TW564412B - Optical information recording medium, optical information recording and reproducing method, optical information recording and reproducing device and method of manufacturing optical information recording medium - Google Patents
Optical information recording medium, optical information recording and reproducing method, optical information recording and reproducing device and method of manufacturing optical information recording medium Download PDFInfo
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564412 A7 B7 五、發明説明(彳) 【發明所屬之技術領域】 本發明係關於藉由照射雷射光,使記錄層材料產生相 變化,可以進行資訊之記錄再生,而且,可以重寫之相變 化型光資訊記錄媒體,特別是,在DVD之2倍速(7. Om/s )線速度以上、CD之8倍速(9.6〜11.2m/s )線速度以上 之高線速度區域之記錄爲可能之相變化型之光資訊記錄媒 體、對於此光資訊記錄媒體之光資訊記錄再生方法以及光 資訊記錄再生裝置、以及光資訊記錄媒體之製造方法。 【習知技術】 可以藉由雷射光之照射之記錄、再生以及抹除之光資 訊記錄媒體之一而廣爲人知者有利用結晶-非結晶間或結 晶-結晶間的相轉換之所謂的相變化型光資訊記·錄媒體。 特別是,在光磁性記錄中,困難之藉由單一光束之覆寫( over-write)容易,記錄再生裝置側之光學系統也單純之故 ,相變化型光資訊記錄媒體之需要變高,已經有CD-RW、 DVD-RW、DVD-RAM等被商品化。 在這些記錄媒體中,爲了可以更快速記錄更多之資訊 ,期待更高密度化或高線速度化。 同樣地,光資訊記錄裝置之記錄速度也益形高速化。 現在,CD系統之最高記錄線速度爲CD-R成爲CD 12倍速、 CD-RW成爲CD 10倍速,至目前爲止之CD-R與CD-RW之記 錄速度經常係CD-R方面先一步達成高速化。例如,CD-RW 爲CD4倍速記錄時,CD-R爲CD8倍速、CD10倍速、CD12倍 ---------雙衣丨丨 (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) -4 - 564412 A7 ___ B7 _ 五、發明説明(2 ) 速’而達成更局速化。 (請先閱讀背面之注意事項再填寫本頁) 其結果,光資訊記錄裝置雖搭載高速對應之主軸馬達 、半導體雷射、控制系統,但是卻以低速記錄CD-RW。其 原因爲CD-RW光碟保有顯示標準的記錄線速度或最高記錄 線速度之資訊,光資訊記錄光至認識該資訊後進行記錄之 故,無法進行最高記錄線速度以上之高速記錄。 又,CD-RW光碟也保有顯示最低記錄線速度之資訊之 故,其記錄線速度係被設計爲幾乎相同滿足最低記錄線速 度與最高記錄線速度,對於光資訊記錄裝置,在高速記錄 之匹配上有顧慮而無法實施。 關於相變化型光資訊記錄媒體,通常媒體之位移線速 度需要最適當化爲適合記錄線速度。 經濟部智慧財產局員工消費合作社印製 此處,位移線速度係表示以下之線速度。如圖18所示 般地,以種種之線速度使相變化型光資訊記錄媒體旋轉, 一面使半導體雷射光追跡在相變化型光資訊記錄媒體之導 引溝,一面藉由半導體雷射光照射,量測將相變化記錄層 加熱在熔點以上而冷卻時之光資訊記錄媒體的反射率或反 射光強度。藉由此量測,獲得如圖19所示之量測結果。圖 19中,伴隨線速度增加之反射率或反射光強度開始降低之 線速度(圖中位移線速度係以箭頭所示之線速度)。 如也詳紙揭示在特開平11-115313號公報般地,控制相 變化型光資訊記錄媒體之位移線速度在保持品質上很重要 。又,在同一公報中也揭示 CD-RW 媒體之 2X〜4Χ(2·4〜5.6m/s)線速度之最適當的位移線速度爲2.5〜 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) Γ5Τ 一 564412 A7 ___ B7__ 五、發明説明(3 ) 5.0m/s 〇 (請先閱讀背面之注意事項再填寫本頁) 但是,由於高密度化,一進行光資訊記錄媒體之窄溝 化、雷射光之短波長化、高NA(孔徑數値)化,光資訊記錄 媒體之熱特性大爲變化,在具有相同記錄層材料或層構成 之相變化型光資訊記錄媒體中,位移線速度大爲不同,因 此,例如在0¥0之2又(7.〇111/8)線速度以上、00之8又(9.6〜 11.2m/s )線速度以上之高密度、高線速度區域中,爲了進 行對相變化型光資訊記錄媒體之記錄,需要就記錄層材料 、層構成、製程條件等再檢討,再設計與記錄線速度、導 引溝之軌距、記錄裝置之雷射光的波長、NA等之條件一致 之位移線速度。 在此種背景之中,習知之CD-RW光碟由於其之記錄線 速度被設計爲幾乎同等滿足最低記錄線速度與最·高記錄線 速度之故,其之位移線速度係未滿最高記錄線速度之〇.85倍 ,無法在此以上之高速下記錄。 經濟部智慧財產局員工消費合作社印製 形成上述光資訊記錄媒體之記錄層用之相變化記錄材 料有:GeTe、GeTeSe、GeTeS、GeSeS、GeSeSb、GeAsSe、 InTe、SeTe、SeAs、Ge-Te-(Sn、Au、Pd)、GeTeSeSb、 GeTeSb、Ag-In-Sb-Te等材料。特別式AglnSbTe材料具有高 感度、非晶質部份之輪廓明確之特徵,被開發爲標記邊緣 (mark-edge )·記錄用之記錄層(參考特開平3-231889號公 報、特開平4- 19 1 089號公報、特開平4-232779號公報、特開 平4-267192號公報、特開平5-345478號公報、特開平6_ 1 66266號公報等)。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -6 - ' -- 564412 A7 ___B7____ 五、發明説明(4 ) (請先閲讀背面之注意事項再填寫本頁) 在特開平3-23 1 889號公報中揭示以I爲I族元素、以ΙΠ 爲III族元素、以V爲V族元素、以VI爲VI族元素,以 Idlll-rVi·) · VI2型之一般組成式所表示之記錄層。但是,在 此種記錄層中,重覆記錄特性並不一定能充分滿足要求者 〇 又,在被使用於揭示在特開平4- 191089號公報之資訊記 錄媒體的記錄層之情形,雖然達成抹除比之提升與高速記 錄,但是重覆記錄特性有問題。進而,關於揭示在特開平 1-303643號公報之資訊記錄媒體,係藉由採用新的結晶構造 ,具有高C/N比與重覆特性,而成爲可以提供保存特性也 優異者,但是,記錄感度與重覆特性不充分。 被使用在揭示於特開平4-232779號公報之資訊記錄媒體 之記錄層的未記錄部份(結晶化部份)之構造係安定相( AgSbTh )與存在於安定相之周圍之非晶質相混合存在者。 因此,重覆記錄特性雖提升,但是,在結晶化部存在微細 之結晶粒邊界,成爲雜訊產生之原因。 經濟部智慧財產局員工消費合作社印製 此雖對如使用記錄再生波長爲780nm程度之雷射光的 CD-RW(compact Disk-ReWritable:可重寫緻密光碟)等地, 具有比較低之記錄密度之光資訊記錄媒體的記錄特性不會 造成重要之不好影響,但是在實現使用波長680nm以下之雷 射光,記錄密度爲 CD-RW之約4倍之 DVD(Digital Versatile Disk :數位萬用光碟)—RAM或更高密度之DVD-RW等之高密度記錄上,會成爲阻礙。進而,關於重覆記錄 特性也殘留問題。 本紙張尺度適用中國國家標準(CNS ) A4規格(210'〆297公釐) ΙΥΙ ~~' 564412 A7 ___ B7 五、發明説明(5 ) (請先閲讀背面之注意事項再填寫本頁) 被使用在特開平4-267 192號公報所揭示之記錄媒體之記 錄層的結晶化部份之構造係由一樣之非晶質相做相分離之 AgSbTea與其它之相(安定相或非晶質相)之混相狀態。其 它之相在非晶質相之情形,產生與揭示在前述之特開平4-23 2779號公報之資訊記錄媒體之情形相同之問題點,在其 它之相爲安定結晶相之情形,如後述般地,伴隨無法獲得 良好之記錄特性之問題。 依據特開平5-345478號公報、特開平6- 1 66268號公報之 情形,也有與上述之情形相同之問題。即關於以AglnSbTe 系或具有擴充這些之lb族元素、Illb族元素、Vb族元素、 以及VIb族元素之相變化記錄材料爲記錄層之光資訊記錄 媒體,並無關於規定構成這些之元素的配位數之記錄媒體 之見識,因此,並無使各構成元素之記錄材料的機能之任 務明確之習知技術。因此,並無依據理論進行AglnSbTe記 錄層之重覆特性或資訊之記錄以及抹除感度等之具體的改 良。 經濟部智慧財產局員工消費合作社印製 又,形成相變化型光資訊記錄媒體之記錄層用之相變 化記錄材料例如如揭示在美國專利第353044 1號詳細說明書564412 A7 B7 V. Description of the invention (彳) [Technical field to which the invention belongs] The present invention relates to the phase change of the recording layer material by irradiating laser light, which can record and reproduce information, and can rewrite the phase change. Type optical information recording media, in particular, it is possible to record in a high linear velocity area at a linear speed higher than 2 times the speed of DVD (7.0 m / s) and a linear speed higher than 8 times the speed of CD (9.6 to 11.2 m / s). Phase-change type optical information recording medium, optical information recording and reproducing method for the optical information recording medium, optical information recording and reproducing device, and manufacturing method of optical information recording medium. [Knowledge technology] One of the optical information recording media that can be recorded, reproduced, and erased by the irradiation of laser light is widely known as a so-called phase that utilizes crystalline-amorphous or crystalline-crystalline phase transition Change light information recording media. In particular, in the case of photomagnetic recording, it is easy to overwrite with a single light beam, and the optical system on the side of the recording / reproducing device is also simple. The need for a phase-change optical information recording medium has increased, and CD-RW, DVD-RW, and DVD-RAM are commercially available. In these recording media, in order to record more information more quickly, higher density or higher line speed is expected. Similarly, the recording speed of the optical information recording device is also increasing. At present, the maximum recording linear speed of the CD system is that CD-R becomes 12 times the speed of CD, and CD-RW becomes 10 times the speed of CD. Until now, the recording speed of CD-R and CD-RW has often reached the high speed of CD-R. Into. For example, when CD-RW is CD4x speed recording, CD-R is CD8x speed, CD10x speed, CD12x --------- Double Outfits 丨 (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 Cooperatives, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -4-564412 A7 ___ B7 _ V. Description of the invention (2) Speed's to achieve more speed . (Please read the precautions on the back before filling this page.) As a result, although the optical information recording device is equipped with a high-speed corresponding spindle motor, semiconductor laser, and control system, it records CD-RW at a low speed. The reason is that a CD-RW disc holds information showing a standard recording linear speed or a maximum recording linear speed, and the optical information is recorded until the information is recorded and recorded at a high speed above the maximum recording linear speed. In addition, the CD-RW disc also holds information showing the minimum recording linear velocity. The recording linear velocity is designed to be almost the same to meet the minimum recording linear velocity and the maximum recording linear velocity. For optical information recording devices, the high-speed recording matches. There are concerns and cannot be implemented. Regarding the phase-change optical information recording medium, the linear velocity of the displacement of the medium usually needs to be optimally adapted to the recording linear velocity. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Here, the linear velocity of displacement refers to the following linear velocity. As shown in FIG. 18, the phase-change optical information recording medium is rotated at various linear velocities, while the semiconductor laser light is traced in the guide groove of the phase-change optical information recording medium, while being irradiated with the semiconductor laser light, Measure the reflectance or reflected light intensity of the optical information recording medium when the phase change recording layer is heated above the melting point and cooled. By this measurement, the measurement result shown in FIG. 19 is obtained. In Fig. 19, the linear velocity at which the reflectance or the intensity of the reflected light starts to decrease as the linear velocity increases (the displacement linear velocity in the figure is the linear velocity indicated by the arrow). As disclosed in detail in Japanese Patent Application Laid-Open No. 11-115313, it is important to control the displacement linear velocity of the phase-change optical information recording medium in order to maintain quality. Also, in the same gazette, the most appropriate displacement linear velocity of the 2X ~ 4 × (2 · 4 ~ 5.6m / s) linear velocity of the CD-RW media is 2.5 ~ This paper standard applies the Chinese National Standard (CNS) A4 standard (210X297 mm) Γ5Τ a 564412 A7 ___ B7__ 5. Description of the invention (3) 5.0m / s 〇 (Please read the precautions on the back before filling out this page) However, due to the high density, Narrow grooves, short wavelengths of laser light, and high NA (number of apertures), thermal characteristics of optical information recording media have greatly changed. In phase-change type optical information recording media with the same recording layer material or layer composition, Displacement linear velocities are very different. Therefore, for example, high density and high linear velocities above 0 ¥ 0 2 (7.〇111 / 8) linear velocity and above 8 0 (9.6 to 11.2 m / s) linear velocity. In the speed area, in order to record the phase-change optical information recording medium, it is necessary to review the recording layer material, layer composition, process conditions, and so on, and then design and record the linear velocity, the gauge of the guide groove, and the lightning of the recording device. The shift of the wavelength of the light, NA and other conditions Speed. In this context, the conventional CD-RW discs are designed to meet the minimum recording linear velocity and the maximum and maximum recording linear velocity because their recording linear velocity is almost equal, so their displacement linear velocity is less than the maximum recording linear velocity. The speed is 0.85 times, and it is impossible to record at a speed higher than this. The phase change recording materials used by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to form the recording layer of the optical information recording medium are: GeTe, GeTeSe, GeTeS, GeSeS, GeSeSb, GeAsSe, InTe, SeTe, SeAs, Ge-Te- ( Sn, Au, Pd), GeTeSeSb, GeTeSb, Ag-In-Sb-Te and other materials. The special AglnSbTe material has the characteristics of high sensitivity and clear outline of the amorphous part, and has been developed as a recording layer for mark-edge and recording (see Japanese Patent Application Laid-Open No. 3-231889, Japanese Patent Application Laid-Open No. 4-19 1 089, JP 4-232779, JP 4-267192, JP 5-345478, JP 6_ 1 66266, etc.). This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -6-'-564412 A7 ___B7____ 5. Description of the invention (4) (Please read the precautions on the back before filling this page) In JP 3 -23 1 889 discloses a general composition formula using I as a group I element, ΙΠ as a group III element, V as a group V element, VI as a group VI element, and Idlll-rVi ·) · Type VI2 The recording layer. However, in such a recording layer, the repeated recording characteristics may not be sufficient to satisfy the requirements. Moreover, in the case of being used to disclose the recording layer of the information recording medium disclosed in Japanese Patent Application Laid-Open No. 4-191089, although the Divide ratio is improved and high-speed recording, but repeated recording characteristics are problematic. Furthermore, the information recording medium disclosed in Japanese Patent Application Laid-Open No. 1-303643 has adopted a new crystalline structure and has a high C / N ratio and repeating characteristics, and has become one that can provide excellent storage characteristics. Insufficient sensitivity and repetition characteristics. The structure used in the unrecorded portion (crystallized portion) of the recording layer of the information recording medium disclosed in Japanese Patent Application Laid-Open No. 4-232779 is a stable phase (AgSbTh) and an amorphous phase surrounding the stable phase. Mixed Beings. Therefore, although the repeated recording characteristics are improved, the existence of fine crystal grain boundaries in the crystallized portion is a cause of noise. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed a compact recording-reproducible compact disc (CD-RW) that uses laser light with a wavelength of approximately 780 nm. The recording characteristics of optical information recording media will not cause important adverse effects, but in the realization of the use of laser light with a wavelength of less than 680nm, the DVD (Digital Versatile Disk: Digital Versatile Disk) has a recording density of approximately four times that of CD-RW — RAM or higher-density DVD-RW and other high-density recording can be an obstacle. Further, there is a problem regarding the repeated recording characteristics. This paper size applies the Chinese National Standard (CNS) A4 specification (210'〆297 mm) ΙΥΙ ~~ '564412 A7 ___ B7 V. Description of the invention (5) (Please read the precautions on the back before filling this page) Used The structure of the crystallized portion of the recording layer of the recording medium disclosed in Japanese Patent Application Laid-Open No. 4-267 192 is a phase separation of AgSbTea and other phases (stable phase or amorphous phase) from the same amorphous phase. Miscible state. When the other phases are in the amorphous phase, the same problems as in the case of the information recording medium disclosed in the aforementioned Japanese Patent Application Laid-Open No. 4-23 2779 arise, and when the other phases are stable crystalline phases, as will be described later. This is accompanied by a problem that good recording characteristics cannot be obtained. According to the circumstances of Japanese Patent Application Laid-Open No. 5-345478 and Japanese Patent Application Laid-open No. 6-16666, there are also problems similar to those described above. That is, the optical information recording medium using the phase change recording material of the AglnSbTe series or with the expansion of the lb group element, the Illb group element, the Vb group element, and the VIb group element as the recording layer, there is no stipulation on the composition of these elements. The knowledge of the recording media with single digits, therefore, there is no known technique for clarifying the function of the recording material of each constituent element. Therefore, there is no specific improvement based on the theory to repeat the characteristics or information recording of AglnSbTe recording layer and erase sensitivity. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and the phase change recording material used to form the recording layer of the phase change optical information recording medium, for example, as disclosed in US Pat. No. 353044 1 detailed description
Se-Sb、Ge-As-Se、In-Te、Se-Te、Se-As 等之所謂的硫族系 合金材料。 進而,以安定性、高速結晶化等之提升爲目的,提案 在〇6-丁6系添加人11(特開昭61-2 19692號公報)、311以及八11( 特開昭61-270190號公報)、Pd(特開昭62- 19490號公報)等之 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公董1 ^ 564412 A7 B7 五、發明説明(6 ) (請先閱讀背面之注意事項再填寫本頁) 材料。又,以記錄/抹除之重覆性能提升爲目的,也有確 定Ge-Te-Se-Sb、Ge-Te-Sb之組成比之材料(特開昭62-73438號公報、特開昭63-228433號公報)之提案等。 但是,其中任何一種都無法說可以滿足相變化型記錄 媒體所被要求之諸特性的全部。特別是,記錄感度、抹除 感度之提升、覆寫時之抹除殘餘之抹除比降低之防止、以 及記錄部、未記錄部之長壽命化成爲應解決之最重要課題 〇 另一方面,在特開昭63-25 1 290號公報中,提案具有由 結晶狀態實質上爲3元以上之多元化合物單層所形成之記錄 層之記錄媒體。此處所謂實質上爲3元以上之多元化合物 單層係指在記錄層中包含具有3元以上之化學量論組成之 化合物(例如In3SbTe2)在90原子%以上者。藉由使用此種 記錄層,以謀求記錄、抹除特性之提升。但是,存在抹除 比小,記錄抹除所需要之雷射功率還未被充分降低等之缺 點。 經濟部智慧財產局員工消費合作社印製 進而,在特開平1 -27733 8號公報中提案具有以(363以1-〇i-yMy(此處,0.4$aS0.7、yS0.2、Μ 爲由 Ag、A:l、As、 Au、Bi、Cu、Ga、Ge、In、Pb、Pt、Se、Si、Sn 以及 Zn 所 形成之群中選擇至少其中1種)所表示之組成的合金所形成 之記錄層之光.資訊記錄媒體。又,此系之基本爲Sb2Te3。 藉由使Sb過剩,提升高速抹除、重覆特性,又,藉由μ之 添加’促進®速抹除。除此之外,藉由D C光之抹除比也大 。但是,在此文獻中,覆寫時之抹除比並無顯示,記錄感 本紙張尺度適财關家鮮(CNS ) A4規格(21GX297公釐)'— 564412 經濟部智慧財產局員工消費合作社印製 A7 __B7 _五、發明説明(7 ) 度也不充分。關於覆寫時之抹除比在本發明者們之檢討結 果中,確認到抹除殘餘。 同樣地,在特開昭60- 177446號公報中,在記錄層使用 由(Ini-xSbx) i-yMy(0.55S xS 0.80、OS 0·20、Μ 係 Au、 Ag、Cu、Pd、Pt、A1、Si、Ge、Ga、Sn、Te、Se、Bi)形成 之合金,又,在特開昭63-228433號公報中,在記錄層使用 由Ge-Sb2Te3-Sb(過剩)形成之合金,但是任何一種都無法滿 足感度、抹除比等之特性。 除此之外,在特開平4- 1 63839號公報中記載藉由在Te-Ge-Sb合金使含有N以形成記錄薄膜之光資訊記錄媒體,在 特開平4-52 1 88號公報中記載在Te-Ge-Se合金使含有這些成 分之中的至少一種成爲氮化物者以形成記錄薄膜之光資訊 記錄媒體,在特開平4-521 89號公報中記載在Te-Ge-Se合金 使吸附N以形成記錄薄膜之光資訊記錄媒體。 但是,即使在這些光資訊記錄媒體也無法獲得具有充 分之特性者。 如上述般地,在習知的光資訊記錄媒體中,特別是, 記錄感度、抹除感度之提升、覆寫時之抹除殘餘之抹除比 之防止、以及記錄部、未記錄部之長壽命化成爲應解決之 最重要課題。 另一方面.,伴隨CD(緻密光碟)之急速普及,開發有只 可以寫入1次之追記型緻密光碟(CD-R ),開始普及於市 場。然而,CD-R在寫入時即使失敗一次,也無法修正之故 ,寫入失敗之光碟也變成不能使用不得不廢棄。因此,期 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) - IQ - (請先閱讀背面之注意事項再填寫本頁) 564412 A7 B7 五、發明説明(8 ) 待修補該缺點之可以重寫之緻密光碟的實用化。 (請先閲讀背面之注意事項再填寫本頁) 被硏究開發之一例爲利用光磁性光碟之可以重寫之緻 密光碟,由於存在覆寫之困難度或與CD-ROM、CD-R之互 換性不好等之缺點之故,原理上有利於互換確保之相變化 型光碟(相變化型光資訊記錄媒體)之實用化開發正活躍 進行著。 繾濟部智慧財產局員工消費合作社印製 利用相變化型光碟之可以重寫的緻密光碟之硏究發表 例有:古谷(其他):第4次相變化記錄硏究會討論會演 講預備稿集,70 ( 1 992 )、神野(其他):第4次相變化 記錄硏究會討論會演講預備稿集,76 ( 1 992 )、川西(其 他):第4次相變化記錄硏究會討論會演講預備稿集,82 (1 992 )、T. Handa(etal) : Jpn· J· Appl. Phys·,32( 1 993)、 米田(其他):第5次相變化記錄硏究會討論會演講預備稿 集,9 ( 1993 )、富永(其他):第5次相變化記錄硏究會 討論會演講預備稿集,5 ( 1 993 )之類者。可是,這些任何 一種都無法充分滿足與CD-ROM或CD_R之互換性確保、記 錄抹除性能、記錄感度、重寫之重覆可能次數、再生次數 、保存安定性等、綜合性能。這些之缺點主要係起因於記 錄材料之組成、構造之抹除比的低下。 由這些情形,乃期望抹除比大、適合於高感度之記錄 、抹除之相變.化型記錄材料之開發、進而,可以以高性能 重寫之相變化型緻密光碟。 本發明者等作爲解決這些缺點之新材料發現提案 AglnSbTe系記錄材料。其代表例可以舉出:特開平心7803 1 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -11 - 564412 A7 __B7 五、發明説明(9 ) (請先閱讀背面之注意事項再填寫本頁) 號公報、特開平 4- 1 23551 號公報、H. Iwasaki(et al):Jpn. J. Appl. Phys·,3 1(1992)461、井手(其他):第3次相變化記 錄硏究會討論會演講預備稿集,102 ( 1 991 ) 、Η·So-called chalcogenide alloy materials such as Se-Sb, Ge-As-Se, In-Te, Se-Te, and Se-As. Furthermore, for the purpose of improving stability and high-speed crystallization, it is proposed to add people 11 (Japanese Patent Application Laid-Open No. 61-2 19692), 311, and 8-11 (Japanese Patent Application Laid-Open No. 61-270190) to the 06-but 6 series. (Gazette), Pd (Japanese Patent Application Laid-Open No. 62-19490) and other paper sizes are applicable to the Chinese National Standard (CNS) A4 specifications (210X297 public manager 1 ^ 564412 A7 B7) 5. Description of the invention (6) (Please read the Please fill in this page again for details) Materials. For the purpose of improving the repeated performance of recording / erasing, there are also materials that determine the composition ratio of Ge-Te-Se-Sb and Ge-Te-Sb (Japanese Patent Laid-Open No. 62- 73438, JP-A-63-228433, etc.). However, none of them can satisfy all the characteristics required for phase change recording media. In particular, recording sensitivity and erasing sensitivity The most important issues that need to be addressed are the improvement of erasing, the reduction of the erasing residue at the time of overwriting, and the longevity of the recording section and the unrecorded section. On the other hand, in JP 63-25 1 290 In Proclamation No., the proposal has diversification from a crystalline state of substantially three yuan or more A recording medium of a recording layer formed by a single layer of a composite. The so-called multi-component compound layer of substantially ternary means that the recording layer contains a compound having a stoichiometric composition of ternary or higher (for example, In3SbTe2). Above 90 atomic%. By using such a recording layer, the recording and erasing characteristics are improved. However, there are disadvantages that the erasing ratio is small and the laser power required for recording erasing has not been sufficiently reduced. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Further, in Japanese Unexamined Patent Publication No. 1-27733 8, the proposal has a value of (363 to 1-〇i-yMy (here, 0.4 $ aS0.7, yS0.2, M as An alloy consisting of at least one selected from the group consisting of Ag, A: 1, As, Au, Bi, Cu, Ga, Ge, In, Pb, Pt, Se, Si, Sn, and Zn) The light of the formed recording layer. Information recording medium. In addition, this system is basically Sb2Te3. By making Sb excessive, the high-speed erasing and repeating characteristics are improved, and the addition of μ is promoted to facilitate rapid erasing. In addition, the erasing ratio by DC light is also large. However, in this document, The erasing ratio of the time is not displayed, the paper size is suitable for the paper and the family (CNS) A4 specification (21GX297 mm) '— 564412 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7 _ V. Description of the invention ( 7) The degree is not sufficient. The erasure ratio at the time of overwriting was confirmed by the inventors' review results, and the erasure residue was confirmed. Similarly, in Japanese Patent Application Laid-Open No. 60-177446, the use of the recording layer by (Ini-xSbx) i-yMy (0.55S xS 0.80, OS 0 · 20, M-based Au, Ag, Cu, Pd, Pt, A1, Si, Ge, Ga, Sn, Te, Se, Bi) Also, in Japanese Patent Application Laid-Open No. 63-228433, an alloy formed of Ge-Sb2Te3-Sb (excess) is used for the recording layer, but neither of them can satisfy characteristics such as sensitivity and erasure ratio. In addition, Japanese Unexamined Patent Publication No. 4- 1 63839 describes an optical information recording medium containing N in a Te-Ge-Sb alloy to form a recording film, and is disclosed in Japanese Unexamined Patent Publication No. 4-52 1 88 An optical information recording medium in which a Te-Ge-Se alloy contains at least one of these components as a nitride to form a recording film is described in Japanese Patent Application Laid-Open No. 4-521 89. N to form an optical information recording medium of a recording film. However, even those optical information recording media cannot obtain sufficient characteristics. As described above, in the conventional optical information recording medium, in particular, the recording sensitivity, the improvement of the erasing sensitivity, the prevention of the erasing ratio of the erasing residue during overwriting, and the length of the recording section and the unrecorded section Life span has become the most important issue to be solved. On the other hand, with the rapid spread of compact discs (CDs), the development of write-once compact discs (CD-R) that can be written only once has begun to spread to the market. However, even if the CD-R fails to write once, it cannot be corrected, and the disc that has failed to write becomes unusable and has to be discarded. Therefore, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-IQ-(Please read the precautions on the back before filling this page) 564412 A7 B7 V. Description of the invention (8) To be repaired The practicality of compact discs that can be rewritten. (Please read the precautions on the back before filling in this page.) An example of researched and developed is a compact disc that can be rewritten using a magneto-optical disc. Due to the difficulty of overwriting or interchange with CD-ROM and CD-R Because of its shortcomings such as poor performance, the practical development of phase-change optical discs (phase-change optical information recording media) that are in principle conducive to interchange guarantee is being actively carried out. Examples of researches on printing compact discs that can be rewritten using phase-change discs by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs include: Gu Gu (Others): The 4th Phase Change Record Research Seminar Workshop Preparatory Speeches , 70 (1 992), Kamano (other): Preparing speeches for the 4th phase change recording research seminar, 76 (1 992), West Sichuan (other): 4th phase change recording research seminar Lecture preparations, 82 (1 992), T. Handa (etal): Jpn · J · Appl. Phys ·, 32 (1 993), Yoneda (Others): Lecture at the 5th Phase Change Record Research Conference Preparatory Manuscripts, 9 (1993), Fuyong (Other): Preparatory Manuscripts of Speeches of the 5th Phase Change Record Research Conference, 5 (1 993) and the like. However, none of these can fully satisfy the compatibility with CD-ROM or CD_R, record erasing performance, recording sensitivity, number of possible rewrites, number of reproductions, storage stability, and other comprehensive performance. These shortcomings are mainly due to the low erasure ratio of the recording material's composition and structure. Under these circumstances, it is expected that a large erasing ratio, suitable for high-sensitivity recording, and erasing phase-change recording materials, and further, a phase-change type compact disc that can be rewritten with high performance. The present inventors have proposed an AglnSbTe-based recording material as a new material finding solution to these disadvantages. Representative examples include: JP Kaixin 7803 1 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -11-564412 A7 __B7 V. Description of the invention (9) (Please read the notes on the back first (Please fill in this page again), JP-A No. 4- 1 23551, H. Iwasaki (et al): Jpn. J. Appl. Phys ·, 3 1 (1992) 461, Ide (Other): Third phase Preparing for lectures on change record seminars, 102 (1 991), ·
Iwasaki(et al):Jpn. J· Appl. Phys·,32( 1993)5241 等。 又,在199 6年10月,作爲可以重寫之緻密光碟(CD-RW )之規格,發行 orange book part III(版本 1.0)。orange book part III(版本1·〇)系對於2x線速度記錄(2.4〜2.8m/s)之 CD-RW之規格之故,在此種低線速度的記錄中,記錄時間 長。因此,期望更高速記錄之可以重寫的緻密光碟。 另一方面,提升相變化記錄之記錄信號的品質之方式 揭示有種種之記錄補償方式。 例如,在特開昭63-266632號公報記載者中,關於利用 結晶化速度大之記錄膜之情形的PWM記錄,利用脈衝列, 記錄長非晶質標記之方式有效。 經濟部智慧財產局員工消費合作社印製 又,在記載於特開昭63-266633號公報以及美國專利第 5 1 5035 1號詳細說明書者中,提高脈衝列之前端以及尾端之 雷射能量,使照射時間變長,抑制標記邊緣之位置搖動以 進行抖動之改良。又,習知上,知道有如記載於特公昭63-29336號公報般地,光碟記錄裝置一面在光碟上照射雷射光 等之光點,·一面掃描,以資訊信號強弱調制雷射光等之光 點,在光碟記.錄資訊信號之方法,又,也知道有再生被記 錄於光碟之資訊信號,藉由監視該再生信號之振幅或記錄 標記之長度,最適當地調整、設定記錄光功率或記錄.光脈 衝之寬幅等之記錄條件之方法。 本紙張尺度適财师家標準(CNS ) A4規格(21GX 297公釐):12 - ~ 564412 A7 B7 五、發明説明(ι〇 ) (諸先閱讀背面之注意事項再填寫本頁) 又,在特開平9- 1 38946號公報 '特開平9- 1 3 8947號公報 、特開平9-21 9021號公報揭示如圖④1所示般地,在資訊記 錄媒體藉由PWM記錄進行資訊之記錄之際,設進行調制後 之信號寬幅爲nT(T係時脈時間)之〇信號的記錄或重寫時之 記錄波爲功率準位e之連續電磁波,設進行調制後信號寬 幅爲nT之1信號的記錄或重寫時之記錄波脈衝列爲具有: 具有時間寬幅X與功率準位a之脈衝部fp,與具有合計爲T 之時間寬幅之功率準位b之低準位脈衝與功率準位c之高 準位脈衝交互以負荷比y合計(η-η’)次連續之多脈衝部 mp,與具有時間寬幅ζ與功率準位d之脈衝部op之電磁波 脈衝歹[J,設 X、y、z 爲0.5TS xS 2.0T、0.4S yS 0.6、0.5T $ 1.0T,設η’爲nj η之正整數(a以及c) ^ (b以 及d)。 經濟部智慧財產局員工消費合作社印製 由習知之技術,大幅謀求了記錄信號品質與覆寫重複 時之安定性之提升、信賴性、泛用性之提升。但是,近年 來,關於重寫型資訊記錄媒體,特別是相變化型光資訊記 錄媒體,要求以1個之資訊記錄媒體可以以複數的線速度 進行記錄(多速度記錄)之技術。 又,要求記錄速度之高速化,也要求有利於高速記錄 之CAV記錄。對於這些之技術要求,以上述之特開平9-1 38946號公報、特開平9- 1 38947號公報、特開平9-21 9021號 公報所記載之技術並無法應付。例如,在具有可以以CD線 速度4x記錄之fp、mp、op之記錄策略中,在8x速度記錄 、以及10x速度記錄之情形,在8x速度記錄、以及ΐ〇χ速度 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 13 - 564412 A7 ___ B7 五、發明説明(11) (請先閲讀背面之注意事項再填寫本頁) g己錄無法獲得充分之信號品質。進而,對CD線速度4x記 錄之部份的ΙΟχ速度記錄之覆寫,或對CD線速度1 Ox記錄 之部份的4x速度記錄之覆寫之由於不同的記錄線速度之覆 寫的信號品質之劣化會成爲問題。又,對CLV記錄之部份 的在CAV記錄之覆寫,或對CAV記錄之部份的在CLV記 錄之覆寫的藉由不同的記錄方式之覆寫中的信號品質之劣 化也成爲問題。 【發明欲解決之課題】 本發明係有鑑於習知技術之上述問題點而完成者,第 1目的爲可以高速記錄之相變化型光資訊記錄媒體、以及 可以充分發揮該光資訊記錄媒體所具有之能力之可以高速 記錄之光資訊記錄再生方法以及光資訊記錄再生裝置之提 又,本發明系有鑑於上述習知技術之上述問題點而完 成者,第2目的爲提供重覆特性、記錄、抹除感度、保存 特性優異之光資訊記錄媒體以及光資訊記錄媒體的製造方 法。 經濟部智慧財產局員工消費合作社印製 進而,獲得完全滿足上述之綜合性能,足以兼顧在更 高速之記錄與在高溫之保存、使用信賴性之確保之相變化 型光碟系習知之課題。除此之外,基於多速度CLV記錄以 及CAV記錄之覆寫信號品質之安定性的提升或以泛用之記 錄策略可以進行記錄一事也是習知之課題。 換言之,本發明爲了全部解決上述習知技術之問題’ ^紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -14- 564412 A7 B7 五、發明説明(12) (請先閲讀背面之注意事項再填寫本頁) 以提供在以高線速區域進行記錄、抹除爲最適當之光資訊 記錄媒體爲第3目的,以提供高速記錄、抹除之信賴性良 好的光資訊記錄媒體爲第4目的,以提供此光資訊記錄媒 體爲可以進行多速度CLV記錄以及CAV記錄之光資訊記錄 媒體爲第5目的。 【解決課題用之手段】 上述課題系藉由如下之(1 )〜(32 )之發明(以下’ 也有記載爲本發明1〜32)而解決。 (1 ) 一種在具有同心圓或螺旋狀之導引溝之透明基板 上至少具有相變化型記錄層,具有顯示標準記錄線速度Vr 以及/或最高記錄線速度Vh之資訊的光資訊記錄媒體,其 特徵爲: 設對於形成在相變化型光記錄層之島部以及或溝部, 照射可以使記錄層材熔化之能量,一面增加線速度,一面 掃描之際,光記錄媒體之反射率與上述能量之照射前相比 ,反射率降低之線速度爲位移線速度V之情形, 經濟部智慧財產局員工消費合作社印製 在聚焦半導體雷射光DC照射於該導引溝之溝部或島部 之際的位移線速度V係滿足:0.85VrS V或0.8 5VhS V之條 件式。 (2)進而,以前述位移線速度爲0.9VrSVS2.0Vr或 0.9VhS VS 2.0Vh爲其特徵之(1)記載之光資訊記錄媒體 〇 (3 )進而,具有可以判別是否爲滿足前述位移線速度 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -15 - 564412 A7 __B7 五、發明説明(13 ) V之條件式之光資訊記錄媒體之資訊之(1 )或(2 )記載之 光資訊記錄媒體。 (請先閲讀背面之注意事項再填寫本頁) (4 )全面結晶化(初期化)前述相變化型記錄層之際 ,其之初期化線速度Vi係滿足〇.5VrS Vig 1.6Vr或0.5VhS ViS1.6Vh之條件式之(1)〜(3)之其一所記載之光資訊 記錄媒體。 (5 )前述導引溝係軌距0 · 2〜1 · 4// m,聚焦半導體雷射 光DC照射於前述導引溝之溝部或鳥部之際的位移線速度V 爲6〜25m/s之(1)〜(4)之其一所記載之光資訊記錄媒 體。 (6 )前述相變化型記錄係未記錄狀態主要爲立方晶格 結晶構造之(1 )〜(5 )之其一所記載之光資訊記錄媒體 〇 (7)前述相變化型記錄層係以SbxTem.xHOSxSSO, X爲原子%)之組成式所代表的材料構成之(1 )〜(6 )之其 一所記載之光資訊記錄媒體。 經濟部智慧財產局員工消費合作社印製 (8 )前述相變化型記錄層係包含由Ga、Ge、Ag、In、 Bi、C、N、0、Si、S選擇之至少一種之元素爲添加元素之 (7 )記載之光資訊記錄媒體。 (9 )前述相變化型記錄層係以(Ag、Ge ) α (In、Ga、 Bi)〃 Sbr Te5之組成式所代表之材料構成,此時,(Ag、Ge )以及(In、Ga、Bi)係意指分別包含括號內之至少一種之 元素,α 、/3 、7 、5 係原子 %,〇·1$α$7、1$/3$15 、61$ r $ 85、20$ 5 S 30之(1)〜(8)之其一所記載之 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -16 - ' 一 564412 A7 B7 五、發明説明(14 ) 光資訊記錄媒體。 (請先閲讀背面之注意事項再填寫本頁) (1 0 )在設η爲1以上之整數、T爲相當於使用在信號 之調制之時脈的週期之時脈時間之情形, 設進行調制後之信號寬幅爲ηΤ之0信號的記錄或重寫 時之記錄光爲功率準位e之連續光,設進行調制後信號寬 幅爲ηΤ之1信號的記錄或重寫時之記錄波脈衝列爲由:具 有時間寬幅X與功率準位a之脈衝部fp,與具有合計爲T 之時間寬幅之功率準位b之低準位脈衝與功率準位c之高 準位脈衝交互以負荷比y合計(m-m’)次連續之多脈衝部 mp,與具有時間寬幅z與功率準位d之脈衝部ep形成之雷 射波脈衝列,進而,分別設X、y、z爲0.125TS xS 2.0T、 0.125S yS 0.87 5、0.125TS 1·0Τ,設 m 爲 1以上之整數, 經濟部智慧財產局員工消費合作社印製 (a以及c ) > e > (b以及d)之記錄條件,可以以比標準記 錄線速度Vi•或最高記錄線速度Vh還高速進行記錄地調整 形成在具有同心圓或螺旋狀之導引溝的透明基板上之第一 保護層、相變化型記錄層、第二保護層、反射層、樹脂層 之各層的厚度之(1 )〜(9 )之其一所記載之光資訊記錄 媒體。 (11 )光資訊記錄媒體之層構成係在基板上至少具有 第一保護層、相變化型記錄層、第二保護層、第三保護層 、反射層、樹脂保護層之(1 )〜(10 )之其一所記載之光 資訊記錄媒體。 (12)第三保護層之構成材料係可以以DC濺鍍法形成 者之(11 )記載之光資訊記錄媒體’。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -17 - 564412 A7 B7 五、發明説明(15) (請先閱讀背面之注意事項再填寫本頁) (13)前述第三保護層之構成材料係包含由C、Si、 SiC、SiN、SiO、Si〇2選擇至少其中一種之物質之(11)或 (1 2 )記載之光資訊記錄媒體。 (14 )前述相變化型記錄層係全面結晶化處理之線速 度比位移線速度還慢之(1 )〜(1 3 )之其一所記載之光資 訊記錄媒體。 (1 5 ) —種光資訊記錄再生方法,其特徵爲:於光資 訊記錄再生裝置設定保有是否爲滿足預先決定之位移線速 度V之條件式之光資訊記錄媒體之固有的資訊之相變化型 的光資訊記錄媒體,由前述光資訊記錄媒體再生前述固有 之資訊,由該資訊判斷是否可以以比前述光資訊記錄媒體 的最高記錄線速度還高的記錄線速度進行記錄,在可能之 情形,以比最高記錄線速度還高之記錄線速度進行記錄再 生。 經濟部智慧財產局員工消費合作社印製 (16) —種光資訊記錄再生裝置,其特徵爲:由保有 是否爲滿足預先決定之位移線速度V之條件式之光資訊記 錄媒體之固有的資訊之相變化型的光資訊記錄媒體再生前 述固有之資訊,由該資訊判斷是否可以以比前述光資訊記 錄媒體的最高記錄線速度還高之記錄線速度進行記錄,在 可能之情形,設定爲以比最高記錄線速度還高之記錄線速 度進行記錄再生。 (17 ) —種光資訊記錄媒體,其係設置由藉由電磁波 之照射使非晶相與結晶相之間變化的相變化記錄材料形成 之記錄層的相變化型之光資訊記錄媒體,其特徵爲:前述 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -18 - 564412 A7 B7 五、發明説明(16) (請先閲讀背面之注意事項再填寫本頁) 相變化記錄材料係由Ag、In、Sb、Te形成,這些元素之鍵 配位數在成膜後之非結晶狀態與初期化後以及資訊抹除後 之結晶狀態爲不同。 (1 8 )前述相變化記錄材料係在其之構成元素之中, 關於Ag與In之對於Te的鍵配位數,在結晶狀態之鍵配位 數比在非結晶狀態之鍵配位數大之(1 7 )記載之光資訊記 錄媒體。 (19 )前述相變化記錄材料係其之構成元素之中,Ag 之對於Te的鍵配位數在非結晶狀態時爲1.5至2.5爲止之範 圍,在結晶狀態時爲3· 5至4.5爲止之範圍之(17)或(18) 記載之光資訊記錄媒體。 (20 )前述相變化記錄材料係其之構成元素之中,In 之對於Te的鍵配位數在非結晶狀態時爲3.0至3.8爲止之範 圍,在結晶狀態時爲3.4至4· 2爲止之範圔之(17)或(18) 記載之光資訊記錄媒體。 經濟部智慧財產局員工消費合作社印製 (2 1 )前述相變化記錄材料係在其之構成元素之中, 關於Sb之對於Te的鍵配位數,在結晶狀態之鍵配位數比 在非結晶狀態之鍵配位數小之(17 )記載之光資訊記錄媒 體。 ( 22)前述相變化記錄材料係其之構成元素之中,Sb 之對於Te的鍵配位數在非結晶狀態時爲2.7至3.5爲止之範 圍,在結晶狀態時爲2.0至2.8爲止之範圍之(21)記載之光 資訊記錄媒體。 (23 )前述相變化型記錄材料之在結晶狀態之構造爲 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) -19- 564412 A7 B7 五、發明説明(17 )Iwasaki (et al): Jpn. J. Appl. Phys., 32 (1993) 5241, etc. In October 1996, the orange book part III (version 1.0) was released as the specification of a rewritable compact disc (CD-RW). The orange book part III (version 1 · 〇) is a specification for a CD-RW with a 2x linear speed record (2.4 to 2.8 m / s). In such a low linear speed record, the recording time is long. Therefore, a rewritable compact disc which is recorded at a higher speed is desired. On the other hand, ways to improve the quality of the recorded signals of phase change recording have revealed various recording compensation methods. For example, in Japanese Unexamined Patent Publication No. 63-266632, PWM recording using a recording film having a high crystallization rate is effective in recording long amorphous marks using a pulse train. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and disclosed in Japanese Patent Application Laid-Open No. 63-266633 and detailed specification of US Patent No. 5 1 503 5-1, the laser energy at the front end and the tail end of the pulse train is increased. Make the irradiation time longer, and suppress the shaking of the position of the edge of the mark to improve the jitter. In addition, conventionally, it is known that, as described in Japanese Patent Publication No. 63-29336, an optical disc recording device irradiates light spots such as laser light on the optical disk while scanning, and modulate light spots such as laser light with information signal strength. The method of recording and recording information signals on a disc, and also knowing that there are information signals recorded on the disc that are reproduced, and by monitoring the amplitude of the reproduced signal or the length of the recording mark, the most appropriate adjustment and setting of the recording optical power or recording. Method of recording conditions such as the width of light pulses. Standards for this paper (CNS) A4 (21GX 297 mm): 12-~ 564412 A7 B7 V. Description of the invention (ι〇) (Please read the notes on the back before filling this page) Also, in Japanese Unexamined Patent Publication No. 9-1 38946 'Japanese Unexamined Patent Publication No. 9- 1 3 8947 and Japanese Unexamined Patent Publication No. 9-21 9021 disclose that when an information recording medium records information by PWM recording as shown in FIG. ④1 Let the signal width after modulation be nT (T clock time). 0 The signal recording or rewriting time is the continuous electromagnetic wave at power level e. Let the signal width after modulation be 1 at nT. The recording wave pulse sequence at the time of signal recording or rewriting is: a pulse part fp having a time width X and a power level a, and a low level pulse having a time width power level b totaling T and The high-level pulses of the power level c interact with the electromagnetic pulses 多 of the multi-pulse portion mp which is continuous (η-η ′) times in total with the load ratio y, and the pulse portion op with a time width ζ and a power level d [J Let X, y, and z be 0.5TS xS 2.0T, 0.4S yS 0.6, 0.5T $ 1.0T, and let η 'be the positive integer of nj η (A and c) ^ (b in and d). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The conventional technology has greatly sought to improve the stability of signal quality, reliability, and versatility when repetitive recording signals are overwritten. However, in recent years, a rewriting type information recording medium, especially a phase change type optical information recording medium, requires a technology in which one information recording medium can record at a plurality of linear speeds (multi-speed recording). In addition, a higher recording speed is required, and a CAV recording that facilitates high-speed recording is also required. With regard to these technical requirements, the technologies described in JP 9-1 38946, JP 9-1 38947, and JP 9-21 9021 cannot be met. For example, in a recording strategy with fp, mp, and op that can be recorded at 4x CD linear speed, in the case of 8x speed recording and 10x speed recording, in 8x speed recording and ΐ〇χ speed, this paper scale applies to the Chinese country Standard (CNS) A4 specification (210X297 mm) _ 13-564412 A7 ___ B7 V. Description of the invention (11) (Please read the precautions on the back before filling out this page) g The recording cannot obtain sufficient signal quality. Furthermore, the overwrite of the 10 × speed record for the part of the CD linear velocity 4x record, or the overwrite of the 4x speed record for the part of the CD linear velocity 1 Ox record, due to the signal quality of the overwrite due to different recording linear speeds The deterioration will become a problem. In addition, the deterioration of the signal quality in the overwriting of the part of the CLV record in the CAV record, or the overwriting of the part of the CAV record in the CLV record by a different recording method also becomes a problem. [Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned problems of the conventional technology. The first object of the present invention is to provide a phase-change optical information recording medium capable of high-speed recording and to fully utilize the optical information recording medium. The invention relates to a method for recording and reproducing optical information capable of high-speed recording and an apparatus for recording and reproducing optical information. The present invention has been made in view of the above-mentioned problems of the conventional technology, and the second object is to provide repeated characteristics, recording, Optical information recording medium with excellent erasing sensitivity and storage characteristics and manufacturing method of optical information recording medium. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Further, the comprehensive performance that satisfies the above-mentioned comprehensive performance is sufficient to take into account the phase change of the higher-speed recording and the preservation at high temperature and the reliability of the use of optical discs. In addition, the stability improvement of the overwrite signal quality based on multi-speed CLV recording and CAV recording or the recording strategy with general-purpose recording strategy is also a known subject. In other words, in order to completely solve the problems of the above-mentioned conventional technology in the present invention, ^ the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -14- 564412 A7 B7 V. Description of the invention (12) (Please read the back Note: Please fill in this page again.) The third objective is to provide the most suitable optical information recording medium for recording and erasing in high-line speed areas. The reliable optical information recording medium for high-speed recording and erasing is The fourth objective is to provide the optical information recording medium as an optical information recording medium capable of performing multi-speed CLV recording and CAV recording as the fifth objective. [Means for solving problems] The above problems are solved by the following inventions (1) to (32) (hereinafter also described as the inventions 1 to 32). (1) an optical information recording medium having at least a phase-change recording layer on a transparent substrate having concentric circular or spiral guide grooves and displaying information of a standard recording linear velocity Vr and / or a maximum recording linear velocity Vh, It is characterized in that the island portion and / or groove portion formed in the phase-change optical recording layer are irradiated with energy that can melt the recording layer material, while increasing the linear velocity, while scanning, the reflectance of the optical recording medium and the above energy Compared with the case before the irradiation, the linear velocity at which the reflectance is reduced is the displacement linear velocity V, which is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs when the focused semiconductor laser light DC is irradiated to the groove or island of the guide groove. The displacement linear velocity V is a conditional expression satisfying: 0.85VrS V or 0.8 5VhS V. (2) Further, the optical information recording medium described in (1) is characterized in that the displacement linear velocity is 0.9VrSVS2.0Vr or 0.9VhS VS 2.0Vh. (3) Furthermore, it is possible to determine whether the displacement linear velocity is satisfied. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -15-564412 A7 __B7 V. Description of the invention (13) The conditional expression of conditional light information recording medium of V. (1) or (2) records Light Information Recording Media. (Please read the precautions on the reverse side before filling in this page) (4) In the case of full crystallization (initialization) of the phase-change type recording layer, the initial linear velocity Vi is 0.5VrS Vig 1.6Vr or 0.5VhS The optical information recording medium described in one of conditional expressions of ViS1.6Vh (1) to (3). (5) The guide groove system has a track pitch of 0 · 2 ~ 1 · 4 // m, and the displacement linear velocity V when the focused semiconductor laser light DC is irradiated on the groove portion or the bird portion of the guide groove is 6 ~ 25m / s The optical information recording medium described in one of (1) to (4). (6) The unrecorded state of the aforementioned phase change recording system is mainly one of the optical information recording media described in (1) to (5) of the cubic crystal structure. (7) The aforementioned phase change recording layer is made of SbxTem .xHOSxSSO (where X is atomic%) constitutes one of the optical information recording media described in (1) to (6). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (8) The aforementioned phase change type recording layer contains at least one element selected from Ga, Ge, Ag, In, Bi, C, N, 0, Si, S as an additional element (7) The recorded light information recording medium. (9) The phase change recording layer is made of a material represented by a composition formula of (Ag, Ge) α (In, Ga, Bi) 〃 Sbr Te5. In this case, (Ag, Ge) and (In, Ga, Bi) means that each element contains at least one of the parentheses, α, / 3, 7, 5 are atomic%, 0.1 $ α $ 7, 1 $ / 3 $ 15, 61 $ r $ 85, 20 $ 5 S 30 of (1) to (8) of this paper size applies to the Chinese National Standard (CNS) A4 specifications (210X297 mm) -16-'564412 A7 B7 V. Description of the invention (14) Optical information records media. (Please read the precautions on the back before filling in this page) (1 0) In the case where η is an integer greater than 1 and T is the clock time equivalent to the period of the clock used in the modulation of the signal, let ’s perform modulation The recording light during the recording or rewriting of the 0 signal of the following signal width is continuous light at the power level e, and the recording wave pulse when the recording or rewriting of the 1 signal of the modulation signal width is ηT is set. The reason is: the pulse part fp with the time width X and the power level a interacts with the low level pulse with the time level power level b totaling T and the high level pulse with the power level c. The load ratio y totals (m-m ') consecutive multi-pulse sections mp, and a laser pulse train formed by a pulse section ep having a time width z and a power level d. Further, X, y, and z are set, respectively. 0.125TS xS 2.0T, 0.125S yS 0.87 5, 0.125TS 1.0T, set m to an integer greater than 1, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (a and c) > e > (b and d) The recording conditions can be recorded at a higher speed than the standard recording linear velocity Vi • or the maximum recording linear velocity Vh. Adjust the thickness of each of the first protective layer, phase change recording layer, second protective layer, reflective layer, and resin layer formed on a transparent substrate with concentric circles or spiral guide grooves (1) to (9) ) One of the recorded optical information recording media. (11) The layer structure of the optical information recording medium includes at least a first protective layer, a phase change recording layer, a second protective layer, a third protective layer, a reflective layer, and a resin protective layer (1) to (10) on the substrate. ) One of the recorded optical information recording media. (12) The constituent material of the third protective layer is an optical information recording medium described in (11), which can be formed by a DC sputtering method. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -17-564412 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before filling this page) (13) The third protection mentioned above The material constituting the layer is an optical information recording medium described in (11) or (1 2) including at least one selected from C, Si, SiC, SiN, SiO, and SiO2. (14) The phase change type recording layer is one of the optical information recording media described in (1) to (1 3) where the linear velocity of the full crystallization process is slower than the linear velocity of displacement. (1 5) — An optical information recording / reproducing method, characterized in that the optical information recording / reproducing device is set to hold a phase change type of information inherent in an optical information recording medium that satisfies a conditional expression satisfying a predetermined displacement linear velocity V. The optical information recording medium reproduces the inherent information from the optical information recording medium, and judges whether the information can be recorded at a recording linear speed higher than the maximum recording linear speed of the optical information recording medium. When possible, Recording and reproduction are performed at a recording linear velocity higher than the maximum recording linear velocity. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (16)-a kind of optical information recording and reproduction device, which is characterized by the inherent information of the optical information recording medium that holds the conditional expression that satisfies the predetermined displacement linear velocity V. The phase-change optical information recording medium reproduces the aforementioned inherent information, and judges whether the information can be recorded at a recording linear speed higher than the maximum recording linear speed of the optical information recording medium, and if possible, sets the ratio to Recording and reproduction are performed at the highest recording linear speed. (17) An optical information recording medium, which is a phase change type optical information recording medium provided with a recording layer formed of a phase change recording material that changes between an amorphous phase and a crystalline phase by irradiation of electromagnetic waves, and has characteristics For: The aforementioned paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -18-564412 A7 B7 V. Description of the invention (16) (Please read the precautions on the back before filling this page) Phase change recording materials It is formed of Ag, In, Sb, Te. The bond coordination number of these elements after film formation is different from the crystalline state after initialization and after information erasure. (18) The aforementioned phase change recording material is among its constituent elements. Regarding the bond coordination number of Ag and In to Te, the bond coordination number in the crystalline state is larger than that in the amorphous state. (1 7) recorded light information recording medium. (19) Among the constituent elements of the aforementioned phase change recording material, the bond coordination number of Ag to Te in the amorphous state ranges from 1.5 to 2.5, and in the crystalline state ranges from 3.5 to 4.5. The optical information recording medium according to (17) or (18) of the scope. (20) Among the constituent elements of the aforementioned phase change recording material, the bond coordination number of In to Te in the amorphous state ranges from 3.0 to 3.8, and in the crystalline state ranges from 3.4 to 4.2. Fan Lizhi's (17) or (18) recorded light information recording medium. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (2 1) The aforementioned phase change recording materials are among its constituent elements. The bond coordination number of Sb to Te in the crystalline state is in the non- The optical information recording medium of (17) having a small bond coordination number in a crystalline state. (22) Among the constituent elements of the aforementioned phase change recording material, the bond coordination number of Sb to Te in the amorphous state ranges from 2.7 to 3.5, and in the crystalline state ranges from 2.0 to 2.8. (21) Recorded light information recording medium. (23) The structure of the aforementioned phase-change recording material in the crystalline state is: This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -19- 564412 A7 B7 V. Description of the invention (17)
NaCl型之(17 )記載之光資訊記錄媒體。 (請先閲讀背面之注意事項再填寫本頁) (24 )前述相變化記錄材料係其之構成元素之中,在 Te佔有之NaCl型構造之C1側存在有多數之空孔之(23) 記載之光資訊記錄媒體。 (25 )前述相變化記錄材料係其之構成元素之中,在 Te應佔有之NaCl型構造之C1側存在7/12至9/12爲止之 範圍的空孔之(24 )記載之光資訊記錄媒體。 (26) —種光資訊記錄媒體之製造方法,其係一種製 作(17 )〜(25 )記載之光資訊記錄媒體之方法,其特徵 爲:在記錄層之成膜時一面以10 °C/ min至50 °C / min之範 圍的一定的速率使基板昇溫,一面以250W至850W之範圍 的功率形成記錄層。 (27 ) —種光資訊記錄媒體,其係在圓盤狀之基板上 至少具有相變化型記錄層之光資訊記錄媒體,其特徵爲: 前述相變化型記錄層之構成元素主要爲Ge、Ga、Sb以及 T e,個別之組成比α、0、r以及5 (原子% )在α + /3 + r + 5 二100時, 經濟部智慧財產局員工消費合作社印製 0.1 ^ α ^ 7 β 61^7^75 22$ 5 S 30。 (28 )在前述相變化型記錄層添加由In、Zn、Sn、Si 、Pb、Co、Cr、Cu、Ag、Au、Pd、Pt、S、Se、Ta、Nb、V 、Bi、Zi·、Ti、A1、Mn、Mo、Rh、C、N 以及 〇 選擇至少一 本纸張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -20 - 564412 A7 _B7 _ 五、發明説明(彳8 ) 種以上之元素之(27 )記載之光資訊記錄媒體。 (請先閲讀背面之注意事項再填寫本頁) (29) Ge以及Ga之組成比爲·8$ α ^ 3之(27)或 (28)記載之光資訊記錄媒體。 (30) Sb以及Te之組成比爲r + 5 ^ 88之(27)〜( 29 )之其中一項記載之光資訊記錄媒體。 經濟部智慧財產局員工消費合作社印製 (3 1 ) —種適用藉由對光資訊記錄媒體照射雷射光’ 使前述光資訊記錄媒體之記錄層產生相變化,進行對於前 述光資訊記錄媒體之資訊的記錄、再生,而且可以重寫之 資訊記錄再生方法之光資訊記錄媒體,而且,調制信號’ 在資訊記錄媒體藉由PWM記錄進行資訊之記錄之際,設進 行調制後之信號寬幅爲nT(T係時脈時間)之0信號的記錄或 重寫時之記錄波爲功率準位e之連續電磁波,設進行調制 後信號寬幅爲nT之1信號的記錄或重寫時之記錄波脈衝列 爲具有:具有時間寬幅χ與功率準位a之脈衝部fp,與具 有合計爲T之時間寬幅之功率準位b之低準位脈衝與功率 準位c之高準位脈衝交互以負荷比y合計(n-n’)次連續之 多脈衝部mp,與具有時間寬幅z與功率準位d之脈衝部op 之脈衝列,設 χ、y、z 爲0.5TSxS2.0T、0.125SyS0.875 、0.125TS 1·0Τ,設 η’爲 n’S η 之正整數(a 以及 c) - e -(b以及d)之可以多速度記錄以及/或CAV記錄之(27) 〜(30 )之其中一項記載之光資訊記錄媒體。 (3 2 )前述脈衝部m p之負荷比y係依據記錄線速度而 增減之(3 1 )記載之光資訊記錄媒體。 關於(17 )〜(25 )之發明,有關由Ag與In與Sb與 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X 297公釐) ' 564412 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(19 )The optical information recording medium of (17) of NaCl type. (Please read the precautions on the back before filling this page) (24) Among the constituent elements of the phase change recording material mentioned above, there are many (23) records on the C1 side of the NaCl-type structure occupied by Te. Light Information Recording Media. (25) Among the constituent elements of the aforementioned phase change recording material, there is an optical information record recorded in (24) with pores ranging from 7/12 to 9/12 on the C1 side of the NaCl type structure that Te should occupy media. (26) A method for manufacturing an optical information recording medium, which is a method for manufacturing the optical information recording medium described in (17) to (25), which is characterized in that the film is formed at a temperature of 10 ° C / The substrate is heated at a constant rate ranging from min to 50 ° C / min, and a recording layer is formed at a power ranging from 250W to 850W. (27) — An optical information recording medium, which is an optical information recording medium having at least a phase-change recording layer on a disc-shaped substrate, which is characterized in that the constituent elements of the phase-change recording layer are mainly Ge, Ga , Sb, and T e, and the individual composition ratios α, 0, r, and 5 (atomic%) at α + / 3 + r + 5 2 100, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 0.1 ^ α ^ 7 β 61 ^ 7 ^ 75 22 $ 5 S 30. (28) Adding In, Zn, Sn, Si, Pb, Co, Cr, Cu, Ag, Au, Pd, Pt, S, Se, Ta, Nb, V, Bi, Zi · to the phase change type recording layer , Ti, A1, Mn, Mo, Rh, C, N and 〇 Select at least one paper size to apply Chinese National Standard (CNS) A4 specification (210X297 mm) -20-564412 A7 _B7 _ V. Description of the invention (彳8) A light information recording medium as described in (27) of more than one element. (Please read the precautions on the back before filling out this page.) (29) The optical information recording medium described in (27) or (28) with a composition ratio of Ge and Ga of 8 $ α ^ 3. (30) An optical information recording medium having a composition ratio of Sb and Te of any one of (27) to (29) of r + 5 ^ 88. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (3 1) —A kind of application that applies laser light to the optical information recording medium to change the recording layer of the aforementioned optical information recording medium to carry out information on the aforementioned optical information recording medium Optical information recording medium for recording, reproduction, and rewritable information recording and reproduction method, and the modulation signal 'when the information recording medium records information by PWM recording, the modulation signal width is set to nT (T system clock time) The 0-signal recording or rewriting recording wave is a continuous electromagnetic wave at the power level e, and the modulation signal is recorded as the nT 1-signal recording or rewriting recording wave pulse. It is listed as having: a pulse part fp with a time width χ and a power level a, interacting with a low level pulse with a time width power level b totaling T and a high level pulse with a power level c The duty ratio y totals (n-n ') consecutive multi-pulse sections mp, and the pulse train of the pulse section op with a time width z and a power level d. SyS0.875, 0.12 5TS 1 · 0Τ, where η 'is a positive integer of n'S η (a and c)-e-(b and d), which can be recorded at multiple speeds and / or CAV records (27) ~ (30) Light Information Recording Media. (3 2) The load ratio y of the pulse portion m p is the optical information recording medium described in (3 1) which increases or decreases according to the recording linear velocity. Regarding the inventions of (17) ~ (25), the relevant standards are applicable by Ag and In and Sb and this paper standard. National National Standard (CNS) A4 specification (210X 297 mm) '564412 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs System A7 B7 V. Description of Invention (19)
Te形成之相變化記錄材料,以X射線繞射、電子射線繞射 等之結果爲基礎檢討其之構造,特別是各元素之鍵配位數 ’發現依據其之配位數,記錄媒體之特性大爲變化。 一般’包含Te、Se、s等之Vib族元素之化合物係被 稱爲硫族化合物’ Vlb族元素係以2配位鍵結之故,構造之 柔軟性大’由於液相凍結,容易玻璃化,很多被使用爲記 錄媒體。另一方面’ lb族之Ag之對於Te的配位數習知上 並不明確’又’ In、Sb之對於Te之配位數也單單依循8-N 法則等,被設爲3配位而已,實際之配位數並不明確。又, 在結晶狀態與非結晶狀態之各元素的鍵配位數是否有差別 也不明確。 但是,在記錄媒體之情形,構成記錄材料之各元素的 鍵配位數被認爲會對光碟特性之記錄感度或認爲·結晶溫度 會影響之抹除感度或保存特性,而且重複特性等造成大的 影響。 即,如依據菲利普之玻璃化形成能之理論( J.C.Phillips: J·,Non-Cryst,Solids 34 ( 1 979) 1 53),玻璃化 在構成元素之平均配位數爲2.45時最爲容易。此係如作成此 種配位數,容易玻璃化,即顯示可以記錄,成爲提升記錄 感度之目標。 又,鍵配.位數大係顯示鍵能大,結晶化溫度上升,導 致抹除感度之降低,進而’防止標記之消失用之保存特性 之提升。又,依據鍵配位數’不單單一相’於混相也可以 相分離,依據此,認爲也有重複特性劣化之情形。如此, 本紙張尺度適用中.國國家標準(CNS ) A4規格(2丨〇><297公釐) -22 · I------------Ί--IT------MW— (請先閲讀背面之注意事項再填寫本頁) 564412 A7 _______B7 _^__ 五、發明説明(20 ) 如可以控制構成記錄材料之各元素的鍵配位數,認爲可以 大幅提升記錄媒體之特性。 (請先閲讀背面之注意事項再填寫本頁) 本發明者們經過銳意檢討之結果,發現記錄層形成用 之材料使用由Ag與In與Sb與Te形成者之記錄媒體,(1 )關於Ag與In之對於Te之鍵配位數,在菲結晶狀態之鍵 配位數與在結晶狀態之鍵配位數不同,結晶狀態者大時, (2 ) Sb之對於Te之鍵配位數反之,結晶狀態者小時,(3 )而且在這些情形,構成爲單層、NaCl型,在Te佔有之 C1側產生多數之空孔時,個別之光碟特性極爲良好。 特別是,(a) Ag之對於Te之鍵配位數在成膜後之非 結晶狀態爲1.5至2.5之範圍,最好爲1.7至2.2之範圍時,(b )In之對於Te之鍵配位在成膜後之非結晶狀態爲3.0至3.8 之範圍,最好爲3.4至3.7之範圍,在結晶狀態爲3.4至4.2之 範圍,最好爲3.5至3.8之範圍時,(c) Sb之對於Te之鍵配 位數在非結晶狀態爲2.7至3.5之範圍,最好爲2.8至3.2之範 圍,在結晶狀態爲2.0至2.8之範圍,最好爲2.4至2.6之範圍 時,知道個別具有優異之光碟特性。 經濟部智慧財產局員工消費合作社印製 具體爲考慮:Ag之對於Te之鍵配位數在成膜後之非 結晶狀態爲1.8、在初期結晶化後爲4.0、In之對於Te之鍵 配位數在成膜後之非結晶狀態爲3.5、在初期結晶化後爲3.7 、Sb之對於Te之鍵配位數在成膜後之非結晶狀態爲3.0、 在初期結晶化後爲2.5之情形,設相變化記錄材料(記錄層 )之組成爲 Ag5In7Sb6QTe28。 在成膜後之非結晶狀態中,Ag之配位數爲1.8之故,Ag 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐1 -23 - " " 564412 A7 B7 五、發明説明(21 ) (請先閲讀背面之注意事項再填寫本頁) 作用於切斷隨機網路之方向的結果,促進結晶化。即,使 初期結晶化容易,成爲均勻具有微細之結晶粒之多結晶狀 態之故,記錄後之標記的S/N比提升。又,初期結晶化後 之平均配位數Z可以由上述之配位數與組成容易求得,Z = 4 X 0.05 + 3.7 X 0.07 + 2.5 X 0.6 + 2.0 X 0.28 = 2.51,極爲接近菲 利普之玻璃化形成能力之最爲容易玻璃化之平均配位數2.45 。此意指初期結晶化後之記錄(玻璃化)容易實現,即記 錄感度良好。 經濟部智慧財產局員工消費合作社印製 又,初期結晶化後之構造爲NaCl型之立方晶單相,記 錄標記之玻璃狀態保持其之近距離秩序之故,不會相分離 地保持該狀態之故,重複之特性也極爲良好。又,記錄後 之配位數係保持初期結晶化後之配位數之故,保持Z = 2.51 ,而且,認爲切斷網路之Ag的配位數也在記錄後保持4之 値之故,在室溫下,標記之結晶化極爲不易進行,導致保 存特性之提升。又,NaCl型構造之Te佔有之C1側的多數 的空孔對於記錄材料之組成比,爲保持NaCl型構造所必要 ,藉由此,記錄層經常保持單層,不會使產生相分離之故 ,重複特性良好,而且,保持安定之相。 進而,爲了獲得本發明之光資訊記錄媒體,記錄層之 製膜法係期望採用申請項26所記載之方法。即,製膜時, 以 1 0 °C / m i η 〜5 0 °C / m i η,最好爲 3 0 °C / m i η 〜4 0 °C / m i η 之 範圍內的昇溫率加溫基板而成膜。目前,並不知道依據此 種方法,爲何在非結晶狀態與結晶狀態下,鍵配位數會產 生差別。又,關於成膜時之成膜率,雖對此鍵配位數有多 本紙張尺度適财酬家鮮(CNS ) Α4規格(21GX297公釐)-24 - ' 564412 經濟部智慧財產局員工消費合作社印製 A7 _ B7五、發明説明(22 ) 少之影響,但是並無法明確知道。可能原因之一係依據成 膜時之基板溫度上升,記錄層之構造由近距離秩序轉爲中 距離秩序。又,DC濺鍍比Rf濺鍍好。 【發明之實施形態】 以下,以【實施形態1】、【實施形態2】、【實施形 感、3】、【實施形態4】之順序,參考圖面詳細說明本發明 之光資訊記錄媒體、光資訊記錄再生方法、光資訊記錄再 生裝置以及光資訊記錄媒體之製造方法。 【實施形態1】 圖1係顯示實施形態1之相變化型之光資訊記錄媒體之 層構成例。基本之構成係在具有導引溝之透明基板21上具 有第一保護層22、記錄層23、第二保護層24、反射層6、厚 塗層7,最好具有第三保護層25。進而,也可以在厚塗層上 具有印刷層8、在基板裏面具有硬塗層9。也可以透過黏著 層10貼合上述之單板光碟之構造。貼合之相反面之光碟可 以爲同樣之單板光碟,也可以爲只是透明基板。又,在貼 合沒有設置印刷層之單板光碟後,在相反面側形成印刷層V 亦可。 基板之材料通常爲玻璃、陶瓷、或樹脂,在成形性、 成本之觀點,以樹脂基板爲合適。 樹脂例雖可舉:聚碳酸酯樹脂、丙烯基樹脂、環氧樹 脂、聚苯乙烯樹脂、丙;)¾腈苯乙燒共聚物樹脂、聚乙烯 (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) _ 25 - 564412 A7 ____ B7 五、發明説明(23 ) 樹脂、聚丙烯、矽系樹脂、氟系樹脂、Abs樹脂、尿烷樹 脂等’但是以成形性、光學特性、成本都優異之聚碳酸酯 、丙烯樹脂爲佳。 (請先閱讀背面之注意事項再填寫本頁) 但是’在將實施形態1之光資訊記錄媒體應用於DVD-ROM可以互換之重寫型光碟之情形,期望滿足形成在使用 的基板的導引溝之寬幅爲〇·1〇〜0.40/zm,最好爲〇·ΐ5〜0·30 // m ’導引溝之深度爲15〜65nm,最好爲25〜50nm之條件 〇 基板之厚度雖無特別限制,但是以〇. 6 mm爲合適,關 於貼合後之光碟的厚度雖無特別限制,以丨」〜爲合 又’在將實施形態1之光資訊記錄媒體應用於CD-RW 之情形,期望導引溝之寬幅爲0.25〜0.65 // m,最好爲0.30 〜0.55//m,該導引溝之深度爲25〜65nm,最好爲30〜55nm 〇 基板之厚度雖無特別限制,以1.2mm爲合適。 經濟部智慧財產局員工消費合作社印製 記錄層以包含引起結晶-非晶質相間之相變化,個別 可以取得安定化或準安定化狀態之Sb、Te,其之組成式爲 SbxTe_.x(40S xS 80,X爲原子%)之相變化型記錄材料,其 記錄(非晶質化)感度·速度、抹除(結晶化)感度·速 度、以及抹除比良好之故,較爲理想。 如於此SbTe材料添加Ga、Ge、Ag、In、Bi、C、N、〇 、Si、S等之元素,可以改善記錄、抹除感度或信號特性、 信賴性等之故,藉由添加之元素與其之組成比,可以控制 ^紙張尺度適用中國國家標準(CNS ) A4規格(21〇X297公釐) -26 - 一 564412 A7 B7 五、發明説明(24 ) 光資訊記錄媒體之特性。 (請先閱讀背面之注意事項再填寫本頁) 添加元素之比率爲0.1〜20原子%,最好爲0.1〜15原子 %。藉由使之爲20原子%以下,可以良好地進行初期化。 又,上述材料依據其之組成比,位移線速度也改變之 故,最適當之記錄線速度也不同。因此,需要依據目的之 記錄線速度以及線速度區域,調整該材料之組成比,控制 位移線速度。由至目前爲止之檢討結果,發現Te之組成比 與移位線速度有高的關連。 對使用在實施形態1之相變化型光資訊記錄媒體之品質 要求,不單要求可以記錄、抹除,也同時要求在高密度、 高線速度區域記錄時之信號的再生安定性或信號的壽命( 信賴性)。 可以綜合滿足這些之記錄層以上述材料系爲優異,特 別是以如下之組成式所代表之材料,其信號的再生安定性 或信號的壽命優異,可以良好進行初期化之故,最爲合適 〇 (Ag Λ Ge ) α(Ιη、 Ga、 Bi)点 SbrTes 經濟部智慧財產局員工消費合作杜印製 但是,(Ag、Ge )以及(In、Ga、Bi )係個別意指包 含括號內之至少一種的元素,,α、/3、r、5係原子%, 0·1^α^7、 l^ySS15、61^7^85、20 $5^30。 進而,具有在初期化後之未記錄狀態之結晶構造爲各 向同性之結晶構造之立方晶格結晶構造,最好爲NaCl型結 晶構造之材料可以與同樣被認爲各向同性高之非晶質相引 起偏差少之相變化,可以高速而且均勻地進行記錄(非晶 -27- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 564412 A7 B7 五、發明説明(冰 (請先閲讀背面之注意事項再填寫本頁} ]2 0 n m。第二保護層之膜厚爲5〜4 5 n m,最好爲7〜4 Ο】ι ΐϋ爲 佳。如在5nm以上,容易發揮作爲耐熱保護層之機能,又 在記錄感度也優異。另一方面,如在4 5 n m以下,不易產生 界面剝離之同時,重複記錄性也良好。 反射層可以使用Al、Au、Ag、Cu、Ta、Ti、W等之金 屬材料,或包含這些元素之合金等。又,爲了耐腐蝕性之 提升、熱傳導率之改善等,對於上述材料添加Cr、Si、Pd 等之元素亦可。添加比率以0.3〜2原子%爲合適。如比0.3原 子%少,耐腐蝕性之效果差。如比2原子%多,熱傳導率降 低太多,不易形成非晶質狀態。 此種反射層可以藉由各種氣相成長法,例如真空蒸鍍 法、濺鍍法、電漿CVD法、光CVD法、離子電鍍法、電子 束蒸鍍法等形成。 合金或金屬層之膜厚以5 0〜2 0 0 n m,最好爲7 0〜1 6 0 n m 爲佳。又,也可以多層化合金或金屬層。在多層化之情形 ,各層之膜厚需要至少在1 Onm以上,多層化膜之合計膜厚 以5 0〜1 6 0 η ιίί爲佳。 經濟部智慈財產局員工消費合作社印製 爲」氧化防止’在反射層之上形成厚塗層。厚塗層一 般爲以.旋轉塗佈所製作之紫外線硬化型樹脂,其之厚度以3 〜1 5 // m爲適當。如在3 // m以上,即使在厚塗層上設置印 刷層之情形,也不易引起信號錯誤之增加。另一方面,藉 由使之在1 5 μ m以下,內部應力之變化少,不易對光碟之 機械特性造成影響之故,較爲理想。 硬塗層一般爲以旋轉塗佈所製作之紫外線硬化型樹脂 一 29 - 本紙張尺度適用中國國家榡準(CN’S ) A4規格(210X 297公麓) 564412 經濟部智慧財產局員工消費合作社印製 A7 _ B7五、發明説明(27 ) ’其之厚度以2〜6//Π1爲適虽。如比2//πι薄,無法獲得充 分之耐擦傷性。藉由使之在6 // m以下,內部應力之變化少 ,不易對光碟之機械特性造成影響之故,較爲理想。 其之硬度以即使以布擦,也不會有大的傷痕之鈴筆硬 度Η以上爲佳。 因應需要,混入導電性之材料,防止帶電以防止塵埃 等之附著也很有效果。 印刷層係以耐擦傷性之確保、品牌名等之標籤印刷、 對於噴墨列表機之油墨容受層之形成等爲目的,一般係藉 由網版印刷法形成紫外線硬化型樹脂。 其厚度以3〜50//m爲適當。如在3/zm以上,層形成時 ,不易產生不均。藉由使之在50/zm以下,內部應力之變 化少,對光碟之機械特性不易造成影響之故,較爲理想。 黏著層可以使用紫外線硬化型樹脂、熱融膠黏著劑、 矽樹脂等之黏著劑。 此種黏著層之材料係在厚塗層或印刷層上,因應材料 ’藉由旋轉塗佈、輥輪塗佈、網版印刷法等之方法塗佈, 進行紫外線照射、加熱、加壓等之處理,與相反面之光碟 貼合。 相反面之光碟可以爲同樣之單板光碟或只是透明基板 ’關於相反面.光碟之貼合面,可以塗佈也可以不塗佈黏著 層之材料。 又,黏著層也可以使用黏著薄板。 黏著層之膜厚雖無限制,但是如考慮材料之塗佈性、 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) -30 - (請先閲讀背面之注意事項再填· 寫本頁) 564412 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(28 ) ^ 硬化性、光碟之機械特性之影響,以5〜10 〇 // m爲佳。 黏著面之範圍雖無特別限制,在應用於DVD以及/或 CD互換性之重寫型光碟之情形,爲了使實施形態1之高速 §己錄成爲可能’爲了確保黏著強度,黏著層之內緣端之位 置期望爲0 15〜40mm,最好爲0 15〜30 mm。 第三保護層係位於透明基板、第一保護層、記錄層、 第二保護層、反射層、厚塗層、印刷層或黏著層之層界面 ,形成目的在於層間之密接性之提升、化學反應之防止、 光學特性之調整、熱物性之調整等。 特別是在第二保護層與反射層之間形成第三保護層之 情形,期望包含C、Si、SiC、SiN、SiO、Si〇2之中至少一 種之物質之材料。 第三保護層之膜厚設爲1〜40nm,最好爲2〜30nm。如 在lnm以上,容易進行安定之界面層之形成。另一方面, 如在40nm以下,不易產生界面剝離,可以獲得層間密接性 之提升效果。 此種第三保護層可以藉由各種氣相成長法,例如真空 蒸鍍法、濺鍍法、電漿CVD法、光CVD法、離子電鍍法、 電子束蒸鍍法等形成。如特別考慮量產性,DC濺鍍法可以 利用泛用之濺鍍裝置之故,爲所期望。 爲了以良妤的品質量產對應實施形態1之高線速度化之 光資訊記錄媒體,要求採用記錄線速度之餘裕廣之故,需 要配合其以調整移位線速度。 移位線速度受熱物性影響之故’依據光資訊記錄媒體 ^紙張尺度適用中國國家標準(CNS ) A4規格(210、/ 297公着1 -31 - '~一 (請先閲讀背面之注意事項再填寫本頁)The phase change recording material formed by Te is reviewed based on the results of X-ray diffraction and electron diffraction, especially the bond coordination number of each element. Great change. Generally, a compound containing a Vib group element such as Te, Se, s, etc. is called a chalcogen compound. A Vlb group element is bonded with a two-coordination bond, and the structure is flexible. Because the liquid phase freezes, it is easily vitrified Many are used as recording media. On the other hand, the coordination number of Ag of the lb family to Te is not clear. And the coordination number of In and Sb to Te are simply set to 3 coordination according to the 8-N rule. The actual coordination number is not clear. It is also unclear whether there is a difference in bond coordination number of each element between the crystalline state and the amorphous state. However, in the case of a recording medium, the bond coordination number of each element constituting the recording material is considered to affect the recording sensitivity of the disc characteristics or the erasing sensitivity or storage characteristics that are affected by the crystallization temperature, and the repeated characteristics cause Great influence. That is, according to Philip's theory of glass transition energy (J.C. Phillips: J., Non-Cryst, Solids 34 (1 979) 1 53), vitrification is the easiest when the average coordination number of constituent elements is 2.45. If such a coordination number is made, it is easy to vitrify, that is, the display can be recorded, and it becomes the goal of improving the recording sensitivity. In addition, a large number of bond numbers indicates that the bond energy is large and the crystallization temperature is increased, resulting in a decrease in erasure sensitivity, and further improvement of storage characteristics for preventing the disappearance of the mark. In addition, depending on the bond coordination number, 'not just a single phase' may be separated from a mixed phase. Based on this, it is considered that the repetitive characteristics may be deteriorated. In this way, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 〇 < 297 mm) -22 · I ------------ Ί--IT-- ---- MW— (Please read the precautions on the back before filling this page) 564412 A7 _______B7 _ ^ __ V. Description of the invention (20) If you can control the key coordination number of each element that constitutes the recording material, consider it possible Significantly improve the characteristics of recording media. (Please read the precautions on the back before filling this page) As a result of an intensive review, the inventors found that the recording layer is formed of a recording medium made of Ag and In, Sb, and Te. (1) About Ag The coordination number for Te with In is different from the coordination number for Te in the phenanthrene crystalline state. When the crystal state is large, (2) Sb has the opposite coordination number for Te. (3) When the crystal state is small, (3) In these cases, it is configured as a single-layer, NaCl type, and when a large number of voids are generated on the C1 side occupied by Te, the individual disc characteristics are extremely good. In particular, when (a) the coordination number of Ag to Te in the amorphous state after film formation is in the range of 1.5 to 2.5, preferably in the range of 1.7 to 2.2, (b) the bonding of Te to Te The amorphous state after film formation is in the range of 3.0 to 3.8, preferably in the range of 3.4 to 3.7. When the crystalline state is in the range of 3.4 to 4.2, and preferably in the range of 3.5 to 3.8, (c) Sb For the coordination number of Te in the amorphous state range of 2.7 to 3.5, preferably in the range of 2.8 to 3.2, and when the crystalline state is in the range of 2.0 to 2.8, preferably in the range of 2.4 to 2.6, it is known that Excellent disc characteristics. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for specific consideration: the amorphous coordination state of Ag after bonding to Te is 1.8, 4.0 after initial crystallization, and the coordination of Te against In In the case where the amorphous state after film formation is 3.5, the initial crystallization is 3.7, and the bond coordination number of Sb to Te is 3.0 in the amorphous state after film formation and 2.5 after initial crystallization, Let the composition of the phase change recording material (recording layer) be Ag5In7Sb6QTe28. In the non-crystalline state after film formation, the coordination number of Ag is 1.8. The paper size of Ag applies the Chinese National Standard (CNS) A4 specification (210X297 mm 1 -23-" " 564412 A7 B7 V. Description of the Invention (21) (Please read the precautions on the reverse side before filling out this page) As a result of cutting off the direction of the random network, it promotes crystallization. That is, it makes the initial crystallization easy and becomes uniform with fine crystal grains. Due to the polycrystalline state, the S / N ratio of the mark after recording is increased. Moreover, the average coordination number Z after the initial crystallization can be easily obtained from the above coordination number and composition, Z = 4 X 0.05 + 3.7 X 0.07 + 2.5 X 0.6 + 2.0 X 0.28 = 2.51, which is very close to Philip ’s glass transition ability. The average coordination number that is the easiest to vitrify is 2.45. This means that the record (vitrification) after initial crystallization is easy to achieve, that is, The recording sensitivity is good. It is printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. After the initial crystallization, the structure is a single-phase cubic crystal of NaCl type. maintain Because of this state, the repeatability is also very good. Also, the coordination number after recording is the same as the coordination number after initial crystallization, and Z = 2.51 is maintained. Moreover, it is considered that the coordination of Ag that cuts off the network The number of digits also remains 4 after recording. At room temperature, the crystallization of the mark is extremely difficult to carry out, leading to an improvement in storage characteristics. In addition, most of the pores on the C1 side occupied by Te in the NaCl-type structure are recorded for recording The composition ratio of the materials is necessary to maintain the NaCl-type structure, and as a result, the recording layer is often kept in a single layer without causing phase separation, the repeatability is good, and a stable phase is maintained. Furthermore, in order to obtain the present invention In the optical information recording medium, the film formation method of the recording layer is expected to adopt the method described in the application item 26. That is, when forming the film, the temperature is 10 ° C / mi η to 50 ° C / mi η, preferably 3 The substrate is formed by heating the substrate at a temperature rise rate in the range of 0 ° C / mi η to 40 ° C / mi η. At present, it is not known why the bond coordination in the amorphous state and the crystalline state according to this method There will be a difference in the number. Also, regarding film formation during film formation Although there are multiple papers for this key, the paper size is suitable for financial rewards (CNS) Α4 size (21GX297mm) -24-'564412 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7 V. Description of the invention (22) The influence of less, but it is not clear. One of the possible reasons is that the structure of the recording layer is changed from a close-range order to a middle-range order based on the substrate temperature rise during film formation. Also, DC sputtering is more than Rf sputtering. [Embodiment of the invention] Hereinafter, the optical information record of the present invention will be described in detail with reference to the drawings in the order of [Embodiment 1], [Embodiment 2], [Embodiment 3,] and [Embodiment 4]. Media, optical information recording and reproducing method, optical information recording and reproducing device, and manufacturing method of optical information recording medium. [Embodiment 1] Fig. 1 shows an example of the layer configuration of a phase-change optical information recording medium according to Embodiment 1. The basic structure includes a first protective layer 22, a recording layer 23, a second protective layer 24, a reflective layer 6, a thick coating layer 7, and preferably a third protective layer 25 on a transparent substrate 21 having a guide groove. Furthermore, a printed layer 8 may be provided on the thick coating layer, and a hard coating layer 9 may be provided on the back surface of the substrate. The above-mentioned structure of the single-plate optical disc may be laminated through the adhesive layer 10. The laminated disc on the opposite side can be the same single-plate disc or just a transparent substrate. Alternatively, after bonding a single-plate optical disc without a printed layer, the printed layer V may be formed on the opposite surface side. The material of the substrate is usually glass, ceramic, or resin, and a resin substrate is suitable in terms of moldability and cost. Examples of resins are: polycarbonate resin, acrylic resin, epoxy resin, polystyrene resin, acrylic;) ¾ Nitrile copolymer resin, polyethylene (Please read the precautions on the back before filling this page } This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) _ 25-564412 A7 ____ B7 V. Description of the invention (23) Resin, polypropylene, silicon resin, fluorine resin, Abs resin, urine Alkane resins, etc., but polycarbonate and acrylic resins that are excellent in moldability, optical properties, and cost are preferred. (Please read the precautions on the back before filling out this page.) However, the optical information recording medium of Embodiment 1 will be used. It is used in the case of DVD-ROM interchangeable rewritable optical discs. It is desirable to satisfy the width of the guide grooves formed on the substrate to be used in the range of 0.1 · 0.4 to 0.40 / zm, and preferably 0 · 05 to 0 · 30 / / m 'The depth of the guide groove is 15 to 65 nm, preferably 25 to 50 nm. Although the thickness of the substrate is not particularly limited, 0.6 mm is suitable. Although there is no particular thickness of the optical disc after bonding, Restrictions, "丨" as a matter of course, will be implemented When the optical information recording medium of state 1 is applied to a CD-RW, the width of the guide groove is expected to be 0.25 to 0.65 // m, preferably 0.30 to 0.55 // m, and the depth of the guide groove is 25 to 65 nm. The thickness of the substrate is preferably 30 ~ 55nm. Although the thickness of the substrate is not particularly limited, 1.2mm is suitable. The employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a recording layer to include the phase change that causes the crystalline-amorphous phase, which can be obtained individually. Sb, Te in a stabilized or quasi-stabilized state, a phase change type recording material whose composition formula is SbxTe_.x (40S xS 80, X is atomic%), and its recording (amorphization) sensitivity, speed, and erasing Desirability (speed of crystallization), speed, and erasing ratio are ideal. For this SbTe material, elements such as Ga, Ge, Ag, In, Bi, C, N, 0, Si, and S are added. Can improve recording, erasing sensitivity, signal characteristics, reliability, etc. By adding elements and their composition ratios, you can control ^ Paper size applies Chinese National Standard (CNS) A4 specification (21〇297mm) -26 -One 564412 A7 B7 V. Description of Invention (24) Special Features of Optical Information Recording Media (Please read the notes on the back before filling this page.) The ratio of added elements is 0.1 to 20 atomic%, preferably 0.1 to 15 atomic%. By setting it to 20 atomic% or less, the initial stage can be performed well. In addition, the above-mentioned materials have different displacement linear velocities depending on their composition ratios, and the most appropriate recording linear velocities are also different. Therefore, it is necessary to adjust the composition ratios of the materials according to the recording linear velocities and linear velocity regions of interest, Controls displacement linear velocity. As a result of the review so far, it has been found that the composition ratio of Te is related to the high linear velocity of displacement. For the quality requirements of the phase-change optical information recording medium used in Embodiment 1, not only can it be recorded and erased, but also the reproduction stability or signal life of the signal when recording in a high density and high linear velocity area ( Reliability). The recording layer that satisfies these requirements is excellent in the above-mentioned materials, especially the materials represented by the following composition formulas, which are excellent in signal reproduction stability or signal life, and can be well initialized. (Ag Λ Ge) α (Ιη, Ga, Bi) Dot SbrTes Printed by consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, (Ag, Ge) and (In, Ga, Bi) individually mean at least A kind of element, α, / 3, r, 5 atomic%, 0 · 1 ^ α ^ 7, l ^ ySS15, 61 ^ 7 ^ 85, 20 $ 5 ^ 30. Furthermore, the crystalline structure having an unrecorded state after initialization is an isotropic crystalline structure, and a cubic lattice crystalline structure, preferably a NaCl-type crystalline structure, may be similar to an amorphous material that is also considered to be highly isotropic. The phase change caused by the mass phase with less deviation can be recorded at high speed and uniformity (amorphous-27- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 564412 A7 B7 V. Description of the invention (ice (please Read the precautions on the back before filling in this page}] 2 0 nm. The thickness of the second protective layer is 5 ~ 4 5 nm, preferably 7 ~ 4 Ο] ι ΐϋ. It is easy to play if it is above 5nm As a heat-resistant protective layer, it also has excellent recording sensitivity. On the other hand, if it is less than 4 5 nm, interfacial peeling is not easy to occur, and repeatability is also good. Al, Au, Ag, Cu, Metal materials such as Ta, Ti, W, or alloys containing these elements, etc. In order to improve corrosion resistance and thermal conductivity, elements such as Cr, Si, and Pd may be added to the above materials. Addition ratio With 0. 3 ~ 2 atomic% is suitable. If it is less than 0.3 atomic%, the effect of corrosion resistance is poor. If it is more than 2 atomic%, the thermal conductivity is reduced too much, and it is not easy to form an amorphous state. Such reflective layers can be used in various ways Vapor deposition method, such as vacuum deposition method, sputtering method, plasma CVD method, photo CVD method, ion plating method, electron beam evaporation method, etc. The film thickness of the alloy or metal layer is 50 to 2000. nm, preferably 70 to 160 nm. Also, alloy or metal layers can be multilayered. In the case of multilayering, the film thickness of each layer must be at least 1 Onm, and the total film thickness of the multilayered film 5 0 ~ 1 6 0 ηί is better. Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs as "oxidation prevention" to form a thick coating on the reflective layer. Thick coatings are generally made by spin coating. The thickness of the UV-curable resin is 3 to 1 5 // m. If it is 3 // m or more, even if a printed layer is provided on a thick coating layer, it is not easy to cause an increase in signal errors. Another On the other hand, by making it less than 15 μm, there is less change in internal stress and it is not easy to adjust The mechanical properties of the dish are affected, which is ideal. The hard coating is generally a UV-curable resin made by spin coating. 29-This paper size applies to China's National Standard (CN'S) A4 (210X 297 feet) ) 564412 Printed by A7 _ B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (27) 'Its thickness should be 2 ~ 6 // Π1. If it is thinner than 2 // πι, it cannot obtain sufficient resistance Abrasion resistance. By setting it below 6 // m, there is less change in internal stress and it is not easy to affect the mechanical characteristics of the disc, which is ideal. The hardness of the bell pen is preferably at least Η even if it is rubbed with a cloth. If necessary, it is also effective to mix conductive materials to prevent electrification to prevent the adhesion of dust and the like. The printing layer is used for the purpose of ensuring abrasion resistance, label printing of a brand name, etc., and for forming an ink receiving layer of an ink jet printer, and the ultraviolet curable resin is generally formed by a screen printing method. Its thickness is suitably 3 to 50 // m. If it is above 3 / zm, unevenness is less likely to occur when the layer is formed. By setting it at 50 / zm or less, the internal stress is less changed and it is difficult to affect the mechanical characteristics of the optical disc, which is ideal. As the adhesive layer, an adhesive such as an ultraviolet curing resin, a hot-melt adhesive, or a silicone resin can be used. The material of this adhesive layer is on a thick coating or a printing layer. According to the material, it is coated by spin coating, roller coating, screen printing, etc., and is subjected to ultraviolet irradiation, heating, pressure, and the like. Handle with the disc on the opposite side. The disc on the opposite side can be the same single-plate disc or just a transparent substrate. 关于 Regarding the opposite side. The bonding surface of the disc can be coated with or without the adhesive layer. As the adhesive layer, an adhesive sheet may be used. Although the film thickness of the adhesive layer is not limited, if the coating properties of the material are taken into account, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -30-(Please read the precautions on the back before filling (Write this page) 564412 Printed A7 B7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (28) ^ The effect of hardenability and mechanical characteristics of optical discs is preferably 5 ~ 10 0 // m. Although the range of the adhesive surface is not particularly limited, when it is applied to DVD and / or CD interchangeable rewritable optical discs, in order to make the high-speed § recorded in Embodiment 1 possible, 'in order to ensure the adhesive strength, the inner edge of the adhesive layer The end position is desirably 0 15 to 40 mm, and preferably 0 15 to 30 mm. The third protective layer is located at the layer interface of the transparent substrate, the first protective layer, the recording layer, the second protective layer, the reflective layer, the thick coating layer, the printing layer, or the adhesive layer, and the purpose is to improve the adhesion between layers and chemical reactions. Prevention, adjustment of optical characteristics, adjustment of thermal properties, etc. In particular, when a third protective layer is formed between the second protective layer and the reflective layer, a material containing at least one of C, Si, SiC, SiN, SiO, and SiO2 is desirable. The film thickness of the third protective layer is 1 to 40 nm, and preferably 2 to 30 nm. If it is above 1 nm, it is easy to form a stable interface layer. On the other hand, if it is 40 nm or less, interfacial peeling is unlikely to occur, and the effect of improving the adhesion between layers can be obtained. Such a third protective layer can be formed by various vapor growth methods such as a vacuum evaporation method, a sputtering method, a plasma CVD method, a photo CVD method, an ion plating method, an electron beam evaporation method, and the like. If mass productivity is specifically considered, it is desirable that the DC sputtering method can use a general-purpose sputtering device. In order to mass-produce the optical information recording medium corresponding to the high linear velocity of the first embodiment with the quality of Liangzhu, it is required to use a wide linear recording velocity. Therefore, it is necessary to adjust the linear velocity of the shift. The reason why the displacement linear velocity is affected by thermal properties 'According to the optical information recording medium ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210, / 297 publication 1 -31-' ~ 1 (Please read the precautions on the back before (Fill in this page)
564412 經濟部智慧財產局員工消費合作杜印製 A7 B7五、發明説明(29 ) 之軌距、雷射光之波長、NA、雷射功率而不同,軌距在0.2 〜1.4// m之相變化型光資訊記錄媒體中,發現聚焦半導體 雷射光DC照射於導引溝之溝部或島部之際的移位線速度在 6〜24m/s很重要。 移位線速度在6m/s以上之情形,可以對應DVD之 2X(7.0m/s)線速度以上,CD之8Χ(9·6〜11.2m/s)線速度以上之 類的筒線速度區域之記錄。另一方面,移位線速度在2 4 m / s 以下之情形,適合於記錄之記錄線速度的區域之記錄感度 不易降低,基於後述之脈衝策略,可以進行良好品質之記 錄。 一般在相變化型光資訊記錄媒體進行重複寫之情形, 可以見到在2次記錄時,抖動增大,在3次記錄以上之重 複寫,抖動降低,重複寫10次以後,抖動安定之現象。此 現象在實施形態1之目的之高速記錄時,明顯出現。因此, 相變化型光資訊記錄媒體之實用上最爲重要之品質乃舉此2 次記錄時之抖動。 圖2係顯示對利用具有最低記錄線速度CD 4倍速( 4.8m/s )、最高記錄線速度CD10倍速(12.0m/s )之資訊之 基板,所製作之種種的移位線速度之相變化型光資訊記錄 媒體以進行2次記錄時之抖動比1000次記錄時還小之記錄功 率、記錄策略爲2次記錄時之抖動。抖動係CD 1倍速再生時 之値,35nm(奈秒)以下爲滿足規格。 由圖2,知道本來CD4倍速與CD10倍速其之抖動變小 之移位線速度爲12m/s。 冢紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) Γ32 - (請先閱讀背面之注意事項再填寫本頁) 564412 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(3〇 ) 但是,市場上之最低記錄線素CD4倍速(4.8m/s )、最 高記錄線速度CD10倍速(12.0m/s)之CD-RW記錄媒體之 移位線速度爲9m/s,爲最高記錄線速度之0.75倍程度,與最 低記錄線速度之CD4倍速匹配,對CD10倍速並不匹配。 爲了使實施形態1之之目的之更高速的記錄成爲可能, 特別是爲了使使用者可以感受高速化,需要實現最高記錄 線速度 CD 10倍速之20%以上之記錄線速度提升(即, 14.4m/s ),爲了滿足規格之35ns以下,由圖2來看,判斷需 要9.5m/s以上之移位線速度。即,需要最高記錄線速度之 0.8倍以上之移位線速度。 進而,爲了達成其以上之高速記錄,例如CD 16倍速( 19.2m/s) 、CD20倍速(24m/s) 、CD24倍速(28.8m/s)之 記錄,需要12、16、19m/s以上之移位線速度。 另一方面,爲了在最低記錄線速度4.8m/s之記錄也在 抖動35ns以下,知道需要使移位線速度在25in/s。即,大約 最高記錄線速度之2倍以下,成爲可以記錄之上限記錄線 速度。 上述說明雖係以CD - RW記錄媒體爲例,但是其他之 相變化型光資訊記錄媒體也同樣地,爲了實現更高速之記 錄’期望記錄媒體具有之最高記錄線速度之至少〇.8倍以上 ’理想爲0·85倍以上,更理想爲〇.9倍以上之移位線速度。 又’圖2記載之各種移位線速度之cd- RW記錄媒體係 適當選擇記錄層之組成、記錄層之厚度、記錄層之不純物 、反射層材料、電介質材料、初期化製程條件等而製作。 (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(21〇χ297公釐) -33- 564412 經濟部智慧財產局員工消費合作社印製 A7 __B7 _ 五、發明説明(31 ) 移位線速度可以依據上述之各構成層之材料、膜厚、 製程條件而調整。 例如,如使記錄層材料之Ag、Ge之組成比變多,可以 使移位線速度變慢,如使In、Ga之組成比變多,可以使移 位線速度變快。又,如使記錄層之膜厚變厚,可以使移位 線速度變慢,如使膜厚變薄,可以使移位線速度變快。 關於第二保護層、反射層,如使熱傳導率變大,可以 使移位線速度變慢,如使熱傳導率變小,可使移位線速度 變快。 關於製程條件之例,在藉由濺鍍法進行記錄層、第一 保護層、第二保護層、第三保護層之形成的情形,如使投 入之基板的溫度低,可以使移位線速度變慢,如使基板之 溫度高,可使移位線速度變快。 又,濺鍍時之共存氣體在Ar之外,如加上N2、〇2,可 以使移位線速度變慢。此時,在靶壽命之初期,移位線速 度變快,在靶壽命之後半,移位線速度變慢。 其它,依據初期化之線速度、雷射功率等之條件,也 可以調整移位線速度。 藉由以上之種種的條件之組合,可以決定移位線速度 之値之故,藉由均衡地調整這些,可以將移位線速度控制 在所期望之値.。 又,關於對應實施形態1之高線速度化之光資訊記錄媒 體,期望使初期化之線速度比移位線速度慢。 如使初期化線速度比移位線速度快,記錄層之溫度上 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) :34 - (請先閲讀背面之注意事項再填寫本頁) 564412 經濟部智慧財產局員工消費合作社印製 A7 _ B7 _ 五、發明説明(32 ) 升不充分,無法均勻地結晶化之故,引起初期化不均,產 生RF信號之錯亂。 進而,初期化線速度Vi以在標準記錄線速度Vr以及 /或最高記錄線速度Vh之0.5倍以上、1.6倍以下爲佳。在 0.5倍以上,初期化可以良好進行,在覆寫性能之點爲佳。 又,如使之在1.6倍以下,記錄層之溫度上升可以良好進行 ,能夠均勻結晶化,可以進行均勻之初期化,能夠防止RF 信號之錯亂。 圖4係顯示實施形態1之記錄再生方法或裝置之實施形 態之一例。即,藉由由主軸馬達形成之驅動手段旋轉驅動 相變化型光資訊記錄媒體。 另一方面,藉由對藉由雷射驅動電路,驅動由記錄再 生用拾取頭之半導體雷射形成之光源,透過光學系統旋轉 之光資訊記錄媒體照射具有圖3所示之fp、mp、ep之脈衝 策略之雷射光,使該光資訊記錄媒體之記錄層產生相變化 以進行記錄。 記錄之資訊的再生係以記錄再生用拾取頭接受由被照 射再生光之光資訊記錄媒體來之反射光而進行。 接著,說明對於實施形態1之光資訊記錄媒體的記錄 層,以記錄信號作爲標記之寬幅之所謂的PMW記錄方式進 行資訊之記錄之情形。 在進行記錄上,調制部係利用時脈,例如以適合重寫 型緻密光碟之資訊記錄之 EFM(Eight-to-Fourteen Modulation:8-14調制)調制方式,或其之改良調制方式調制 (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(210X297公釐) -35 - 564412 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(33 ) 應記錄信號。 在進行PMW記錄之際,係以設進行調制後之信號寬幅 爲ηΤ(η係指定之値,T係時脈時間,即相當於使用在信號 之調制之時脈的週期之時間)之0信號的記錄或重寫時之記 錄光爲功率準位e之連續光,設進行調制後信號寬幅爲ηΤ 之1信號的記錄或重寫時之記錄波脈衝列爲由:具有時間寬 幅χ與功率準位a之脈衝部fp,與具有合計爲Τ之時間寬 幅之功率準位b之低準位脈衝與功率準位c之高準位脈衝 交互以負荷比y合計(m-m’)次連續之多脈衝部mp,與具 有時間寬幅z與功率準位d之脈衝部ep形成之雷射波脈衝 歹[J,進而,分別設 X、y、z 爲0.12 5TSx$2.0T、0.125SyS 0.875、0·125Τ$ zS l.OT,設m爲1以上之正整數,(a以及 c) > e> (b以及d)而進行。 圖3係顯示m = 3、m、2時之例。 實施形態1之光資訊記錄媒體的記錄再生裝置係具有 讀入顯示被設定之光碟的最高記錄線速度之資訊,而且, 讀入其它之光碟的固有資訊,進行可有以最高記錄線速度 以上之線速度記錄之判斷的手段。 例如,如流程地顯示其之一例,則如下述。 1 .實施形態1之相變化型光資訊記錄媒體被設定在驅 動部之托盤。. 2 _驅動部再生容納在實施形態1之相變化型光資訊記 錄媒體之ID資訊或辨識資訊。 3 .對照與預先被儲存在驅動部之相變化型光資訊記錄 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -36 - ' — (請先閲讀背面之注意事項再填寫本頁) 564412 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(34 ) 媒體所容納者相同之ID資訊或辨識資訊與在上述2.再生之 ID資訊或辨識資訊。 4 ·藉由ID資訊或辨識資訊之對照,辨識被設定在驅 動部之相變化型光資訊記錄媒體之本性、特性等。 5·由預先儲存之記錄方法之一覽表選擇與在上述4辨 識之光碟匹配之記錄方法’開始對相變化型光資訊記錄媒 體之記錄動作。 以下,顯示實施例,具體說明實施形態1,但是實施形 態1之發明並不由這些實施例所限定。 實施例1 藉由射出成形,製作具有溝寬0.55/z m、溝深30nm之導 引溝之聚碳酸酯基板,在此基板上,依序藉由濺鍍法積層 第一保護層、記錄層、第二保護層、以及反射層。基板溫 度爲55°C投入濺鍍裝置。 在基板放入最高記錄線速度爲CD10倍速(12m/s)之資 訊。 第一保護層以及第二保護層係使用ZnS.Si〇2,膜厚分 別設爲 9 0 n m、3 0 n m。 記錄層係使用Ge2ln8Sb68Te22,厚度設爲16nm。 反射層係使用AlTi(Ti含有量0.5重量%),厚度爲140nm 〇 其結果,形成基板/ZnS · Si〇2(90nm)/記錄層(16nm) /ZnS · Si〇2(30nm)/AlTi(140nm)之層構成之積層物。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ^37 - (請先閲讀背面之注意事項再填寫本頁) 564412 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(35) 進而,在反射層上形成藉由紫外線硬化型樹脂之旋轉 塗佈之厚塗層,製作相變化型光資訊記錄媒體之單板光碟 〇 接著,藉由具有大口徑LD(光束直徑200 X 1 /zm)之初 期化裝置,以速度7.0m/s、電力85 0mW、進給120/z m,由內 周朝向外周,以一定線速度全面結晶化。 聚焦波長780nm之半導體雷射光DC照射該導引溝之溝 部以量測如此獲得之光資訊記錄媒體之移位線速度。其結 果,移位線速度爲12.8m/s,爲最高記錄線速度之1.1倍。 接著,此光資訊記錄媒體之盤首紋時間、盤尾紋時間 、最高記錄功率碼、光碟形式之各碼資訊之組合的編碼列 設定在具有可以16倍速記錄之淸單之光資訊記錄裝置。 此光資訊記錄裝置首先讀入盤首紋時間、盤尾紋時間 、最高記錄功率碼、光碟形式。 接著,光資訊記錄裝置依據這些之組合,判斷是否可 以以最高記錄線速度以上之記錄線速度進行記錄,判斷可 以以最高記錄線速度以上之記錄線速度CD 1 6倍速進行記錄 之光碟。 接著,藉由以記錄線速度CD 16倍速在CD - ROM可以 再生之格式進行記錄。其結果,記錄初期以及覆寫1〇〇〇次 後之抖動良好。 進而,在溫度80°C、溼度85%環境內,放置500小時之 保存試驗後,沒有見到記錄層之氧化以及信號特性之變化 ,可以獲得良好之保存信賴性。 (請先閱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) -38 - 564412 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(36 ) 如上述般地,對於具有最高記錄線速度CD10倍速之資 訊的相變化型光資訊記錄媒體,可以實現在CD 1 6倍速之高 速的記錄。 實施例2 藉由射出成形,製作具有溝寬0.2// m、溝深27nm之導 引溝之聚碳酸酯基板,在此基板上,依序藉由濺鍍法積層 第一保護層、記錄層、第二保護層、第三保護層以及反射 層。基板溫度爲55°C投入濺鍍裝置。 在基板放入最高記錄線速度爲8.44m/s之資訊。 第一保護層以及第二保護層係使用ZnS.SiCh,第三保 護層係使用SiC,膜厚分別設爲75nm、10nm、3nm。 記錄層係使用Ag〇.5Gei.5Ga8Sb68Te22,厚度設爲14nm。 反射層係使用AlTi(Ti含有量0.5重量%),厚度爲140nm 〇 其結果,形成基板/ZnS · Si〇2(75nm)/記錄層(14nm) /ZnS · SiCh(10nm)/SiC(3nm)/AlTi(140nm)之層構成之積層物 〇 進而,在反射層上形成藉由紫外線硬化型樹脂之旋轉 塗佈之厚塗層,製作相變化型光資訊記錄媒體之單板光碟 〇 接著,藉由具有大口徑LD(光束直徑200 X 1 /zm)之初 期化裝置,以速度l〇.〇m/s、電力850mW、進給120 // m,由 內周朝向外周,以一定線速度全面結晶化。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐Ί ^39 - (請先閲讀背面之注意事項再填寫本頁) 564412 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(37 ) 聚焦波長660nm之半導體雷射光DC照射該導引溝之溝 部以量測如此獲得之光資訊記錄媒體之移位線速度。其結 果,移位線速度爲14.4m/s,爲最高記錄線速度之1.7倍。 接著,此光資訊記錄媒體之盤首紋時間、盤尾紋時間 、最高記錄功率碼、光碟形式之各碼資訊之組合的編碼列 設定在具有可以DVD4倍速記錄之淸單之光資訊記錄裝置。 此光資訊記錄裝置首先讀入盤首紋時間、盤尾紋時間 、最高記錄功率碼、光碟形式。 接著,光資訊記錄裝置依據這些之組合,判斷是否可 以以最高記錄線速度以上之記錄線速度進行記錄’判斷可 以以最高記錄線速度以上之記錄線速度DVD4倍速進行記錄 之光碟。 ^ 接著,藉由以記錄線速度DVD4倍速在DVD — ROM可 以再生之格式進行記錄。其結果,記錄初期以及覆寫1〇⑻ 次後之抖動良好。 進而,在溫度80°C、溼度85%環境內,放置500小時之 保存試驗後,沒有見到記錄層之氧化以及信號特性之變化 ,可以獲得良好之保存信賴性。 如上述般地,對於具有最高記錄線速度4.88m/s之資訊 的相變化型光資訊記錄媒體,可以實現在DVD4倍速之高速 的記錄。 實施例3〜14 藉由射出成形,形成聚碳酸酯基板,在此基板上’依 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -40 - (請先閱讀背面之注意事項再填寫本頁) 564412 Α7 Β7 五、發明説明(38)564412 Consumer cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs Du printed A7 B7 V. Invention description (29) The gauge, laser light wavelength, NA, and laser power vary, and the gauge varies from 0.2 to 1.4 // m In the optical information recording medium, it is important to find that the linear velocity of the displacement when the focused semiconductor laser light DC is irradiated to the groove portion or the island portion of the guide groove is 6 to 24 m / s. When the linear speed of the displacement is above 6m / s, it can correspond to the linear speed area of the DVD such as 2X (7.0m / s) or more, and CD 8 × (9.6 to 11.2m / s) Its record. On the other hand, when the displacement linear velocity is less than 2 4 m / s, the recording sensitivity of a region suitable for recording at a linear velocity of recording is not easily reduced. Based on the pulse strategy described later, a good quality recording can be performed. Generally, in the case of repeated writing in a phase-change optical information recording medium, it can be seen that the jitter increases when the recording is performed twice, and the jitter is reduced when the writing is repeated more than three times. After ten times of repeated writing, the jitter is stable. . This phenomenon is apparent during high-speed recording for the purpose of the first embodiment. Therefore, the most important practical quality of the phase-change optical information recording medium is the jitter during the two recordings. Fig. 2 shows the phase change of various shifted linear velocities produced on a substrate using information having the lowest recording linear velocity CD 4 times (4.8 m / s) and the highest recording linear velocity CD 10 times (12.0 m / s). The optical information recording medium has a recording power with less jitter when performing two recordings and a recording strategy of jitter during two recordings. The jitter is the same as when CD is being reproduced at 1x speed. 35nm (nanosecond) or less meets the specifications. From FIG. 2, it is known that the linear velocity of the shift of the original CD4 speed and the CD10 speed is small, and the displacement linear speed is 12 m / s. The mound paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) Γ32-(Please read the precautions on the back before filling in this page) 564412 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3) However, the CD-RW recording medium with the lowest recording linear speed CD4 times (4.8m / s) and the highest recording linear speed CD10 times (12.0m / s) has a displacement linear speed of 9m / s, which is The maximum recording linear speed is about 0.75 times, which matches the minimum recording linear speed of CD4 times, and does not match the CD10 times. In order to make higher-speed recording possible for the purpose of Embodiment 1, especially in order to allow users to experience high speed, it is necessary to achieve a recording linear speed increase of 20% or more of the 10 times the maximum recording linear speed CD (ie, 14.4m). / s), in order to meet the specification below 35ns, judging from FIG. 2, it is judged that a shift linear velocity of more than 9.5m / s is required. That is, a displacement linear velocity of 0.8 times or more the highest recording linear velocity is required. Furthermore, in order to achieve more than the high-speed recording, for example, CD 16x speed (19.2m / s), CD20x speed (24m / s), CD24x speed (28.8m / s), requires 12, 16, 19m / s or more Shift linear speed. On the other hand, in order to record at a minimum recording linear velocity of 4.8 m / s, the jitter should be less than 35 ns, and it is known that the shift linear velocity needs to be 25 in / s. That is, the maximum recording linear velocity is approximately twice the maximum recording linear velocity or less, which is the upper limit of the recording linear velocity. Although the above description is based on a CD-RW recording medium as an example, other phase-change optical information recording media are also the same. In order to achieve higher-speed recording, it is desirable that the recording medium has at least 0.8 times the maximum recording linear speed. 'It is ideally 0.85 times or more, and more preferably 0.9 times or more the linear speed of displacement. Also, the cd-RW recording media of various displacement linear velocities described in FIG. 2 are produced by appropriately selecting the composition of the recording layer, the thickness of the recording layer, the impurities of the recording layer, the material of the reflective layer, the dielectric material, and the conditions of the initializing process. (Please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specification (21 × 297 mm) -33- 564412 Printed by A7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs __B7 _ 5 2. Description of the invention (31) The linear displacement speed can be adjusted according to the materials, film thickness, and process conditions of the above-mentioned constituent layers. For example, if the composition ratio of the Ag and Ge of the recording layer material is increased, the shift line speed can be made slower. If the composition ratio of In and Ga is increased, the shift line speed can be made faster. If the film thickness of the recording layer is made thicker, the displacement linear velocity can be made slower. If the film thickness is made thin, the displacement linear velocity can be made faster. Regarding the second protective layer and the reflective layer, if the thermal conductivity is made larger, the displacement linear velocity can be made slower, and if the thermal conductivity is made smaller, the displacement linear velocity can be made faster. As an example of process conditions, in the case where the recording layer, the first protective layer, the second protective layer, and the third protective layer are formed by a sputtering method, if the temperature of the substrate to be put is low, the displacement linear velocity can be increased. Slower, if the temperature of the substrate is high, the linear speed of the shift can be increased. In addition, the coexisting gas at the time of sputtering is outside Ar, and if N2 and O2 are added, the displacement linear velocity can be slowed down. At this time, at the beginning of the target life, the displacement linear velocity becomes faster, and at the latter half of the target life, the displacement linear velocity becomes slower. In addition, the linear velocity of the shift can be adjusted based on the conditions of the initial linear velocity and laser power. The combination of the above conditions can determine the linear velocity of the shift, and by adjusting these in a balanced manner, the linear velocity of the shift can be controlled to a desired level. In the optical information recording medium corresponding to the high linear velocity of the first embodiment, it is desirable to make the linear velocity of the initialization slower than the linear velocity of the shift. If the initial linear velocity is faster than the linear velocity of the shift, the paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) for the temperature of the recording layer: 34-(Please read the precautions on the back before filling this page ) 564412 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7 _ V. Description of the invention (32) Insufficient liters and inability to crystallize uniformly, resulting in uneven initialization and RF signal confusion. Furthermore, the initializing linear velocity Vi is preferably 0.5 times to 1.6 times the standard recording linear velocity Vr and / or the maximum recording linear velocity Vh. At 0.5 times or more, the initialization can be performed well, and it is preferable in terms of overwriting performance. Moreover, if it is 1.6 times or less, the temperature rise of the recording layer can be performed well, uniform crystallization can be performed, uniform initialization can be performed, and disturbance of the RF signal can be prevented. Fig. 4 shows an example of an embodiment of a recording / reproducing method or apparatus according to the first embodiment. That is, the phase change type optical information recording medium is rotationally driven by a driving means formed by a spindle motor. On the other hand, by driving a light source formed by a semiconductor laser of a pickup head for recording and reproduction by a laser drive circuit, the optical information recording medium rotated through the optical system is irradiated with fp, mp, and ep shown in FIG. 3 The laser light of the pulse strategy causes a phase change in the recording layer of the optical information recording medium for recording. The recorded information is reproduced by receiving the reflected light from the optical information recording medium that is irradiated with the reproduced light. Next, a description will be given of a case where information is recorded on a recording layer of the optical information recording medium according to the first embodiment by a so-called PMW recording method in which a recording signal is used as a mark. In recording, the modulation unit uses the clock, such as the EFM (Eight-to-Fourteen Modulation: 8-14 modulation) modulation method suitable for information recording of rewritable compact discs, or its modified modulation method (please (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -35-564412 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (33 ) The signal should be recorded. When performing PMW recording, the width of the modulated signal is set to ηT (where η is the specified range, and T is the clock time, which is equivalent to the period of the clock used in the modulation of the signal). The recording light during signal recording or rewriting is continuous light at the power level e, and the recording wave pulse sequence during recording or rewriting of a signal having a modulated signal width of ηT is used as a reason: it has a time width of χ Interact with the pulse part fp of the power level a, the low level pulse with a time-wide power level b totaling T and the high level pulse of the power level c, and the total load ratio y (m-m ' ) Times of continuous multi-pulse section mp, and laser pulses 形成 [J formed by a pulse section ep with time width z and power level d [J, further, set X, y, z to 0.12 5TSx $ 2.0T, 0.125 SyS 0.875, 0.125T $ zS l.OT, set m to a positive integer of 1 or more, and (a and c) > e > (b and d). Figure 3 shows an example when m = 3, m, and 2. The recording / reproducing device of the optical information recording medium according to the first embodiment is capable of reading and displaying information on the maximum recording linear speed of the set optical disc, and reading the inherent information of other optical discs, and performing recording at a speed higher than the maximum recording linear speed. Means of judging linear velocity recording. For example, if one example is displayed in a flow, it is as follows. 1. A phase-change type optical information recording medium according to the first embodiment is set on a tray of a drive unit. 2 _ The drive unit reproduces ID information or identification information contained in the phase-change optical information recording medium of Embodiment 1. 3. Contrast with the phase change optical information record stored in the driver in advance. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -36-'— (Please read the precautions on the back before filling in this Page) 564412 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (34) The ID information or identification information of the media holder is the same as the ID information or identification information reproduced in 2. above. 4 · Identify the nature and characteristics of the phase change optical information recording medium set in the driver by comparing ID information or identification information. 5. Select a recording method that matches the disc identified in the above 4 from the list of recording methods stored in advance to start the recording operation on the phase-change optical information recording medium. Hereinafter, examples will be shown and the first embodiment will be specifically described, but the invention of the first embodiment is not limited to these examples. Example 1 A polycarbonate substrate having a guide groove with a groove width of 0.55 / zm and a groove depth of 30 nm was produced by injection molding. On this substrate, a first protective layer, a recording layer, and a sputtering layer were sequentially laminated by sputtering. A second protective layer, and a reflective layer. The substrate temperature was set at 55 ° C. Put the information that the maximum recording linear speed is 10 times the speed of CD (12m / s) on the substrate. The first protective layer and the second protective layer were made of ZnS.SiO2, and the film thicknesses were set to 90 nm and 30 nm respectively. Ge2ln8Sb68Te22 was used as the recording layer, and the thickness was set to 16 nm. The reflective layer is made of AlTi (Ti content 0.5% by weight) and has a thickness of 140 nm. As a result, a substrate / ZnS · SiO2 (90nm) / recording layer (16nm) / ZnS · SiO2 (30nm) / AlTi ( 140nm). This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ^ 37-(Please read the notes on the back before filling this page) 564412 A7 B7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs (35) Further, a thick coating of spin-coated UV-curable resin is formed on the reflective layer to produce a single-plate optical disc of a phase-change optical information recording medium. Then, a large-diameter LD (beam diameter 200) X 1 / zm) initialization device, with a speed of 7.0m / s, power 8500mW, feed 120 / zm, from the inner periphery to the outer periphery, full crystallization at a certain linear velocity. A semiconductor laser light DC with a focusing wavelength of 780 nm irradiates the groove portion of the guide groove to measure the displacement linear velocity of the optical information recording medium thus obtained. As a result, the displacement linear velocity was 12.8 m / s, which was 1.1 times the highest recording linear velocity. Next, the code row of the combination of the first pattern time, the last pattern time of the optical information recording medium, the highest recording power code, and each code information in the form of an optical disc is set in an optical information recording device having a document capable of recording at 16 times the speed. This optical information recording device first reads the first time of the disc, the last time of the disc, the highest recording power code, and the disc form. Next, the optical information recording device judges whether or not recording can be performed at a recording linear velocity higher than the highest recording linear velocity based on the combination of these, and determines an optical disc that can be recorded at a recording linear velocity CD 16 times higher than the highest recording linear velocity. Next, recording is performed in a format that can be reproduced on a CD-ROM at a recording linear speed of 16 times the speed of a CD. As a result, the jitter was good at the beginning of recording and after overwriting 1,000 times. Furthermore, after storage test for 500 hours in an environment with a temperature of 80 ° C and a humidity of 85%, no oxidation of the recording layer and no change in signal characteristics were observed, and good storage reliability was obtained. (Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -38-564412 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Explanation (36) As described above, the phase-change optical information recording medium having the highest recording linear velocity CD10 times the speed can record at a high speed of CD 16 times. Example 2 A polycarbonate substrate having a guide groove with a groove width of 0.2 // m and a groove depth of 27 nm was produced by injection molding. On this substrate, a first protective layer and a recording layer were sequentially laminated by sputtering. , A second protective layer, a third protective layer, and a reflective layer. The substrate temperature was put into a sputtering device at 55 ° C. Put the information on the substrate with the highest recording linear speed of 8.44m / s. The first protective layer and the second protective layer were made of ZnS.SiCh, and the third protective layer was made of SiC, and the film thicknesses were set to 75 nm, 10 nm, and 3 nm, respectively. As the recording layer, Ag0.5Gei.5Ga8Sb68Te22 was used, and the thickness was set to 14 nm. The reflective layer is made of AlTi (Ti content 0.5% by weight) and has a thickness of 140 nm. As a result, a substrate / ZnS · SiO 2 (75 nm) / recording layer (14 nm) / ZnS · SiCh (10 nm) / SiC (3 nm) is formed. / AlTi (140nm) layered layered product. Furthermore, a thick coating was formed on the reflective layer by spin coating of a UV-curable resin to produce a single-plate optical disc of a phase change optical information recording medium. Next, borrowed From the initializing device with a large-diameter LD (beam diameter 200 X 1 / zm), the speed is 100.0 m / s, the power is 850mW, and the feed is 120 // m. Crystallize. This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm297 ^ 39-(Please read the precautions on the back before filling out this page) 564412 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (37) The semiconductor laser light DC with a focused wavelength of 660 nm irradiates the groove portion of the guide groove to measure the displacement linear velocity of the optical information recording medium thus obtained. As a result, the displacement linear velocity is 14.4 m / s, which is the highest recording The linear speed is 1.7 times. Next, the code sequence of the combination of the first time of the disc, the last time of the disc, the highest recording power code, and the information of each code in the form of a disc in this optical information recording medium is set to a list capable of recording at 4x speed The optical information recording device. This optical information recording device first reads the first time of the disc, the last time of the disc, the highest recording power code, and the form of the optical disc. Then, the optical information recording device judges whether it can use the highest recording line based on these combinations. Recording at a recording linear speed above the speed 'Judgment A disc that can be recorded at a recording linear speed DVD 4 times faster than the maximum recording linear speed. ^ Next, recording was performed in a DVD-ROM reproducible format at a recording linear speed of 4 times the speed of the DVD. As a result, the jitter was good at the beginning of the recording and after overwriting 10 times. Furthermore, the temperature was 80 ° C and the humidity was 85%. In the environment, after 500 hours of storage test, no oxidation of the recording layer and no change in signal characteristics were observed, and good storage reliability was obtained. As mentioned above, for information with the highest recording linear speed of 4.88m / s, Phase-change optical information recording media can achieve 4 times the speed of DVD. Example 3 ~ 14 Polycarbonate substrate is formed by injection molding. On this substrate, the Chinese National Standard (CNS) is applied according to the paper size. A4 specifications (210X297 mm) -40-(Please read the precautions on the back before filling this page) 564412 Α7 Β7 V. Description of the invention (38)
序藉由濺鍍法積層第一保護層、記錄層、第二保護層、第 三保護層以及反射層。 I (請先閱讀背面之注意事項再填寫本頁) 第一保護層以及第二保護層係使用ZnS.Si〇2,第三保 護層係使用SiC,膜厚分別設爲80nm、10nm、5nm。 記錄層係使用表1所示之組成,厚度設爲15nm。 反射層係使用Ag,形成基板/ ZnS . Si〇2(80nm)/記錄 層(15nm) /ZnS · Si〇2(10nm)/SiC(5nm)/Ag(140nm)之層構成 〇 進而,在反射層上形成藉由紫外線硬化型樹脂之旋轉 塗佈之厚塗層,製作相變化型光資訊記錄媒體之單板光碟 〇 接著,藉由具有大口徑LD(光束直徑200 X 1 /zm)之初 期化裝置,進行光資訊記錄媒體之記錄層之初期化。 之後,關於聚碳酸酯基板厚度0.6mm之單板光碟,在 厚塗層上透過黏著層貼合聚碳酸酯基板,在聚碳酸酯基板 之表面(貼合面之相反面)側形成印刷層,作成貼合光碟 〇 經濟部智慧財產局員工消費合作社印製 表1係彙整顯示聚碳酸酯基板厚度與單板或貼合之光 碟構成、軌距、記錄層組成之各製作條件、與記錄、再生 獲得之媒體所使用之裝置的拾取頭之波長、移位線速度、 記錄線速度與評估結果。 評估結果之抖動特性以時脈時間T標準化之σ / T(%) 定義之。 由表1所示結果可以明白地,在任何一種之實施例中 本紙張尺度適财關家鮮(CNS ) Α4規格(21GX 297公釐)-41 - 564412 A7 B7 五、發明説明(39 ) ,初期以及覆寫1 〇〇〇次後之抖動特性都良好。 進而,在溫度80°c、溼度85%環境內,放置500小時之 保存試驗後,沒有見到記錄層之氧化以及信號特性之變化 ,可以獲得良好之保存信賴性。 (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(210X 297公釐) -42 - 564412 A7 B7 五、發明説明(40 ) 經濟部智慧財產局員工消費合作社印製The first protective layer, the recording layer, the second protective layer, the third protective layer, and the reflective layer are laminated by sputtering. I (Please read the precautions on the back before filling out this page) The first and second protective layers are made of ZnS.SiO2, and the third protective layer is made of SiC. The film thickness is set to 80nm, 10nm, and 5nm, respectively. The recording layer has a composition shown in Table 1 and has a thickness of 15 nm. The reflective layer is formed by using Ag to form a substrate / ZnS.Si02 (80nm) / recording layer (15nm) / ZnS · SiO2 (10nm) / SiC (5nm) / Ag (140nm). A thick coating is formed on the layer by spin-coating with a UV-curable resin to produce a veneer disc of a phase-change optical information recording medium. Then, at the initial stage with a large-diameter LD (beam diameter 200 X 1 / zm) The device initializes the recording layer of the optical information recording medium. After that, for a veneer disc with a thickness of 0.6 mm on a polycarbonate substrate, a polycarbonate substrate was bonded through an adhesive layer on a thick coating layer, and a printed layer was formed on the surface of the polycarbonate substrate (the opposite side of the bonding surface). Create a laminated disc 0. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 1 is a collection of the production conditions of the polycarbonate substrate thickness and the veneer or laminated disc structure, track gauge, and recording layer composition. The wavelength, displacement linear velocity, recording linear velocity, and evaluation result of the pickup head of the device used for the obtained medium. The jitter characteristics of the evaluation result are defined as σ / T (%) normalized to the clock time T. From the results shown in Table 1, it can be clearly understood that in any of the embodiments, the paper size is suitable for wealth and family (CNS) A4 specifications (21GX 297 mm)-41-564412 A7 B7 V. Description of the invention (39) The jitter characteristics were good at the initial stage and after the overwrite of 1,000 times. Furthermore, after a storage test of 500 hours in an environment with a temperature of 80 ° C and a humidity of 85%, no oxidation of the recording layer and no change in signal characteristics were observed, and good storage reliability was obtained. (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 (210X 297 mm) -42-564412 A7 B7 V. Invention Note (40) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
評估結果 〇 〇 〇 〇 〇 〇 〇 o 〇 〇 〇 〇 抖動特性 (σ/Τ)(%) DOW 1000 CN ON CO OO o 〇\ OO OO CNl On CO ON <NI OO CO OO csi OO l〇 ON C<1 ON OO ON 初期 〇〇 卜 r—H 卜 OO 卜 寸 卜 〇 OO VD 卜 o t— CO 卜 CN VO csi OO OO 卜 寸 OO 記錄線 速 度 (m/s) Ό On Ό 〇\ 14.4 14.4 <NI ON τ—H 〇 卜 o 卜 o 卜 o 寸 r-H 24.0 o r- 14.0 煺 5 甿叫鹋 OO 〇\ 10.5 CO i ' < ο un r-H OO r-H Csl 1/Ί σ\ 10.0 un VO i—H cn CN o On υη CO 1 ( 評估 波長 (nm) 〇 OO 卜 〇 OO r- 〇 OO 卜 〇 OO 卜 〇 OO 卜 〇 Ό ο o VO VO o VO Ό o 〇 〇 寸 〇 〇 寸 製作條件 記錄層組成 <D Η OO CNl Csl <N C<l 寸 C<1 cs C<l 〇 CO CO CNl 寸 OQ CO CO CNl csi VO <N CO cs GO CNl VO 寸 VO OO ON VO 寸 r- 寸 VO ο 卜 OO 卜 crs vo o 卜 cd Ο o o 寸 ON CO in ο o CO OO 03 VO cn h-1 VO o 寸 r-H o O CO 卜 o o <D o t—H 寸 o r—H τ—H o o CN CO o r- < 〇 CO < CO o VD 1 < o r-H CO r-H CN o τ-H o 軌距 (Mm) 寸 r—H 寸 r-H 寸 r-H 寸 τ—H 寸 H 0.74 0.74 0.74 0.74 0.74 (N 〇 CNl o 單板 單板 單板 單板 單板 貼合 貼合1 貼合 貼合 貼合 貼合 貼合 摊1 » 5 CNl r-H CNl r—H CN| CN) τ—H c〇 τ—H Ό 〇 o o o o VD 〇 o CO 寸 v〇 OO as o r-H r-H τ—H CN CO r-H 寸 H (請先閲讀背面之注意事項再填寫本貢) 、11 鮮 本纸張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -43 - 564412 經濟部智慧財產局員工消費合作社印製 A7 _____B7 _五、發明説明(41 ) 【實施形態2】 依據實施形態2之相變化型之光資訊記錄媒體係以Ag、 In、Sb以及Te爲主要構成元素,其特徵爲進而添加由週期 表第Illb、IVb以及5b族選擇之至少1種之特定之元素。藉 由此,與習知之相變化型之光資訊記錄媒體相比,係在高 線速、高密度記錄爲充分之媒體特性,特別是重複記錄、 初期以及重複記錄後之保存信賴性優異之相變化記錄材料 〇 以下,更詳細說明實施形態2。 依據實施形態2之光資訊記錄媒體係在基板上依序積 層下部保護層、記錄層、上部保護層、反射層,該記錄層 係以已經敘述之Ag、In、Sb以及Te爲主構成元素,進而 於其添加由週期表第Illb、IVb以及5b族選擇至少1種之特 定之元素。而且,將製膜後之媒體中的記錄層進行由非晶 質相變化爲結晶相之所謂的初期化,作成結晶相者。 此處,在實施形態2中,最好主構成元素之Ag、In、 Sb以及Te之各元素的原子比以下述(2)式之關係: (Agaln^Sbr ) 1-5 Te ό (2) (式中,〇.1<。<1〇、1$^^2〇、9〇$7<1〇〇、0 + y8+r=l〇〇、〇.2S5 $0.35。)表示時,上述記錄層在形 成結晶相時,一樣地形成NaCl型構造。 於此,在實施形態2中,最好在此NaCl型之結晶相中 ,Ag、In、Sb位於相當於Na側,Te位於相當於C1側,而 且,Te在此側並不佔有100%,而具有空孔,有使揮發優異 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 「44 - 一 (請先閱讀背面之注意事項再填寫本頁) 564412 經濟部智慧財產局員工消費合作社印製 B7五、發明説明(42 ) 之初期以及重複記錄特性之傾向。 藉由此,成爲即使重複非晶質相與結晶相之相變化以 進行記錄,不易引起組成變化之共晶組成。又,於更高線 速使之高速結晶化上,使一面保持此種狀態,一面增加Sb 以及In、減少Ag爲合適。 又,在實施形態2中,關於其之結晶化速度,首先Sb 與Te相比,原子半徑大,在非晶質相中,對於Te之鍵配 位數約3配位,容易引起結晶化之故,結晶化速度快,而且 ,在比較低之溫度也會引起。因此,Sb量相當多之情形, 保存信賴性顯著變差。 又,In比Sb其原子半徑更大,鍵配位數也在非晶質中 ,比Sb高,約3.5配位,結晶化速度快。又,其之詳細雖不 ^明白,在更高溫中,會高速結晶化,在由室溫製70〜80°C 中,不易引起結晶化。或認爲係In具有妨礙藉由Sb之結晶 化之功能。 進而,關於其之結晶化速度,Ag之原子半徑雖比Te 大,但是配位數約2配位之故,非晶質相安定之故,結晶化 速度比較慢。又,在高速記錄中,即使進行重複記錄,不 易引起組成變化,而且,高速產生結晶化,要求可以確保 保存信賴性之最適當組成範圍。但是,即使在上述組成範 圍,要滿足全.部之特性也有限度。特別是保存信賴性在高 速記錄中不易確保。 ' 因此,檢視上述之事實關係,由記錄媒體之信賴性確 保之觀點,在高速記錄之重複記錄特性優異,而且,爲了 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -45 - (請先閲讀背面之注意事項再填寫本頁) 564412 A7 ____ B7 _ 五、發明説明(43 ) 確保非晶質相之環境安定性,在上述主構成元素中作爲添 加之添加元素,於實施形態2中可以適當添加週期表Illb、 IVb以及5b族之至少一種之元素。 (請先閲讀背面之注意事項再填寫本頁) 又,這些添加元素特別是對於構成元素Te之鍵能爲 200k;f/mol以上,或爲了使結晶速度變快,這些添加元素之 原子半徑以O.lnm以上、0.20nm以下爲合適。 又,此鍵能儘可能大,最好以250k〗/mol以上爲合適。 又,即使使其値大,在使相變化之際,需要大的能量之故 ,最好以500kJ/mol以下爲合適。 進而,該添加元素在元素週期表之Illb、IVb以及5b族 之中,原子量愈少之元素,藉由添加,結晶化溫度有愈高 之傾向之故,由保存信賴性之觀點,最好添加比構成元素 . 之Sb或In其原子量小之元素。 因此,這些添加元素之中,例如關於B、Al、Ti、C、 Si、Ge、Sn、Pb、P、As以及Bi等,於表3顯示其之原子 半徑以及對於Te之鍵能。由此表,添加元素最好適當添加 Al、Si、Ge、Sn以及P等,其中特別以Ge爲合適。 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) -46 - 564412 A7 B7 五、發明説明(44 ) 經濟部智慧財產局員工消費合作社印製 【e撇】 保存試驗後之抖動 增加量(%) cn cn 寸 cn v〇 cn 一 i—H t—H cn 寸 vn cn 寸 寸 寸 寸 cn 寸 寸 重複記錄後抖動增 加量(%) cn CO 寸 in cn <N r—< <N <N <N 1—Η Ό c4 (N cn cn Ol un ϊ—H cn cs 記錄線速 (m/s) oo oo τ—H Τ—H σ\ to oo OO O cK oo 卜 oo wo in oo wn 卜 vn oo 1—Ή 添加量(at%) τ—t cs τ—H <N T™* OJ CN CO i—H OJ — OJ CN cn <N cn 1—1 <N CN 1~* OJ 添加元素 s 5 CD 〇 CO 構成元素(at%) 24.5 24.5 VO <N <N c^l <N CN CN <N <N Oi 23.5 24.5 cn <N (N CN CN 03 <N <N 1 22.5 22.5 23.5 | 22.5 <N 05 24.5 | 23.5 24.5 CN (N (N CN 69.9 OO s OO VO oo S O s cK s L T〇5_l O VO r-h O O ο r—H 〇 o O ON v〇 | 69.5 〇 Τ—H VO 03 £ wn CO to VO cn vn v〇 wn 寸 cn to in 寸 m t/S 寸 V〇 寸 in 寸 in v〇 vd CO to CO <N (N to to IQ in — in wo in vn wo vn vn CN 一 實施例21 實施例22 實施例23 實施例24 實施例25 實施例26 實施例27 實施例28 實施例29 實施例30 實施例31 實施例32 辑 * 實施例34 實施例35 丨 實施例36 實施例37 實施例38 |實施例39 j實施例40 實施例41 |實施例42 比較例1 比較例2 |比較例3 比較例4 (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(210X297公釐) -47 - 564412 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(45 ) 又,這些添加元素之添加量如太多,有使結晶化速度 變慢之傾向,使重複特性變差。又,原子半徑比In、Sb小 ,鍵能愈大之元素,其傾向愈強。因此,在最適當之添加 量之範圍內,對於I η量之添加量經常以少者爲佳。特別是 ,In量少之情形,有顯著降低結晶化速度之元素。另一方 面,Ti、Pb以及Bi有提高結晶化速度之效果,如太多,重 複記錄特性雖好,但是結晶化溫度顯著降低,有降低保存 信賴性之傾向。 又,在實施形態2中,在將如上述之記錄層使用於記 錄媒體之情形,下部保護層、上部保護層係由ZnS與Si〇2 形成,可以合適設置其之莫耳比ZnS:Si〇2爲50: 50〜90:10之 範圍,最好莫耳比80 : 20附近之保護層。又,因應需要, 也可以適當使用ZnS-SiCh系之複合物以外之氧化物、氮化 物或其之混合物。 其之下部保護層的膜厚由保持記錄層之耐環境保護性 、不使製膜時之由於熱的應力緩和而由基板剝離之觀點’ 其之膜厚以25〜250nm之範圍爲佳。又,關於上部保護層’ 係抑制重複記錄時由於熱應力之增加而變形、密接性之降 低、記錄時之熱傳導率不使記錄感度降低之程度的膜厚’ 其之膜厚以5〜25nm之範圍爲佳。 又,反射層通常以低廉者爲合適,雖使用A1或Ag等 之金屬或其合金,但是因應需要,也可以適當使用熱傳導 率比保護層高,熱傳導率更高之金屬或其合金。又’其膜 厚可以適當使用50〜200ηηι之範圍。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -48 - (請先閲讀背面之注意事項再填寫本頁) 訂 564412 經濟部智慧財產局員工消費合作社印製 A7 ___ B7 __ 五、發明説明(46 ) 由以上,依據實施形態2之相變化型光資訊記錄媒體例 如當成可以重寫之記錄媒體,波長在400〜680nm之範圍可 以適當記錄再生。又,爲了提升其之記錄密度,更藉由使 物鏡之孔徑數値在0.60以上可以容易使之成爲可能。 又,記錄通常有記錄於基板之溝的情形、記錄於溝以 及溝與溝之間的島之情形之兩者。總之爲了提升密度、容 量,藉由使基板之軌距變窄而成爲可能。節距在0.8 // m即 可。溝的深度以15nm〜60nm爲佳。如在15nm以下,無法有 安定之追跡。 由以上,關於使用依據實施形態2之光資訊記錄媒體 的記錄方法,於圖5顯示在高速、高密度之記錄再生的特性 。由圖5可以明白地,照射在記錄媒體之雷射光的發光脈衝 .具有記錄、抹除、偏壓之3種準位,而且,記錄、抹除功 率比再生功率高,進而,偏壓功率在再生功率以下。偏壓 功率係照射記錄功率後之功率,係使形成非晶質相所必要 者。此脈衝進而由前端脈衝(1脈衝)、複數脈衝列、冷 卻脈衝(1脈衝)所形成,使記錄標記之邊緣部成爲陡峭 之同時,需要使記錄之位置、記錄之標記的長度正確。此 種記錄發光脈衝適合於高速記錄,使記錄層之材料、組成 成爲最適當者。 其結果,記錄頻率爲20MHz製80MHz程度,記錄功率 最大爲15mW。記錄再生線速可以對應CLV或CAV之兩方 ,最大線速爲15m/s之程度,更好爲3.0m/s製12m/s。 以下,雖以實施形態2之具體的實施例21〜42做說明 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -49 - (請先閱讀背面之注意事項再填寫本頁) 564412 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(47 ) ,但是實施形態2並不限定於這些。 實施例21〜42 使用基板之溝距0.74 // m、溝寬0· 3 // m、溝深3 5nm、厚 度0.6mm之聚碳酸酯製基板,在其上藉由濺鍍法積層下部 保護層、記錄層、上部保護層以及反射層之各層。對下部 保護層施以莫耳組成比(mol%)爲ZnS:Si〇2 = 80:20之保護 膜,其之膜厚爲75nm。又,於表2顯示記錄層之構成元素 以及添加元素之組成比(at· % )。又,記錄層之膜厚都設爲 膜厚20nm。又,關於上部保護層,與下部保護層同樣地設 爲ZnS:Si〇2 = 80:20 (mol%),膜厚設爲15nm。又,反射層 係使用A1合金,厚度設爲120nm。進而,塗佈紫外線硬化 樹脂,使用沒有膜之基板貼合,製作厚度1.2mm之實施形 態2之記錄媒體。 接著,利用LD,以指定之條件初期化後,使記錄層結 晶化。記錄再生係使用波長650nm、物鏡ΝΑ0.65之拾取頭, 藉由CLV對於各記錄層以表2所示之線速,記錄密度成爲 0.265 // m/bit地加以記錄。 又,記錄資料之調制方式係(8、1 6 )調制。其之記錄 功率最大爲15mW,抹除功率爲記錄功率之0.45〜0.55倍, 偏壓功率爲〇.5.mW,再生功率爲〇.8mW。 在此種條件下,量測對於一次記錄之重複記錄1 〇〇〇〇次 後的抖動增加量以及80°C、85%RH、1000小時後之抖動增加 量。又,抖動係以視窗寬幅去除之値,單位爲%。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 50 - (請先閱讀背面之注意事項再填寫本頁) 564412 A7 --------B7 五、發明説明(48 ) 【表2】 添加元素 鍵能 原子半徑 X --—-- kJ/mol nm B -------- 350 0.085 A1 ----- 270 0.125 T1 <200 0.19 C <200 0.07 Si 450 0.11 Ge 460 0.125 Sn 360 0.145 Pb 250 0.18 P 300 0.1 As <200 0.115 Bi 230 0.16 (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 構成元素 鍵能 原子半徑 kJ/mol nm Ag 196 0.16 In 220 0.155 Sb 280 0.145 該結果由表2可以明白地,實施例2 1〜42與沒有添加 之習知例(比較例1〜4 )比較,可以不樣低重複記錄次數 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ^51 - ' 564412 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(49 ) 地提升保存信賴性。又’特別是在添加2at%之添加元素Ge 之情形,知道重複次數良好,特別是信賴性大幅提升。又 ,在以Ag、In、Sb以及Te爲主構成元素之記錄層中,藉 由使這些添加元素之添加量爲最適當,更高速之記錄成爲 可能,重複記錄特性提升,可以發揮提升保存信賴性之效 果。 由以上,如依據實施形態2,相變化型光資訊記錄媒 體之特徵爲:其之記錄層係在主構成元素之AglnSbTe系添 加滿足特定之條件之由週期表Illb、IVb以及5b所選擇之添 加兀素’而且滿足(Again彡SbrXe ) 之原子組成比 之關係式之記錄層。 藉由此,與習知之相變化型光資訊記錄媒體相比,能 夠提供:可以在高密度、高線速度進行記錄,而且,即使 重複記錄,特性也不會劣化,信賴性高之相變化型光資訊 記錄媒體。 又,可以發揮此種特性之相變化型光資訊記錄媒體於 其之利用領域爲大容量光檔案、數位視頻光碟等所期待。 【實施形態3】 接著,參考圖面說明實施形態3之光資訊記錄媒體的 構成。如圖6之剖面圖所示般地,在此光資訊記錄媒體中, 係在基板2 1上依序設置由電介質形成之下部耐熱保護層 22、記錄層23、由電介質形成之上部耐熱保護層24、反射 層25。耐熱保護層不一定在設計在記錄層之兩側,但是在 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) -52 - (請先閲讀背面之注意事項再填寫本頁) 564412 經濟部智慧財產局員工消費合作社印製 A7 __ B7 五、.發明説明(50 ) 基板爲聚碳酸酯樹脂之類的耐熱性低之材料的情形,期望 設置下部耐熱保護層。 基板2 1之材料通常爲玻璃、陶瓷或樹脂,樹脂基板在 成形性、成本之觀點爲合適。代表之樹脂的具體例爲:聚 碳酸酯樹脂、丙烯基樹脂、環氧樹脂、聚苯乙烯樹脂、丙 烯腈苯乙烯共聚物樹脂、聚乙烯樹脂、聚丙烯、矽系樹脂 、氟系樹脂、ABS樹脂、尿烷樹脂等,但是以加工性、光 學特性等之觀點,以聚碳酸酯爲佳。又,基板之形狀並不 限定於碟狀,也可以爲卡狀或薄板狀。 耐熱保護層,即電介質層係使用(ZnS ) SQ . (SiCh)2。, 藉由濺鍍法進行膜形成。此電介質層具有作爲耐熱保護層 之機能與作爲光干涉層之機能之故,需要最大限度活用這 些機能。因此,膜厚設爲200A〜3000A,最好爲3 50A〜 2000A。在未滿200A之情形,失掉作爲耐熱保護層之機能, 又,如超過3000A,容易產生界面剝離。 又,實施形態3之記錄層一般係藉由濺鍍法以進行膜 形成,其膜厚爲100A〜1 000A,理想爲200A〜3 50A。如比 1 00A薄,光吸收能降低,失掉作爲記錄層之機能。另一方 面,如比1 000A厚,透過光變少之故,無法期待干涉效果。 反射層例如以A1合金形成。其之膜形成係藉由濺鍍法進行 。膜厚爲500A〜2000A,理想爲700A〜1 500A。 以下’藉由實施例5 1〜實施例5 5更具體說明實施形態 (請先閱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) 564412 A7 B7 五、發明説明(51) 實施例5 1 (請先閲讀背面之注意事項再填寫本頁) 在形成軌距0.7// m、深度600A之溝的厚度0.6mm、直徑 120// m之聚碳酸酯基板上,依序藉由濺鍍法積層圖6所示之 下部耐熱保護層、記錄層、上部耐熱保護層以及反射層, 製作相變化型光資訊記錄媒體。 此處,耐熱保護層係使用(ZnS ) 8〇 · (Si〇2)2〇,反射層 係使用Al-Ti合金。又,下部耐熱保護層之膜厚爲1200A, 上部耐熱保護層之膜厚爲350A,反射層之膜厚爲800A。 記錄層之膜厚爲210A,以以下之濺鍍條件進行DC濺鍍 。又,記錄層用之?巴組成比爲Ag5ln7Sb6GTe28。 投入電力:0.5kW 氣體流量:Ai·、15sccm 成膜氣體壓力:1.0mTorr 經濟部智慧財產局員工消費合作社印製 基板溫度:25°C開始,以30°C/min之速率昇溫 又,爲了解析所獲得之光資訊記錄媒體之記錄層之構 造,另外準備該解析用之玻璃基板。記錄層之初期結晶化 係以高輸出半導體雷射進行。又,記錄層之構造解析,特 別是相變化記錄材料之構成元素的配位數、結晶構造,係 使用X射線繞射、電子射線繞射、EX APS (廣域X射線吸收 微細構造)等。將其結果顯示於表4。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -54 - 564412 A7 B7 結晶構造 Te之空孔 率(% ) NaCl 型 66 五、發明説明(52 )Evaluation result 〇〇〇〇〇〇〇〇〇 〇〇〇〇 jitter characteristics (σ / T) (%) DOW 1000 CN ON CO OO o 〇 \ OO OO CNl On CO ON < NI OO CO OO csi OO l〇ON C < 1 ON OO ON Early stage 〇〇 卜 r—H OO OO 寸 〇OO VD 卜 ot— CO CN VO csi OO OO 寸 OO Recording linear velocity (m / s) Ό On Ό 〇 \ 14.4 14.4 < NI ON τ—H 〇b o b o b b o inch rH 24.0 o r- 14.0 煺 5 rogue called 鹋 OO 〇 \ 10.5 CO i '< ο un rH OO rH Csl 1 / Ί σ \ 10.0 un VO i— H cn CN o On υη CO 1 (Evaluation wavelength (nm) 〇OO 〇 〇OO r- 〇OO 〇OO 〇OO 〇OO 〇 o VO VO o VO Ό o 〇〇inch〇〇inch production condition recording layer Composition < D Η OO CNl Csl < N C < l inch C < 1 cs C < l 〇CO CO CNl inch OQ CO CO CNl csi VO < N CO cs GO CNl VO inch VO OO ON VO inch r- inch VO ο OO OO Cr vo o cd Ο oo inch ON CO in ο o CO OO 03 VO cn h-1 VO o inch rH o O CO oo < D ot—H inch or—H τ—H oo CN CO o r- < 〇CO < CO o VD 1 < o rH CO rH CN o τ-H o gauge (Mm) inch r—H inch rH inch rH inch τ—H inch H 0.74 0.74 0.74 0.74 0.74 (N 〇CNl o single board single board single board single board single board lamination 1 Fitting Fitting Fitting Fitting Booth 1 »5 CNl rH CNl r—H CN | CN) τ—H c〇τ—H Ό 〇oooo VD 〇o CO Inch v〇OO as o rH rH τ— H CN CO rH Inch H (Please read the notes on the back before filling in this tribute), 11 Fresh paper sizes are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -43-564412 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the consumer cooperative A7 _____B7 _V. Description of the invention (41) [Embodiment 2] The phase-change type optical information recording medium according to Embodiment 2 uses Ag, In, Sb, and Te as main constituent elements, and is further characterized by Add at least one specific element selected from Groups 111b, IVb and 5b of the periodic table. Therefore, compared with the conventional optical information recording medium of phase change type, it has sufficient media characteristics at high line speed and high density recording, especially the phase with excellent storage reliability after repeated recording, initial stage and after repeated recording. Hereinafter, the change recording material 0 will be described in more detail. The optical information recording medium according to the second embodiment is a layer in which a lower protective layer, a recording layer, an upper protective layer, and a reflective layer are sequentially laminated on a substrate. The recording layer is composed of Ag, In, Sb, and Te, which have already been described. Furthermore, at least one specific element selected from Groups 111b, IVb, and 5b of the periodic table is added thereto. In addition, the recording layer in the medium after film formation is changed to a so-called initial phase from an amorphous phase to a crystalline phase, thereby forming a crystalline phase. Here, in Embodiment 2, the atomic ratio of each of the main constituent elements Ag, In, Sb, and Te preferably has a relationship of the following formula (2): (Agaln ^ Sbr) 1-5 Te ό (2) (In the formula, 0.1 <. ≪ 10, 1 $ ^^ 20, 90 $ 7 < 100, 0 + y8 + r = 100, 0.2S5 $ 0.35.) When expressed, the above When the recording layer forms a crystalline phase, a NaCl type structure is formed uniformly. Here, in Embodiment 2, it is preferable that in this NaCl-type crystal phase, Ag, In, and Sb are located on the side corresponding to Na, Te is located on the side corresponding to C1, and Te does not occupy 100% on this side. It has holes and has excellent volatility. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) "44-One (Please read the precautions on the back before filling this page) 564412 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Consumption cooperatives print B7 V. The initial stage of invention description (42) and the tendency to repeat recording characteristics. With this, it becomes a eutectic composition that does not easily cause composition changes even if the phase changes of the amorphous phase and the crystalline phase are repeated for recording. In addition, for high-speed crystallization at a higher line speed, it is appropriate to maintain this state while increasing Sb and In and decreasing Ag. In the second embodiment, regarding the crystallization rate, first, Sb Compared with Te, the atomic radius is large. In the amorphous phase, the coordination number for Te bonds is about 3, which is easy to cause crystallization, and the crystallization speed is fast. Moreover, it will also cause at a relatively low temperature. So, the amount of Sb In many cases, the storage reliability is significantly deteriorated. In addition, In has a larger atomic radius than Sb, and the bond coordination number is also in amorphous, higher than Sb, about 3.5 coordination, and the crystallization speed is fast. Although the details are not clear, it will crystallize at a higher temperature at a higher temperature, and it is difficult to cause crystallization at a temperature of 70 to 80 ° C. Or it is considered that In has a function that prevents crystallization by Sb Regarding its crystallization rate, although the atomic radius of Ag is larger than Te, the coordination number is about 2 and the amorphous phase is stable, so the crystallization rate is relatively slow. Also, in high-speed recording, Even if repeated recording is performed, it is not easy to cause composition changes, and high-speed crystallization is required to ensure the most appropriate composition range that can ensure the reliability of storage. However, even within the above composition range, the characteristics of all parts are limited. In particular, there is a limit. Reliability in preservation is not easily ensured in high-speed recording. 'Therefore, from the viewpoint of the factual relationship as described above, the reliability of the recording medium is assured. It has excellent repetitive recording characteristics in high-speed recording. Use Chinese National Standard (CNS) A4 specification (210X297 mm) -45-(Please read the precautions on the back before filling this page) 564412 A7 ____ B7 _ V. Description of the invention (43) Ensure the stability of the amorphous phase environment As an added element to the above main constituent elements, at least one element of Groups Illb, IVb, and 5b of the periodic table can be appropriately added in Embodiment 2. (Please read the precautions on the back before filling this page) For these additional elements, the bond energy of the constituent element Te is 200 k; f / mol or more, or in order to increase the crystallization speed, the atomic radius of these additional elements is preferably from 0.1 nm to 0.20 nm. In addition, the bond can be as large as possible, and it is preferable that the bond is more than 250 k / mol. In addition, even if it is made large, it is preferable to use 500 kJ / mol or less because a large amount of energy is required to change the phase. Furthermore, the element with a smaller atomic weight among the Illb, IVb, and 5b groups of the periodic table of the element has a tendency to increase the crystallization temperature. From the viewpoint of preserving reliability, it is best to add An element having a smaller atomic weight than Sb or In, which is a constituent element. Therefore, among these additional elements, for example, B, Al, Ti, C, Si, Ge, Sn, Pb, P, As, and Bi, etc., the atomic radius and the bond energy to Te are shown in Table 3. From this table, it is preferred that Al, Si, Ge, Sn, P, and the like be added as appropriate. Among these, Ge is particularly suitable. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Employees 'Cooperatives This paper is printed in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) -46-564412 A7 B7 V. Description of the Invention (44) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics [E skimming] Jitter increase after storage test (%) cn cn inch cn v〇cn i-H t-H cn inch vn cn inch inch inch inch cn inch inch jitter increase after repeated recording (%) cn CO inch in cn < N r— < < N < N < N 1—Η Ό c4 (N cn cn Ol un ϊ—H cn cs Recording line speed (m / s) oo oo τ—H Τ—H σ \ to oo OO O cK oo Bu oo wo in oo wn bu vn oo 1—Ή Addition amount (at%) τ—t cs τ—H < NT ™ * OJ CN CO i—H OJ — OJ CN cn < N cn 1-1 < N CN 1 ~ * OJ Additive element s 5 CD 〇CO Constituent element (at%) 24.5 24.5 VO < N < N c ^ l < N CN CN < N < N Oi 23.5 24.5 cn < N (N CN CN 03 < N < N 1 22.5 22.5 23.5 | 22.5 < N 05 24.5 | 23.5 24.5 CN (N (N CN 69.9 OO s OO VO oo SO s cK s LT〇5_l O VO rh OO ο r—H 〇o O ON v〇 | 69.5 〇Τ—H VO 03 £ wn CO to VO cn vn v〇wn inch cn to in inch mt / S inch V〇 inch in inch in v〇vd CO to CO < N (N to to IQ in — in wo in vn wo vn vn CN Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Series * Implementation Example 34 Example 35 丨 Example 36 Example 37 Example 38 | Example 39 j Example 40 Example 41 | Example 42 Comparative Example 1 Comparative Example 2 | Comparative Example 3 Comparative Example 4 (Please read the note on the back first Please fill in this page again for this matter) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -47-564412 A7 B7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (45) If the amount of the element is too much, it tends to slow down the crystallization rate and deteriorate the repeatability. In addition, the element with a smaller atomic radius than In and Sb, and the larger the bond energy, the stronger the tendency. Therefore, in the range of the most appropriate addition amount, the addition amount of I η amount is always preferably smaller. In particular, when the amount of In is small, there are elements that significantly reduce the crystallization rate. On the other hand, Ti, Pb, and Bi have the effect of increasing the crystallization rate. If it is too much, the repeated recording characteristics are good, but the crystallization temperature is significantly reduced, which tends to reduce the reliability of storage. In the second embodiment, when the above-mentioned recording layer is used for a recording medium, the lower protective layer and the upper protective layer are formed of ZnS and Si0, and the molar ratio ZnS: Si can be appropriately set. 2 is a protective layer in the range of 50: 50 ~ 90: 10, preferably around a molar ratio of 80:20. If necessary, oxides, nitrides, or mixtures thereof other than ZnS-SiCh-based composites can also be suitably used. The film thickness of the lower protective layer is from the viewpoint of maintaining the environmental resistance of the recording layer and preventing the substrate from peeling off due to thermal stress during film formation. The film thickness is preferably in the range of 25 to 250 nm. In addition, the upper protective layer is a film thickness that suppresses deformation due to an increase in thermal stress during repeated recording, a decrease in adhesion, and a thermal conductivity during recording that does not reduce the recording sensitivity. The film thickness is 5 to 25 nm. The range is better. In addition, the reflective layer is generally suitable as a low-cost one. Although a metal such as A1 or Ag or an alloy thereof is used, a metal or an alloy having a higher thermal conductivity than the protective layer may be appropriately used as required. The film thickness can be appropriately used in the range of 50 to 200 nm. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -48-(Please read the notes on the back before filling out this page) Order 564412 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___ B7 __ 5 (46) From the above, the phase-change optical information recording medium according to the second embodiment is, for example, a rewritable recording medium, and a wavelength in a range of 400 to 680 nm can be appropriately recorded and reproduced. In addition, in order to increase the recording density, it is possible to make it easier by setting the aperture number of the objective lens to 0.60 or more. In addition, the recording usually includes both the case of recording on a groove of a substrate, the case of recording on a groove, and the case of an island between a groove and a groove. In short, in order to increase the density and capacity, it is possible to narrow the track pitch of the substrate. The pitch is 0.8 // m. The depth of the groove is preferably 15 nm to 60 nm. If it is below 15nm, there is no stable trace. From the above, the recording method using the optical information recording medium according to the second embodiment shows the characteristics of high-speed, high-density recording and reproduction in FIG. 5. It can be clearly seen from FIG. 5 that the light emitting pulses of the laser light irradiated on the recording medium have three levels of recording, erasing, and bias, and the recording and erasing power is higher than the reproduction power. Regenerative power below. The bias power is the power after the recording power is irradiated, and it is necessary to form an amorphous phase. This pulse is further formed by a leading pulse (1 pulse), a complex pulse train, and a cooling pulse (1 pulse). To make the edge of the recording mark steep, it is necessary to make the recording position and the length of the recording mark correct. Such a recording light emission pulse is suitable for high-speed recording, and the material and composition of the recording layer are most suitable. As a result, the recording frequency was approximately 80 MHz at 20 MHz, and the maximum recording power was 15 mW. Recording and reproducing line speed can correspond to both CLV or CAV. The maximum line speed is about 15m / s, and more preferably 3.0m / s and 12m / s. In the following, although specific examples 21 to 42 of the second embodiment are used for explanation, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -49-(Please read the precautions on the back before filling this page) 564412 The A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The Invention Description (47), but Embodiment 2 is not limited to these. Examples 21 to 42 A substrate made of polycarbonate with a groove pitch of 0.74 // m, a groove width of 0.3 m // a groove depth of 35 nm, and a thickness of 0.6 mm was used, and the lower part of the substrate was protected by a sputtering method. Layers, recording layers, upper protective layers, and reflective layers. A protective film with a molar composition ratio (mol%) of ZnS: SiO2 = 80:20 was applied to the lower protective layer, and its film thickness was 75 nm. Table 2 shows composition ratios (at ·%) of constituent elements and additional elements of the recording layer. The film thickness of the recording layer was set to 20 nm. The upper protective layer was set to ZnS: SiO2 = 80:20 (mol%) in the same manner as the lower protective layer, and the film thickness was 15 nm. The reflective layer is made of A1 alloy and has a thickness of 120 nm. Furthermore, an ultraviolet curable resin was applied and bonded using a substrate without a film to produce a recording medium of Embodiment 2 having a thickness of 1.2 mm. Then, the recording layer is crystallized after initializing it under specified conditions using LD. The recording and reproduction system uses a pickup head with a wavelength of 650 nm and an objective lens NA 0.65, and records each recording layer at a linear velocity shown in Table 2 by CLV at a recording density of 0.265 // m / bit. The modulation method of the recorded data is (8, 16) modulation. The maximum recording power is 15mW, the erasing power is 0.45 to 0.55 times the recording power, the bias power is 0.5.mW, and the reproduction power is 0.8mW. Under these conditions, the amount of jitter increase after repeated recording of 10,000 times for one recording and the amount of jitter increase after 80 ° C, 85% RH, and 1000 hours were measured. In addition, the jitter is removed by the width of the window, and the unit is%. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) _ 50-(Please read the precautions on the back before filling this page) 564412 A7 -------- B7 V. Description of the invention (48 ) [Table 2] Adding element bond energy Atomic radius X ----- kJ / mol nm B -------- 350 0.085 A1 ----- 270 0.125 T1 < 200 0.19 C < 200 0.07 Si 450 0.11 Ge 460 0.125 Sn 360 0.145 Pb 250 0.18 P 300 0.1 As < 200 0.115 Bi 230 0.16 (Please read the precautions on the back before filling this page) Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumption Cooperative, Printed Key Elements Atomic radius kJ / mol nm Ag 196 0.16 In 220 0.155 Sb 280 0.145 This result can be clearly understood from Table 2. In Example 2, 1 to 42 is compared with the conventional example (Comparative Examples 1 to 4) without addition, which may not be as low. Number of repeated recordings This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 51-'564412 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (49) To improve the reliability of preservation. Also, especially in the case where Ge is added at 2at%, it is known that the number of repetitions is good, and especially the reliability is greatly improved. In addition, in the recording layer mainly composed of Ag, In, Sb, and Te, by making the addition amount of these added elements the most appropriate, higher-speed recording is possible, the repeated recording characteristics are improved, and the reliability of preservation can be exerted. Sexual effects. From the above, according to Embodiment 2, the phase-change optical information recording medium is characterized in that its recording layer is added to the AglnSbTe system of the main constituent element, and the addition selected by the periodic table Illb, IVb, and 5b to meet specific conditions is added.素素 'and a recording layer that satisfies the relationship of the atomic composition ratio (Again 彡 SbrXe). As a result, compared with the conventional phase-change type optical information recording medium, it can provide a high-density, high-reliability phase-change type that can record at a high density and a high linear velocity. Optical information recording media. In addition, a phase-change type optical information recording medium that can exhibit such characteristics is expected to be used in large-capacity optical files, digital video discs, and the like. [Embodiment 3] Next, the configuration of an optical information recording medium according to Embodiment 3 will be described with reference to the drawings. As shown in the cross-sectional view of FIG. 6, in this optical information recording medium, a lower heat-resistant protective layer 22 made of a dielectric, a recording layer 23, and an upper heat-resistant protective layer made of a dielectric are sequentially disposed on a substrate 21. 24. Reflective layer 25. The heat-resistant protective layer is not necessarily designed on both sides of the recording layer, but the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) applies to this paper size -52-(Please read the precautions on the back before filling this page) 564412 Printed A7 __ B7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (50) When the substrate is a low heat-resistant material such as polycarbonate resin, it is desirable to provide a lower heat-resistant protective layer. The material of the substrate 21 is usually glass, ceramic or resin, and a resin substrate is suitable from the viewpoints of moldability and cost. Specific examples of the resin are: polycarbonate resin, acrylic resin, epoxy resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyethylene resin, polypropylene, silicon resin, fluorine resin, ABS Resin, urethane resin, etc., but from the viewpoint of processability, optical characteristics, etc., polycarbonate is preferred. The shape of the substrate is not limited to a dish shape, and may be a card shape or a thin plate shape. (ZnS) SQ. (SiCh) 2 is used as the heat-resistant protective layer, that is, the dielectric layer. Film formation is performed by a sputtering method. Because this dielectric layer has a function as a heat-resistant protective layer and a function as a light interference layer, it is necessary to make the most of these functions. Therefore, the film thickness is set to 200A to 3000A, and preferably 3 50A to 2000A. When it is less than 200A, the function as a heat-resistant protective layer is lost. If it exceeds 3000A, interfacial peeling is likely to occur. The recording layer of the third embodiment is generally formed by a sputtering method, and the film thickness is 100A to 1,000A, and preferably 200A to 350A. If it is thinner than 100A, the light absorption energy is reduced, and the function as a recording layer is lost. On the other hand, if it is thicker than 1,000A, the transmitted light will be reduced, and the interference effect cannot be expected. The reflective layer is formed of, for example, an Al alloy. The film formation is performed by a sputtering method. The film thickness is 500A to 2000A, and preferably 700A to 1,500A. In the following, the embodiment will be described in more detail by way of Example 5 1 to Example 5 (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 564412 A7 B7 V. Description of the invention (51) Example 5 1 (Please read the precautions on the back before filling this page) When forming a groove with a gauge of 0.7 // m, a depth of 600A, a thickness of 0.6mm, and a diameter of 120 // m On the polycarbonate substrate, the lower heat-resistant protective layer, the recording layer, the upper heat-resistant protective layer, and the reflective layer shown in FIG. 6 were sequentially laminated by sputtering to produce a phase-change optical information recording medium. Here, the heat-resistant protective layer is made of (ZnS) 80 (SiO2) 20, and the reflective layer is made of Al-Ti alloy. The film thickness of the lower heat-resistant protective layer is 1200 A, the film thickness of the upper heat-resistant protective layer is 350 A, and the film thickness of the reflective layer is 800 A. The film thickness of the recording layer was 210 A, and DC sputtering was performed under the following sputtering conditions. Also, what is the recording layer used for? The Palestinian composition ratio is Ag5ln7Sb6GTe28. Input power: 0.5kW Gas flow rate: Ai ·, 15sccm Film-forming gas pressure: 1.0mTorr Printed substrate temperature of employee consumer cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs: Starting at 25 ° C, heating up at a rate of 30 ° C / min. A structure of a recording layer of the obtained optical information recording medium was prepared, and a glass substrate for analysis was prepared. The initial crystallization of the recording layer is performed by a high-output semiconductor laser. The structural analysis of the recording layer, especially the coordination number and crystal structure of the constituent elements of the phase change recording material, uses X-ray diffraction, electron-ray diffraction, and EX APS (Wide Area X-Ray Absorption Microstructure). The results are shown in Table 4. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -54-564412 A7 B7 Crystal structure Te porosity (%) NaCl type 66 V. Description of the invention (52)
ΐ ^ A 配位數(f 卜於Te) 非結晶狀態 結晶狀態 Ag 1.8 4.1 In 3.5 3.8 Sb 2.9 2.4 關於光資訊記錄媒體之信_特性,係利用波長635ηηι之 光源,以記錄線速度3.5m/s、EFM隨機圖案進行覆寫之重複 g己錄’以該時之3 T信號之抖動記錄公寓依存性進行評估。 再生時之線速爲3.5m/s。在表5顯示其結果。又,圖7係顯 示X射線繞射光譜。 (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 【表5】 記錄功率(mW) 8 9 10 11 12 13 抖動(n s ) 覆寫次數 1 8.5 8.3 8.0 7.8 7.7 7.6 1000 8.5 8.4 8.2 8.0 8.0 7.9 3000 8.7 8.6 8.5 8.3 8.4 8.4 5000 8.8 8.8 8.8 8.8 8.9 8.9 10000 9.0 9.0 9.1 9.1 9.2 9.3 1 5000 9.3 9.3 9.4 9.5 9.6 9.8 20000 9.6 9.6 9.8 9.9 10.1 10.3 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -55 - 564412 A7 B7 五、發明説明(53 ) 又,於此表中,8、9、10、…係記錄功率(m w ) ,1、 1000、3000、…係覆寫次數。又,8_5、8.3、8.0、…係抖動 (ns)(以下之表7、9、11、13、15、17也相同)。 實施例52 記錄層之成膜條件之基板溫度爲開始,以1(rc / min速率使之昇溫以外,與實施例5 1完全相同地製作光資訊 記錄媒體。將該時之記錄層的構造解析結果顯示於表6,將 X射線繞射光譜顯示於圖8,將信號特性顯示於表7 $^ ^ A coordination number (f in Te) amorphous state crystalline state Ag 1.8 4.1 In 3.5 3.8 Sb 2.9 2.4 The characteristics of the optical information recording medium are based on the use of a light source with a wavelength of 635 ηη at a recording linear velocity of 3.5 m / s, EFM random pattern is overwritten repeatedly g Ji Lu 'Evaluation of apartment dependency with jitter of 3 T signal at that time. The linear speed during regeneration is 3.5 m / s. The results are shown in Table 5. Fig. 7 shows an X-ray diffraction spectrum. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 5] Recording power (mW) 8 9 10 11 12 13 Jitter (ns) Number of overwrites 1 8.5 8.3 8.0 7.8 7.7 7.6 1000 8.5 8.4 8.2 8.0 8.0 7.9 3000 8.7 8.6 8.5 8.3 8.4 8.4 5000 8.8 8.8 8.8 8.8 8.9 8.9 10000 9.0 9.0 9.1 9.1 9.2 9.3 1 5000 9.3 9.3 9.4 9.5 9.6 9.8 20000 9.6 9.6 9.8 9.9 10.1 10.3 This paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) -55-564412 A7 B7 V. Description of invention (53) In this table, 8, 9, 10, ... are recording power (mw), 1, 1000, 3000, ... is the number of overwrites. In addition, 8_5, 8.3, 8.0, ... are jitters (ns) (the same applies to the following tables 7, 9, 11, 13, 15, and 17). Example 52 The substrate temperature of the film formation conditions of the recording layer was started, and an optical information recording medium was produced in exactly the same manner as in Example 51 except that the substrate was heated at a rate of 1 (rc / min). The structure of the recording layer at this time was analyzed The results are shown in Table 6, the X-ray diffraction spectrum is shown in Figure 8, and the signal characteristics are shown in Table 7.
Te之空孔 率(%) 65 (請先閱讀背面之注意事項再填寫本頁)Te porosity (%) 65 (Please read the notes on the back before filling in this page)
【表6】 配位數(對於Te) 非結晶狀態 結晶狀態 Ag 1.7 4.0 In 3.3 3.6 Sb 2.8 2.2 結晶構造[Table 6] Coordination number (for Te) Amorphous state Crystal state Ag 1.7 4.0 In 3.3 3.6 Sb 2.8 2.2 Crystal structure
NaCl 型 經濟部智慧財產局員工消費合作社印製 準 標 家 國 國 -中 用 |適 尺 一張 -紙 本 56 564412 A7 B7 五、發明説明(54 ) 【表7】 記錄功率(mW) 8 9 10 11 12 13 抖動(ns) 覆寫次數 1 8.5 8.2 8.0 7.9 7.8 7.7 1000 8.5 8.3 8.2 8.1 8.0 7.9 3000 8.7 8.6 8.5 8.4 8.4 8.3 5000 8.9 8.8 8.8 8.8 8.9 8.9 10000 9.1 9.1 9.2 9.2 9.3 9.4 1 5000 9.4 9.4 9.5 9.6 9.7 9.8 20000 9.7 9.7 9.8 10.1 10.2 10.4 實施例53 記錄層之成膜條件之基板溫度爲25 °C開始,以50 °C / min速率使之昇溫以外,與實施例5 1完全相同地製作光資訊 記錄媒體。將該時之記錄層的構造解析結果顯示於表8,將 X射線繞射光譜顯示於圖9,將信號特性顯示於表9。 (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8】 配位數(對於 Te) 結晶構造 Te之空孔 率(% ) 非結晶狀態 結晶狀態 Ag 2.0 4.3 NaCl 型 67 In 3.6 4.0 Sb 3.1 2.6 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -57- 564412 A7 B7五、發明説明(55 ) 【表9】 記錄功率(mW) 8 9 10 11 12 13 抖動(n s ) 覆寫次數 1 8.3 8.2 7.9 7.7 7.6 7.5 1000 8.4 8.3 8.1 7.9 7.9 7.8 3000 8.6 8.5 8.4 8.2 8.2 8.3 5000 8.7 8.7 8.6 8.6 8.7 8.7 10000 8.9 8.9 8.9 9.0 9.1 9.2 1 5000 9.2 9.2 9.3 9.4 9.5 9.7 20000 9.5 9.5 9.7 9.8 10.0 10.2 實施例54 設記錄層之靶組成爲Ag3In1C)Sb63Te24以外,與實施例51 完全相同地製作光資訊記錄媒體。將該時之記錄層的構造 解析結果顯示於表10,將X射線繞射光譜顯示於圖10,將 信號特性顯示於表11 〇 (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 【表10】 配位數( f 於 Te) 結晶構造 Te之空孔 率(% ) 非結晶狀態 結晶狀態 Ag 1.5 3.8 NaCl 型 69 In 3.4 3.6 Sb 2.7 2.3 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐) -58- 564412 A7 B7 五、發明説明(56 ) 【表 :1】 記錄功率(mW) 8 9 10 11 12 13 抖動(ns) 覆寫次數 1 8.4 8.3 8.1 7.8 7.7 7.6 1000 8.4 8.4 8.2 8.0 8.0 7.9 3000 8.6 8.6 8.4 8.3 8.3 8.3 5000 8.8 8.8 8.7 8.7 8.7 8.8 10000 9.0 9.0 9.0 9.1 9.2 9.3 1 5000 9.3 9.3 9.4 9.5 9.6 9.8 20000 9.6 9.6 9.8 9.9 10.1 10.3 實施例55 設記錄層之靶組成爲Ag8In3Sb68Te21以外,與實施例51 完全相同地製作光資訊記錄媒體。將該時之記錄層的構造 解析結果顯示於表1 2,將X射線繞射光譜顯示於圖1 1,將 信號特性顯示於表1 3。 (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 【表12】 配位數(t; f 於 Te) 結晶構造 Te之空孔 率(%) 非結晶狀態 結晶狀態 Ag 1.8 3.9 NaCl 型 73 In 3.1 3.7 Sb 2.7 2.5 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) -59- 564412 B7 五、發明説明(57 ) 【表13】 記錄功率(mW) 8 9 10 11 12 13 抖動(ns) 覆寫次數 1 8.4 8.3 8.2 7.9 7.8 7.7 1000 8.4 8.4 8.2 8.1 8.1 8.0 3000 8.6 8.6 8.4 8.4 8.4 8.4 5000 8.8 8.8 8.7 8.8 8.8 8.9 10000 9.0 9.0 9.0 9.2 9.3 9.4 1 5000 9.3 9.3 9.4 9.6 9.7 9.9 20000 9.6 9.6 9.8 9.9 10.1 10.3 (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 比較例5 1 成膜時,不進行基板溫度之昇溫,以功率850W成膜以 外,與實施例5 1完全相同地製作光資訊記錄媒體。將該時 之記錄層的構造解析結果顯示於表14,將X射線繞射光譜 顯示於圖12,將信號特性顯示於表15。 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) -60- 564412 A7 r—Β7 五、發明説明(58 ) __【表14】 配位數(對於Te) 結晶構造 Te之空孔 率(% ) 非結晶狀態 結晶狀態 1.9 2.0 NaCl 型 66 ^_In 3.7 3.7 __Sb 3.1 3.1 【表15】 功率(mW) 8 9 10 11 12 13 11¾ ( ns) i寫次數 — 1 8.8 8.7 8.6 8.6 8·5 8.3 _ 1000 9.0 9.0 8.9 9.0 9.0 9.0 — 3000 9.4 9.5 9.5 9.5 9.6 9.6 5000 9.9 10.0 10.0 10.1 10.2 10.3 10000 10.5 10.7 10.8 10.9 11.1 11.3 15000 11.5 11.8 12.0 12.2 12.8 13.0 20000 13.1 13.5 13.8 14.1 15.1 15.9 (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 比較例5 2 在成膜時,不進行基板溫度之昇溫,以功率200W成膜 之外,與實施例5 1完全相同地製作光資訊記錄媒體。將該 時之記錄層的構造解析結果顯示於表1 6,將X射線繞射光 譜顯示於圖13,將信號特性顯示於表17。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -61 - 564412 A7 B7 五、發明説明(59 ) 【表16】 配位數(對於Te) 結晶構造 Te 之空 孔率(%) 非結晶狀態 結晶狀態 Ag 1.2 1.2 不明 69 In 3.1 3.2 Sb 3.1 3.0 【表17】 記錄功率(mW) 8 9 10 11 12 13 抖動(ns) 覆寫次數 1 9.1 9.1 9.0 8.8 8.7 8.6 1000 9.5 9.5 9.4 9.3 9.3 9.2 3000 9.9 9.9 9.9 9.8 9.9 9.9 5000 10.3 10.2 10.2 10.3 10.4 10.5 10000 11.1 11.3 11.4 11.7 12.1 12.6 1 5000 15.1 15.7 15.9 16.1 16.8 17.4 20000 - - - - — • (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 由以上之表4〜表14與圖7〜圖13可以明白地,由實施 例51製實施例55,記錄層之構造係NaCl型,(200 )之反射 強爲其特徵。 又,關於Ag、In、Sb之對於Te之鍵配位數,則如下 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -62 - 564412 A7 _________B7 五、發明説明(60 ) 述: (請先閲讀背面之注意事項再填寫本頁) (1 )在Ag之情形:於非晶質時,依據成膜條件,鍵 配位數雖有差別,但是在1.5〜2.0之範圍。又,在結晶質時 ,在3 · 8〜4.3之範圍,結晶質時之鍵配位數比非晶質時之鍵 配位數大。 (2 )在In之情形:於非晶質時,在3_丨〜3· 6之範圍, 在結晶質時,在3.6〜4.0之範圍,與Ag相同地,結晶質時 之鍵配位數比非晶質時之鍵配位數大。 (3)在Sb之情形:在非晶質時,爲2.7〜3·丨之範圍, 在結晶質時,爲2.2〜2·6之範圍,非晶質時之鍵配位數比結 晶質時之鍵配位數大。 這些實施例5 1〜55之光資訊記錄媒體的信號特性都良 好,可以在8mW至13mW之廣範圍的功率進行記錄,而且, 高感度。又,關於重複特性,可以使用至2萬次程度,極 爲良好。又關於保存特性,在80%RΗ、80°C之溫溼度條件下 ’放置200小時後,確認到信號特性也沒有劣化,具有高耐 候性。 經濟部智慧財產局員工消費合作社印製 另一方面,在比較例51、52中,知道Ag之鍵配位數在 非結晶狀態與結晶狀態其差別不見,特別是在結晶狀態之 鍵配位數小。依據與實施例之成膜條件之差別,比較例之 結果與實施例之結果不同之原因雖然不明,但是在比較例 51、52之X射線繞射光譜與實施例51〜55之該者中,確認 到不同點。即,比較例51爲NaCl型雖與實施例51〜55相同 ,但是(220 )面強,在(311)面成長。又,在比較例52中 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -63 - 564412 A7 B7 五、發明説明(61 ) ,(220 )面可視爲分離爲2。比較例5 1、52與實施例5 1〜 5 5之個別X射線繞射光譜之差也顯現在所獲得之光資訊記 錄媒體的信號特性。即,在比較例5 1、52中,與實施例5 1 〜5 5相比,可見到感度之降低外,重複記錄特性大爲降低 。此係顯示記錄層(記錄膜)之構造,特別是鍵配位數與 光資訊記錄媒體的信號特性大有關係。 【實施形態4】 圖14係說明實施形態4之光資訊記錄媒體的一例用之 圖。基板構成係在具有導引溝之基板3 1上具有第1保護層 32、記錄層33、第2保護層34、反射層35、厚塗層36。進而 ,理想爲在厚塗層上具有印刷層37,在基板鏡面具有硬塗 層3 8。 基板之材料通常爲玻璃、陶瓷、或樹脂,在成形性、 成本之觀點,以樹脂基板爲合適。樹脂例可舉··聚碳酸酯 樹脂、丙烯基樹脂、環氧樹脂、聚苯乙烯樹脂、丙烯腈苯 乙烯共聚物樹脂、聚乙烯樹脂、聚丙烯、矽系樹脂、氟系 樹脂、ABS樹脂、尿烷樹脂等。又,在這些樹脂中,以成 形性、光學特性、成本都優異之聚碳酸酯、丙烯樹脂爲佳 〇 但是,在將實施形態4之光資訊記錄媒體應用於可以 重寫之緻密光碟(CD-RW )之情形,期望賦予以下之特定 的條件。該條件爲:形成在使用之基板之導引溝(groove ) 之寬幅爲0.25〜0·65 // m,合適爲0.30〜0_55 // m,該導引溝 (請先聞讀背面之注意事項再填寫本頁)NaCl-type Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumption Cooperative, Printed quasi-standard home country-China use | A piece of suitable size-paper 56 564412 A7 B7 V. Description of invention (54) [Table 7] Recording power (mW) 8 9 10 11 12 13 Jitter (ns) Number of overwrites 1 8.5 8.2 8.0 7.9 7.8 7.7 1000 8.5 8.3 8.2 8.1 8.0 7.9 3000 8.7 8.6 8.5 8.4 8.4 8.3 5000 8.9 8.8 8.8 8.8 8.9 8.9 10000 9.1 9.1 9.2 9.2 9.3 9.4 1 5000 9.4 9.4 9.5 9.6 9.7 9.8 20000 9.7 9.7 9.8 10.1 10.2 10.4 Example 53 The substrate temperature of the film formation conditions of the recording layer was 25 ° C and the temperature was raised at a rate of 50 ° C / min. Optical information recording media. The structure analysis results of the recording layer at this time are shown in Table 8, the X-ray diffraction spectrum is shown in FIG. 9, and the signal characteristics are shown in Table 9. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 8] Coordination number (for Te) Porosity of crystalline structure Te (%) Non-crystalline state Crystal state Ag 2.0 4.3 NaCl type 67 In 3.6 4.0 Sb 3.1 2.6 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -57- 564412 A7 B7 V. Description of the invention (55) [Table 9] Recording power (mW) 8 9 10 11 12 13 Jitter (ns) Number of overwrites 1 8.3 8.2 7.9 7.7 7.6 7.5 1000 8.4 8.3 8.1 7.9 7.9 7.8 3000 8.6 8.5 8.4 8.2 8.2 8.3 8.3 5000 8.7 8.7 8.6 8.6 8.7 8.7 10000 8.9 8.9 8.9 9.0 9.1 9.2 1 5000 9.2 9.2 9.3 9.4 9.5 9.7 20000 9.5 9.5 9.7 9.8 10.0 10.2 Example 54 Assuming that the target composition of the recording layer was Ag3In1C) Sb63Te24, an optical information recording medium was produced in the same manner as in Example 51. The structure analysis results of the recording layer at this time are shown in Table 10, the X-ray diffraction spectrum is shown in Figure 10, and the signal characteristics are shown in Table 11 〇 (Please read the precautions on the back before filling this page) Wisdom of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Property Bureau [Table 10] Coordination number (f in Te) Porosity (%) of crystalline structure Te Non-crystalline state crystalline state Ag 1.5 3.8 NaCl type 69 In 3.4 3.6 Sb 2.7 2.3 This paper size applies China National Standard (CNS) A4 specification (210X297 mm) -58- 564412 A7 B7 V. Description of invention (56) [Table: 1] Recording power (mW) 8 9 10 11 12 13 Jitter (ns) Overwrite Frequency 1 8.4 8.3 8.1 7.8 7.7 7.6 1000 8.4 8.4 8.2 8.0 8.0 7.9 3000 8.6 8.6 8.4 8.3 8.3 8.3 5000 8.8 8.8 8.7 8.7 8.7 8.8 10000 9.0 9.0 9.0 9.0 9.1 9.2 9.3 1 5000 9.3 9.3 9.4 9.5 9.6 9.8 20000 9.6 9.6 9.8 9.9 10.1 10.3 Example 55 Assuming that the target composition of the recording layer is Ag8In3Sb68Te21, an optical information recording medium is produced in exactly the same manner as in Example 51. The analysis results of the structure of the recording layer at this time are shown in Table 12; the X-ray diffraction spectrum is shown in Figure 11; and the signal characteristics are shown in Table 13. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 12] Coordination number (t; f in Te) Crystal structure Porosity (%) of amorphous state Crystallized state Ag 1.8 3.9 NaCl type 73 In 3.1 3.7 Sb 2.7 2.5 This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -59- 564412 B7 V. Description of the invention (57) [Table 13] Recording power (MW) 8 9 10 11 12 13 Jitter (ns) Number of overwrites 1 8.4 8.3 8.2 7.9 7.8 7.7 1000 8.4 8.4 8.2 8.1 8.1 8.0 3000 8.6 8.6 8.4 8.4 8.4 8.4 5000 8.8 8.8 8.7 8.8 8.8 8.9 10000 9.0 9.0 9.0 9.2 9.3 9.3 9.4 1 5000 9.3 9.3 9.4 9.6 9.7 9.9 20000 9.6 9.6 9.8 9.9 10.1 10.3 (Please read the precautions on the back before filling out this page) Comparative Example 5 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs An optical information recording medium was produced in the same manner as in Example 51 except that the film was formed at a power of 850 W when the temperature was raised. The structure analysis results of the recording layer at this time are shown in Table 14, the X-ray diffraction spectrum is shown in Fig. 12, and the signal characteristics are shown in Table 15. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -60- 564412 A7 r—B7 V. Description of the invention (58) __ [Table 14] Coordination number (for Te) Crystal structure Te Porosity (%) Amorphous state Crystalline state 1.9 2.0 NaCl type 66 ^ _In 3.7 3.7 __Sb 3.1 3.1 [Table 15] Power (mW) 8 9 10 11 12 13 11¾ (ns) i Number of writes — 1 8.8 8.7 8.6 8.6 8 · 5 8.3 _ 1000 9.0 9.0 8.9 9.0 9.0 9.0 — 3000 9.4 9.5 9.5 9.5 9.6 9.6 5000 9.9 10.0 10.0 10.1 10.2 10.3 10000 10.5 10.7 10.8 10.9 11.1 11.3 15000 11.5 11.8 12.0 12.2 12.8 13.0 20000 13.1 13.5 13.8 14.1 15.1 15.9 (Please (Please read the notes on the back before filling in this page) Comparative Example 5 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 During film formation, the substrate temperature was not increased, and the film was formed at a power of 200W, as in Example 5 1 The optical information recording medium is made exactly the same. The structure analysis results of the recording layer at this time are shown in Table 16; the X-ray diffraction spectrum is shown in Fig. 13; and the signal characteristics are shown in Table 17. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -61-564412 A7 B7 V. Description of invention (59) [Table 16] Coordination number (for Te) Crystal structure Te porosity (% ) Non-crystalline state Ag 1.2 1.2 Unknown 69 In 3.1 3.2 Sb 3.1 3.0 [Table 17] Recording power (mW) 8 9 10 11 12 13 Jitter (ns) Number of overwrites 1 9.1 9.1 9.0 8.8 8.7 8.6 1000 9.5 9.5 9.4 9.3 9.3 9.2 3000 9.9 9.9 9.9 9.8 9.9 9.9 5000 10.3 10.2 10.2 10.3 10.4 10.5 10000 11.1 11.3 11.4 11.7 12.1 12.6 1 5000 15.1 15.7 15.9 16.1 16.8 17.4 20000-----• (Please read the notes on the back before filling in this Page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs From Tables 4 to 14 and Figures 7 to 13 above, it can be clearly understood that the structure of the recording layer is of the NaCl type according to Example 55 from Example 51, (200) The strong reflection is its characteristic. In addition, regarding the coordination numbers of Te, Ag, In, and Sb to Te, the following paper standards apply the Chinese National Standard (CNS) A4 specifications (210X297 mm) -62-564412 A7 _________B7 5. Description of the invention (60) : (Please read the precautions on the reverse side before filling out this page) (1) In the case of Ag: In the case of amorphous, depending on the film formation conditions, the bond coordination number is different, but it is in the range of 1.5 to 2.0. In the case of crystalline materials, the bond coordination number in the case of crystalline materials is larger than that in the case of amorphous materials in the range of 3 · 8 to 4.3. (2) In the case of In: In the case of amorphous, in the range of 3 ~ 丨 ~ 3.6, in the case of crystalline, in the range of 3.6 to 4.0, the same as Ag, the bond coordination number in the crystalline The bond coordination number is larger than that in the amorphous state. (3) In the case of Sb: In the case of amorphous, it is in the range of 2.7 ~ 3 · 丨; in the case of crystalline, it is in the range of 2.2 ~ 2 · 6; The key coordination number is large. The signal characteristics of the optical information recording media of 1 to 55 in these embodiments are all good, and recording can be performed at a wide range of power from 8 mW to 13 mW, and the sensitivity is high. In addition, the repeatability can be used up to 20,000 times, which is extremely good. Regarding storage characteristics, it was confirmed that the signal characteristics did not deteriorate even after being left for 200 hours under the conditions of 80% RΗ and temperature and humidity of 80 ° C, and had high weather resistance. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. On the other hand, in Comparative Examples 51 and 52, it is known that the bond coordination number of Ag is not in the amorphous state and the crystalline state. small. According to the difference in film formation conditions from the examples, the reasons for the differences between the results of the comparative examples and the examples are unknown, but among the X-ray diffraction spectra of comparative examples 51 and 52 and those of examples 51 to 55, Confirm the difference. That is, Comparative Example 51 is a NaCl type, which is the same as Examples 51 to 55, but has a (220) plane and grows on a (311) plane. Also, in Comparative Example 52, the paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -63-564412 A7 B7 5. In the description of the invention (61), the (220) plane can be regarded as a separation of 2. The difference in the individual X-ray diffraction spectra of Comparative Examples 5 and 52 and Examples 5 to 5 5 also appeared in the signal characteristics of the obtained optical information recording medium. That is, in Comparative Examples 5 1 and 52, compared with Examples 5 1 to 55, it was seen that the repeat recording characteristics were greatly reduced in addition to the decrease in sensitivity. This is the structure of the display recording layer (recording film), especially the key coordination number, which is strongly related to the signal characteristics of the optical information recording medium. [Embodiment 4] Fig. 14 is a diagram for explaining an example of an optical information recording medium according to Embodiment 4. The substrate structure includes a first protective layer 32, a recording layer 33, a second protective layer 34, a reflective layer 35, and a thick coating layer 36 on a substrate 31 having a guide groove. Furthermore, it is desirable to have a print layer 37 on the thick coating layer and a hard coating layer 38 on the substrate mirror surface. The material of the substrate is usually glass, ceramic, or resin, and a resin substrate is suitable in terms of moldability and cost. Examples of the resin include polycarbonate resin, acrylic resin, epoxy resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyethylene resin, polypropylene, silicon resin, fluorine resin, ABS resin, Urethane resin, etc. Among these resins, polycarbonate and acrylic resins which are excellent in moldability, optical characteristics, and cost are preferred. However, the optical information recording medium of Embodiment 4 is applied to a rewritable compact optical disc (CD- RW), the following specific conditions are expected to be imposed. The conditions are as follows: the width of the guide groove (groove) formed on the substrate used is 0.25 ~ 0 · 65 // m, suitably 0.30 ~ 0_55 // m, the guide groove (please read the note on the back first) (Fill in this page again)
、1T 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) -64- 564412 A7 _B7 _^_ 五、發明説明(62 ) 之深度爲250〜650A,合適爲300〜550A。基板之厚度雖無 特別限制,以1.2mm或0.6mm爲合適。 (請先閲讀背面之注意事項再填寫本頁) 記錄層33由於以包含Ge、Ga、Sb、Te之4元素系之相 變化型記錄材料爲主成分而含有之材料在記錄(非晶質化 )感度.記錄速度、抹除(結晶化)感度.抹除速度、以 及抹除比極爲良好之故,很合適。但是,GeGaSbTe依據其 之組成比,存在最適當之記錄線速度之故,依據爲其目的 之記錄線速度以及線速度區域,需要調整GeGaSbTe之組成 比。至目前爲止之檢討結果,發現GeGaSbTe記錄層之Te 的組成比與記錄線速度有高的相關。 實施形態4之光資訊記錄媒體所要求之品質,不單可 以記錄抹除,也同時要求信號之再生安定性或信號之壽命 。可以綜合滿足這些之記錄層以GeGaSbTe系爲優異,個別 之組成比61:、/9、7、5(原子%)設爲(^+/3+71+5=100 時’在: 0.1 ^ a ^7.0 經濟部智慧財產局員工消費合作社印製 61 $ r $ 75 22^ 5 ^ 30 之情形,有效果。、 1T Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -64- 564412 A7 _B7 _ ^ _ 5. The depth of the description of the invention (62) is 250 ~ 650A, suitable for 300 ~ 550A. Although the thickness of the substrate is not particularly limited, 1.2 mm or 0.6 mm is suitable. (Please read the precautions on the back before filling this page.) The recording layer 33 is recorded as a material containing a 4-element phase change type recording material of Ge, Ga, Sb, and Te as the main component (amorphous). ) Sensitivity. Recording speed, erasing (crystallization) sensitivity, erasing speed, and erasing ratio are very good, which is very suitable. However, since GeGaSbTe has the most suitable linear velocity for recording based on its composition ratio, the composition ratio of GeGaSbTe needs to be adjusted based on the linear velocity and the linear velocity region for its purpose. As a result of the review so far, it has been found that the composition ratio of Te in the GeGaSbTe recording layer is highly correlated with the recording linear velocity. The quality required by the optical information recording medium of Embodiment 4 not only can record and erase, but also requires the stability of signal reproduction or the life of the signal. A recording layer that satisfies these comprehensively is superior to GeGaSbTe, and the individual composition ratios 61 :, / 9, 7, 5 (atomic%) are set to (^ + / 3 + 71 + 5 = 100) at: 0.1 ^ a ^ 7.0 The printing of 61 $ r $ 75 22 ^ 5 ^ 30 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is effective.
Ge超過7.0at%、Ga超過9at%、Sb超過75at%,信號之 再生安定性或信號之壽命不夠。Te之含有量對再結晶化線 速度大有影響之故,即使藉由記錄層厚或其它層之熱傳導 率而控制,至少以22at%以上30at%以下爲佳。 ^紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -65 - ' ~"" 564412 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明(63 ) 又’提升信號之再生安定性或信號之壽命的方法以在 記錄層添加由:In、Zn、Sn、Si、Pb、Co、Cr、Cu、Ag、 Au、Pd、Pt、S、Se、Ta、Nb、V、Bi、Zr、Ti、A1、Mn、 Mo、Rh ' C、N以及〇選擇之至少一種以上之元素爲有效 果。信號之再生劣化或信號之壽命降低其原因爲非晶質標 記之結晶化,爲了抑制非晶質標記之結晶化,在記錄層添 加由前述元素選擇至少一種以上之元素爲有效果。此機制 雖不明確,認爲這些元素係進入GeGaSbTe之空間的空隙, 形成化學鍵,與GeGaSbTe形成化合物或合金,成爲抑制非 晶質標記之結晶化之添加劑。因此,原子半徑小、與 GeGaSbTe之化學鍵能大,化學鍵多之元素有效果。特別是 C、N、〇、Si、Sn、Ag有效果。這些添加元素之量以記錄 層之7at%以下有效果。藉由使之在7at%以下,可以維持 GeGaSbTe記錄層之本來具有之記錄抹除特性,能夠抑制抹 除殘餘。 又,光資訊記錄媒體之高線速記錄.抹除之保存信賴 性係極爲重要之項目。在實施形態4中,關於Ge與Ga之 組成的關係,在-8 S α · /3 S 3時,發現可以兼顧高線速對應 性與保存信賴性之平衡。在α - /3超過3時,可以見到記錄 .抹除時之最適當線速有變慢之傾向。又,在α Α未滿-8 時,光資訊記錄媒體之保存性不足夠。因起,在-8 $ α - /3 S 3時,在取得兩者之特性的平衡上有效果。 進而,線速度變得更高速,光資訊記錄媒體之反射率 ,特別是初期化時之反射率確保變得重要。在實施形態4 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) ^66- ~" (請先閲讀背面之注意事項再填寫本頁) 564412 A7 B7 五、發明説明(64 ) 中,關於Sb與Te之組成的關係,藉由使r + 5 ^ 88,發現 可以到達初期化時所必要之反射率。 (請先閲讀背面之注意事項再填寫本頁) 記錄層之膜厚以10〜50nm爲佳,更好爲12〜30nm。進 而,如考慮抖動等之初期特性、覆寫特性、量產特性,以 14〜25nm爲合適。使之在10nm以上,光吸收能不會降低, 可以獲得良好之記錄特性。又,使之在50nm以下,可以進 行高速、均勻之相變化。此種記錄層藉由各種氣相成長法 ,例如真空蒸鍍法、濺鍍法、電漿CVD法、光CVD法、離 子電鍍法、電子束蒸鍍法等形成。其中,濺鍍法在量產性 、膜質等優異。 第1保護層(電介質層)以及第2保護層(電介質層) 之材料可舉:Si〇、Si〇2、Zn〇、Sn〇2、Al2〇3、Ti〇2、Ιιΐ2〇3 、MgO、ZrCh等之金屬氧化物,Si3N4、AIN、TiN、BN、ZrN 等之氮化物,ZnS、In2S3、TaS4等之硫化物,SiC、TaC、 B4C、WC、TiC、ZrC等之碳化物或鑽石狀碳或彼等之混合 物。 經濟部智慧財產局員工消費合作社印製 這些材料可以以單體作爲保護層,也可以爲相互之混 合物。又,因應需要,也可以包含不純物。進而,因應需 要,也可以多層化電介質層。但是,第1保護層以及第2保 護層之熔點需要比記錄層高。此種第1保護層以及第2保護 層之材料可以藉由各種氣象成長法,例如真空蒸鍍法、濺 鍍法 '電漿CVD法、光CVD法、離子電鍍法、電子束蒸鍍 法等形成。其中,濺鍍法在量產性、膜質等優異。 第1保護層之膜厚對反射率大有影響。爲了以78Onm與 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) Γβ7 - — ~~ 564412 A7 B7 五、發明説明(65 ) (請先閱讀背面之注意事項再填寫本頁) 65 0nm之再生波長滿足CD-RW光碟規格之反射率〇·15〜0·25 ,要求第1電介質層爲65〜130nm。藉由設定爲此膜厚,可 以獲得滿足65 Onm之DVD的再生波長之反射率、DVD之再 生互換性。第2電介質層之膜厚以15〜45nm爲佳,更好爲20 〜40nm。藉由使之爲15nm以上,可以良好作用爲耐熱保護 層,不易產生感度之降低。另一方面,藉由使之在45nm以 下,不易產生界面剝離,能夠防止重複記錄性能之降低。 反射層可以使用Al、Au、Ag、Cu、Ta、Ti、W等之金 屬材料,或彼等之合金等。又,添加元素可以使用Cr、Ti 、Si、Cu、Ag、Pd、Ta等。此種反射層可以藉由各種氣相 成長法,例如真空蒸鍍法、.濺鍍法、電漿CVD法、光(:乂0 法、離子電鍍法、電子束蒸鍍法等形成。合金或金屬層之 膜厚以70〜200nm爲佳,合適爲100〜160nm。又,也可以多 層化合金或金屬層。在多層化之情形,各層之膜厚至少需 要在10nm以上,多層化膜之合計膜厚以50〜160nm爲佳。 經濟部智慧財產局員工消費合作社印製 在反射層之上期望作爲其之氧化防止而具有厚塗層。 厚塗層一般爲以旋轉塗佈所製作之紫外線硬化樹脂。其膜 厚以3〜15// m爲適當。使之在3μιη以上,在設計印刷層之 情形,可以防止錯誤之發生。另一方面,在1 5 // m以下, 內部應力不會變大,不易對光碟之機械特性造成影響。 硬塗層一般爲以旋轉塗佈所製作之紫外線硬化樹脂。 其厚度以2〜6// m爲適當。藉由使之在2/zm以上,可以獲 得充分之耐擦傷性。在6 // m以下,內部應力不大,不易對 光碟之機械特性造成影響。其硬度以即使以布擦,也不會 -68- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 564412 Μ ____Β7_ 五、發明説明(66 ) 有大的傷痕之鉛筆硬度Η以上爲佳。因應需要,混入導電 性之材料,防止帶電以防止塵埃等之附著也很有效果。 (請先閱讀背面之注意事項再填寫本頁) 一般在多速度記錄以及CAV記錄之情形,在低線速度 中,成爲過剩之記錄功率,在高線速度中,成爲記錄功率 不足。因此,取得記錄線速度與記錄功率之平衡很重要。 具體之方法爲愈是高線速記錄之情形,需要愈高功率,一 般可視爲CD-R等。 圖15係說明記錄脈衝波形用之圖。在實施形態4中, 發現使圖1 5之多脈衝部(以下,記爲mp部)之負荷比以記 錄線速度使之增減爲有效。此處敘述之負荷比係將mp部之 低準位脈衝的功率準位b之時間以mp部之時間寬幅去除者 。又,此資訊記錄方法在記錄層爲以Ge、Ga、Sb、Te爲主 成分之資訊記錄媒體中特別有效。此係以Ge、Ga、Sb、Te 爲主成分之記錄層的熱物性與本記錄脈衝波匹配之故。 圖16係顯示實施形態4之一例之CD — RW之4x〜1 Ox記 錄之多速度記錄的記錄波形。此例係也對應內周4.8m/s、外 周12.0m/s之CAV記錄。在此例中,記錄線速度4.8、9.6、 經濟部智慧財產局員工消費合作社印製 12.Om/s,個別mp部之負荷比爲〇·625、0.5、0.375,配合記 錄線速度之增加,減少mp部之負荷比。在4.8m/s之低線速 度記錄中,藉由使mp部之記錄脈衝變細,減輕多餘之熱損 傷,而且,藉.由使mp部之冷卻時間變長,可以記錄邊緣之 位置偏差少之標記。另一方面,在12·Om/s之高線速度記錄 中,藉由使mp部之記錄脈衝變寬,對記錄膜給予可以相變 化之儘可能之能量。又,高速之故,m P部之冷卻時間即使 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) :69- 564412 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明(67 ) 端,記錄層之急冷條件齊備’可以記錄邊緣之位置偏差少 之標記。 在伴隨記錄層之熔化、急冷之相變化型光資訊記錄媒 體中,記錄脈衝之mp部之貪荷在0.5附近之情形’取得記 錄層之熔化、急冷之平衡,在種種之信號品質、覆寫上有 利。 因此,在考慮驅動部-媒體之匹配上,在多速度記錄 之任何記錄線速設定mp部之負荷比0.5成爲課題。在實施 形態4中,使mp部之負荷比成爲0.5之記錄線速度比(最 低記錄線速度+最高記錄線速度)/ 2大,在最高記錄線速 以下爲有效。在可以多速度記錄之驅動部中廣被利用之記 錄線速度係最高記錄線速度。在CAV記錄中,在容易受到 機械特性之影響的外周部成爲高速記錄。因此,即使在 C A V記錄,高速記錄之信號品質更形重要。由此,實用上 爲了進行更高信賴性之記錄,將信賴性高之mp部的負荷比 0.5之記錄脈衝波形設定在高速記錄側爲有效。進而,使mp 部之負荷比成爲0.5之記錄線速度比0.55x (最低記錄線速度 +最高記錄線速度)大,而且在最高記錄線速度以下,更爲 有效。 圖17係說明實施形態4之光資訊記錄媒體的記錄再生 裝置之實施形態之圖。藉由由主軸馬達形成之驅動手段, 旋轉驅動相變化型光資訊記錄媒體,藉由光源驅動手段之 雷射驅動電路,驅動由半導體雷射形成之光源,藉由記錄 再生用拾取頭,由前述半導體雷射透過末圖示出之光學系 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐) Γ7〇^ (請先閲讀背面之注意事項再填寫本頁) 564412 Α7 Β7 五、發明説明(68 ) 統,對光資訊記錄媒體照射以圖16所示之記錄線速度增減 mp部之負荷比之雷射光,使前述光資訊記錄媒體之記錄層 產生相變化,以記錄再生用拾取頭接受由光資訊記錄媒體 來之反射光,進行對於光資訊記錄媒體之資訊的記錄或再 生。 又,記錄再生用拾取頭之最適當記錄功率係藉由記錄 功率設定手段之記錄功率設定電路而設定。又’相變化型 光資訊記錄媒體之記錄再生裝置係以記錄再生用拾取頭對 相變化型光資訊記錄媒體照射雷射光’使前述光資訊記錄 媒體之記錄層產生相變化,進行對於光資訊記錄媒體之資 訊的記錄、再生,而且,可以重寫之相變化型光記錄再生 裝置,具備以調制部調制應記錄信號,以記錄再生用拾取 頭記錄於光資訊記錄媒體,以進行資訊之記錄之記錄手段 〇 包含此拾取頭之記錄手段係對於光資訊記錄媒體之記 錄層,以記錄記錄作爲標記之寬幅之信號的標記之所謂的 PWM記錄方式進行資訊之記錄。記錄手段係在調制部利用 時脈,以例如適用在重寫型緻密光碟之資訊記錄之 EFM(Eiglit-to-Fourteen Modulation ·· 8 : 14調制)調制方式或 其之改良調制方式調制應記錄之信號。 記錄手段在進行PWM記錄之際,係以設進行調制後之 信號寬幅爲nT(n係指定之値,T係時脈時間,即相當於使 用在信號之調制之時脈的週期之時間)之〇信號的記錄或重 寫時之記錄光爲功率準位e之連續光,設進行調制後信號 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~7η\ · (請先閲讀背面之注意事項再 衣丨 I:填寫本頁When Ge exceeds 7.0 at%, Ga exceeds 9 at%, and Sb exceeds 75 at%, the regeneration stability of the signal or the life of the signal is insufficient. The content of Te greatly affects the recrystallization linear velocity. Even if it is controlled by the thickness of the recording layer or the thermal conductivity of other layers, it is preferably at least 22 at% or more and 30 at% or less. ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -65-'~ " " 564412 Α7 Β7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives The method of reproducing stability or signal life is to add in the recording layer by: In, Zn, Sn, Si, Pb, Co, Cr, Cu, Ag, Au, Pd, Pt, S, Se, Ta, Nb, V , Bi, Zr, Ti, A1, Mn, Mo, Rh'C, N, and at least one selected from the elements are effective. The deterioration of the signal reproduction or the reduction of the signal life is caused by the crystallization of the amorphous mark. In order to suppress the crystallization of the amorphous mark, it is effective to add at least one element selected from the foregoing elements to the recording layer. Although this mechanism is not clear, these elements are considered to enter the voids in the space of GeGaSbTe, form chemical bonds, form compounds or alloys with GeGaSbTe, and become an additive to suppress the crystallization of amorphous marks. Therefore, elements with small atomic radii, large chemical bond energy with GeGaSbTe, and many chemical bonds are effective. In particular, C, N, O, Si, Sn, and Ag are effective. The amount of these added elements is effective at 7at% or less of the recording layer. By setting it to 7 at% or less, the recording erasing characteristic originally possessed by the GeGaSbTe recording layer can be maintained, and erasing residues can be suppressed. In addition, high linear speed recording and erasure reliability of optical information recording media are extremely important items. In the fourth embodiment, regarding the relationship between the composition of Ge and Ga, at -8 S α · / 3 S 3, it was found that the balance between high line speed correspondence and storage reliability can be taken into account. When α-/ 3 exceeds 3, records can be seen. The optimum line speed at the time of erasing tends to be slower. When α Α is less than -8, the storage stability of the optical information recording medium is insufficient. Therefore, at -8 $ α-/ 3 S 3, it is effective in achieving the balance between the two characteristics. Furthermore, the linear velocity becomes higher, and it is important to ensure the reflectance of the optical information recording medium, especially the reflectance at the time of initializing. In the fourth embodiment, the paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ^ 66- ~ " (Please read the precautions on the back before filling out this page) 564412 A7 B7 V. Description of the invention (64) In the relationship between the composition of Sb and Te, r + 5 ^ 88 was found, and it was found that the reflectance necessary for the initialization can be reached. (Please read the notes on the back before filling this page) The film thickness of the recording layer is preferably 10 ~ 50nm, more preferably 12 ~ 30nm. Furthermore, considering the initial characteristics, overwrite characteristics, and mass production characteristics of jitter, etc., 14 to 25 nm is suitable. When it is 10 nm or more, the light absorption energy is not reduced, and good recording characteristics can be obtained. Furthermore, by making it 50 nm or less, high-speed and uniform phase change can be performed. Such a recording layer is formed by various vapor growth methods such as a vacuum evaporation method, a sputtering method, a plasma CVD method, a photo CVD method, an ion plating method, an electron beam evaporation method, and the like. Among them, the sputtering method is excellent in mass productivity and film quality. The materials of the first protective layer (dielectric layer) and the second protective layer (dielectric layer) include: Si〇, Si〇2, Zn〇, Sn〇2, Al2〇3, Ti〇2, Iιΐ2 03, MgO, Metal oxides such as ZrCh, nitrides such as Si3N4, AIN, TiN, BN, ZrN, sulfides such as ZnS, In2S3, and TaS4, carbides or diamond-like carbons such as SiC, TaC, B4C, WC, TiC, ZrC, etc. Or a mixture of them. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs These materials can be used as a protective layer or a mixture of each other. If necessary, impurities may be contained. Further, if necessary, a plurality of dielectric layers may be formed. However, the melting points of the first protective layer and the second protective layer need to be higher than those of the recording layer. The materials of the first protective layer and the second protective layer can be formed by various meteorological growth methods, such as a vacuum evaporation method, a sputtering method, a plasma CVD method, a photo CVD method, an ion plating method, and an electron beam evaporation method. form. Among them, the sputtering method is excellent in mass productivity and film quality. The film thickness of the first protective layer greatly affects the reflectance. In order to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) at 78Onm and this paper size Γβ7-— ~ 564412 A7 B7 V. Description of the invention (65) (Please read the precautions on the back before filling out this page) 65 The reproduction wavelength of 0 nm satisfies the reflectivity of the CD-RW disc specification from 0.15 to 0.25, and the first dielectric layer is required to be 65 to 130 nm. By setting the film thickness to this, it is possible to obtain reflectance that satisfies the reproduction wavelength of a DVD of 65 Onm and interchangeability of DVD reproduction. The film thickness of the second dielectric layer is preferably 15 to 45 nm, and more preferably 20 to 40 nm. By setting it to 15 nm or more, it can function well as a heat-resistant protective layer, making it difficult to cause a decrease in sensitivity. On the other hand, by making it 45 nm or less, interfacial peeling is less likely to occur, and it is possible to prevent degradation of repeated recording performance. As the reflective layer, a metal material such as Al, Au, Ag, Cu, Ta, Ti, W, or the like, or an alloy thereof can be used. As the additive element, Cr, Ti, Si, Cu, Ag, Pd, Ta, or the like can be used. Such a reflective layer can be formed by various vapor growth methods, such as a vacuum evaporation method, a sputtering method, a plasma CVD method, a light (乂 0 method, an ion plating method, an electron beam evaporation method, etc.), an alloy or The film thickness of the metal layer is preferably 70 to 200 nm, and is suitably 100 to 160 nm. Also, an alloy or metal layer may be multilayered. In the case of multilayering, the film thickness of each layer needs to be at least 10 nm or more, the total of the multilayered film The film thickness is preferably 50 ~ 160nm. It is printed on the reflective layer by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and is expected to have a thick coating for its oxidation prevention. The thick coating is generally UV-cured by spin coating. Resin. Its film thickness is suitable to be 3 ~ 15 // m. If it is more than 3 μm, it can prevent errors when designing printed layers. On the other hand, internal stress will not be below 15 / m Larger, it is difficult to affect the mechanical characteristics of the optical disc. The hard coating layer is generally a UV-curing resin made by spin coating. Its thickness is preferably 2 to 6 // m. By making it 2 / zm or more, Full abrasion resistance can be obtained. 6 // m or less, the internal stress is not large, and it is not easy to affect the mechanical characteristics of the disc. Its hardness is not even if it is rubbed with a cloth -68- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) 564412 Μ ____ Β7_ V. Description of the invention (66) Pencils with large scars are better than Η. It is also effective to mix conductive materials to prevent electrification to prevent dust from adhering if necessary. (Please read the back first) Please note this page before filling in this page) Generally, in the case of multi-speed recording and CAV recording, at low linear speeds, it becomes excessive recording power, and at high linear speeds, it becomes insufficient recording power. Therefore, the recording linear speed and recording The balance of power is very important. The specific method is that the higher the line speed recording is, the higher the power is required, which can generally be regarded as CD-R, etc. Figure 15 is a diagram for explaining the pulse waveform recording. In the fourth embodiment, it was found It is effective to increase and decrease the load ratio of the multi-pulse section (hereinafter referred to as the mp section) at the recording linear velocity in FIG. 15. The load ratio described here is a low level pulse of the mp section. The time of the power level b is broadly removed by the time of the mp section. Moreover, this information recording method is particularly effective in an information recording medium whose recording layer is mainly composed of Ge, Ga, Sb, Te. This is based on Ge, The thermal physical properties of the recording layer whose main components are Ga, Sb, and Te match this recording pulse wave. Fig. 16 shows a multi-speed recording waveform of a 4x ~ 1 Ox recording of CD-RW, which is an example of Embodiment 4. This example also corresponds to a CAV record of 4.8m / s on the inner periphery and 12.0m / s on the outer periphery. In this example, the linear velocity of the record is 4.8, 9.6, and the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economy printed 12.Om/s. The load ratio of the mp section is 0.625, 0.5, and 0.375. In accordance with the increase in the recording linear velocity, the load ratio of the mp section is reduced. In the low linear velocity recording of 4.8m / s, the recording pulse of the mp section is made thinner to reduce unnecessary thermal damage. Furthermore, by increasing the cooling time of the mp section, the position deviation of the recording edge can be reduced. Of the tag. On the other hand, in the high linear velocity recording at 12 · Om / s, by widening the recording pulse in the mp section, the recording film is given as much energy as possible that can be phase-changed. Also, due to the high speed, the cooling time of the m P section is applicable to the Chinese national standard (CNS) A4 specification (210X297 mm): 69- 564412 Α7 Β7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy At the end of (67), the quenching condition of the recording layer is complete, and a mark with less positional deviation of the edge can be recorded. In the phase change type optical information recording medium accompanied by the melting and rapid cooling of the recording layer, the burr load of the mp part of the recording pulse is around 0.5 'to achieve the balance of melting and rapid cooling of the recording layer, and the quality On the favorable. Therefore, in consideration of the drive-media matching, setting the load ratio of the mp section to 0.5 at any recording line speed for multi-speed recording becomes a problem. In the fourth embodiment, the recording linear velocity ratio (lowest recording linear velocity + highest recording linear velocity) / 2 in which the load ratio of the mp section is 0.5 is large, and it is effective below the maximum recording linear velocity. The recording linear speed that is widely used in a drive section capable of multi-speed recording is the highest recording linear speed. In the CAV recording, a high-speed recording is performed on an outer peripheral portion that is easily affected by mechanical characteristics. Therefore, even in CAV recording, the signal quality of high-speed recording is more important. Therefore, in practice, it is effective to set a recording pulse waveform having a load ratio of 0.5 or more on the high-speed recording side for a recording with higher reliability on the mp section with higher reliability. Furthermore, it is more effective to make the load linear ratio of the mp part to be 0.5 and the recording linear velocity to be greater than 0.55x (the minimum recording linear velocity + the maximum recording linear velocity), and below the maximum recording linear velocity. Fig. 17 is a diagram illustrating an embodiment of a recording / reproducing apparatus for an optical information recording medium according to the fourth embodiment. The phase change type optical information recording medium is rotationally driven by the driving means formed by the spindle motor, the light source formed by the semiconductor laser is driven by the laser driving circuit of the light source driving means, and the pickup head for recording and reproduction is used by the foregoing The optical system shown in the last figure for semiconductor laser transmission is applicable to this paper. National National Standard (CNS) A4 (210X297 mm) Γ7〇 ^ (Please read the precautions on the back before filling this page) 564412 Α7 Β7 Five The invention description (68) system irradiates the optical information recording medium with laser light that increases or decreases the load ratio of the mp section at the recording linear velocity shown in FIG. 16 to cause a phase change in the recording layer of the aforementioned optical information recording medium to record and reproduce The pickup head receives the reflected light from the optical information recording medium, and records or reproduces information on the optical information recording medium. The optimum recording power of the recording / reproducing pickup is set by a recording power setting circuit of the recording power setting means. "The recording and reproducing device of the phase change optical information recording medium irradiates laser light to the phase change optical information recording medium with a pickup for recording and reproduction" causes the phase change of the recording layer of the optical information recording medium to perform optical information recording. Recording and reproduction of media information, and a rewritable phase change type optical recording and reproduction device, which is provided with a modulating unit to modulate a recording signal, and records and reproduces a pick-up head to record on the optical information recording medium for information recording Recording means 0 The recording means including the pickup head records information in a so-called PWM recording method of recording a mark of a wide signal as a mark for a recording layer of an optical information recording medium. The recording means uses the clock in the modulation section to modulate the information to be recorded with an EFM (Eiglit-to-Fourteen Modulation · 8: 14 modulation) modulation method suitable for information recording on a rewritable compact disc or its improved modulation method. signal. The recording method is to set the modulation signal width as nT when performing PWM recording (n is the specified range, and T is the clock time, which is equivalent to the period of the clock used for the modulation of the signal) The recording light during the recording or rewriting of the 〇 signal is continuous light at the power level e, and the signal after modulation is set. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ 7η \ · (please first Read the precautions on the back 丨 I: Fill out this page
、1T 經濟部智慧財產局員工消費合作社印製 564412 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(69) 寬幅爲nT之1信號的記錄或重寫時之記錄波脈衝列爲由: 具有時間寬幅χ與功率準位a之脈衝部fp,與具有合計爲Τ 之時間寬幅之功率準位b之低準位脈衝與功率準位c之高 準位脈衝交互以負荷比y合計(n-)次連續之多脈衝部 mp,與具有時間寬幅z與功率準位d之脈衝部op形成之雷 射波脈衝列,進而,分別設前述χ、y、z爲0.5TS 2.0T 、0.125$ y $ 0.87 5、0.125TS zS 1.0T,設 η 爲 1以上之正整 數,(a以及c ) > e > (b以及d)。圖1 6係r^ = 1之情形。 以下,藉由實施例進一步說明實施形態4。 形成遇有寬0.5// m、深度35nm之導引溝之1.2mm厚的 聚碳酸酯基板,在此基板上依序藉由濺鍍法積層第1保護 層、記錄層、第2保護層以及反射層。第1保護層以及第 2保護層係使用ZnSSiCh,膜厚分別設爲90nm、30iim。 記錄層係使用表1 8之實施例所示之組成,膜厚爲1 8nm 〇 反射層係使用鋁合金,形成基板/ZnSSi〇2(90nm)/ GeGaSbTe(18nm)/ZnSSi〇2(30nm)/Al 合金(140nm)之層構成 〇 進而,形成紫外線硬化樹脂之藉由旋轉塗佈之硬塗層 、厚塗層,製作相變化型光資訊記錄媒體。 接著,藉由具有大口徑LD之初期化裝置,進行光資訊 記錄媒體之記錄層之全面結晶化處理。進而,在厚塗層上 形成印刷層。 以以上之方法獲得之相變化型光資訊記錄媒體係以記 ^紙張尺度適用中國國家標準(〇奶)八4規格(210父297公釐) -72 - 一 (請先閲讀背面之注意事項再填寫本頁) 564412 A7 ___ B7 __ 五、發明説明(7〇 ) 請 先 閲 讀 背 之 注 載在表18之實施例61〜66之記錄線速度、以及具有mp部之 負荷比之脈衝波做記錄。在本實施例使用之光記錄裝置係 與圖17所示者相同,利用具有波長780nm、NA0.5之拾取頭 者。記錄信號設爲被EFM調制之輸入信號。以1.2m/s再生 以個別之線速記錄之信號之結果,個別爲22ns、20ns、23ns 可以獲得良好之初期抖動。在個別之記錄線速度之覆寫 1000次後之抖動分別爲32ns、30ns、33ns,良好。 又,在溫度80°C、溼度85%環境內,保存500小時後, 沒有見到記錄層之氧化以及光碟特性之變化,獲得良好之 保存特性。 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) -73 - 564412 A7 B7 五、發明説明(71 ) 經濟部智慧財產局員工消費合作社印製 mp部負荷比 外周 0.36 i 0.2 0.375 0.33 0.375 0.125 中間 0.48 0.24 0.5 0.375 0.5 0.175 內周 0.6 0.375 0.625 0.5 0.625 0.275 記錄線速(m/s) 外周 ID • Ο Csl OO CN cn ^~1 r—i j1 寸 r—H 中間 10 24 9.6 12 9.6 38.4 內周 5 12 4.8 6 4.8 19.2 記錄層組成(at%) 2 r-H CO <υ CNl CS OO cvl 〇 csi CNl CNJ CNl CO CO C<J 75 67 61 66 61 64.8 〇 t-H η σ\ 卜 … cn . oo (D 〇 r-H <N d 寸卜 CO · 〇 實施例 ,—1 CSI CO 寸 Ό Ό \〇 (請先閱讀背面之注意事項再填寫本頁)1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 564412 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (69) Recording wave pulse train when recording or rewriting a signal with a width of 1 nT The reason: The pulse part fp with the time width χ and the power level a interacts with the low level pulse with the time level power level b totaling T and the high level pulse of the power level c to load A laser pulse train formed by a total of (n-) consecutive multi-pulse sections mp and a pulse section op having a time width z and a power level d, and further set the aforementioned χ, y, and z to 0.5 respectively. TS 2.0T, 0.125 $ y $ 0.87 5, 0.125TS zS 1.0T, let η be a positive integer of 1 or more, (a and c) > e > (b and d). Figure 16 shows the case of r ^ = 1. Hereinafter, Embodiment 4 will be further described by way of examples. A 1.2-mm-thick polycarbonate substrate with a guide groove having a width of 0.5 // m and a depth of 35 nm was formed, and a first protective layer, a recording layer, a second protective layer, and Reflective layer. The first protective layer and the second protective layer were made of ZnSSiCh, and the film thicknesses were set to 90 nm and 30 μm, respectively. The recording layer uses the composition shown in the examples in Table 18, and the film thickness is 18 nm. The reflective layer uses aluminum alloy to form a substrate / ZnSSi〇2 (90nm) / GeGaSbTe (18nm) / ZnSSi〇2 (30nm) / A layer structure of an Al alloy (140 nm) was formed. Further, a hard coat layer and a thick coat layer formed by spin coating of an ultraviolet curable resin were formed to produce a phase change type optical information recording medium. Next, a full-scale crystallization process is performed on the recording layer of the optical information recording medium by an initializing device having a large-diameter LD. Further, a printed layer is formed on the thick coating layer. The phase-change type optical information recording medium obtained by the above method is in accordance with the Chinese standard (0 milk) 8 4 specifications (210 father 297 mm) on the paper scale. -72-1 (Please read the precautions on the back before (Fill in this page) 564412 A7 ___ B7 __ V. Description of the invention (70) Please read the note below for the recording linear velocity of Examples 61 to 66 in Table 18 and the pulse wave with the load ratio of the mp section for recording . The optical recording device used in this embodiment is the same as that shown in Fig. 17, and a pickup having a wavelength of 780 nm and NA 0.5 is used. The recording signal is set as an input signal modulated by EFM. As a result of reproducing signals recorded at individual line speeds at 1.2m / s, individual 22ns, 20ns, and 23ns can achieve good initial jitter. After 1000 times of overwriting of individual recording linear speeds, the jitters were 32 ns, 30 ns, and 33 ns, respectively, which was good. In addition, after storage for 500 hours in an environment with a temperature of 80 ° C and a humidity of 85%, no oxidation of the recording layer and a change in the characteristics of the optical disc were observed, and good storage characteristics were obtained. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Employees 'Cooperatives This paper is printed in accordance with the Chinese National Standard (CNS) A4 specifications (210X297 mm) -73-564412 A7 B7 V. Description of the invention (71) Printed by the Intellectual Property Bureau of the Ministry of Economics' Consumers Cooperative Load ratio of mp section 0.36 i 0.2 0.375 0.33 0.375 0.125 Middle 0.48 0.24 0.5 0.375 0.5 0.175 Inner periphery 0.6 0.375 0.625 0.5 0.625 0.275 Recording line speed (m / s) Outer ID • 〇 Csl OO CN cn ^ ~ 1 r—i j1 Inch r—H Middle 10 24 9.6 12 9.6 38.4 Inner week 5 12 4.8 6 4.8 19.2 Recording layer composition (at%) 2 rH CO < υ CNl CS OO cvl 〇csi CNl CNJ CNl CO CO C < J 75 67 61 66 61 64.8 〇tH η σ \ Bu ... cn. Oo (D 〇rH < N d inch CO CO · 〇 Example, -1 CSI CO inch Ό Ό \ 〇 (Please read the precautions on the back before filling this page)
、1T 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) -74 - 564412 經濟部智慧財產局員工消費合作社印製 A7 B7 _五、發明説明(72 ) 【發明之效果】 如依據本發明(1 )、( 2 ),可以提供以比最高記錄 線速度還大之線速可以進行記錄之光資訊記錄媒體。 如依據本發明(3 ),可以區別習知光碟與本發明之光 碟之故,可以提供不會錯誤地對習知的光碟以比最高記錄 線速度還快之速度進行記錄之光資訊記錄媒體。 如依據本發明(4 ) 、( 5 ),進而,可以提供信號品 質良好之光資訊記錄媒體,如依據本發明(6 ) 、( 7 )、 (9) 、(14),進而,可以提供覆寫特性優異之光資訊記 錄媒體,如依據本發明(8 ) 、(11),可以提供信賴性優 異之光資訊記錄媒體,如依據本發明(8 ) 、(12) 、(13 )、(14),可以提供量產性優異之光資訊記錄媒體。 如依據本發明(10 ),藉由現有之泛用性光資訊記錄 裝置之微調整,可以提供可以以比最高記錄線速度還高之 線速進行記錄之光資訊記錄媒體。 如依據本發明(1 5 )、( 1 6 ),判斷是否可以以比最 高記錄線速度還高之記錄線速度進行記錄,只在可以之情 形,以比最高記錄線速度還大之記錄線速度進行記錄,可 以提供不會錯誤記錄之光資訊記錄再生方法以及裝置。 又,如依據本發明之(17 )〜(25 ),可以提供功率 餘裕優異,重複特性、記錄.抹除感度、保存特性良好之 相變化型光資訊記錄媒體。又,如依據本發明之(26 ), 在製造上述光資訊記錄媒體之情形,可以效率良好地形成 具有上述特性之記錄層(記錄膜)。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -75- — (請先閲讀背面之注意事項再填寫本頁) 564412 經濟部智慧財產局員工消費合作社印製 A7 B7_五、發明説明(73 ) 又,如依據本發明之(27 ),設光資訊記錄媒體記錄 層之主要構成元素爲〇6、0&、31)、丁6,藉由特定化膜厚以 及記錄層之組成,在高線速區域(4.8〜45m/s)之記錄·抹 除成爲可能,而且,可以獲得信號之再生安定性或信號之 壽命等之總和特性優異之光資訊記錄媒體。 如依據本發明之(28 ),係一種記錄層之主成分爲Ge 、Ga、Sb、Te之光資訊記錄媒體,藉由在記錄層添加由: In、Zn、Sn、Si、Pb、Co、Cr、Cu、Ag、Au、Pd、Pt、S、 Se、Ta、Nb、V、Bi、Zr、Ti、A卜 Mn、Mo、Rh、C、N 以 及0選擇至少一種以上之元素,可以獲得高線速區域之信 號的再生安定性或信號之壽命之提升的光資訊記錄媒體。‘ 如依據本發明之(29 ),於記錄層之主成分中,藉由 特定化Ge-Ga間之組成關係,可以獲得兼顧高線速對應性 與保存信賴性之平衡的光資訊記錄媒體。 如依據本發明之(30 ),在記錄層之主成分中,藉由 特定化Sb-Te間之組成關係,可以獲得在高線速區域中’ 到達初期化時或記錄·抹除時所必要之反射率之光資訊記 錄媒體。 如依據本發明之(3 1 ),特定化光資訊記錄媒體各層 之膜厚以及記錄層之組成,而且,以PWM記錄進行對光資 訊記錄媒體之資訊記錄之際,藉由特定化進行信號之記錄 或重寫時之記錄波脈衝列之fp與ep之時間寬幅與mp之負 荷比,可以獲得藉由泛用之記錄策略之高線速記錄之光資 訊記錄媒體。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -76- (請先閱讀背面之注意事項再填寫本頁) 564412 A7 B7 五、發明説明(74) (請先閲讀背面之注意事項再填寫本頁) 如依據本發明之(32),在以PWM記錄進行對光資訊 記錄媒體之資訊記錄之際,藉由依據記錄線速度增減進行 信號之記錄或重寫時之記錄波脈衝列之脈衝部mp之負荷比 ,可以獲得能夠進行多速度記錄或CAV記錄之光資訊記錄 媒體。 【圖面之簡單說明】 圖1係顯示實施形態1之光資訊記錄媒體之構成例之圖 〇 圖2係顯示2次記錄抖動之位移線速度依存性之圖。 圖3係顯示實施形態1之記錄脈衝波形之例圖。 係顯示輸入信號。 係顯示圖案A之記錄脈衝波形。 係顯示圖案B之記錄脈衝波形。 係顯示圖案C之記錄脈衝波形。 圖4係顯示實施形態1之記錄再生之實施形態例之圖。 經濟部智慧財產局員工消費合作社印製 圖5係顯示設置依據實施形態2之記錄層之相變化型記 錄媒體之記錄脈衝波形之槪念圖。 圖6係顯示實施形態3之光資訊記錄媒體之構造的剖面 圖。 圖7係顯示在實施例5 1製作之光資訊記錄媒體之記錄層 的構造解析結果之X射線繞射光譜之說明圖。 圖8係顯示在實施例52製作之光資訊記錄媒體之記錄層 的構造解析結果之X射線繞射光譜之說明圖。 本紙張尺度適用中國國家標準(CNS ) Μ規格(210X 297公釐) -77 - ~ 564412 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(75 ) 圖9係顯示在實施例53製作之光資訊記錄媒體之記錄層 的構造解析結果之X射線繞射光譜之說明圖。 圖10係顯示在實施例54製作之光資訊記錄媒體之記錄 餍的構造解析結果之X射線繞射光譜之說明圖。 圖11係顯示在實施例55製作之光資訊記錄媒體之記錄 層的構造解析結果之X射線繞射光譜之說明圖。 圖12係顯示在比較例51製作之光資訊記錄媒體之記錄 層的構造解析結果之X射線繞射光譜之說明圖。 圖13係顯示在比較例52製作之光資訊記錄媒體之記錄 餍的構造解析結果之X射線繞射光譜之說明圖。 圖14係說明實施形態4之光資訊記錄媒體之一例用之 圖。 圖15係說明記錄脈衝波形用之圖。 圖16係顯示實施形態4之一例之CD— RW之4x〜1 Ox記 錄之多速度記錄之記錄波形圖。 圖17係說明實施形態4之光資訊記錄媒體之記錄再生 裝置的實施形態用之圖。 圖1 8係位移線速度之評估系統圖。 圖19係位移線速度之評估結果圖。 【標號說明】. 1 :基板, 2 :第一保護層, 3 :記錄層, 本^張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) :78 -~~ 一 (請先閲讀背面之注意事項再填寫本頁) ••I裝·、 1T This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -74-564412 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs _V. Description of the invention (72) [Effect of the invention] According to the present invention (1) and (2), it is possible to provide an optical information recording medium capable of recording at a line speed higher than the maximum recording line speed. According to the present invention (3), the conventional optical disc can be distinguished from the optical disc of the present invention, and an optical information recording medium can be provided which does not erroneously record the conventional optical disc at a faster speed than the highest recording linear speed. According to the present invention (4) and (5), further, an optical information recording medium with good signal quality can be provided, and according to the present invention (6), (7), (9), (14), further, an overlay can be provided. Optical information recording media with excellent writing characteristics, such as those according to the present invention (8) and (11), can provide optical information recording media with excellent reliability, such as according to the present invention (8), (12), (13), (14) ), Can provide optical information recording media with excellent mass productivity. According to the invention (10), with the fine adjustment of the existing general-purpose optical information recording device, an optical information recording medium capable of recording at a line speed higher than the highest recording line speed can be provided. For example, according to the present invention (1 5) and (16), it is determined whether recording can be performed at a recording linear velocity higher than the maximum recording linear velocity, and only when possible, at a recording linear velocity higher than the maximum recording linear velocity. Recording can provide a method and a device for recording and reproducing optical information without erroneous recording. In addition, according to the inventions (17) to (25), a phase change type optical information recording medium having excellent power margin, excellent repeatability, recording, erasing sensitivity, and storage characteristics can be provided. Further, according to the aspect (26) of the present invention, in the case of manufacturing the above-mentioned optical information recording medium, a recording layer (recording film) having the above characteristics can be efficiently formed. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -75- — (Please read the notes on the back before filling out this page) 564412 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ Description of the invention (73) In addition, according to (27) of the present invention, the main constituent elements of the recording layer of the optical information recording medium are 0, 0, 0, 31) and D6. By specifying the film thickness and the thickness of the recording layer, The composition enables recording and erasing in a high-line-speed area (4.8 to 45 m / s), and it is possible to obtain an optical information recording medium excellent in the sum of characteristics such as signal reproduction stability and signal life. According to the invention (28), an optical information recording medium whose main component is Ge, Ga, Sb, Te is added to the recording layer by adding: In, Zn, Sn, Si, Pb, Co, Cr, Cu, Ag, Au, Pd, Pt, S, Se, Ta, Nb, V, Bi, Zr, Ti, Ab, Mn, Mo, Rh, C, N, and 0.Choose at least one or more elements to obtain Optical information recording medium that reproduces the stability of signals in high-speed areas or improves the life of signals. ‘According to (29) of the present invention, in the main component of the recording layer, by specifying the composition relationship between Ge and Ga, it is possible to obtain an optical information recording medium that balances high linear speed correspondence and storage reliability. According to (30) of the present invention, in the main component of the recording layer, by specifying the composition relationship between Sb-Te, it is possible to obtain the 'necessary when initializing or recording and erasing in the high linear velocity region. The reflectance of light information recording media. According to (3 1) of the present invention, the film thickness of each layer of the optical information recording medium and the composition of the recording layer are specified, and when the information recording of the optical information recording medium is performed by PWM recording, the signal is specified by the specificization. When recording or rewriting, the time width of fp and ep of the pulse wave sequence of the recording wave and the load ratio of mp can obtain an optical information recording medium for high-line-speed recording by a universal recording strategy. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -76- (Please read the precautions on the back before filling this page) 564412 A7 B7 V. Description of the invention (74) (Please read the precautions on the back first Please fill in this page for more details.) According to (32) of the present invention, when recording information on the optical information recording medium by PWM recording, the signal is recorded or rewritten when the signal is recorded or rewritten according to the increase or decrease of the recording linear velocity. The duty ratio of the pulse portion mp of the pulse train can obtain an optical information recording medium capable of multi-speed recording or CAV recording. [Brief description of the drawing] Fig. 1 is a diagram showing a configuration example of an optical information recording medium according to the first embodiment. Fig. 2 is a diagram showing the dependence of the displacement linear velocity of the second recording jitter. Fig. 3 is a diagram showing an example of a recording pulse waveform in the first embodiment. The input signal is displayed. It is the recording pulse waveform of display pattern A. It is the recording pulse waveform of display pattern B. It is the recording pulse waveform of display pattern C. FIG. 4 is a diagram showing an example of the recording and reproduction in the first embodiment. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 5 is a schematic diagram showing the recording pulse waveform of a phase-change recording medium provided with a recording layer according to the second embodiment. Fig. 6 is a sectional view showing the structure of an optical information recording medium according to the third embodiment. Fig. 7 is an explanatory diagram showing an X-ray diffraction spectrum of a structure analysis result of a recording layer of an optical information recording medium produced in Example 51; Fig. 8 is an explanatory diagram showing an X-ray diffraction spectrum of a structure analysis result of a recording layer of an optical information recording medium prepared in Example 52; This paper size applies the Chinese National Standard (CNS) M specification (210X 297 mm) -77-~ 564412 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (75) Figure 9 is shown in Example 53 An explanatory diagram of an X-ray diffraction spectrum of a structure analysis result of a recording layer of the produced optical information recording medium. Fig. 10 is an explanatory diagram showing an X-ray diffraction spectrum of a structure analysis result of a recording chirped optical information recording medium produced in Example 54; Fig. 11 is an explanatory view showing an X-ray diffraction spectrum of a structure analysis result of a recording layer of the optical information recording medium produced in Example 55. Fig. 12 is an explanatory diagram showing an X-ray diffraction spectrum of a structure analysis result of a recording layer of an optical information recording medium produced in Comparative Example 51; FIG. 13 is an explanatory diagram showing an X-ray diffraction spectrum of a structure analysis result of a recording ridge of an optical information recording medium produced in Comparative Example 52. FIG. Fig. 14 is a diagram for explaining an example of an optical information recording medium according to the fourth embodiment. Fig. 15 is a diagram for explaining the recording of a pulse waveform. Fig. 16 is a recording waveform diagram showing multi-speed recording of 4x to 1 Ox recording of CD-RW as an example of the fourth embodiment. Fig. 17 is a diagram for explaining an embodiment of a recording / reproducing apparatus for an optical information recording medium according to the fourth embodiment. Fig. 18 Diagram of the 8-series displacement linear velocity evaluation system. Fig. 19 is a graph showing the evaluation results of the displacement linear velocity. [Label description]. 1: substrate, 2: first protective layer, 3: recording layer, this standard is applicable to China National Standard (CNS) A4 specification (210X297 mm): 78-~~ (Please read the back first (Please fill in this page again)
、1T 564412 kl B7五、發明説明( 4 :第二保護層, 5 :第三保護層, 6 :反射層, 7 :厚塗層, 8 :印刷層, ^ :印刷層, 9 :硬塗層, 1 0 :黏著層 21 :基板 22 :下部耐熱保護層 2 3 :記錄層 24 :上部耐熱保護層 2 5 :反射散熱層 3]:基板 3 2 :第1保護層 3 3 :記錄層 34 :第2保護層 (請先閱讀背而之注意事項再填寫本頁) -裝· 、\一吞 經濟部智竑財產局貞工消費合作社印製 3 3 3 層層 層層 射塗刷塗 反厚印硬 本紙張尺度適用中國國家標準(CNS ) Λ4規格(2]〇Χ 297公釐) 一 79 -1T 564412 kl B7 V. Description of the invention (4: second protective layer, 5: third protective layer, 6: reflective layer, 7: thick coating layer, 8: printing layer, ^: printing layer, 9: hard coating layer 10: Adhesive layer 21: Substrate 22: Lower heat-resistant protective layer 2 3: Recording layer 24: Upper heat-resistant protective layer 2 5: Reflective heat dissipation layer 3]: Substrate 3 2: First protective layer 3 3: Recording layer 34: The second protective layer (please read the precautions before filling in this page)-installed, printed by Yitong, the Ministry of Economic Affairs, Zhizheng Property Bureau, Zhengong Consumer Cooperative, 3 3 3 The size of printed hard paper is in accordance with Chinese National Standard (CNS) Λ4 specification (2) 〇 × 297 mm) 79-
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JP2000280726A JP4019135B2 (en) | 2000-09-14 | 2000-09-14 | Optical recording medium and recording method therefor |
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JP2000310536 | 2000-10-11 | ||
JP2000367361 | 2000-12-01 | ||
JP2001088516 | 2001-03-26 |
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