201001553 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種附有氧化物層之基體及其製造方法。 【先前技術】 以摻錫氧化細（ITO，Indium Tin Oxide)為代表之·透明導 電膜正成為液晶顯示元件（LCD，Liquid Crystal Device)或 電漿顯示面板（PDP，Plasma Display Panel)等平板顯示器 (FPD，Flat Panel Display)、以及太陽電池等電子裝置之必 需材料。透明導電膜之通常之製造方法如下。 首先，使用濺鍍法等於基體上形成透明導電膜，其後藉 由圖案化將不需要之部分去除。圖案化有各種方法，但多 使用光微影法（Photolithography)。 然而，光微影法存在步驟數多之潛在性問題。尤其，伴 隨FPD中之基板之大型化而成為導致生產性惡化之較大主 要原因。 又，由於難以製作大型之光罩，故作為代替光微影法之 透明導電膜之圖案化法，業界對雷射圖案化法（laser patterning)進行研究（參照專利文獻1、2)。其原因在於： 與光微影法相比較，雷射圖案化法之步驟數少，且製程之 穩定性高。 又，由於低電阻特性等原因，廣泛應用於FPD等之IT0 存在銦金屬之資源枯竭之潛在性問題。因此，作為可代替 IT0之透明導電膜，業界正進行氧化錫等之開發（專利文獻 3)。 140353.doc 201001553 刻之耐久性高，故使用酸 。因此，對於氧化錫亦進 仁疋，由於氧化錫對於化學姓 之光微影法之應用#際上較困難 行雷射圖案化法之研究。 二’二Λ知如下之方法：於玻璃基板1之上設置氧化物 變質 …、射田射先’使被對象物之照射部位 .2 猎由槽中之濕式姓刻（wet etching)將去除部4 矛、’從而於作為電極之部位獲得所需之圖案（參照圖5)。 作為利用雷射之加工技術，已知有如下之方法：當 • 〇成石央基板上形成折射率不同之介電體多層膜之介 :體遮罩進行圖案化時，預先於介電體多層膜之上面形成 二屬層，然後利用雷射光對介電體多層膜與金屬層同時進 打1虫刻’純將金屬I去除（專利文獻4)。 已知有利用雷射剝蝕法（丨aser ablati〇 來製造光電子裝置之方法(專利文獻5)d 先前技術文獻 專利文獻 專利文獻1 ·曰本專利特開2001-526〇2號公報 專利文獻2 .曰本專利特開2005-108668號公報 專利文獻3:曰本專利4〇18839號公報 專利文獻4 :曰本專利特開平1 〇_263871號公報 專利文獻5 :曰本專利特表2007-533091號公報 【發明内容】 [發明所欲解決之問題] 於雷射圖案化法中，藉由雷射光與被對象物（材料）之關 140353.doc 201001553 係而大致決定該被對象物之加工 餘地較少。又，透明導電膜 1提升生產性之 ^ %肤遇书加工性 進行透明導電膜之圖案化加工之牛 雜 匕為了確保 需採取設置較多的雷射圖幸彳卜# ,王之處理能力，必 的田射圖案化裝置等應對措施。 又，於透明導電膜之加工中， ^ ^ '加工時所必需之動力十 心性寻而言’多使m線雷射光⑽咖 = 而，於紅外線雷射光之波長區域中，氧化錫之加工性)低= το，因此成為特別顯著之問題。 _ ;201001553 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to a substrate with an oxide layer and a method of manufacturing the same. [Prior Art] The transparent conductive film represented by ITO (Indium Tin Oxide) is becoming a flat panel display such as a liquid crystal display (LCD) or a plasma display panel (PDP). (FPD, Flat Panel Display), and the necessary materials for electronic devices such as solar cells. A general manufacturing method of a transparent conductive film is as follows. First, a sputtering method is used to form a transparent conductive film on the substrate, and then unnecessary portions are removed by patterning. There are various methods for patterning, but photolithography is often used. However, the photolithography method has a potential problem of a large number of steps. In particular, the large size of the substrate in the FPD has become a major cause of deterioration in productivity. Further, since it is difficult to produce a large-sized photomask, the laser patterning method has been studied as a patterning method for a transparent conductive film instead of the photolithography method (see Patent Documents 1 and 2). The reason is that: compared with the photolithography method, the number of steps of the laser patterning method is small, and the stability of the process is high. Further, due to low resistance characteristics and the like, it is widely used in the potential problem of resource depletion of indium metal in IT0 such as FPD. Therefore, the industry is developing tin oxide and the like as a transparent conductive film that can replace IT0 (Patent Document 3). 140353.doc 201001553 The durability is high, so use acid. Therefore, for tin oxide, it is also difficult to perform the laser patterning method because of the application of tin oxide to the chemical lithography method. The second 'two knows the following method: the oxide is degraded on the glass substrate 1; the shot is shot first to make the object irradiated. 2 The hunting is removed by the wet etching in the groove. Part 4 Spear, 'and thus obtain the desired pattern as the part of the electrode (refer to Figure 5). As a processing technique using a laser, there is known a method in which a dielectric mask is formed on a substrate of a different refractive index when a dielectric mask is formed on a substrate, and a dielectric mask is used in advance. A two-layer layer is formed on the upper surface of the film, and then the dielectric multilayer film and the metal layer are simultaneously irradiated with laser light to remove the metal I by pure laser light (Patent Document 4). A method of manufacturing an optoelectronic device by using a laser ablation method (Patent Document 5) is known. Patent Document 1 Patent Document 1 Patent Publication No. 2001-526 No. 2 Patent Document 2 . Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 2005-108668. Patent Document 3: Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] In the laser patterning method, the processing of the object is roughly determined by the relationship between the laser light and the object (material) 140353.doc 201001553. In addition, the transparent conductive film 1 enhances the productivity of the product. The processing of the transparent conductive film is carried out in order to ensure that a large number of laser images are required to be taken. The ability, the necessary field-shooting patterning device, etc. In addition, in the processing of the transparent conductive film, ^ ^ 'the necessary power for processing, the ten-heartedness of the 'much of the m-ray laser light (10) coffee = and Infrared laser light Wavelength region, workability tin oxide) Low = το, and therefore a problem of significant especially. _ ;
本發明之目的在於提供—種可應對大型基板、生產" 好、且工品質優異之附有氧化物層之基體之製造心 及附有氧化物層之基體。 [解決問題之技術手段] 即，本發明之態樣1提供一種附有經圖案化之氧化物層 之基體之製造方法，其包括如下步驟：於基體上依序形‘ 表現出透明導電性之氧化物層、金屬I ;自金屬層之外表 面側，向金屬層照射能量密度為0.3〜1〇 J/cm2、重複頻率 為1〜100 kHz、脈衝寬度為i ns〜i叩之脈衝雷射光，將脈 衝雷射光之照射部位之金屬層與氧化物層去除；以及藉由 姓刻將金屬層去除。 態樣2提供如態樣1之附有氧化物層之基體之製造方法， 其中脈衝雷射光之波長為1047〜1064 nm。 態樣3提供如態樣1或2之附有氧化物層之基體之製造方 法’其中藉由一次之脈衝雷射光所照射之照射部位之面積 為1 mm2以上。 態樣4提供如態樣1、2或3之附有氧化物層之基體之製造 140353.doc 201001553 方法其中每照射一次脈衝雷射 能棉s妲似，▲ 移動—次照射部位。 L樣5棱供如態樣i、2、3或4之 ^ 1有虱化物層之基體之 衣以方法，其中以15,〇〇〇 mm2/s以 雷射光。 上之照射速度照射脈衝 態樣6提供如態樣1、2、3、 夕制，土 士、+ $ 5之附有氧化物層之基體 之衣&方法，其中氧化物層為 $ 勹軋化錫或摻錫氧化銦。 態奴7棱供如態樣丨至6 + m +、+ 項之附有氧化物層之基體 之^方法，其中氧化物層之膜厚為1〇 一 _。 態樣8提供如態樣丨至7中任— 項之附有氧化物層之基體 “方法，其中金屬層係由選自由a"、co、Cr、SUMMARY OF THE INVENTION An object of the present invention is to provide a substrate for a substrate having an oxide layer which can cope with a large substrate and which is excellent in quality and excellent in work quality, and a substrate having an oxide layer. [Technical means for solving the problem] That is, Aspect 1 of the present invention provides a method of manufacturing a substrate with a patterned oxide layer, comprising the steps of: forming a transparent conductivity on a substrate in a sequential shape Oxide layer, metal I; from the outer surface side of the metal layer, the metal layer is irradiated with a pulsed laser light having an energy density of 0.3 to 1 〇 J/cm 2 , a repetition frequency of 1 to 100 kHz, and a pulse width of ns to i 叩The metal layer and the oxide layer of the irradiated portion of the pulsed laser light are removed; and the metal layer is removed by the surname. Aspect 2 provides a method of fabricating a substrate with an oxide layer as in Aspect 1, wherein the wavelength of the pulsed laser light is 1047 to 1064 nm. The aspect 3 provides a method of producing a substrate having an oxide layer as in the aspect 1 or 2, wherein the area of the irradiated portion irradiated by the primary pulsed laser light is 1 mm 2 or more. Aspect 4 provides the fabrication of a substrate with an oxide layer as in Aspect 1, 2 or 3. 140353.doc 201001553 The method is characterized in that each time a pulsed laser energy is applied, the ▲ movement-sub-irradiation portion. The L-like 5 ribs are provided with a substrate of a telluride layer as in the form i, 2, 3 or 4, wherein the laser is irradiated with 15, 〇〇〇 mm 2 /s. The irradiation rate of the upper illuminating pulse pattern 6 provides a coating & method of the substrate with an oxide layer as in the aspect 1, 2, 3, eve, toast, + 5, wherein the oxide layer is rolled Tin or tin-doped indium oxide. The state of the slave 7 is supplied to the substrate of the 6 + m + , + term with an oxide layer, wherein the film thickness of the oxide layer is 1 〇 _. Aspect 8 provides a method as described in the following paragraph - the substrate with an oxide layer "in the method, wherein the metal layer is selected from a", co, Cr,
Cu、Fe、M。、Ni、Sn、Zr^v所組成之群中之至少一種 以上之金屬構成。 態樣9提供如態樣1至8中任一 τ仗項之附有乳化物層之基體 之製造方法’其中金屬層係由非磁性體之金屬構成。 態樣1〇提供如態樣1至9中任-項之时氡化物層之基體 之製造方法，其中金屬層之膜厚為3〜】〇()nm。 態樣Η提供一種附有氧化物層之基體，其係藉由如態樣 1至1〇中任—項之附有氧化物層之基體之製造方法而製 造。 態樣12提供-種電子以，其係將如態樣11之附有氧化 物層之基體的氧化物層用作電極而形成。 於上述之各態樣中，包括金屬層中含有氡之情形。 又，於上述態樣中，較好的是於基體上形成有1〇〇個以 上之氧化物層之圖案。進而較好的是於基體上形成有2〇〇 140353.doc 201001553 個以上之氧化物層之圖幸。 茶 又’於將附有氧化物層之基體 之氧化物層用作顯示面核 + 板之包極之情形時，能夠適合顯示 畫面之像素的圖案個數較好 平乂对的疋例如500〜2000個。又，較 好的是對應於高密度鞀千 ·"、貝不之面板，實施短間距•高精細之 圖案化。 於上述態樣中，較好的县气& & p ^ 于的疋虱化物層係由選自由氧化銦、 氧化錫、推錫氧化銦、氣化拉 乳化鋅、氧化鈦及氧化鋁所組成之 群中之一種以上之材料構成。 ；辽心樣中，於製膜方法為磁控•濺鍍之情形時，較 好的疋金屬膜之材料不為磁性體。即，特別好的是金屬層 係由選自由Ag、A卜〇、λ,γ 〇 6 Cu、Mo、Sn及V所組成之群中 之至少一種以上之金屬構成。 其中，即便於具有磁性之Fe、c〇、犯之情形時，只要對 乾材之操作加以注意’則亦可製膜成能夠使用之金屬層。 又，於上述態樣中，較好的是電子裝置為顯示面板。進 而較好的是顯示面板為咖或卿。χ，較好的是上述之 電子裝置為太陽電池模組。於上述態樣中，由於金屬層可 藉由濕式蝕刻或乾式蝕刻（dry etching)而容易地去除，因 此不會導致步驟整體之生產性惡化。本發明可應用於各種 电子衣置其中，尤其適合於電極根數多之高精細之大型 …頁示面板之生產。本發明例如適合於晝面之對角尺寸為 106 cm以上，或者作為晝面之電極構成，行側為】根以 上，且列侧為768根以上之大型面板。本發明尤其適合於 高解析度圖像之顯示面板之製造。 140353.doc 201001553 [發明之效果] 於本發明中，可使氧化物層之雷射圖案化加工之生產性 與加工品質得到飛躍性提昇。本發明對於包含ITO或氧化 錫之透明氧化物層有效。尤其適合於在敍刻速度方面存在 錫，圖案化。又，可抑制對於欲形成之表現忠 透月V $性之氧化物層之損傷。 又’本發明可使卿或太陽電池模组用之附有透明導電 膜之基板之生產性飛躍性提昇，並且可降低生 【實施方式】 於本發明中’於基體上’除作為被對象物之氧化物層以 卜’亦複合形成有金屬層。對於該經複 脈衝雷射％，並且在實質上 霉'、、、射 个耵丞體造成損害之情況 照射部之氧化物層與金屬層同時去除，從而可獲得所需Z 加工物體，即可於基體上獲得經圖案化之氧化物層。 通常，金屬與氧化物相比較，φ RB ^ 田射加工性良好。於本發 月中’將金屬用作雷射圖宰化味夕沾丄 ^ 茱化時之輔助層。一般認為藉由 除氧化物層之外設置金屬層， 了使金屬層自脈衝雷射光 吸收之能量傳遞至氧化物層。 尤所 結果，氧化物層之雷射加工性 丨柃幵。金屬層之位置並盖 特別限定，就於雷射照射後去 …、 切 交云除輔助層之容易性而言，齡 好的是形成於表層侧。又，全屬 .^ 屬層亦可形成兩層以上之褶 數層。於此情形時，亦可將金凡 卜 之間。 屬層3又置於氧化物層與基體 圖1係本發明之構成之示音性 W性面圖，圖中揭示有基體 140353.doc 201001553 1、氧化物層2、作為輔助層而發揮功能之金屬岸3、去除 部4、雷射光源50、雷射光線51、以及遮罩7。於該構成Cu, Fe, M. And at least one of the group consisting of Ni, Sn, and Zr^v is composed of a metal. Aspect 9 provides a method of producing a substrate having an emulsion layer as in any of the aspects 1 to 8 wherein the metal layer is composed of a metal of a non-magnetic body. The method for producing a substrate of a telluride layer as in any of the first to the ninth aspects, wherein the thickness of the metal layer is 3 to 〇() nm. The aspect Η provides a substrate to which an oxide layer is attached, which is produced by a method of producing a substrate having an oxide layer as in any of the aspects 1 to 1 . The aspect 12 provides an electron which is formed by using an oxide layer of the substrate of the oxide layer as the state 11 as an electrode. In each of the above aspects, the case where the metal layer contains germanium is included. Further, in the above aspect, it is preferred that a pattern of more than one oxide layer is formed on the substrate. Further preferably, a pattern of 2 〇〇 140353.doc 201001553 oxide layers is formed on the substrate. In the case where the oxide layer of the substrate with the oxide layer is used as the envelope of the surface core + the plate, the number of patterns suitable for displaying the pixels of the picture is preferably a flat pair, for example, 500~ 2000. Further, it is preferable to carry out short-pitch and high-definition patterning in accordance with the panel of high-density · · 、 、 、 、. In the above aspect, the preferred gas phase of the gas phase && p ^ is selected from the group consisting of indium oxide, tin oxide, tin indium oxide, vaporized emulsified zinc, titanium oxide and aluminum oxide. One or more of the constituent groups are composed of materials. In the case of the Liaoxin sample, when the film forming method is magnetic control or sputtering, the material of the better base metal film is not a magnetic body. That is, it is particularly preferable that the metal layer is composed of at least one metal selected from the group consisting of Ag, A, λ, γ 〇 6 Cu, Mo, Sn, and V. Among them, even in the case of magnetic Fe, c, or sin, the metal layer which can be used can be formed by paying attention to the operation of the dry material. Further, in the above aspect, it is preferable that the electronic device is a display panel. Further preferably, the display panel is a coffee or a clerk. Preferably, the electronic device described above is a solar cell module. In the above aspect, since the metal layer can be easily removed by wet etching or dry etching, the productivity of the entire step is not deteriorated. The invention can be applied to various electronic clothes, and is especially suitable for the production of a high-definition large-sized display panel with a large number of electrodes. The present invention is suitable, for example, for a large-sized panel having a diagonal dimension of 106 cm or more, or an electrode as a kneading surface, a row side being a root or more, and a row side being 768 or more. The invention is particularly suitable for the manufacture of display panels for high resolution images. 140353.doc 201001553 [Effects of the Invention] In the present invention, the productivity and processing quality of the laser patterning processing of the oxide layer can be greatly improved. The present invention is effective for a transparent oxide layer comprising ITO or tin oxide. It is especially suitable for tin and patterning in terms of speed. Further, it is possible to suppress damage to the oxide layer which is loyal to the month V $ property to be formed. Further, the present invention can greatly improve the productivity of a substrate with a transparent conductive film for a solar cell module or a solar cell module, and can reduce the growth. [Embodiment] In the present invention, the object is removed from the substrate. The oxide layer is also composited with a metal layer. For the complex pulsed laser %, and in the case where the mold is substantially damaged, the oxide layer of the illuminating portion and the metal layer are simultaneously removed, so that the desired Z-processed object can be obtained. A patterned oxide layer is obtained on the substrate. Generally, the metal φ RB ^ field processability is good compared with the oxide. In the middle of this month, the metal was used as the auxiliary layer of the laser smear. It is believed that by disposing a metal layer in addition to the oxide layer, the energy absorbed by the metal layer from the pulsed laser light is transferred to the oxide layer. In particular, the laser processing properties of the oxide layer are flawed. The position of the metal layer and the cover are particularly limited, and it is formed on the surface side in terms of the ease of removing the auxiliary layer after the laser irradiation. Moreover, all of the genus layers can form two or more layers of pleats. In this case, you can also between Jinfanbu. The genus layer 3 is further placed on the oxide layer and the substrate. FIG. 1 is a schematic representation of the structure of the present invention. The substrate 140353.doc 201001553 1 is shown, and the oxide layer 2 functions as an auxiliary layer. The metal bank 3, the removal portion 4, the laser light source 50, the laser beam 51, and the mask 7. In this composition
於基體（玻璃基板）i上形成有具有透明導電性之包含氧 化錫之氧化物層2，以及包含選自A g AILr、Mo、SnZn合 金或Sn中之金屬之金屬層3。自雷射光源5〇， 性之雷射光51自金屬層3之外*而如—防 定肌衝 s j之外表面側母照射一次則移動一 -人照射位置’ 一面隔著遮罩7進行照射，將金 物層2去除’藉此形成去 '”羊 ,.^ 後猎由蝕刻將金屬層 3去除，從而形成附有氧化物層之基體。 圖2係本發明之示意性羋 ,.^ +面圖，圖中透明導電膜被圖案 化成線狀。以上述方或％從/θ X侍之附有氧化物層之基體可用 作LCD或PDP之透明電 土體了用 極受到雷射圖案化加工。料顯^面之像素數對應之電 前之示意性平面圖，圖2⑻传進=)係進行雷射圖案化 平面圖。 ⑻係進仃雷射圖案化後之示意性 圖3係關於本發明之 β A本牛驟的^ 礼化物層之基體之製造方法之 丞本步驟的流程圖。 〜 圖4係本發明之進行 PI ., n圖案化之情形時之示意性平面 圖。此外，圖4(A)係進行 十面 4CB)r^. ^ 圖木化刖之不意性平面圖，圖 4(B)係進仃圖案化後之 ΰ 術之步驟變化之示意圖，…面圖。圖5係表示先前技 於本發明中，金屬岸 c〇、Cr、c 日之材料較好的是選自由Ag' Α卜 之至少一種。只…、Snzn、S1^v所組成之群中 、為膜之形成、利用雷射照射之去 140353.doc 201001553 除、以及蝕刻去除之障礙’則金屬層之材料亦可為合金。 尤其’就其容易形成、或者於雷射照射後將輔助層去除 時之作業特性之方面而言，較好的是選自由卸、A卜。、An oxide layer 2 containing tin oxide having transparent conductivity and a metal layer 3 containing a metal selected from Ag aILr, Mo, SnZn alloy or Sn are formed on the substrate (glass substrate) i. From the laser light source 5〇, the laser light 51 of the nature is outside the metal layer 3; and if the surface of the surface is illuminated once, the surface side is irradiated once, then the one-person illumination position is moved, and the surface is illuminated by the mask 7. The gold layer 2 is removed 'by forming a 'go', and the metal layer 3 is removed by etching to form a substrate with an oxide layer. FIG. 2 is a schematic diagram of the present invention, . In the figure, the transparent conductive film is patterned into a line shape. The substrate with the oxide layer attached to /θ X from the above square or % can be used as a transparent electric earth body for an LCD or a PDP. The processing is shown in Fig. 2(8): =) is a laser patterning plan. (8) Schematic diagram of the laser patterning after entering the laser. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 4 is a schematic plan view showing a case where the PI., n patterning is performed in the present invention. FIG. 4(A) is a four-sided 4CB)r^. ^ Unplanned plan of Fig. 4(B) The schematic diagram of the steps of the subsequent steps of the sputum is shown in Fig. 5. It is shown in the prior art that the material of the metal bank c〇, Cr, c is preferably selected from at least one of Ag'. In the group consisting of only..., Snzn, and S1^v, the formation of a film, the use of laser irradiation, 140353.doc 201001553, and the obstacle of etching removal, the material of the metal layer may also be an alloy. It is preferably selected from the viewpoint of the workability when the auxiliary layer is removed after laser irradiation, and is preferably selected from the group consisting of unloading, A, and
Cu Μ。及Zn、811所組成之群中之至少一種材料。於去除 輔助層時，使用可不損傷氧化物層而僅去除金屬層之蝕刻 法。具體而言，可使用濕式㈣或乾式姓刻。 就银刻之均勻性或容易性等而言，較好的是使用渴式姓 刻。濕式I虫刻中所使用之藥液係考慮到輔助層之種 化物層對藥液之耐久性，而使用就钱刻速度等觀點而 合適者。 、，例如’於輔助層為Ag、AI、Cu或Mo之情形日夺，鱗酸、 硝自夂、乙酸及水之混合物較為適合。於Μ、％、a —合金之情形時，除上述以外，可使用氫氧化鈉溶液等 物於輔助層為之情形時，硝酸㈣、過氯酸及 合二：Γ墙酸飾銨、確酸及水之混合物較為適 方：…設定為—，此於生產性或管理 於雷射圖案化加工中，藉由雷射照射，自被加 翔物作為碎片而堆積於周圍，導致加工品質下降 =::Γ金屬層位於表層，故可於將辅助物 於二::::=:r碎一。對應 常，就作^積，來去除金屬層。通 案化之氧化物ΐ觀點而言，較好的是對於將基體上之經圖 、物層用作透明電極之特定電極面，總括地去除 140353.doc -10- 201001553 金屬層。 就膜厚或膜質之均勻性之方面而言，用作輔助層之金屬 層較好的是藉由濺鍍而形成。濺鍍壓力較適當的是 Pa。又，背壓較好的是lx10-6〜lxl〇-2 Pa。基板溫度為室溫 〜300 C ’特別好的是15〇〜3〇〇。(^。 金屬層除金屬成分以外，亦可含有氧。如下所述，於本 發明之實施例中，當形成氧化物層時，藉由自外部導入之Cu Μ. And at least one of the group consisting of Zn and 811. When the auxiliary layer is removed, an etching method which removes only the metal layer without damaging the oxide layer is used. Specifically, a wet (four) or dry type can be used. In terms of uniformity or easiness of silver engraving, it is preferable to use a thirsty name. The chemical liquid used in the wet type I insect is considered to be suitable for the durability of the chemical layer of the auxiliary layer in terms of the speed of the chemical solution. For example, in the case where the auxiliary layer is Ag, AI, Cu or Mo, a mixture of scalylic acid, nitric acid, acetic acid and water is suitable. In the case of bismuth, %, or a-alloy, in addition to the above, when a sodium hydroxide solution or the like is used as the auxiliary layer, nitric acid (tetra), perchloric acid, and hexahydrate: ammonium sulphate, acid The mixture of water and water is more suitable: ... is set to -, in production or management in laser patterning processing, by laser irradiation, piled up around the object as a fragment, resulting in a decline in processing quality = :: The ruthenium metal layer is located on the surface layer, so the auxiliary can be broken at two::::=:r. Correspondingly, the product is removed to remove the metal layer. From the viewpoint of the generalized oxide ruthenium, it is preferred to collectively remove the metal layer of 140353.doc -10- 201001553 for the specific electrode surface on which the pattern and the object layer on the substrate are used as transparent electrodes. The metal layer used as the auxiliary layer is preferably formed by sputtering in terms of film thickness or uniformity of film quality. The sputtering pressure is more suitable for Pa. Further, the back pressure is preferably lx10-6~lxl〇-2 Pa. The substrate temperature is room temperature ~ 300 C ' particularly good is 15 〇 ~ 3 〇〇. (^. The metal layer may contain oxygen in addition to the metal component. As described below, in the embodiment of the present invention, when the oxide layer is formed, it is introduced from the outside.
乳或自氧化物才產生之氧，而形成含有氧之氣體環境。 金屬層與氧化物層通常可利用不同之製程法來製膜，但較 好的是使用同-製膜裝置在線連續地形成金屬層與氧化物 層。即，特別好的是以同_製程法，並使用同一製膜褒置 連續地進行處理。 於此If形時’有金屬層中含有氧之情況。金屬層中之氧 相對於總成分，較好的是。〜2〇原子％。若氧之含量超過 原子％，m當進行雷射圖案化時，提昇氧化物之加工性之 效果減小。 為了使金屬層中之氧相於她士 乳相對於總成分而為0〜20原子％，只 要於成膜中使用含有氧元夸名 礼π常之耽體（例如混合有〇2或c〇2氣 體與氬氣之混合氣體）即可。 較好的是使金屬層之膜厘幺 , 興曰芡犋厚為3〜1〇〇 nm。若未達3 nm，則 當進行雷射圖案化時，接異氫作从^ t 杈昇乳化物之加工性之效果減小。 若超過100 nm，則接1 仏 則挺幵虱化物之加工性之效果反而減小。 又，於膜厚過大之情形時，合 曰對補助層形成及於雷射圖案 化後之輔助層之去除會產生負荷，故欠佳。 140353.doc 201001553 氧化物層亦可形成兩層以上之複數層。例如可形成美體 /氧化物層1/氧化物層2/金屬層、基體/氧化物層金屬層/ 氧化物層2/金屬層等構成。 曰 〃表現岀透明導電性之氧化物層較好的是選自由氧化鋼、The oxygen produced by the milk or from the oxide forms a gaseous environment containing oxygen. The metal layer and the oxide layer can usually be formed by different process methods, but it is preferable to form the metal layer and the oxide layer in-line continuously using the same-film forming apparatus. That is, it is particularly preferable to carry out the treatment continuously using the same film forming method and the same film forming method. In the case of the If shape, there is a case where oxygen is contained in the metal layer. The oxygen in the metal layer is preferably relative to the total composition. ~ 2 〇 atomic %. If the content of oxygen exceeds atomic %, the effect of improving the processability of the oxide is reduced when laser patterning is performed. In order to make the oxygen phase in the metal layer 0 to 20 atomic % relative to the total composition of the milk, as long as it is used in the film formation, the body containing the oxygen atom is used (for example, mixed with 〇2 or c〇). 2 gas and argon mixed gas) can be. Preferably, the film of the metal layer is centiated to a thickness of 3 to 1 〇〇 nm. If it is less than 3 nm, when the laser patterning is performed, the effect of the addition of hydrogen to the processability of the emulsion is reduced. If it exceeds 100 nm, the effect of the processability of the bismuth compound decreases. Further, in the case where the film thickness is too large, the formation of the auxiliary layer after the formation of the auxiliary layer and the removal of the auxiliary layer after the laser patterning is unsatisfactory. 140353.doc 201001553 The oxide layer can also form a plurality of layers of more than two layers. For example, a body/oxide layer 1 / oxide layer 2 / metal layer, a substrate / oxide layer metal layer / oxide layer 2 / metal layer can be formed.曰 〃 shows that the transparent conductive oxide layer is preferably selected from the group consisting of oxidized steel,
軋化錫、氧化辞、氧化鈦以及氧化鋁所組成之群中之至少 一種以上。 V 進而’就透明性、導電性、去除金屬層時之耐久性等方 面而言，表現出透明導電性之氧化物層較好的是叮 化錫。 4礼 乳化物層可㈣電子束蒸鑛法、_法、離子電錢法等 而开乂成。於本發明中，就膜厚或膜質之均句性方面而言， 較好的是濺鍍法。 賤鑛氣體較好的是氬氣與氧氣之混合氣體，氧氣濃度較 好的是G.2〜4體積％。_壓力較適當的是(M〜2 Pa。又， 好較lxlG.6〜lxlG_2 Pa。較好的是將基板溫度設定 '"、至，亚〜3〇〇C，特別好的是設定為150〜3〇(TC。 較好的是使氧化物層 犋烊馮10 nm〜1 μΓη。若未達1〇 nm，則作為氧化物屉 初層之功此不充分，若超過丨 透明性受損以外，實降上錐以土认 矛' .. '際上難以去除脈衝雷射光之照射部位 之輔助層（金屬層）與氧化物層。 於本發明中，並不特別需 南要在乳化物層與基體之間形成 “运射加工性之基礎層(例如樹脂等卜 但是’亦可為了愈堂身 孑八 ’、+加性不同之目的（基體之鹼性 成分之擴散阻隔箄）， 在乳化物層與基體之間形成基礎 140353.doc 201001553 層（二氧化矽膜等）。此外，基礎層可為於雷射加工時，與 氧化物層及金屬層一同被去除者，亦可為不被去除而殘存 者。基礎層較好的是利用濺鍍法而形成。 本發明中所使用之基體並非必需為平面且板狀，可為曲 面且亦可為異型狀。作為基體，可列舉透明或不透明之玻 璃基板'陶瓷基板、樹脂膜等。 基體較好的是透明。就強度及耐久性方面而言，特別好 的疋玻璃基板。作為玻璃基板，可例示無色透明之鈉鈣玻 璃基板、石英玻璃基板、硼矽玻璃基板、無鹼玻璃基板。 就強度及穿透率方面而言，基板之厚度較好的是〇.4〜3At least one or more of the group consisting of rolled tin, oxidized, titanium oxide, and alumina. V and further, in terms of transparency, conductivity, durability in removing a metal layer, etc., the oxide layer exhibiting transparent conductivity is preferably tin oxide. 4 emulsification layer can be (4) electron beam steaming method, _ method, ion money method, etc. In the present invention, in terms of the film thickness or the uniformity of the film quality, a sputtering method is preferred. The barium ore gas is preferably a mixed gas of argon gas and oxygen gas, and the oxygen concentration is preferably G. 2 to 4% by volume. _ pressure is more appropriate (M ~ 2 Pa. Again, better than lxlG.6 ~ lxlG_2 Pa. It is better to set the substrate temperature '", to, sub ~ 3 〇〇 C, particularly good is set to 150~3〇(TC. It is better to make the oxide layer 犋烊10 nm~1 μΓη. If it is less than 1〇nm, it is not enough as the initial layer of the oxide drawer. In addition to the damage, it is difficult to remove the auxiliary layer (metal layer) and the oxide layer of the irradiated portion of the pulsed laser light. In the present invention, it is not particularly necessary to emulsify in the south. Between the layer and the substrate, a "base layer for transport processing (such as resin, etc.) can also be used for the purpose of different functions of the body (the diffusion barrier of the alkaline component of the matrix). Forming a base 140353.doc 201001553 layer (cerium oxide film, etc.) between the emulsion layer and the substrate. Further, the base layer may be removed together with the oxide layer and the metal layer during laser processing, or It is preferably left unremoved. The base layer is preferably formed by sputtering. The base body is not necessarily a flat plate and may be a curved surface and may be a profiled shape. Examples of the substrate include a transparent or opaque glass substrate 'ceramic substrate, a resin film, etc. The substrate is preferably transparent. In terms of strength and durability. In terms of properties, the glass substrate is preferably a colorless transparent soda lime glass substrate, a quartz glass substrate, a boron germanium glass substrate, or an alkali-free glass substrate. The thickness of the substrate is preferably 〇.4~3
可於本發明中使用之脈衝雷射光之波長為7〇〇〜15〇〇 nm。若為該波段，則與基體與脈衝雷射光之相互作用相 比，表現出透明導電性之氧化物層與脈衝雷射光之相互作 用變得特別大，故較好。特別好的是使脈衝雷射光之波長 為1047〜1064 nm。就可使用能夠高功率振盪之通用之雷射 加工機（YAG、YLF、YVO雷射等）之方面而言亦較好。 又，使用可輸出脈衝光之類型雷射加工機，由於使經由 遮罩而將經圖案成型之脈衝雷射光照射於氧化物層上，變 得容易進行氧化物層之圖案化，故較好。 、v …上ps。若脈 衝雷射光之脈衝寬度未達丨ns，則難以使用高功率之雷射 加工機，又，熱之影響減小而變得無法形成均質之圖案。 又，由於金屬層之效果降低而欠佳。x，若脈衝寬度超過 140353.doc 201001553 1 μδ，則熱之影響增大，而錄p 1〜、 '文什無法忽視照射部位之周圍 之熱影響層，從而變得盔法 丁…、在形成精細之圖案，故欠佳。 更好的是使脈衝寬度為i 〇 又，就加工性之方面而言 ns〜100 ns 〇 利用脈衝雷射光之照射而進行之氧化物層或金屬層之去 除較好的是以一次昭、射央m γ ^ 及進仃。於使用能量密度低之脈衝 雷射光對照射部照射複數次之加工方法之情形時，由於第 '一次照射以後之加工性盘楚 .η7_ , /、第一。人知、射相比較下降，故變得 無法實施均質之加工，因此欠佳。 較好的疋照射以-次照射之脈衝雷射光僅可去除氧化物 層與金屬層之能量密度以上之脈衝雷射光。此外，即便於 人，、、、射進订加工之情形時，由於脈衝雷射光之脈衝照 射略微具有重疊部分而進行，因此亦會於重疊部分照射兩 次以上之脈衝雷射光。 較好的是使脈衝雷射光之能量密度為0.3〜H) JW。若 未達0.3心2’則照射部之氧化物層未完全去除而形成 膜殘留，故欠佳。若超過1〇 W，則變得無法忽視基體 之損傷。 藉由_人之脈衝雷射光所照射之照射部位之面積較 好的是1 mm2以上。 脈衝雷射光係自形成有氧化物層或金屬層之外表面側進 > ”射若自未形成有氧化物層或金屬層之側進行照射， 則脈衝雷射光會於基體中傳播，因基體之吸收所引起之能 量知失增大，且氧化物層之加工性下降，故欠佳。 140353.doc -14- 201001553 進而’本發明提供一種藉由上述製造方法所形成之附有 氧化物層之基體。又，本發明提供一種將該附有氧化物層 之基體之氧化物層用作電極之電子裝置。具體而言，本發 明提供一種顯示面板或太陽電池模組。 實施例 以下’列舉例1〜來對本發明進行說明，但本發明並不 限定於以下實施例。例1、3、i 4及丨5為比較例，例2、 4〜13、16〜19為本發明之實施例。 (例1) 對厚2.8 mmx長1〇〇 mmx寬100 mm之PDP用高應變點玻 璃（旭琐子製造之PD200)基板進行清洗後，將其作為基板 而设置於錢鐘裝置上。利用直流磁控濺鍍法，使用IT〇(相 對於1〜〇3與Sn〇2之總量，含有10質量。/。之Sn〇2)靶材，於 基板上形成厚度為120 nm之ITO層，從而獲得附有ITO層 之玻璃基板。濺鍍氣體使用含有2體積％之A氣之Ar氣。 背壓為lxl〇_3 pa ’濺鍍氣壓為〇 4 Pa，電力密度為3 5 W/cm2。又，基板溫度為25(rc。 對該附有ITO層之玻璃基板自ITO層侧照射脈衝雷射 光。脈衝雷射光使用藉由脈衝類型之Yb_光纖雷射（Yb_ Fiber Laser)之脈衝雷射光（波長為1〇64 nm)。該脈衝雷射 光具有高斯（Gaussian)型之能量分布6，照射部之功率為5 W。又，脈衝寬度為丨〇〇 ns，照射直徑為丨〇〇 μηι，照射數 為一次，頻率為20 kHz。然後，對藉由脈衝雷射光之照射 所形成之圖案直徑5進行測定（參照圖6)。 140353.doc -15- 201001553 利用光學顯微鏡來觀察經雷射照射之照射部位，並對經 圖案化之部分之直徑進行測定，然後對圖案直徑5進行^ 價。由於脈衝雷射光具有高斯型之能量分布，故越是更加 及收脈衝雷射光之能量而易於被去除，圖案直徑$變得越 大，因此藉由對圖案直徑5進行評價，可對雷射加工對象 物之加工性進行評價。此外，藉由其他的評價可知，於上 述評價中圖案直徑5達到5〇 _之樣品於使用經均質化之脈 衝雷射光時之可加工的最低能量密度為6.6 W，而圖案 直徑5達到56 _之樣品為以w。即，於本評價中，於 圖案直徑5自50 μΐΏ成為56 _之情形時，雷射加工性相當 :提：：約2.8倍。此外’此處所謂圖案直捏5,係指可： ^ 一次照射而形成於基體上㈣化物層之去 =為最終欲形成之電子裝置之透明電極所必需之： 二:照射脈衝雷射光即可。為了 !個部位之線間圖案 化，I7為了使相鄰之透明電極之線 口 ^ 可藉由-次照射㈣成 ^ 〃要對應於 定之位置依序照射即可。/，、=/脈衝雷射光對於特 之配置構成，任意地進行 ^應於複雜之像素電極 _ 緣狀之圖案化。圖6 #干咅，Η： 地表示連續且直線狀之圖案化之情況。 …、、 ^實㈣量產水準進行雷射㈣化 衝光。又，圖案化之間隙尺寸變得勺貝化之脈 源與被加工物之間配置遮革’於田射光 定。即，為了對應於特定之圖宏間隱尺寸進行控制來劃 光標記於被加工物上之方^素’以使被遮罩切取之雷射 達仃雷射照射（參照圓”。於此 140353.doc • J6 - 201001553 十月形時，由於可利用足夠之光源動力，因此可將藉由—次 之脈衝雷射光所照射之照射部位之面積設定為1 mm2以 上。 (例2) 於例1之附有ITO層之玻璃基板之該IT0層之上，將殘存 氣體排氣後，使用Cr金屬靶材，利用直流磁控濺鍍法，於 Ar氣J衣i兄下开^成厚度為1丨nm之輔助層。背壓為ιχι〇·3 Pa’滅鐘氣壓為0.3 pa，投入電力密度為1 w/cm2。又，基 板溫度為250°C。 對本例之附有輔助層之玻璃基板，自膜面側照射與例！ 相同之脈衝雷射光。繼而，為了對IT〇層之圖案直徑進行 評價’而利用蝕刻液將基板整個面之輔助層去除。蝕刻液 使用硝酸鈽銨、過氯酸及水之混合物。藉由蝕刻液之處 理，於ΙΤΟ層上實質上未觀察到損傷。 以與例1相同之方式，利用光學顯微鏡對本例之ΙΤ〇層之 圖案直徑進行評價，將結果示於表1。 (例3) 於例1中所使用之玻璃基板之上，利用直流磁控濺鍍 法’使用含有Ta2〇5與ΖηΟ之Sn02靶材（相對於總量，含有 9.6質量％之ThO5，且含有0.5質量。/。之ZnO)，形成厚度為 140 nm之Sn〇2層，從而獲得附有Sn02層之玻璃基板。 濺鍍氣體使用含有2體積％之02氣之Ar氣。背壓為ix10-3 Pa，濺鍍氣壓為〇_4 Pa，電力密度為3·5 W/cm2。又，基板 溫度為250°C。 140353.doc -17· 201001553 對於本例之附有Sn〇2層之玻璃基板，自膜面側照射與例 1相同之脈衝雷射光，並利用與例丨相同之方法測定圖案直 徑，將結果示於表1。 (例4〜15) 於例3之附有Sn〇2層之玻璃基板的該Sn〇2層之上，將殘 存氣體排氣後’使用Ag金屬乾材、A1金屬乾材、Cr金屬乾 材、Mo金屬靶材或ITO靶材，利用直流磁控濺鍍法，形成 表1中所示之膜厚與構成之輔助層。 濺鍍氣體使用Ar氣環境（形成Ag、A：l、Cr及Mo之情形） 或含有2體積。/。之〇2氣之Ar氣（形成ITO之情形）。背壓為 lxl〇_3 Pa，濺鍍氣壓為0.3 Pa，投入電力密度為！ w/cm2。 又’基板溫度為250。(：。 對於該等例4〜1 5之附有輔助層之玻璃基板，自外表面側 照射與例1相同條件之脈衝雷射光。繼而，為了對氧化錫 層之圖案直徑進行評價，而利用蝕刻液將基板整個面之輔 助層去除。 敍刻液使用磷酸、硝酸、乙酸及水之混合物（去除Ag、 乂及Mo之情形）’硝酸鈽銨、過氯酸及水之混合物（去除Cr 之情形）’或者鹽酸、氯化鐵（III)及水之混合物（去除IT〇之 情形）。 藉由餘刻液之處理，於Sn02層上實質上未觀察到損傷。 利用光學顯微鏡，以與例1相同之方式對例4〜1 5之Sn02層 之圖案直徑進行評價。將其結果示於表1。 140353.doc -18- 201001553 [表l] 例 層構成 金屬層 之厚度 (nm) 氧化物層之 圖案直徑 (nm) 氧化物層 之厚度 (nm) 碎片之 評價 綜合評價 1 Glass/ITO 58 120 Δ Δ 2 Glass/ITO/Cr 11 66 120 〇 〇 3 Glass/Sn〇2 - 45 140 Δ Δ 4 Glass/Sn〇2/Ag 14 60 140 〇 〇 5 Glass/Sn02/Ag 43 54 140 〇 〇 6 Glass/Sn〇2/Ag 59 56 140 〇 〇 7 Glass/Sn02/Al 15 58 140 〇 〇 8 Glass/SnCVAl 45 56 140 〇 〇 9 Glass/Sn02/Al 73 57 140 〇 〇 10 Glass/Sn〇2/Cr 11 64 140 〇 〇 11 Glass/Sn〇2/Cr 33 63 140 〇 〇 12 Glass/SnCVMo 11 62 140 〇 〇 13 Glass/Sn〇2/Mo 33 59 140 〇 〇 14 Glass/Sn02/IT0 15 45 140 〇 Δ 15 Glass/Sn02/IT0 37 46 140 〇 Δ 此外，於上述表1所示之碎片評價中，將無膜（氧化物） 殘留之情形評價為「0」，將有少量膜（氧化物）殘留之情形 評價為「A」。又，於綜合評價中，在氧化物層中使用ITO 之例中，將圖案直徑大於5 8 μιη且無膜（氧化物）殘留之情 形評價為「〇」，將圖案直徑為58 μιη以下或有少量膜（氧化 物）殘留之情形評價為「Δ」。進而，在氧化物層中使用 Sn〇2之例中，將圖案直徑大於46 μηι且無膜（氧化物）殘留 之情形評價為「〇」，將圖案直徑為46 μιη以下或有少量膜 140353.doc 19· 201001553 (氧化物）殘留之情形評價為「△」。 由上述之表1可知，當使用Ag、A卜Cr或Mo作為輔助層 時，氧化物之圖案直徑大幅提昇。另一方面，可知於無輔 助層之情形時圖案直徑較小。 又，當將ITO作為代替金屬層之輔助層時，幾乎未產生 圖案直徑之增加。由以上可知，藉由將金屬作為輔助層， 可使氧化物之圖案直徑大幅增大。 換吕之，相應地，藉由加快生產步驟之節拍，可提昇整 之生產I"生或者，可知藉由使每一台雷射加工裝置之負 何下降’可大幅減少步驟整體之生產成本。 進而，利用光學顯微鏡及掃描型電子顯微鏡對例卜15之 照射脈衝雷射光之照射部位之周圍的碎片之程度進行觀 察。例2及例4〜15係於去除輔助層後進行觀察。例i及例3 係於利用磷酸、石肖酸、乙酸及水之混合物在室溫下浸潰5 分鐘後進行觀察。 此可確_，例2及例4〜1 5與例1及例3相比，碎片減 ^推測其原因在於：當去除輔助層肖，堆積於輔助層上 之碎片被去除。 (例16〜19) s =於使用Sn、以及上述例4〜15之中“ο:之圖案直徑得到 提幵之Mo作為輔助層的情形M吏用在實際以量產水準進 行雷^圖案化時所使用的經均質化之脈衝光進行評價。具 而。在田射光源與被加工物之間配置遮罩，並對間隙 尺寸進订控制’以使被遮罩切取之雷射光標記於被加工物 1403534. -20· 201001553 上之方式進行雷射照射（參照圖丨）。於此情形時，由於可利 用足夠之光源動力，因此可將藉由一次之脈衝雷射光所照 射之照射部位之面積設定為！酿2以上。又，加工時之脈 衝雷射光之能量密度、反覆次數及脈衝寬度分別設定為 3-3 J/cm2、6 kHz以及 50 ns。 ，於例3之附有Sn〇2層之玻璃基板之上，將殘存氣體排氣 後使用811金屬靶材，利用直流磁控濺鍍法，於該Sn〇2層 r, 之上形成表2中所示之膜厚與構成之辅助層。 1 濺鍍氣體使用Ar氣環境（形成M〇之情形）或含有2體積％ 之〇2氣之Ar氣（形成Sn之情形卜背壓為1χ1〇·3 &，濺鍍氣 壓為0.3 Pa’投入電力密度為i銜咖2。又，基板溫度為 250〇C。 對於該等例16〜19之附有辅助層之玻璃基板，自外表面 側照射上述經均質化之脈衝雷射光。繼而，為了對氧化錫 層之圖案直徑進行評價，而利用姓刻液將基板整個面之輔 」 助層去除。#刻液使用磷酸、硝酸、乙酸及水之混合物 (去除Mo之情形）’或者氫氧化納溶液與水之混合物（去除 Sn之情形）。為了確認雷射蝕刻周邊部之氧化錫層之狀況 而利用光學顯微鏡進行評價。將其結果示於表2。 [表2] 例 膜構成 —， 金屬層之 厚度 氧化物層 之厚度 (nm) 反應層之 有無 綜合評價 15 Glass/Sn02/Sn 6.1 150 〇 ◎ 17 Glass/Sn02/Sn 0.2 150 〇 ◎ 18 Glass/Sn02/Mo 0.1 ~~~~ 150 Δ 〇 19 Glass/Sn02/Mo 0.2 ~~ -~~~ 150 Δ 〇 140353.doc 201001553 此外，於上述表2所示之「反應層之有無」中，將未觀 察到反應層之情形評價為「〇」，將觀察到少量反應層之情 形評價為「Δ」。又，於综合評價巾，將未觀察到^層且 表1中之综合評價亦為「〇」之情形評價為「◎」，將未觀 察到反應層或者表！中之綜合評價為「。」之情形評價為 「〇」° 當使用Mo作為輔助層時，存在Sn〇2層與河〇層之反應 層。另-方面’當使用Sn作為輔助層時，未觀察到反應 層。一般認為其原因在於，如與”〇相比較，與Sn〇2層之 反應性更少’故一般認為Sn更適合作為輔助層。 以上詳細且參照特定之實施態樣對本發明進行了說明， 但本領域之技術人員當知，可不脫離本發明之精神與範圍 而加以各種變更或修正。 本申請案係基於2008年5月曰所申請之曰本專利申請 案200W26G26者，並將其内容作為參照而引用人本申請 案中。 [產業上之可利用性] 本發明可用於大型PDP、LCD等之顯示面板之製造或者 太陽電池模組之製造。 【圖式簡單說明】 圖Ϊ係表示本發明之構成之示意性剖面圖。 圖2(A)及圖2(B)係表示本發明之構成之示意性平面圖， 圖2(A)係進行雷射圖案化前之示意性平面圖，圖2(b)係進 行雷射圖案化後之示意性平面圖。 140353.doc -22- 201001553 圖3係本發明之流程圖。 圖4(A)及圖4(B)係表示本發明之其他構成之示意性平面 圖，圖4(A)係進行圖案化前之示意性平面圖，圖4(B)係進 行圖案化後之示意性平面圖。 圖5(A)〜圖5(E)係先前例之說明圖。 圖6係本發明之說明圖。 【主要元件符號說明】 1 基體 2 氧化物層 3 金屬層（輔助層） 4 去除部 5 圖案直徑 6 能量分布 7 遮罩 50 雷射光源 5 1 雷射光線 140353.doc -23-The pulsed laser light that can be used in the present invention has a wavelength of 7 〇〇 to 15 〇〇 nm. In the case of this wavelength band, it is preferable that the interaction between the oxide layer exhibiting transparent conductivity and the pulsed laser light is particularly large as compared with the interaction between the substrate and the pulsed laser light. It is particularly preferable to make the wavelength of the pulsed laser light 1047 to 1064 nm. It is also preferable in terms of a general-purpose laser processing machine (YAG, YLF, YVO laser, etc.) capable of high-power oscillation. Further, it is preferable to use a laser processing machine capable of outputting pulsed light by irradiating the patterned pulsed laser light onto the oxide layer via the mask to facilitate patterning of the oxide layer. , v ... on ps. If the pulse width of the pulsed laser light is less than 丨ns, it is difficult to use a high-power laser processing machine, and the influence of heat is reduced to make it impossible to form a homogeneous pattern. Moreover, it is not preferable because the effect of the metal layer is lowered. x, if the pulse width exceeds 140353.doc 201001553 1 μδ, the influence of heat increases, and the record p 1~, 'Wensh can not ignore the heat-affected layer around the irradiated part, thus becoming a helmet... Fine patterns, so it is not good. It is better to make the pulse width i 〇 and, in terms of processability, ns~100 ns 〇 the removal of the oxide layer or the metal layer by the irradiation of the pulsed laser light is preferably one shot and one shot. Central m γ ^ and into the 仃. When using a pulsed laser beam with a low energy density to illuminate the irradiation unit for a plurality of times, the processing is performed after the first irradiation. η7_, /, first. Knowing and shooting are relatively low, so it becomes impossible to perform homogeneous processing, so it is not good. Preferably, the erbium-irradiated pulsed laser light can only remove pulsed laser light having an energy density above the oxide layer and the metal layer. Further, even in the case of a person, a, or a shot, since the pulse irradiation of the pulsed laser light slightly overlaps, the pulsed laser light is irradiated twice or more in the overlapping portion. Preferably, the energy density of the pulsed laser light is 0.3 to H) JW. If it is less than 0.3 center 2', the oxide layer of the irradiated portion is not completely removed to form a film residue, which is not preferable. If it exceeds 1 〇 W, it becomes impossible to ignore the damage of the substrate. The area of the irradiated portion irradiated by the pulsed laser light of the human is preferably 1 mm 2 or more. The pulsed laser light is irradiated from the side of the surface formed with the oxide layer or the metal layer. If the radiation is irradiated from the side where the oxide layer or the metal layer is not formed, the pulsed laser light propagates in the substrate due to the substrate. The energy loss caused by the absorption is increased, and the workability of the oxide layer is lowered, which is not preferable. 140353.doc -14- 201001553 Further, the present invention provides an oxide layer formed by the above manufacturing method. Further, the present invention provides an electronic device using the oxide layer of the substrate with the oxide layer as an electrode. Specifically, the present invention provides a display panel or a solar cell module. The present invention will be described by way of example 1 but the present invention is not limited to the following examples. Examples 1, 3, i 4 and 丨 5 are comparative examples, and examples 2, 4 to 13, 16 to 19 are examples of the present invention. (Example 1) A PDP having a thickness of 2.8 mm x 1 mm and a width of 100 mm was cleaned with a high strain point glass (PD200 manufactured by Asahi), and then mounted on a clock device as a substrate. DC magnetron sputtering, using IT (With respect to the total amount of 1~〇3 and Sn〇2, containing 10 mass% of SnS2) target, an ITO layer having a thickness of 120 nm is formed on the substrate, thereby obtaining a glass substrate with an ITO layer. The sputtering gas uses Ar gas containing 2% by volume of A gas. The back pressure is lxl〇_3 pa 'The sputtering pressure is 〇4 Pa, the power density is 35 W/cm2. Also, the substrate temperature is 25 (rc) The glass substrate with the ITO layer is irradiated with pulsed laser light from the side of the ITO layer. The pulsed laser light uses pulsed laser light of a Yb_Fiber laser (Yb_Fiber Laser) (wavelength of 1 〇 64 nm) The pulsed laser light has a Gaussian type energy distribution 6 and the power of the illuminating part is 5 W. Further, the pulse width is 丨〇〇ns, the irradiation diameter is 丨〇〇μηι, the number of irradiations is once, and the frequency is 20 kHz. Then, the pattern diameter 5 formed by irradiation of pulsed laser light is measured (refer to Fig. 6). 140353.doc -15- 201001553 An optical microscope is used to observe the irradiated portion irradiated by the laser, and the pattern is patterned. The diameter of the portion is measured, and then the pattern diameter 5 is priced. Since the pulsed laser light has a Gaussian-type energy distribution, the more the pulsed laser light is more easily removed, the larger the pattern diameter is, so the laser processing can be performed by evaluating the pattern diameter 5 The workability of the object was evaluated. Further, it was found from other evaluations that the sample having a pattern diameter of 5 of 5 〇 in the above evaluation had a minimum energy density of 6.6 W when using homogenized pulsed laser light. The sample with a pattern diameter of 5 up to 56 _ is in w. That is, in the case of the evaluation, when the pattern diameter 5 was changed from 50 μΐΏ to 56 _, the laser processability was equivalent: about: 2.8 times. In addition, 'the so-called pattern straight pinch 5 here means that: ^ can be formed on the substrate by one irradiation (four) of the layer of the compound = necessary for the transparent electrode of the electronic device to be formed finally: Second: irradiate the pulsed laser light . In order to pattern the lines between the parts, I7 can be made to sequentially illuminate the line of the adjacent transparent electrodes by the -sub-irradiation (four) to ^. The /, and =/pulse laser light is arbitrarily arranged for the configuration of the complex pixel electrode _ edge. Fig. 6 #干咅,Η: The ground indicates the continuous and linear patterning. ...,, ^ (4) Mass production level for laser (four)ization. Further, the patterning gap size is such that the scuttle of the spoon source and the workpiece are disposed in the field. That is, in order to control the hidden size corresponding to the specific picture macro, the square element marked on the workpiece is light-cutted so that the laser beam that is masked and cut reaches the laser irradiation (refer to the circle). .doc • J6 - 201001553 In the case of the October shape, since the sufficient light source power can be used, the area of the irradiation portion irradiated by the pulsed laser light can be set to 1 mm 2 or more. (Example 2) In Example 1 On the IT0 layer of the glass substrate with the ITO layer, the residual gas is exhausted, and the Cr metal target is used, and the thickness is 1 by the DC magnetron sputtering method under the Ar gas. The auxiliary layer of 丨nm. The back pressure is ιχι〇·3 Pa', the gas pressure is 0.3 pa, the input power density is 1 w/cm 2 , and the substrate temperature is 250 ° C. For this example, the glass substrate with the auxiliary layer is attached. The film is irradiated with the same pulse laser light as in the example! In order to evaluate the pattern diameter of the IT layer, the auxiliary layer of the entire surface of the substrate is removed by an etching solution. The etching solution uses ammonium cerium nitrate and perchloric acid. a mixture of acid and water. In the same manner as in Example 1, the pattern diameter of the ruthenium layer of this example was evaluated by an optical microscope, and the results are shown in Table 1. (Example 3) The glass substrate used in Example 1 Above, using a DC magnetron sputtering method, a Sn02 target containing Ta2〇5 and ΖηΟ (containing 9.6 mass% of ThO5 and containing 0.5 mass% of ZnO) is used to form a thickness of 140. The Sn2 layer of nm is obtained to obtain a glass substrate with a Sn02 layer. The sputtering gas uses Ar gas containing 2% by volume of 02 gas. The back pressure is ix10-3 Pa, and the sputtering pressure is 〇_4 Pa, electric power. The density is 3·5 W/cm 2 , and the substrate temperature is 250 ° C. 140353.doc -17· 201001553 For the glass substrate with the Sn 〇 2 layer in this example, the same pulse as in Example 1 is irradiated from the film side. The laser light was measured and the pattern diameter was measured in the same manner as in Example. The results are shown in Table 1. (Examples 4 to 15) On the Sn 2 layer of the glass substrate with the Sn 2 layer attached in Example 3, After exhausting the residual gas, 'Use Ag metal dry material, A1 metal dry material, Cr metal dry material, Mo metal target or ITO target The DC magnetron sputtering method was used to form the auxiliary layer of the film thickness and composition shown in Table 1. The sputtering gas was in an Ar gas atmosphere (in the case of forming Ag, A: 1, Cr, and Mo) or contained 2 volumes. The gas of 2 gas (in the case of ITO formation). The back pressure is lxl〇_3 Pa, the sputtering pressure is 0.3 Pa, the input power density is ! w/cm 2 , and the 'substrate temperature is 250. (:. With respect to the glass substrates with the auxiliary layers of the examples 4 to 15 described above, pulsed laser light of the same conditions as in Example 1 was irradiated from the outer surface side. Then, in order to evaluate the pattern diameter of the tin oxide layer, the auxiliary layer on the entire surface of the substrate was removed by an etching solution. A mixture of phosphoric acid, nitric acid, acetic acid and water (in the case of removing Ag, antimony and Mo), a mixture of ammonium cerium nitrate, perchloric acid and water (in the case of removing Cr), or hydrochloric acid or ferric chloride (III) ) and a mixture of water (in the case of removing IT). No damage was substantially observed on the Sn02 layer by the treatment of the residual etching solution. The pattern diameters of the Sn02 layers of Examples 4 to 15 were evaluated in the same manner as in Example 1 by an optical microscope. The results are shown in Table 1. 140353.doc -18- 201001553 [Table l] Thickness of the metal layer of the example layer (nm) Pattern diameter of the oxide layer (nm) Thickness of the oxide layer (nm) Evaluation of the fragment Comprehensive evaluation 1 Glass/ITO 58 120 Δ Δ 2 Glass/ITO/Cr 11 66 120 〇〇3 Glass/Sn〇2 - 45 140 Δ Δ 4 Glass/Sn〇2/Ag 14 60 140 〇〇5 Glass/Sn02/Ag 43 54 140 〇〇6 Glass/ Sn〇2/Ag 59 56 140 〇〇7 Glass/Sn02/Al 15 58 140 〇〇8 Glass/SnCVAl 45 56 140 〇〇9 Glass/Sn02/Al 73 57 140 〇〇10 Glass/Sn〇2/Cr 11 64 140 〇〇11 Glass/Sn〇2/Cr 33 63 140 〇〇12 Glass/SnCVMo 11 62 140 〇〇13 Glass/Sn〇2/Mo 33 59 140 〇〇14 Glass/Sn02/IT0 15 45 140 〇Δ 15 Glass/Sn02/IT0 37 46 140 〇Δ In addition, in the evaluation of the fragments shown in Table 1 above, the absence of film (oxide) was evaluated as "0", and a small amount of film (oxide) remained. The situation is evaluated as "A". Further, in the comprehensive evaluation, in the case of using ITO in the oxide layer, the case where the pattern diameter is larger than 5 8 μm and no film (oxide) remains is evaluated as "〇", and the pattern diameter is 58 μm or less or The case where a small amount of film (oxide) remained was evaluated as "Δ". Further, in the case of using Sn 〇 2 in the oxide layer, the case where the pattern diameter is larger than 46 μm and no film (oxide) remains is evaluated as "〇", and the pattern diameter is 46 μm or less or a small amount of film 140353. Doc 19· 201001553 The case of (oxide) residue was evaluated as "△". As is apparent from Table 1 above, when Ag, A, Cr or Mo is used as the auxiliary layer, the pattern diameter of the oxide is greatly increased. On the other hand, it can be seen that the pattern diameter is small in the case of no auxiliary layer. Further, when ITO is used as an auxiliary layer instead of the metal layer, an increase in pattern diameter hardly occurs. From the above, it can be seen that by using a metal as an auxiliary layer, the pattern diameter of the oxide can be greatly increased. In other words, by speeding up the beat of the production steps, it is possible to improve the overall production I" or, by knowing how to reduce the negative impact of each laser processing unit, the production cost of the entire step can be greatly reduced. Further, the degree of the fragments around the irradiation portion of the pulsed laser light irradiated by the example 15 was observed by an optical microscope and a scanning electron microscope. Example 2 and Examples 4 to 15 were observed after removing the auxiliary layer. Examples i and 3 were observed after being immersed for 5 minutes at room temperature using a mixture of phosphoric acid, tartaric acid, acetic acid and water. This is confirmed by the fact that the fragments are reduced in comparison with the examples 1 and 3, and the reason is that the fragments deposited on the auxiliary layer are removed when the auxiliary layer is removed. (Examples 16 to 19) s = In the case of using Sn and the above-mentioned Examples 4 to 15, "O: The pattern diameter of the pattern is obtained as the auxiliary layer M" is used to actually perform the patterning by mass production. The homogenized pulsed light used in the evaluation is evaluated. A mask is placed between the field light source and the workpiece, and the gap size is controlled so that the laser light that is masked and cut is marked on the Laser irradiation (refer to Figure 丨) is performed on the method of 1403534. -20· 201001553. In this case, since sufficient light source power can be utilized, the irradiation portion irradiated by one pulse of laser light can be used. The area is set to be 2 or more. In addition, the energy density, the number of times of repetition, and the pulse width of the pulsed laser light during processing are set to 3-3 J/cm2, 6 kHz, and 50 ns, respectively, and Sn is attached to Example 3. On the two-layer glass substrate, the remaining gas is exhausted, and then the 811 metal target is used, and the film thickness and composition shown in Table 2 are formed on the Sn layer 2 layer by DC magnetron sputtering. Auxiliary layer. 1 Splash gas using Ar gas environment (formation of M〇) Or Ar gas containing 2% by volume of 〇2 gas (in the case of forming Sn, the back pressure is 1χ1〇·3 &, the sputtering gas pressure is 0.3 Pa', and the input power density is i. 2, the substrate temperature is 250 〇 C. For the glass substrates with the auxiliary layers of the examples 16 to 19, the homogenized pulsed laser light was irradiated from the outer surface side. Then, in order to evaluate the pattern diameter of the tin oxide layer, the last name was used. The engraving removes the auxiliary layer from the entire surface of the substrate. #刻液 uses a mixture of phosphoric acid, nitric acid, acetic acid and water (in the case of removing Mo)' or a mixture of sodium hydroxide solution and water (in the case of removing Sn). The state of the tin oxide layer in the peripheral portion of the laser etching was confirmed and evaluated by an optical microscope. The results are shown in Table 2. [Table 2] Example Film Composition - Thickness of Metal Layer Thickness of Oxide Layer (nm) Reaction Layer Comprehensive evaluation of 15 Glass/Sn02/Sn 6.1 150 〇 ◎ 17 Glass/Sn02/Sn 0.2 150 〇 ◎ 18 Glass/Sn02/Mo 0.1 ~~~~ 150 Δ 〇19 Glass/Sn02/Mo 0.2 ~~ -~~ ~ 150 Δ 〇140353.doc 201001553 In addition, in Table 2 above In the case of "the presence or absence of the reaction layer", the case where the reaction layer was not observed was evaluated as "〇", and the case where a small amount of the reaction layer was observed was evaluated as "Δ". Further, in the comprehensive evaluation towel, no observation was made. In the case where the comprehensive evaluation in Table 1 is also "〇", it is evaluated as "◎", and the case where the comprehensive evaluation in the reaction layer or the table is not observed is evaluated as "〇". In the auxiliary layer, there is a reaction layer of the Sn 〇 2 layer and the river raft layer. Another aspect] When Sn was used as the auxiliary layer, no reaction layer was observed. It is generally considered that the reason is that Sn is more suitable as an auxiliary layer as compared with "〇, which is less reactive with the Sn 〇 2 layer." The present invention has been described above in detail with reference to specific embodiments, but A person skilled in the art will recognize that various changes and modifications may be made without departing from the spirit and scope of the invention. The present application is based on the patent application No. 200W26G26 filed in May 2008, the content of which is incorporated by reference. In the present application, the present invention can be applied to the manufacture of a display panel of a large PDP, an LCD, or the like, or the manufacture of a solar cell module. [Simplified description of the drawings] 2(A) and 2(B) are schematic plan views showing the configuration of the present invention, and Fig. 2(A) is a schematic plan view before laser patterning, and Fig. 2 (Fig. 2 (Fig. 2) b) is a schematic plan view after laser patterning. 140353.doc -22- 201001553 Fig. 3 is a flow chart of the present invention. Fig. 4(A) and Fig. 4(B) are diagrams showing other configurations of the present invention. Sexual plan, Figure 4 (A) is attached Fig. 4(B) is a schematic plan view showing a pattern before the patterning. Fig. 5(A) to Fig. 5(E) are explanatory views of the prior art. Fig. 6 is an explanatory view of the present invention. [Main component symbol description] 1 Base 2 Oxide layer 3 Metal layer (auxiliary layer) 4 Removal part 5 Pattern diameter 6 Energy distribution 7 Mask 50 Laser light source 5 1 Laser light 140353.doc -23-