201107509 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種靶材之製造方法，詳言之，係關於 一種氧化鋅系透明導電濺鍍靶材之製造方法。 【先前技術】 透明導電氧化物已被廣泛應用在液晶、電漿、電致發光 等平面顯示器，以及非晶石夕、微晶石夕、銅銦鎵栖等 薄膜型太陽電池之透明電極層（膜）中。目前商用最常見的 透明導電膜層是以直流磁控濺鍍的方式，利用電漿離子化 之氬離子轟擊成膜材料（即濺鍍靶材），而使靶材内大量之 原子從表面被擊出並飛濺沈積於基板上來形成膜層，故濺 鍍時需要有特性良好、可穩定成膜之濺鍍靶材。 所謂穩定成膜之靶材係指在濺鍍時不容易產生異常放電 (Arcing)者。異常放電會造成電漿放電不安定，因而損壞 到鍍膜的品質，同時亦將產生粗大粒子分別附著於靶材和 鍍膜上。其中，粒子附著並沈積在靶材表面上即形成所謂 結球（Nodule)，導致靶材使用壽命的降低；而粒子附著於 膜層上即形成所謂濺斑（Splash)，造成薄膜的品質和特性 惡化。 在習知技術中供濺鍍透明導電膜用之靶材，其係將原料 粉末製作成形後，利用加熱燒結方式來形成塊狀的燒結體 靶材。其中，習知技術有從靶材製程方面著手，可改善異 吊放電的兩個重點為提升燒結體靶材的電阻率和密度。目 前習知技術_最常被使用之透明導電燒結靶材，是主成分 1377l3.d〇i 201107509 為氧化銦並添加了氧化錫的銦錫氧化物（Indium Tin Oxide ’ ITO)，其商用靶材電阻率可達以下， 而靶材相對密度已達到99%以上》 然而，由於ITO含大量稀有金屬銦，製造成本昂貴且有 日漸枯竭的可能，因此乃有礦源豐富、成本低廉之氧化鋅 系透明導電材料被提出（期刊文獻：Thin s〇lid Films，v 124, 1985, ρ.43·47)。氧化鋅系透明導電材料係以氧化鋅為主成 分’並添加了 η型滲雜元素（例如，硼（B)、鋁⑷）、鎵 # (Ga)、姻（Ιη)、紀⑺、銃、矽（Si)、鍺（Ge)…等）而形 成的透明導電體，其中最好的摻雜有以鋁（A1)摻雜形成的 AZO(AlUminum Doped Zinc 〇xide)或以鎵（Ga)滲雜形成的 GZO(Gallium Doped Zinc Oxide)兩種，但目前這些燒結體 的體電阻率仍遠不及於ITO。 有關改善ΔΖΟ之燒結濺鍵乾之密度和電阻率方面，例如 曰本專利公告第02-149459號，其揭示採用氬氣（Ar)氣氛燒 φ 結AZ〇比在空氣中燒結可獲得更高的燒結靶材密度和電阻 率燒結雄、度達到5.6 g/cm3，電阻率達到5X ，雖 然密度可達99%，但電阻率仍遠不及於IT〇 ;曰本專利公 告第07-258836號，其揭示ΑΖΟ採用較細粒徑之氧化鋁粉 末摻雜混合，燒結後可達到5.65 g/cm3的密度和3xi〇-3Q_em 的電阻率，電阻率一樣仍遠不及於IT〇 ;曰本專利公開第 2007-238375號，其揭示升溫至燒結溫度時將空氣切換成 氮氣或全程使用氮氣氣氛，對ΑΖ〇燒結後可得到相當低之 靶材電阻率，其實施例最佳之電阻值可達到48xl〇.4^cm， 1377l3.doc 201107509 但文獻中此法得到的最高燒結密度只有5,3 6 g/cm3。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a target, and more particularly to a method for producing a zinc oxide-based transparent conductive sputtering target. [Prior Art] Transparent conductive oxides have been widely used in flat-panel displays such as liquid crystal, plasma, and electroluminescence, and transparent electrode layers of thin film solar cells such as amorphous, microcrystalline, and copper indium gallium ( In the film). At present, the most common transparent conductive film layer in commercial use is a DC magnetron sputtering method, which uses a plasma ionized argon ion to bombard a film forming material (ie, a sputtering target), so that a large number of atoms in the target are The film layer is formed by being shot and splashed on the substrate, so that a sputtering target having good characteristics and stable film formation is required for sputtering. The target for stable film formation refers to a person who does not easily cause abnormal discharge (Arcing) during sputtering. Abnormal discharge can cause the plasma discharge to be unstable, thus damaging the quality of the coating, and also causing coarse particles to adhere to the target and the coating. Wherein, the particles adhere to and deposit on the surface of the target to form a so-called Nodule, which leads to a decrease in the service life of the target; and the particles adhere to the film layer to form a so-called Splash, which deteriorates the quality and characteristics of the film. . In the prior art, a target for sputtering a transparent conductive film is obtained by forming a raw material powder and then forming a bulk sintered target by a heating and sintering method. Among them, the prior art has started from the target process, and the two key points for improving the isostatic discharge are to increase the resistivity and density of the sintered body target. At present, the most commonly used transparent conductive sintered target is a commercial component which is a main component of 1377l3.d〇i 201107509 is indium tin oxide (Indium Tin Oxide 'ITO) which is indium oxide and added with tin oxide. The resistivity can be up to the following, and the relative density of the target has reached more than 99%. However, since ITO contains a large amount of rare metal indium, it is expensive to manufacture and has the potential to be depleted. Therefore, it is rich in mineral resources and low in cost. Conductive materials were proposed (Journal: Thins slid Films, v 124, 1985, ρ. 43.47). The zinc oxide-based transparent conductive material is mainly composed of zinc oxide and adds n-type dopant elements (for example, boron (B), aluminum (4)), gallium # (Ga), marriage (Ιη), Ji (7), 铳, A transparent conductor formed by bismuth (Si), germanium (Ge), etc., wherein the best doping is AZO (AlUminum Doped Zinc 〇xide) doped with aluminum (A1) or galvanized (Ga) There are two types of GZO (Gallium Doped Zinc Oxide), but the bulk resistivity of these sintered bodies is still far less than that of ITO. Regarding the improvement of the density and resistivity of the ΔΖΟ 烧结 溅 溅 , , , , , , , , 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 采用 采用 采用Sintering target density and resistivity sintered male degree reached 5.6 g/cm3, resistivity reached 5X, although the density reached 99%, but the resistivity is still far less than IT〇; 曰 Patent Publication No. 07-258836, It is revealed that ΑΖΟ is doped with alumina powder of finer particle size, and can reach a density of 5.65 g/cm3 and a resistivity of 3xi〇-3Q_em after sintering, and the resistivity is still far less than that of IT 〇; No. 238375, which discloses that the air is switched to nitrogen when the temperature is raised to the sintering temperature or the nitrogen atmosphere is used in the whole process, and a relatively low target resistivity can be obtained after sintering, and the optimum resistance value of the embodiment can reach 48xl. 4^cm, 1377l3.doc 201107509 However, the highest sintered density obtained by this method in the literature is only 5,3 6 g/cm3.
有關改善GZO之燒結濺鍍乾之密度和電阻率方面，例如 曰本專利公告第10-306367號，其揭示GZO再選擇性地添 加1~5%之氧化欽、氧化錯、氧化結或氧化銦等，可提升 GZO靶材之燒結密度和電阻率，降低異常放電，其實施例 最佳之燒結密度為5.2 g/cm3及電阻率為5><l〇-3Q-cm，電阻 率一樣仍遠不及於ιτο;曰本專利公告第10_297964號中， 其揭示將氧化鋅和氧化鎵粒徑細化至丨μίη以下，並控制升 溫速率及適度導入氧氣進行燒結，可獲得燒結密度為5.$ g/cm3及電阻率為5χΐ〇·3Ω-ί；Γη之GZO靶材密度和電阻率，電 阻率一樣仍遠不及於！T0;台灣專利公開第2〇〇7〇246〇號、 第200706664號及第2GG73G646號中，其揭示對咖添加含 量20〜250 ppm、粒徑i μιη以下之氧化鋁、氧化錯或同時添 加氧化鋁及氧化鍅，可提升燒結密度及電阻率，其中實^ 例最佳之燒結密度為5 64 g/cm3及電阻率為丨 1 u j 電阻率仍遠不及於ITO。 练合觀之，上述專利文獻揭示之技術雖對氧化辞系透印 導電燒結乾材之密度和電阻率有些許㊣升，㉟其電阻 大幅高於ΙΤ0,仍為較不佳之濺鍍靶材。 因此，有必要提供一創新且富有進步性之氧化 導電濺鍍靶材之製造方法，以解決上述問題。 八0; 【發明内容】 本發明提供一種 法，包括以下步驟 氧化鋅系透明導電濺鍍靶材之製造方 • (a)混合原料粉末及含碳物質粉 不’該 137713.doc 201107509 ::包括氧化辞粉末及至少一推雜元素，該換雜元素 材為農度；（b)進行-成型步驟，以形成錢把基 :，及⑷進行—燒結緻密化步驟，以形成透明導電濺鑛乾 材〇 本發日^化鋅系透明導電_乾材製造方法，在製程中 添加適量的含碳物質，再進行燒結緻密化製程，藉由碳與 2化鋅作用而形成更多導電載子濃度來降低電阻率，所製 付之乳化鋅系透明導絲材不僅密度高且電阻率小，其中 電阻率的降低並未造成燒结密 導雷μ且士 ^錢、“度的下降’故氧化辞系透明 ，電乾材具有較佳之㈣品質及㈣的特性良好之特性， 明Γ雷材水準十分接近。另外，本發明之氧化辞系透 料係以氧化辞為主成分，並含有η型擦雜元素而 導電之特性，其中該氧化辞系列材料之料源充 足、價格便宜，故生產成本低。 【實施方式】 圖1顯示本發明氧化辞㈣明導電賤鍍乾材之製造方去 如首先，參考步驟SU’混合原料粉末及含碳物質 -(J如’以乾式球磨或澄式球磨方式進行粉末混合）， 其中，該原料粉末包括氧化鋅粉末及至少—摻雜元素。，該 具有一捧雜濃度。在本實施例中，該含碳物質;; 末係選自石墨、碳化物及有機含碳高分子至少其令之— 較佳地’在步驟川中所添加之該含碳物質粉末之碳人旦 範圍為百萬分之50至500(50 ppm〜5〇〇 ppm卜其中，：： 化物可為碳化矽，該有機含碳高分子可為硬脂酸鋅。" 137713.doc 201107509 在本實施例中，該摻雜元素係選自n型摻雜元素，例 如，該η型摻雜元素可選自爛（B)、銘（A1)、鎵（Ga)、銦 (⑷、紀⑺、銳（SC)、邦i)、錯（Ge)及其混合物所組成之 群。較佳地’該η型摻雜元素係為鋁，其摻雜濃度為〇 5至 3.5重量百分比（Wt%)，或者，該η型摻雜元素可為鎵，其 摻雜濃度為1.0至7.0重量百分比（wt%)。 參考步驟S12，進行一成型步驟，以形成濺鍍靶基材。 其中’本發明可選擇性地以乾壓、冷均壓或鑄槳成形方式 進行該成型步驟。 參考步驟S13，進行一燒結緻密化步驟，以形成透明導 電減鑛把材。纟中，本發明可選擇性地以常壓燒結、正壓 燒結、熱壓燒結或熱㈣燒結方式進行該燒結緻密化步 驟。較佳地’纟步驟S13中，燒結溫度係為12〇吖至 1500〇C，並且於氮氣或惰性氣體(例如：氬氣(Ar))氣氛中 進行該燒結緻密化步驟。 表一顯示本發明氧化辞系透明導電濺鍍靶材製造方法與 習知濺鍵料製造方法所製得之錢料之比較結果。雖 然本發明實例1-6與習# t匕較例i之燒結m約為56 g/cm3，然而本發明實例1-6之電阻率為2.22-2.91χΐ〇·4Ω_ cm，習知比較例i之電阻率為】& i 47χ ι 〇·3ω_，本發明 方法所製付之濺鍍靶材之電阻率遠優於習知於方法所製得 之濺鍍靶材之電阻率，已接近銦錫氧化物（ITO)。 于 137713.doc 201107509 表一For improving the density and resistivity of the dry sputtering of GZO, for example, Patent Publication No. 10-306367 discloses that GZO selectively adds 1 to 5% of oxidized, oxidized, oxidized or indium oxide. Etc., the sintered density and resistivity of the GZO target can be improved, and the abnormal discharge can be reduced. The optimum sintered density of the embodiment is 5.2 g/cm3 and the resistivity is 5><l〇-3Q-cm, and the resistivity is still the same.远 ι ο ι ι ι ι ι ι ι ι ι ι ι 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化g/cm3 and resistivity are 5χΐ〇·3Ω-ί; Gη GZO target density and resistivity, the resistivity is still far behind! T0; Taiwan Patent Publication No. 2〇〇7〇246〇, No. 200706664 and No. 2GG73G646, which disclose an alumina added with a content of 20 to 250 ppm, a particle size of i μηη or less, oxidation or simultaneous oxidation. Aluminum and yttrium oxide can increase the sintered density and resistivity. The best sintered density is 5 64 g/cm3 and the resistivity is u1 uj. The resistivity is still far less than ITO. In view of the practice, the technique disclosed in the above patent documents has a slight increase in the density and electrical resistivity of the oxidized lexicon-transparent conductive sintered dry material, and its resistance is significantly higher than ΙΤ0, which is still a poor sputtering target. Therefore, it is necessary to provide an innovative and progressive method of manufacturing an oxidized conductive sputter target to solve the above problems. OBJECTS OF THE INVENTION The present invention provides a method comprising the following steps: a manufacturer of a zinc oxide-based transparent conductive sputtering target material; (a) a mixed raw material powder and a carbonaceous material powder are not included in the 137713.doc 201107509: An oxidized powder and at least one dopant element, the substitution element is an agronomic degree; (b) performing a forming step to form a carbon base: and (4) performing a sintering densification step to form a transparent conductive splashing dry Material 〇 化 ^ Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z In order to reduce the electrical resistivity, the prepared emulsified zinc-based transparent guide wire material has high density and low electrical resistivity, and the decrease in electrical resistivity does not cause the sintering of the dense guided thunder and the oxidation of the "degree" The vocabulary is transparent, the electric dry material has the characteristics of (4) quality and (4) good characteristics, and the level of alum is very close. In addition, the oxidized bacterium of the present invention is mainly composed of oxidized words and contains η type. Rubbing elements The characteristics of electricity, wherein the oxidation source series material has sufficient material source and low price, so the production cost is low. [Embodiment] FIG. 1 shows the manufacture of the oxidation word (four) of the invention, and the manufacture of the conductive material is as follows: SU' mixed raw material powder and carbonaceous material-(J such as 'powder mixing by dry ball milling or clear ball milling method), wherein the raw material powder comprises zinc oxide powder and at least - doping element, which has a heteropoly concentration In this embodiment, the carbonaceous material is at least selected from the group consisting of graphite, carbide, and organic carbon-containing polymer, and at least the carbon person of the carbonaceous material powder added in the step is preferably The range is from 50 to 500 parts per million (50 ppm to 5 ppm ppm), wherein: the compound may be tantalum carbide, and the organic carbon-containing polymer may be zinc stearate. "137713.doc 201107509 In an embodiment, the doping element is selected from an n-type doping element, for example, the n-type doping element may be selected from the group consisting of rotten (B), inscription (A1), gallium (Ga), indium ((4), Ji (7), a group consisting of sharp (SC), state i), fault (Ge), and mixtures thereof. The n-type doping element is aluminum with a doping concentration of 〇5 to 3.5% by weight (Wt%), or the n-type doping element may be gallium with a doping concentration of 1.0 to 7.0% by weight. (wt%) Referring to step S12, a molding step is performed to form a sputtering target substrate. [The present invention can selectively perform the molding step in a dry pressing, cold equalizing or cast pad forming manner. Reference step S13 A sintering densification step is performed to form a transparent conductive ore-reducing material. In the crucible, the present invention may selectively perform the sintering densification step in a normal pressure sintering, a positive pressure sintering, a hot press sintering or a thermal (four) sintering manner. Preferably, in the step S13, the sintering temperature is from 12 Torr to 1,500 Torr C, and the sintering densification step is carried out in an atmosphere of nitrogen or an inert gas (for example, argon (Ar)). Table 1 shows the comparison results of the method for producing the oxidized transparent conductive sputtering target of the present invention and the conventional method for producing a sputtering material. Although the sintering m of the inventive examples 1-6 and the comparative example i is about 56 g/cm3, the resistivity of the inventive examples 1-6 is 2.22-2.91 χΐ〇·4 Ω_cm, a conventional comparative example i The resistivity is 】& i 47χ ι 〇·3ω_, the resistivity of the sputtering target prepared by the method of the invention is much better than the resistivity of the sputtering target prepared by the method, and is close to indium. Tin oxide (ITO). At 137713.doc 201107509 Table 1
氧化鋅系統 含碳物質 燒結密度 (g/cm3) 體電阻率 (Ω-cm)Zinc oxide system Carbonaceous material Sintering density (g/cm3) Volume resistivity (Ω-cm)
本發明氧化鋅系透明導電濺鍍靶材製造方法，在製程中 添加適量的含碳物質，再進行燒結緻密化製程，藉由碳與 氧化鋅作用而形成更多導電載子濃度來降低電阻率，所製 付之氧化鋅系透明導電靶材不僅密度高（大於56 g/cm3)且 電阻率小（小於3·〇χΐ〇_4Ω-(；ιη),其中電阻率的降低並未造 成燒結密度的下降，故氧化鋅系透明導電靶材具有較佳之 濺鍍品質及鍍膜的特性良好之特性，其與ΙΤ〇靶材水準十 分接近。另外，本發明之氧化辞系透明導電材料係以氧化 鋅為主成分，並含有η型摻雜元素而形成具透明導電之特 性，其中該氧化鋅系列材料之料源充足、價格便宜，故生 產成本低。 上述實施例僅為說明本發明之原理及其功效，並非限制 本發明。因此習於此技術之人士對上述實施例進行修改及 變化仍不脫本發明之精神。本發明之權利範圍應如後述之 137713.doc 201107509The method for manufacturing a zinc oxide-based transparent conductive sputtering target according to the present invention comprises adding an appropriate amount of a carbonaceous substance in a process, and performing a sintering densification process, and forming a concentration of more conductive carriers to reduce the resistivity by the action of carbon and zinc oxide. The zinc oxide-based transparent conductive target produced is not only high in density (greater than 56 g/cm3) but also low in electrical resistivity (less than 3·〇χΐ〇_4 Ω-(; ιη), wherein the decrease in resistivity does not cause sintering Since the density is lowered, the zinc oxide-based transparent conductive target has better sputtering quality and good characteristics of the coating, and is very close to the target of the cerium target. In addition, the oxidized transparent conductive material of the present invention is oxidized. Zinc is a main component and contains an n-type doping element to form a transparent conductive property, wherein the zinc oxide series material has sufficient material source and low price, so the production cost is low. The above embodiments are merely illustrative of the principle of the present invention and The invention is not limited to the invention, and modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the scope of the invention. 137713.doc 201107509
申請專利範圍所列。 【圖式簡單說明】 圖1顯示本發明氧化鋅系透明導電濺鍍靶材之製造方法 流程圖。 137713.docThe scope of the patent application is listed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method of producing a zinc oxide-based transparent conductive sputtering target of the present invention. 137713.doc