201011122 九、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，尤其涉及一種可節省 前驅體溶液並延長霧化發生器使用壽命之薄膜製備裝置。 【先前技術】 半導體薄膜於電子器件、太陽能電池、功能材料、光 蠱電化學製氫等領域具有廣泛之應用。目前常用之半導體薄 膜材料之製備方法有化學氣相沈積法（Chemical201011122 IX. Description of the invention: [Technical field of the invention] The present invention relates to a film preparation apparatus, and more particularly to a film preparation apparatus which can save a precursor solution and prolong the service life of the atomization generator. [Prior Art] Semiconductor thin films have a wide range of applications in electronic devices, solar cells, functional materials, and photoelectrochemical hydrogen production. The currently used semiconductor thin film material preparation method is chemical vapor deposition (Chemical)
Deposition，CVD)、磁控濺射法、溶膠凝膠法及噴霧熱分解 法等，溶膠凝膠法為受歡迎製備方法之一，其具有生長溫 度低、沈積面積大、生長速度快、工藝易於控制等優點。 喷霧熱分解法為近年來逐漸發展起來之化合物半導體薄膜 製備方法，該方法相較於溶膠凝膠法具有良好之取向性及 外延性’且成本低、無需多次鐘膜。常見之噴霧熱分解技 籲術係將待鍍膜之前驅體溶液霧化，再用載氣將霧化之待鍍 膜前驅體溶液攜帶至加熱之基板表面形成薄膜。常用前驅 體溶液霧化方式有高速離心霧化、壓力式霧化、氣流式霧 化以及超聲波霧化等。 傳統之超聲波霧化裝置包括容器、位於容器内之霧化 發生器（通常為壓電振動片）以及安裝於霧化發生器上之 液位控制器。谷器内填充有前驅體溶液，工作時，由於電 子尚頻震盪，霧化發生器高頻諧振從而將前驅體溶液分子 結構打散而產生霧滴。採用該霧化裝置，當加入容器中之 5 201011122 -前驅體溶液液位過低，霧化發生器會因高頻振動發熱且得 *不到及時冷卻而遭到損壞。為保護霧化發生器，於其上安 •裝液位控制器，容器中之液位必須超過液位控制器之高 度，霧化裝置才能工作。然而，由於霧化發生器與待霧化 之前驅體溶液直接接觸，前驅體溶液可能腐蝕霧化發生器 從而縮短霧化發生器之使用壽命。 有鑑於此，提供一種可節省前驅體溶液並延長霧化發 •生器使用壽命之薄膜製備裝置實為必要。 【發明内容】 一種薄膜製備裝置包括霧化裝置以及薄膜沈積裝置。 該霧化裝置用於霧化前驅體溶液。該薄膜沈積裝置用於將 霧化之前驅體溶液喷至基板表面以形成薄膜。該霧化裝置 包括容器、振動傳遞膜以及振動元件。該振動傳遞膜將容 器分隔成第一收容部及第二收容部。該第一收容部填充有 ⑩振動傳遞液體。該第二收容部用於填充前驅體溶液。該振 動疋件位於第一收容部，用於產生振動，並使振動藉由該 振動傳遞液體、振動傳遞膜傳遞至前驅體溶液，從而使前 驅體溶液霧化。 相較於先前技術，上述薄臈製備裝置之霧化裝置具有 如下優點：第一，藉由振動傳遞液體、振動傳遞膜對前驅 體溶液傳遞振動以將前驅體溶液霧化，無需前驅體溶液與 振動元件直接接觸從而延長振動元件之使用壽命；第二， 薄膜製備裝置並不限制容置於霧化裝置内之前驅體溶液之 201011122 - 體積，只需加入少量前驅體溶液即可發生霧化並於基板表 ‘ 面鏡膜。 【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，為本實施例提供之一種薄臈製備裝置 100，其用於將前驅體溶液霧化以於基板表面鍍膜。薄膜製 β備裝置100包括霧化裝置10以及薄膜沈積裝置20。 霧化裝置10用於將前驅體溶液霧化，請參閱圖1，霧 化裝置10包括容器11、振動傳遞膜12以及振動元件13。 振動傳遞膜12將容器11分隔成第一收容部14及第二 收容部15。第一收容部14充有振動傳遞液體16。振動傳 遞液體16可傳播振動，例如超聲波，本技術方案中，為避 免振動元件13被腐蝕’振動傳遞液體16可為曱醇、乙醇、 丙酮等液態有機物或水。 ♦ 第二收容部15用於填充前驅體溶液。第二收容部15 包括遠離第一收容部14之頂端15a以及靠近振動傳遞膜12 之底端15b，頂端15a之尺寸小於底端15b之尺寸。第二收 各部15靠近底端15b處具有進氣口 17以及進液口 18。進 氣口 17用於往第二收容部15内充入載氣，用於將霧化之 ，驅體溶液攜帶至基板表面，載氣可為氮氣或氬氣等惰性 氣體。進液口 18用於往第二收容部15内加入前驅體溶液， 以補充霧化後減少之前驅體溶液。優選地，進液口 18與填 充於第一收谷部15之前驅體溶液之液面間之距離為3cm至 201011122 8cm 振動元件13位於第一收 充於第一收容部15之前驅遞真 化。振動傳遞膜物傳遞振動m:驅體溶液霧 動傳遞膜12為聚乙烯膜 、曰’本實施例中，振 其產生之振動可為超聲波。振動70件13可為I電振動片， 優選地，當容器 第一收谷部15由透明材質製成 時’霧化裝置10可包括一斑裳一队一 * 何買裏成 ^ ^ 與第一收各部15相對之紅外檢 ，裝置’用於檢測前驅體溶液霧化後液滴之直徑大小。 可理#霧化裝置1G藉由振動傳遞膜U將振動傳遞 液體16密封於第-收容部14内，故本技術方案提供之霧 化裝置jG之第-收容部14無需設置液位控制器，只需於 第收谷°卩14充入足量之振動傳遞液體16即可保證振動 元件13不會因發熱而損壞。 薄膜沈積裝置20包括導管21、加熱台22及喷頭23。 加熱台22用於承載並加熱基板。噴頭23與加熱台22相對， 用於對加熱之基板表面喷出霧化之前驅體溶液。喷頭23包 括相對之連接端24及喷出端25,連接端24連接於導管21， 喷出端25之尺寸大於連接端24之尺寸。優選地，為避免 氣霧進入大氣中對環境造成污染’加熱台22及喷頭23可 設置於一密閉之沈積室内，該沈積室可收集並處理廢氣。 導管21用於連接霧化裝置10與喷頭23，以將經霧化裝置 1〇霧化後之前驅體溶液傳輸至喷頭23。具體地，導管21 8 201011122 - 與霧化裝置10之第二收容部15相連通。 * 請參閱圖2，下面以超聲波喷霧熱分解法於基板200 * 表面鍍釕薄膜為例說明該薄膜製備裝置100之使用方法， 可包括以下步驟： 第一步，製備前驅體溶液300並加入第二收容部15 中。配置0.001mol/L之三（戊烷-2，4-二酮基）釕之甲醇 溶液100ml，將該前驅體溶液300自進液口 18加入至第二 收容部15内，具體地，該前驅體溶液300承載於振動傳遞 —膜12，同時與第二收容部15之底端15b之内壁相接觸。 第二步，提供基板200，將其放置於加熱台22。對加 熱台22通電以加熱基板200。基板200可為玻璃、矽晶片 或陶瓷。本實施例中，將基板200加熱至300°C。 第三步，對前驅體溶液300進行霧化。具體地，振動 元件13產生超聲波，並使超聲波藉由該振動傳遞液體16、 振動傳遞膜12傳遞至前驅體溶液300，從而使前驅體溶液 參300霧化。 第四步，往第二收容部15内充入載氣，以將霧化之前 驅體溶液攜帶至加熱之基板200表面以形成薄膜。 自進氣口 17往第二收容部15内充入載氣。本實施例 中，進氣口 17位於前驅體溶液300之液面以上5cm。載氣 與霧化之前驅體溶液300形成氣霧，由於第二收容部15之 頂端15a之尺寸小於底端15b之尺寸，因此，氣霧到達頂 端15a流速增大。流速較大之氣霧依次經過導管21，並由 喷頭23喷出，由於喷頭23之噴出端25之尺寸大於連接端 201011122 -24之尺寸，氣霧到達噴出端25時流速減小，以便氣霧喷出 * 穩定。維持喷霧狀態30-60分鐘，即可於基板200之表面得 * 到亮黑色之釕薄膜。將所得之釕薄膜進行高溫退火可得氧 化釕薄膜，請參閱圖3，為本技術方案實施例所得氧化釕薄 膜之SEM照片。 相較於先前技術，上述薄膜製備裝置100之霧化裝置 10具有如下優點：第一，藉由振動傳遞液體16、振動傳遞 膜12對前驅體溶液300傳遞振動以將前驅體溶液300霧 ®化，無需前驅體溶液300與振動元件13直接接觸從而延長 了振動元件13之使用壽命；第二，薄膜製備裝置100並不 限制容置於霧化裝置10内之前驅體溶液300之體積，只需 加入少量前驅體溶液300即可發生霧化並於基板表面鍍膜。 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 參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。 【圖式簡單說明】 圖1為本發明實施例提供之薄膜製備裝置之結構示意 圖。 圖2為使用本發明實施例提供之薄膜製備裝置製備釕 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 201011122 · • 氧化釕薄膜之掃描電子顯微鏡（SEM)照片。 - 【主要元件符號說明】 薄膜製備裝置 100 霧化裝置 10 薄膜沈積裝置 20 容器 11 振動傳遞膜 12 振動元件 13 第一收容部 14 第二收容部 15 頂端 15a 底端 15b 振動傳遞液體 16 進氣口 17 進液口 18 導管 21 加熱台 22 喷頭 23 連接端 24 喷出端 25 基板 200 前驅體溶液 300 11Deposition, CVD), magnetron sputtering, sol-gel method and spray pyrolysis method, sol-gel method is one of the popular preparation methods, which has low growth temperature, large deposition area, fast growth speed and easy process. Control and other advantages. The spray pyrolysis method is a method for preparing a compound semiconductor film which has been gradually developed in recent years, and which has good orientation and epitaxy as compared with the sol-gel method, and has low cost and does not require multiple bell films. The common spray pyrolysis technique atomizes the precursor solution before coating, and then carries the atomized precursor solution to be sprayed onto the surface of the heated substrate to form a film. Commonly used precursor solution atomization methods include high-speed centrifugal atomization, pressure atomization, airflow atomization, and ultrasonic atomization. A conventional ultrasonic atomizing device includes a container, an atomizing generator (usually a piezoelectric vibrating piece) located inside the container, and a level controller mounted on the atomizing generator. The barn is filled with a precursor solution. During operation, due to the frequent oscillation of the electrons, the atomization generator resonates at a high frequency to break up the molecular structure of the precursor solution to generate droplets. With the atomizing device, when the liquid level of the precursor solution is too low, the atomizing generator is heated due to high frequency vibration and is not damaged by timely cooling. In order to protect the atomization generator, a liquid level controller is installed on it, and the liquid level in the container must exceed the height of the liquid level controller, and the atomization device can work. However, since the atomizing generator is in direct contact with the precursor solution to be atomized, the precursor solution may corrode the atomizing generator to shorten the life of the atomizing generator. In view of this, it is necessary to provide a film preparation apparatus which can save a precursor solution and prolong the life of the atomization generator. SUMMARY OF THE INVENTION A film preparation apparatus includes an atomization device and a thin film deposition device. The atomizing device is used to atomize the precursor solution. The thin film deposition apparatus is for spraying a precursor solution before atomization onto a surface of a substrate to form a thin film. The atomizing device includes a container, a vibration transmitting film, and a vibrating member. The vibration transmission film divides the container into a first housing portion and a second housing portion. The first housing portion is filled with 10 vibration transmitting liquid. The second receiving portion is used to fill the precursor solution. The vibrating element is located at the first receiving portion for generating vibration, and the vibration is transmitted to the precursor solution by the vibration transmitting liquid and the vibration transmitting film, thereby atomizing the precursor solution. Compared with the prior art, the atomizing device of the above-mentioned thin crucible preparing device has the following advantages: first, by transmitting a vibration through a vibration, a vibration transmitting film transmits vibration to the precursor solution to atomize the precursor solution, without the precursor solution and The vibrating element is in direct contact to prolong the service life of the vibrating element. Secondly, the film preparation device does not limit the volume of the 201011122-volume of the precursor solution contained in the atomizing device, and only a small amount of the precursor solution can be added to atomize and On the substrate table 'mirror film. [Embodiment] Hereinafter, embodiments of the present invention will be further described in detail with reference to the accompanying drawings. Please refer to FIG. 1 , which is a thin crucible preparing apparatus 100 for atomizing a precursor solution to coat a surface of a substrate. The film preparation apparatus 100 includes an atomization apparatus 10 and a thin film deposition apparatus 20. The atomizing device 10 is for atomizing the precursor solution. Referring to Fig. 1, the atomizing device 10 includes a container 11, a vibration transmitting film 12, and a vibrating member 13. The vibration transmission film 12 divides the container 11 into a first housing portion 14 and a second housing portion 15. The first housing portion 14 is filled with the vibration transmitting liquid 16. The vibration transmitting liquid 16 can propagate vibrations such as ultrasonic waves. In the present embodiment, in order to prevent the vibrating member 13 from being corroded, the vibration transmitting liquid 16 may be a liquid organic substance such as decyl alcohol, ethanol or acetone or water. ♦ The second housing portion 15 is used to fill the precursor solution. The second receiving portion 15 includes a top end 15a away from the first receiving portion 14 and a bottom end 15b adjacent to the vibration transmitting film 12, and the top end 15a is smaller in size than the bottom end 15b. The second receiving portion 15 has an intake port 17 and a liquid inlet port 18 near the bottom end 15b. The air inlet port 17 is for charging a carrier gas into the second housing portion 15 for carrying the atomized solution to the surface of the substrate. The carrier gas may be an inert gas such as nitrogen or argon. The liquid inlet port 18 is for adding a precursor solution to the second receiving portion 15 to supplement the atomized solution and reduce the precursor solution. Preferably, the distance between the liquid inlet port 18 and the liquid level of the body solution before filling the first valley receiving portion 15 is 3 cm to 201011122 8 cm. The vibration element 13 is located before the first charging portion 13 is charged. . The vibration transmitting film transmits vibration m: the body fluid spray film 12 is a polyethylene film, 曰' In the present embodiment, the vibration generated by the vibration may be ultrasonic waves. The vibration 70 member 13 may be an I electric vibrating piece. Preferably, when the first trough portion 15 of the container is made of a transparent material, the atomizing device 10 may include a spotted team, a team, a body, a body, and a first The infrared detection of the respective parts 15 is used to detect the diameter of the droplets after the atomization of the precursor solution. The atomizing device 1G seals the vibration transmitting liquid 16 in the first accommodating portion 14 by the vibration transmitting film U. Therefore, the first accommodating portion 14 of the atomizing device jG provided by the present technical solution does not need to be provided with a liquid level controller. It is only necessary to fill a sufficient amount of the vibration transmitting liquid 16 in the first valley to ensure that the vibrating element 13 is not damaged by heat. The thin film deposition apparatus 20 includes a duct 21, a heating stage 22, and a shower head 23. The heating stage 22 is used to carry and heat the substrate. The showerhead 23 is opposed to the heating stage 22 for ejecting the atomized precursor solution onto the heated substrate surface. The spray head 23 includes an opposite connection end 24 and a discharge end 25, the connection end 24 being connected to the conduit 21, the discharge end 25 being sized larger than the connection end 24. Preferably, in order to prevent the aerosol from entering the atmosphere, the environment is contaminated. The heating station 22 and the spray head 23 may be disposed in a sealed deposition chamber which collects and treats the exhaust gas. The conduit 21 is used to connect the atomizing device 10 and the spray head 23 to transfer the precursor solution to the spray head 23 after atomization by the atomizing device 1 . Specifically, the conduit 21 8 201011122 - is in communication with the second receiving portion 15 of the atomizing device 10. * Referring to FIG. 2, the method for using the film preparation apparatus 100 on the surface of the substrate 200* by ultrasonic spray pyrolysis is exemplified below, which may include the following steps: In the first step, the precursor solution 300 is prepared and added. In the second housing portion 15. 100 ml of a methanol solution of 0.001 mol/L of tris(pentane-2,4-dione) hydrazine is disposed, and the precursor solution 300 is added from the liquid inlet 18 to the second housing portion 15, specifically, the precursor The body solution 300 is carried on the vibration transmission film 12 while being in contact with the inner wall of the bottom end 15b of the second housing portion 15. In the second step, the substrate 200 is provided and placed on the heating stage 22. The heating stage 22 is energized to heat the substrate 200. The substrate 200 can be glass, tantalum wafer or ceramic. In this embodiment, the substrate 200 is heated to 300 °C. In the third step, the precursor solution 300 is atomized. Specifically, the vibrating element 13 generates ultrasonic waves, and the ultrasonic waves are transmitted to the precursor solution 300 by the vibration transmitting liquid 16, and the vibration transmitting film 12, thereby atomizing the precursor solution ginseng 300. In the fourth step, the second accommodating portion 15 is filled with a carrier gas to carry the atomized precursor solution to the surface of the heated substrate 200 to form a film. The carrier gas is filled into the second housing portion 15 from the air inlet port 17. In the present embodiment, the intake port 17 is located 5 cm above the liquid level of the precursor solution 300. The carrier gas and the atomization before the atomization solution 300 form an aerosol. Since the size of the tip end 15a of the second housing portion 15 is smaller than the size of the bottom end 15b, the flow rate of the aerosol reaching the tip end 15a is increased. The gas mist having a large flow rate passes through the conduit 21 in sequence, and is ejected by the nozzle 23, and since the size of the ejection end 25 of the nozzle 23 is larger than the size of the connection end 201011122 - 24, the flow velocity is reduced when the aerosol reaches the ejection end 25, so that the flow rate is reduced. The aerosol spray* is stable. By maintaining the spray state for 30-60 minutes, a bright black film can be obtained on the surface of the substrate 200. The obtained ruthenium film is subjected to high temperature annealing to obtain a ruthenium oxide film. Referring to Fig. 3, an SEM photograph of the ruthenium oxide film obtained in the embodiment of the present invention is shown. Compared with the prior art, the atomizing device 10 of the above-described film preparing apparatus 100 has the following advantages: First, the vibration is transmitted to the precursor solution 300 by the vibration transmitting liquid 16 and the vibration transmitting film 12 to mist the precursor solution 300. The precursor solution 300 is not required to be in direct contact with the vibrating member 13 to extend the service life of the vibrating member 13. Second, the thin film preparation device 100 does not limit the volume of the precursor solution 300 contained in the atomizing device 10, A small amount of the precursor solution 300 is added to atomize and coat the surface of the substrate. In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art of the present invention in light of the spirit of the present invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a film preparing apparatus according to an embodiment of the present invention. Fig. 2 is a schematic view showing the preparation of a ruthenium film using the film preparation apparatus provided in the embodiment of the present invention. Fig. 3 is a scanning electron microscope (SEM) photograph of a 201011122 · • yttrium oxide film prepared by using the film preparation apparatus provided by the embodiment of the present invention. - [Major component symbol description] Film preparation apparatus 100 Atomization apparatus 10 Thin film deposition apparatus 20 Container 11 Vibration transmission film 12 Vibration element 13 First housing portion 14 Second housing portion 15 Top end 15a Bottom end 15b Vibration transmission liquid 16 Air inlet 17 inlet port 18 conduit 21 heating station 22 nozzle 23 connection end 24 ejection end 25 substrate 200 precursor solution 300 11