽也能夠於可穿透的隔片層之纖維合成樹脂的摺 疊處理中形成，例如UV光可固化丙烯酸酯，係分離地提供 -10- 本纸張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) I24668l
發明説明 在。亥基板上。於高密度記錄中，此溝槽的高度為例如〇·6_ 〇_8 # m，而寬度為0.5 # m。 π在度记錄及抹除能夠因使用短波長的雷射而實現，例 如用670 nm或更短的波長。 :由於真空沉積、電子束真空沉積、化學蒸汽沉積、離子 電錢或錢鑛’相位改變記錄層能夠適用於基板β當使用濺 鍍時’能夠應用含有期望的量氧或氮的Ge_Te祕目標，或 能夠使用由Ge-Te所組成的⑽目標，因而對韻氣體控制 氧或氮的量。尤其，減錄氣體中氧或氮的濃度按體積計算 介於幾乎0與·間。該㈣沉積為非結晶狀並展現低的反 =°為了組成適當的具有高反射的記錄層該層首先必須 完成結晶化’ it常稱為初始化。為了上述目的，以溶爐加 熱該記錄層達到超過Ge_Te、Ge-Te_〇stGeTe-N的結晶 溫度，例如19〇 t。或者，以具有足夠功率的雷射光束來 加熱如多碳酸脂的纖維合成樹脂基板。於該索例中，例如 記錄器，雷射光束掃描移動的記錄層能夠實現上述。接著 該非結晶狀層被局部加熱到結晶化該層所需的溫度，避免 該基板遭受不利的熱負載。 藉由實施範例及相關的附圖，更詳細地說明根據本發明 的光學資訊媒體，其中： 該維 圖1顯示根據本發明之光學資訊媒體的概略剖面圖 沒有標示刻度； 圖2顯示兩條GexTei〇〇^_h值與完成抹㈣間（單位 為ns)的相關曲線，比較已知媒體的完成抹除時間與根據本 •11 - 1246681
發明之媒體的完成抹除時間； —圖3顯示根據本發明之媒體的以伙办"記錄層，其氧含 量與完成抹除時間（單位為ns)的相關曲線。 t施範例 圖1中具有基板1的資訊媒體20，可藉由雷射光束1〇的裝 置來抹除記錄。在其上提供堆疊層2。堆疊層2有第一介電 層5與第二介電層7,能夠在非結晶狀與結晶狀間改變的記 錄層6 ’以及反射層3。巾該記錄層配置在第一介電層5與第 二介電層7之間。記錄層6由慣用的化合物^49^〜5所組 成。此外，記錄層6的化合物所包含的的量可提高到 5 at·%。而該記錄層的厚為28 nm，對67〇 的雷射光波長 最好。 第一介電層5與第二介電層7是以川4,而且於本發明中是 和記錄層6相連接。丁“…是以川4好的替代物。第一介電層$ 與第二介電層7的厚度為5 nm。 反射層3由A1所組成，其厚度為1〇〇Ilm。 第三介電層4與第四介電層8,例如（ZnS)8〇(Si〇2)2〇，於本 發明中各自與第一介電層5與第二介電層7相鄰接。第三介 電層的厚度為20 nm，而第四介電層的厚度為9〇 nn^於此 一堆疊中，當雷射光的波長為670 nm時，非結晶狀反射Ra 為3.8%，而晶狀反射1^為36.5%。、 基板1是多碳酸脂圓盤形的基板，其直徑為12〇 mm，而 厚度為0.6 mm。 覆蓋層9由如UV固化樹脂Daicure SD645所組成，其厚度 -12- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1246681 A7 ______ __B7 五、發明説明) 一——：--— 為100 於本發明中是和第四介電層8相鄰接。 當所使用的雷射光波長為405㈣時，記錄層6的厚度最好 為！5 nm，而第三電與第四介電層4, 8各自的厚度最好為 2〇及135 nm。但堆疊2的其餘層及基板】仍未改變。於堆疊〕 中’當雷射光的波長為405 nm時，非結晶狀反射以為〇8% ，而晶狀反射Rc為22.9%。 圖2顯示GexTe10()-x記錄層中χ值與完成抹除時間（cet)的 相關曲線21，根據圖1的11，1>1，1]^堆疊中，該記錄層與以川4 的第；介電層及第二介電層7相連接，但沒有氧加入記錄層 6°當將第-及第二介電層的原料更換為（ZnS)w(si〇2 時 ，其對照曲線為所顯示的另一曲線22。如此能推斷根據本 發明使用第-及第二介電層的媒體，根據本發明能降低達 到大概3因子的完成抹除時間。 圖3顯示根據圖i的堆疊，記錄層6的化合物以4951^5〇5中 氧含量提高到3.5%時，對完成抹除時間（單位為ns)影響的曲 線23。當加入氮時’也能獲得相類似的影響。因此，最佳 實施例中，慣用的記錄層6是（^49 51^5〇5，於本發明中其氧 含量為1.87 at·%。 於本發明中，提供一種可重寫相位改變光學資訊媒體， 例如DVR-blue，具有Ge-Te化合-物的記錄層至少與一介電層 相連接，而該介電層由Ta&Si的氧化物、以及八丨的氮化物 、或Si的碳化物所組成，具有廣泛可使用的合成範圍，因 此容易製造具有低完成抹除時間（CET)值，並適合直接覆寫 及高資料速率的記錄，而且在7.2 m/s或更高的線性速度能 -13· 本紙張尺€财g S家標準(CNS) A鐵葛；297公爱)

Claims (1)

  1. 1246¾¾26577號專利申請案 中文申請專利範圍替換本(94年7月) •、申請專利範圍 1· 一種可由雷射光束（10)裝置來抹除記錄的光學資訊媒體 (20)該雷射光束具有雷射光波長，而該資訊媒體（2〇)包 括基板（1)及提供在該基板上的堆疊層（2)，該堆疊層 (2)包括第一介電層（5)與第二介電層（7)、能夠在非結晶 狀與結晶狀間改變的一記錄層（6)、以及一反射層（3)，而 舌己錄層（6)配置於第一介電層（5)與第二介電層（7)之間， 其特徵為 該記錄層（6)包含式GexTe1G()-x之化合物， 其中X是Ge的因子，單位為原子百分比（at〇/〇)，而且χ-的範圍為44<χ<52.5， 第一介電層（5)所包含的化合物，挑選自以與以的氧化 物、Si與Α1的氮化物及Si的碳化物所組成的群組，且其 係與該記錄層（6)相接觸。 2. 如申請專利範圍第1項之光學資訊媒體（2〇)，其特徵為第 二介電層（7)所包含的化合物’挑選自由1^與8丨的氧化物 、Si與A1的氮化物及si的碳化物所組成的群組，且其係 與該記錄層（6)相接觸。 ' 3. 如申請專利範圍第2項之光學資訊媒體（20)，其特徵為第 一介電層（5)所包含的化合物係挑選自τ~〇5及8丨3乂的群 組’而且第二介電層（7)所包含的化合物係挑選自 及Si3N4的群組。 4. 如申請專利範圍第3項之光學資訊媒體（20)，其特徵為第 一介電層（5)與第二介電層（7)的厚度最多為15mn。 5. 如申請專利範圍第4項之光學資訊媒體（2〇)，其特徵為第 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1246681 、申請專利範圍 A8 B8 C8 D8 一介電層（5)與第二介電層（7)之厚度的範圍為2，1〇 。 .如申請專利範圍第1、2、3、4或5項之光學資訊媒體（2〇) ’其特徵為該記錄層（6)之化合物的含氧量同時提高到 5at.0/〇 〇 •如申请專利範圍第1、2、3、4或5項之光學資訊媒體（20)， 其特徵為該記錄層（6)之化合物的含氮量同時提高到5at.%。 8·如申請專利範圍第1項之光學實訊媒體（20)，其特徵為該 反射層（3)包含至少一種挑選自a卜Ti、Au、Ag、Cu、 Rh、Pt、Pd、Ni、Co、Μη、Cr、Mo、W、Hf及 Ta所組. 成群組之金屬，包括其合金。 9_ 一種可由雷射光束（10)裝置以高速度記錄的光學資訊媒 體（20)，該雷射光束具有雷射光波長，而該資訊媒體 (20)包括一基板（丨）及提供在該基板上的堆疊層，該堆 豐層（2)包括一第一介電層（5)與一第二介電層（7)、能夠 在非結晶狀與結晶狀間改變的記錄層（6)、以及反射層 (3)，而記錄層（6)係配置於第一介電層（5)與第二介電層 (7)之間，其特徵為 -該記錄層<6)包含式GexTei()()-x之化合物， 其中X是Ge的因子，單位為at 〇/0，而且X的範圍為 44<χ<52·5， "第一介電層（5)所包含的化合物，挑選自Ta與Si的氧化 物、Si與A1的氮化物及Si的碳化物所組成的群組，且和 記錄層（6)相接觸，其中介於雷射光束與該媒體之間的相 對速度至少是7.2 m/s。 -2- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)
    裝 訂 m 1246681 上手>
    圖
    2
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