201028214 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種薄膜製備裝置，尤其涉及一種前驅體溶 液中各纽分混合均勻之薄膜製備裝置。 ' 【先前技術】201028214 VI. Description of the Invention: [Technical Field] The present invention relates to a film preparation apparatus, and more particularly to a film preparation apparatus in which a precursor is uniformly mixed in a precursor solution. 'Prior art
目前’薄膜製程技術廣泛應用於半導體工業及精密機械 上，由於利用薄膜製程技術所生產之產品具有相當高之附加價 值，使薄膜製程技術與薄膜材料被廣泛應用於研究與實際， 時帶來鍍膜技術之迅速發展。 、不 氧化鋅薄膜是一種廣泛應用於各種工業產品之透明 膜’其可以提高產品表面之光澤度並保護產品表面不被劃傷 為達到提高薄膜之電阻、增加薄膜之光吸收特性、降低薄膜 應力等目的’通常往氧化鋅薄膜内掺雜鋁、銦、銅、鐵或錫 元素。如葛水兵等人發表於材料科學與工程2〇〇〇年第三 ^文獻《ΖηΟ:Α1透明導電膜之製備及其性能之研究》^之介 先前技術中，往氧化鋅薄膜中摻雜鋁、錫等元 法係以辞源溶液作域膜溶液，以含紹、鮮摻雜元辛』 =^雜継液，賴麟_摻_溶接混合得到= 膜,==體寺鍍膜之基板表面以製備薄 准Μ用該直U式传到之前驅體溶液中 ^雜^容=以有效混合，導致所得薄膜結晶 佳。^ 發魏學反應而 斫出田彳產物，細產物―驅體溶液，亦會影響鑛膜品質。 201028214 【發明内容】 有鑑於此，提供一種前驅體溶液中各組分混合勻之薄 膜製備裝置實屬必要。 一種薄膜製備系統包括前驅體溶液製備裝置與薄膜沈積 裝置。所述刖驅體溶液製備裝置包括儲液罐、汽化裝置與吸收 塔。所述儲液罐與所述汽化裝置均與所述吸收塔相連通。所述 儲液罐用於儲存鑛膜溶液並向吸收塔提供鑛膜溶液V斤述汽化 裝置用於汽化摻雜劑溶液並向吸收塔提供汽化後之摻雜劑溶 液。所述珥收塔用於使錢膜溶液吸收汽化後之摻雜劑溶液溶液 ❹ 從而得到前驅體溶液。所述薄膜沈積裝置用於將前驅體溶液導 至待鍍膜之基板表面以形成薄膜。 相較於先前技術，上述薄膜製備裝置之前驅體溶液製備 裝置包括汽化裝置與吸收塔，汽化裝置可使摻雜劑溶液汽化， 吸收塔可使鍍膜溶液充分吸收汽化後之摻雜劑溶液，從而得到 各組分充分混合之前驅體溶液，進而使得薄膜沈積裝置得到相 態均勻之薄膜。此外，該薄膜製備裝置還可方便地控制前驅體 溶液之組分。 【實施方式】 下面將結合附圖對本發明實施例作進一步詳細說明。 請參閱圖1，本實施例提供一種薄膜製備裝置1〇，其用 於製備前驅體溶液並將該前驅體溶液導至待鍍膜之基板表面 以形成薄膜。薄膜製備裝置1〇包括前驅體溶液製備裝置丨丨 薄膜沈積裝置12。 、 所述前驅體溶液製備裝置11用於製備前驅體溶液。前驅At present, the thin film process technology is widely used in the semiconductor industry and precision machinery. Because the products produced by the thin film process technology have a relatively high added value, the thin film process technology and the film material are widely used in research and practice, and the coating is brought. Rapid development of technology. , Zinc Oxide Thin Film is a transparent film widely used in various industrial products. It can improve the gloss of the surface of the product and protect the surface of the product from scratching. It can improve the resistance of the film, increase the light absorption characteristics of the film, and reduce the film stress. Etc. 'There is usually a zinc oxide film doped with aluminum, indium, copper, iron or tin. For example, Ge Shuibing and others published in the third year of the material science and engineering, "The work of ΖηΟ: Α1 transparent conductive film and its properties" ^ In the prior art, doping aluminum into zinc oxide film The tin and other elementary systems use the source solution as the domain membrane solution to contain the sputum and fresh doping xinxin 』 =^ miscellaneous sputum, and the lining _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The preparation of the thin bismuth is transmitted to the precursor solution by the straight U type to effectively mix, resulting in good crystallization of the obtained film. ^ The Wei Xue learning reaction and the fine product - the body solution will also affect the quality of the mineral film. SUMMARY OF THE INVENTION In view of the above, it is necessary to provide a thin film preparation apparatus in which a mixture of components in a precursor solution is uniformly mixed. A film preparation system includes a precursor solution preparation device and a thin film deposition device. The cockroach body solution preparation device comprises a liquid storage tank, a vaporization device and an absorption tower. The liquid storage tank and the vaporization device are both in communication with the absorption tower. The liquid storage tank is for storing a mineral film solution and providing a mineral film solution to the absorption tower. The vaporization device is for vaporizing the dopant solution and supplying the vaporized dopant solution to the absorption tower. The concentrating tower is configured to cause the money film solution to absorb the vaporized dopant solution solution to obtain a precursor solution. The thin film deposition apparatus is for guiding a precursor solution to a surface of a substrate to be coated to form a thin film. Compared with the prior art, the precursor preparation device of the above film preparation device comprises a vaporization device and an absorption tower, and the vaporization device can vaporize the dopant solution, and the absorption tower can sufficiently absorb the vaporized dopant solution by the coating solution, thereby The components are thoroughly mixed with the precursor solution, thereby allowing the thin film deposition apparatus to obtain a film having a uniform phase. Further, the film preparing apparatus can conveniently control the components of the precursor solution. [Embodiment] Hereinafter, embodiments of the present invention will be further described in detail with reference to the accompanying drawings. Referring to Fig. 1, this embodiment provides a thin film preparation apparatus 1 for preparing a precursor solution and guiding the precursor solution to a surface of a substrate to be coated to form a thin film. The film preparing apparatus 1 includes a precursor solution preparing device 薄膜 a film deposition device 12. The precursor solution preparation device 11 is used to prepare a precursor solution. Predecessor
體溶液製備裝置11包括汽化裝置11〇、儲液罐111與吸收玟 112 〇 D 5 201028214 π化裝置110用於加熱摻雜劑溶液以使其汽化。本實施 例中，况化裝置110包括容置腔11〇1與加熱部11〇2。所述容 置腔lioi用於容置待汽化之摻雜劑溶液。所述加熱部n〇2用 於對容置腔1101内之摻雜劑溶液提供熱量以使摻雜劑溶液汽 化。優選地，汽化裝置110之容置腔11〇1上方可設置一載氣 入口，往其中充入載氣（如氮氣）以使載氣帶動汽化後之摻雜 劑溶液進入吸收塔。 儲液罐111用於儲存鍍膜溶液並向吸收塔丨12提供鍍膜溶 液。儲液罐111具有一閥門1110用於調節進入吸收塔112之 P 鍍膜溶液之流量。 吸收塔112用於使鍍膜溶液吸收汽化後之摻雜劑溶液從 而得到前驅體溶液。本實施例中，所述吸收塔112為板式吸收 塔’其具有吸收室1120。所述吸收室1120包括頂部1121、底 部1122與複數塊塔板1123。所述頂部1121與底部1122相對。 所述複數塊塔板1123位於頂部1121與底部1122之間，用於 使汽化後之摻雜劑溶液與鑛膜溶液充分且均勻混合。塔板1123 可為篩孔塔板’其上均勻開設有孔徑為3_8mm之篩孔。所述 頂部1121處開設有進液口 1124。所述進液口 1124用於與儲液 罐111相連通’以供儲液罐m内之鍍膜溶液進入吸收室 1120 ’從而可使鑛膜溶液自頂部112i處進入吸收室112〇後， 依次經過複數塊塔板1123向底部1122處流動。靠近吸收室 1120之底部1122開設有進氣口 1125與出液口 1126。所述進 氣口 1125用於供汽化後之摻雜劑溶液進入吸收室112〇，從而 可使汽化後之摻雜劑溶液從靠近底部1122處進入吸收室1120 後到達塔板1123 ’經過筛孔時分散成小股氣流並以氣泡之形 式通過鍍膜溶液層並與鍍膜溶液充分均勻混合，從而得到混合 效果較好之前驅體溶液。所述出液口 1126與薄膜沈積裝置12 相連通’用於向薄膜沈積裝置12輸出前驅體溶液。 優選地’所述前驅體溶液製備裝置11還包括一微波加熱 6 201028214 器113。戶斤述微波力σ熱器H3套設於吸收塔ill外部，用於對 該吸收塔111加熱以利於前驅體溶液進入薄膜沈積裝置12 成膜。 本實施例中，進液口 1124開設於頂部1121，進氣口 1125 開設於底部1122，故於吸收過程中，鍍膜溶液與汽化後之摻 雜劑溶液之流動方向相逆。可理解，進液口 U24與進氣口 U25 還可同時開設於頂部1121，從而所述吸收塔内之鍍膜溶液與 汽化後之摻雜劑溶液採取並流之方式混合。另外，所述塔板 1123不僅限於為篩孔塔板，還可為浮閥塔板或泡罩塔板。所 參述吸收塔不僅限於為板式塔，還可為填料塔或湍球塔等。 薄膜沈積裴置12包括導管12卜喷頭122與加熱台123。 導管/21連接於前驅體溶液製備裝置^，用於將前驅體溶液 導入薄膜沈積裝置12。具體地，導管121與吸收塔112之出 液口 1126相連通。喷頭122包括相對之連接端124與喷出端 125。連接端124連接於導管121。噴出端125與加熱台123 相對，且其橫截面積大於連接端124之橫截面積。優選地，喷 頭122連接於一旋轉汽缸，該旋轉汽缸使得喷頭122可旋轉， 從而可增加喷頭122之喷射面積。加熱台123用於承載並加熱 待鍍膜之基板。為避免前驅體溶液進入大氣中對環境造成污 染，喷頭122及加熱台123均設置於一密閉之沈積室内， 該沈積室126可收集並處理廢氣。 優選地，薄膜沈積裝置12還可以包括一超聲波霧化裝 置’所述超聲波霧化裝置可以設置於導管121與噴頭122之 ，，用於前驅體溶液霧化成微米級霧滴後由喷頭122喷出並於 待鍍膜之基板表面形成薄膜。如此，可節省前驅體溶液並提高 所得薄膜之均勻度。 請參閱圖2 ’下面以於待鍍膜之基板1〇〇上喷射前驅體溶 液200以制得氧化鋅中摻雜銘薄膜為例說明該薄膜製備裝置 7 201028214 ίο之使用方法，可包括以下步驟： 第一步’提供鍍膜溶液201與摻雜劑溶液202。配置 0.09mol/L之醋酸鋅之乙醇溶液作為鍍膜溶液2〇1並儲存於儲 液罐111。將適量氣化銘溶解於乙醇作為捧雜劑溶液202並容 置於容置腔1101。摻雜劑溶液202中氯化鋁之含量視氡化鋅 薄膜中所需鋁之摻雜量而定。 第二步，提供待鍍膜之基板100，將其放置於加熱台123 並對待錄膜之基板100加熱。待鍍膜之基板1〇〇可為金屬、玻 璃、石夕晶片或陶竟。本實施例中’待鑛膜之基板1〇〇為氧化紹 參 材質，對該待鍍膜之基板100加熱至320。〇。 第三步’使汽化後之摻雜劑溶液202進入吸收塔112並 自底部1122向頂部1121方向流動，同時調節閥門ιι10使適 量鍍膜溶液201進入吸收塔112，從而鍍膜溶液201自頂部 1121向底部1122方向流動過程中於塔板1123上與汽化後之掺 雜劑溶液202充分均勻混合，形成混合效果較好之前驅體溶液 200。 將容置腔1101内之摻雜劑溶液202加熱至11〇。(：左右 時，摻雜劑溶液202汽化。汽化後之摻雜劑溶液202從底部 ❹ 1122處之進氣口 1125進入吸收室1120。同時，鍍膜溶液201 從頂部1121處之進液口 1124進入吸收室1120,二者混合大約 一小時，鑛膜溶液201可吸收大部分汽化後之摻雜劑溶液202 並得到前驅體溶液200。具體地，汽化後之摻雜劑溶液202於 塔板1123上以氣泡之形態分散於鍍膜溶液201中。吸收完成 後’前驅體溶液200從底部1122之出液口 1126流出，未被完 全吸收之汽化後之摻雜劑溶液202可從吸收塔112之頂部1121 排出。 第四步，將前驅體溶液200導至薄膜沈積裝置12，從而 於加熱之待鍍膜之基板100表面形成薄膜。 201028214 ^驅體溶液200經由導管121到達喷頭122之連 4 並自噴出端125喷至加熱之待鑛膜之基板1〇〇表面，此 ==驅體溶液2GG與沈積室126内之氧氣接觸錄氧化獅 薄板面形成換_呂元素之氧化鋅薄膜。該 $為巧色，請參_ 3，為本技術方案實施例所得之推雜 有紹兀•素之氧化鋅薄膜之SEM照片。 鮮技術，上述薄膜製備裝置1G之前驅體溶液製 備裝置11包括沉化裝置110與吸收塔112，汽化裝置11〇 ❹ 掺雜劑溶液汽化’吸收塔112可使鑛膜溶液充分吸收汽化後之 摻雜劑溶液’從而制各組分充分齡之前驅體絲·，進 而使得薄膜沈積裝置12得到相態均勻之薄膜。此外，該薄膜 製備裝置10還可方便地控制前驅體溶液200之組分。 、 綜上所述，本發明確已符合發明專利之要件，遂依法提 出專利申請。惟，以上所述者僅為本發明之較佳實施方式，自 不能以此限制本案之申請專利範圍。舉凡熟悉本案技藝之人士 援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申 請專利範圍内。 ❹ 【圖式簡單說明】 圖1為本技術方案實施例提供之薄膜製備裝置之結構示意圖。 圖2為使用本技術方案實施例提供之薄膜製備裝置製備摻雜 有鋁元素之氧化鋅薄膜之示意圖。 ^ 圖3為使用本發明實施例提供之薄膜製備裝置制得之摻雜鋁 元素之氧化辞薄膜之掃描電子顯微鏡（SEM)照片。 【主要元件符號說明】 201028214The bulk solution preparation device 11 includes a vaporization device 11A, a reservoir 111, and an absorption 玟 112 〇 D 5 201028214 The π device 110 is used to heat the dopant solution to vaporize it. In the present embodiment, the conditioning device 110 includes a housing chamber 11〇1 and a heating portion 11〇2. The receiving chamber lioi is for accommodating a dopant solution to be vaporized. The heating portion n〇2 is used to supply heat to the dopant solution in the accommodating cavity 1101 to vaporize the dopant solution. Preferably, a carrier gas inlet may be disposed above the accommodating chamber 11 〇 1 of the vaporization device 110, and a carrier gas (such as nitrogen) is charged therein to cause the dopant solution to be vaporized by the carrier gas to enter the absorption tower. The liquid storage tank 111 is for storing the plating solution and supplying a coating solution to the absorption tower 12. The reservoir 111 has a valve 1110 for regulating the flow rate of the P coating solution entering the absorption tower 112. The absorption tower 112 is for allowing the plating solution to absorb the vaporized dopant solution to obtain a precursor solution. In the present embodiment, the absorption tower 112 is a plate type absorption tower' having an absorption chamber 1120. The absorption chamber 1120 includes a top portion 1121, a bottom portion 1122, and a plurality of trays 1123. The top portion 1121 is opposite the bottom portion 1122. The plurality of trays 1123 are located between the top portion 1121 and the bottom portion 1122 for sufficiently and uniformly mixing the vaporized dopant solution with the mineral film solution. The tray 1123 may be a sieve tray plate having a sieve opening having a pore diameter of 3_8 mm uniformly formed thereon. A liquid inlet 1124 is opened at the top portion 1121. The liquid inlet 1124 is used to communicate with the liquid storage tank 111 to allow the coating solution in the liquid storage tank m to enter the absorption chamber 1120', so that the mineral film solution can enter the absorption chamber 112 from the top 112i, and then pass through A plurality of trays 1123 flow toward the bottom 1122. The bottom 1122 of the absorption chamber 1120 is provided with an air inlet 1125 and a liquid outlet 1126. The air inlet 1125 is used for the vaporized dopant solution to enter the absorption chamber 112〇, so that the vaporized dopant solution can enter the absorption chamber 1120 from near the bottom 1122 and reach the tray 1123' through the mesh. When dispersed into a small stream of gas and passed through the coating solution layer in the form of bubbles and thoroughly mixed with the coating solution, a precursor solution having a better mixing effect is obtained. The liquid outlet 1126 is in communication with the thin film deposition apparatus 12 for outputting a precursor solution to the thin film deposition apparatus 12. Preferably, the precursor solution preparation device 11 further includes a microwave heating 6 201028214 device 113. The microwave force sigma heater H3 is disposed outside the absorption tower ill for heating the absorption tower 111 to facilitate film formation of the precursor solution into the thin film deposition apparatus 12. In this embodiment, the liquid inlet 1124 is opened at the top portion 1121, and the air inlet 1125 is opened at the bottom portion 1122. Therefore, during the absorption process, the coating solution is opposite to the flow direction of the vaporized dopant solution. It can be understood that the inlet U24 and the inlet U25 can be simultaneously opened at the top portion 1121, so that the coating solution in the absorption tower is mixed with the vaporized dopant solution in a cocurrent manner. Further, the tray 1123 is not limited to a sieve tray, but may be a float tray or a bubble tray. The absorption tower is not limited to a plate tower, but may be a packed tower or a turret. The film deposition apparatus 12 includes a nozzle 12 and a heating stage 123. The conduit / 21 is connected to a precursor solution preparation device for introducing the precursor solution into the thin film deposition device 12. Specifically, the conduit 121 is in communication with the liquid outlet 1126 of the absorption tower 112. The showerhead 122 includes opposing connection ends 124 and ejection ends 125. The connection end 124 is connected to the conduit 121. The discharge end 125 is opposite to the heating stage 123 and has a cross-sectional area larger than the cross-sectional area of the connection end 124. Preferably, the spray head 122 is coupled to a rotary cylinder that allows the spray head 122 to be rotated, thereby increasing the spray area of the spray head 122. The heating stage 123 is used to carry and heat the substrate to be coated. In order to prevent the precursor solution from entering the atmosphere and polluting the environment, the showerhead 122 and the heating station 123 are disposed in a sealed deposition chamber, and the deposition chamber 126 collects and processes the exhaust gas. Preferably, the thin film deposition device 12 may further include an ultrasonic atomizing device. The ultrasonic atomizing device may be disposed on the conduit 121 and the showerhead 122 for spraying the precursor solution into a micron-sized mist droplet and then spraying by the nozzle 122. A film is formed on the surface of the substrate to be coated. Thus, the precursor solution can be saved and the uniformity of the resulting film can be improved. Please refer to FIG. 2 hereinafter, the method of using the precursor film of the zinc oxide in the zinc oxide film to prepare the film preparation device 7 201028214 ίο, may include the following steps: The first step 'provides the coating solution 201 and the dopant solution 202. An ethanol solution of 0.09 mol/L of zinc acetate was placed as a coating solution 2〇1 and stored in the reservoir 111. An appropriate amount of gasification is dissolved in ethanol as a dopant solution 202 and placed in the accommodating chamber 1101. The amount of aluminum chloride in the dopant solution 202 depends on the amount of aluminum required in the zinc telluride film. In the second step, the substrate 100 to be coated is provided, placed on the heating stage 123, and the substrate 100 to be recorded is heated. The substrate 1 to be coated may be metal, glass, stone wafer or ceramic. In the present embodiment, the substrate 1 to be cast film is made of oxidized ginseng, and the substrate 100 to be coated is heated to 320. Hey. The third step is to make the vaporized dopant solution 202 enter the absorption tower 112 and flow from the bottom 1122 to the top portion 1121 while adjusting the valve ι 10 to bring the appropriate amount of the coating solution 201 into the absorption tower 112, so that the coating solution 201 is from the top 1121 to the bottom. During the flow in the 1122 direction, the vaporized dopant solution 202 is sufficiently uniformly mixed on the tray 1123 to form a precursor solution 200 having a better mixing effect. The dopant solution 202 in the accommodating chamber 1101 is heated to 11 Torr. (When left and right, the dopant solution 202 is vaporized. The vaporized dopant solution 202 enters the absorption chamber 1120 from the inlet 1125 at the bottom ❹ 1122. At the same time, the coating solution 201 enters from the inlet 1124 at the top 1121. The absorption chamber 1120 is mixed for about one hour, and the mineral film solution 201 can absorb most of the vaporized dopant solution 202 and obtain the precursor solution 200. Specifically, the vaporized dopant solution 202 is on the tray 1123. The bubble solution is dispersed in the coating solution 201. After the absorption is completed, the precursor solution 200 flows out from the liquid outlet 1126 of the bottom portion 1122, and the vaporized dopant solution 202 which is not completely absorbed can be from the top portion 1121 of the absorption tower 112. In the fourth step, the precursor solution 200 is guided to the thin film deposition device 12 to form a thin film on the surface of the substrate 100 to be coated. 201028214 ^ The body solution 200 reaches the junction of the showerhead 122 via the conduit 121 and is self-discharged. The end 125 is sprayed onto the surface of the substrate 1 to be heated to be coated with the film, and the == the body solution 2GG and the oxygen in the deposition chamber 126 are contacted with the oxidized lion sheet to form a zinc oxide film for the _Lu element. color Please refer to _ 3 for the SEM photograph of the zinc oxide film obtained by the embodiment of the technical solution. The fresh film, the above-mentioned film preparation device 1G precursor solution preparation device 11 includes a deposition device 110 and The absorption tower 112, the vaporization device 11 汽 the dopant solution vaporizes the 'absorption column 112, so that the mineral film solution can sufficiently absorb the vaporized dopant solution' to prepare the precursors of the respective precursors, thereby making the film deposition The film 12 obtains a film having a uniform phase. In addition, the film preparing device 10 can also conveniently control the components of the precursor solution 200. In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention, and the scope of the patent application of the present invention should not be limited thereto. Any equivalent modifications or changes made by those skilled in the art to the spirit of the present invention should be It is included in the scope of the following patent application. ❹ [Simplified description of the drawings] Fig. 1 is a schematic structural view of a thin film preparation apparatus provided by an embodiment of the present technical solution. Technical Solution Example A schematic diagram of a zinc oxide film doped with aluminum element is prepared by a thin film preparation apparatus. ^ FIG. 3 is a scanning electron of an aluminum oxide-doped oxidized film prepared by using the thin film preparation apparatus provided by the embodiment of the present invention. Microscope (SEM) photo. [Main component symbol description] 201028214
薄膜製備裝置 10 前驅體溶液製備裝置 11 汽化裝置 110 容置腔 1101 加熱部 1102 儲液罐 111 閥門 1110 吸收塔 112 吸收室 1120 頂部 1121 底部 1122 塔板 1123 進液口 1124 進氣口 1125 出液口 1126 微波加熱器 113 薄膜沈積裝置 12 導管 121 喷頭 122 加熱台 123 連接端 124 喷出端 125 沈積室 126 待鍍膜之基板 100 前驅體溶液 200 鍍膜溶液 201 摻雜劑溶液 202Film preparation apparatus 10 precursor solution preparation apparatus 11 vaporization apparatus 110 accommodation chamber 1101 heating part 1102 liquid storage tank 111 valve 1110 absorption tower 112 absorption chamber 1120 top 1121 bottom 1122 tray 1123 inlet port 1124 inlet port 1125 outlet port 1126 Microwave heater 113 Thin film deposition device 12 Catheter 121 Nozzle 122 Heating station 123 Connection end 124 Discharge end 125 Deposition chamber 126 Substrate to be coated 100 Precursor solution 200 Coating solution 201 Dopant solution 202