TWI460300B - Film formation apparatus - Google Patents

Film formation apparatus Download PDF

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Publication number
TWI460300B
TWI460300B TW101150225A TW101150225A TWI460300B TW I460300 B TWI460300 B TW I460300B TW 101150225 A TW101150225 A TW 101150225A TW 101150225 A TW101150225 A TW 101150225A TW I460300 B TWI460300 B TW I460300B
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film forming
forming apparatus
film
pair
arm
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TW101150225A
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Chinese (zh)
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TW201339344A (en
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Satoru Ozaki
Shirou Takigawa
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Shimadzu Corp
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/34Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3402Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
    • H01J37/3405Magnetron sputtering
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/34Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411Constructional aspects of the reactor
    • H01J37/3447Collimators, shutters, apertures

Description

成膜裝置Film forming device

本發明是有關於一種於單一的腔室(chamber)內,對工件(work)執行利用濺鍍(sputtering)的成膜及利用電漿化學氧相沈積(chemical vapor deposition,CVD)的成膜的成膜裝置。The invention relates to a film formation by sputtering in a single chamber and film formation by plasma chemical vapor deposition (CVD) in a single chamber. Film forming device.

例如,汽車的頭燈(headlamp)的反射罩(reflector)、計量儀器(meters)是使用射出成型的塑膠製品。而且,對於該等塑膠製品而言,以賦予鏡面拋光(mirror finish)、金屬質感為目的,將鋁等金屬作為靶材(target)而利用濺鍍進行成膜。接著,於利用濺鍍進行成膜之後,為防止金屬膜的氧化,利用電漿CVD而執行氧化矽保護膜等的成膜。For example, reflectors and meters of headlamps of automobiles are injection molded plastic articles. In addition, for the purpose of imparting a mirror finish and a metallic texture, a metal such as aluminum is used as a target to form a film by sputtering. Next, after film formation by sputtering, in order to prevent oxidation of the metal film, film formation such as a ruthenium oxide protective film is performed by plasma CVD.

於此種情形時,先前是將藉由射出成型機射出成型的工件暫時以一定量儲料(stock)之後,於其他工廠執行濺鍍或電漿CVD的成膜。於此種情形時,為了執行高品質的成膜,必須對工件表面附著的水分等的吸附氣體充分地真空排氣而予以除去。因此,先前是將多個工件一併設置於腔室內,藉由如油擴散泵(oil diffusion pump)、渦輪分子泵(turbo molecular pump)、低溫抽氣泵等的超高真空泵,對腔室內進行充分的真空排氣,將水分等的吸附氣體除去之後進行成膜作業。因此,不僅需要大型的裝置,而且處理需要較長時間。In this case, the film formed by injection molding from the injection molding machine is temporarily stocked in a certain amount, and then sputtering or plasma CVD film formation is performed in other factories. In such a case, in order to perform high-quality film formation, it is necessary to sufficiently evacuate and adsorb the adsorbed gas such as moisture adhering to the surface of the workpiece. Therefore, in the past, a plurality of workpieces are collectively disposed in the chamber, and the chamber is fully filled by an ultra-high vacuum pump such as an oil diffusion pump, a turbo molecular pump, or a low-temperature air pump. The vacuum evacuation removes the adsorbed gas such as moisture and then performs a film forming operation. Therefore, not only a large device is required, but also the processing takes a long time.

而且,利用濺鍍成膜後的工件被搬送至其他成膜裝置,於該成膜裝置的腔室內利用HMDSO(六甲基二矽氧烷,hexamethyldisiloxane)等的單體(monomer)氣體而進行電漿CVD,藉此於濺鍍成膜後的表面上進行保護膜的成膜。Further, the workpiece after the sputtering film formation is transferred to another film forming apparatus, and is electrically operated by a monomer gas such as HMDSO (hexamethyldioxane) or the like in the chamber of the film forming apparatus. The slurry CVD is used to form a film of the protective film on the surface after the sputtering film formation.

而且,亦提出有一種裝置,其於同一腔室內執行濺鍍成膜與複合成膜或聚合成膜。於專利文獻1中,揭示有一種成膜裝置,將濺鍍用電極與複合成膜或聚合成膜用電極配置於以規定距離相隔的位置上。於該成膜裝置中,首先將工件與濺鍍電極對向配置,並且向腔室內導入惰性氣體,然後對濺鍍電極施加直流而執行濺鍍成膜。其次,移動工件而使工件與複合成膜或聚合成膜用電極對向配置,並且向腔室內導入HMDSO等的單體氣體,然後對複合成膜或聚合成膜用電極施加射頻電壓,執行複合成膜或聚合成膜。該專利文獻1所記載的成膜裝置中,具有於未使用的靶材上配置擋板(shutter)的構成。Further, there has been proposed a device which performs sputtering film formation and composite film formation or polymerization film formation in the same chamber. Patent Document 1 discloses a film forming apparatus in which a sputtering electrode, a composite film formation or a polymerization film formation electrode are disposed at a position separated by a predetermined distance. In this film forming apparatus, first, a workpiece is placed opposite to a sputtering electrode, an inert gas is introduced into the chamber, and then a direct current is applied to the sputtering electrode to perform sputtering. Next, the workpiece is moved to face the composite film formation or the polymerization film formation electrode, and a monomer gas such as HMDSO is introduced into the chamber, and then a radio frequency voltage is applied to the composite film formation or the polymerization film formation electrode to perform compounding. Film formation or polymerization into a film. In the film forming apparatus described in Patent Document 1, a shutter is disposed on an unused target.

而且,於專利文獻2中,揭示有一種成膜裝置,具有兼用做濺鍍用電極與電漿聚合用電極的兼用電極。於該成膜裝置中,首先向腔室內導入惰性氣體,然後對兼用電極施加直流或射頻而執行濺鍍成膜,其次向腔室內導入HMDSO等的單體氣體,對兼用電極施加射頻電壓而執行電漿聚合成膜。Further, Patent Document 2 discloses a film forming apparatus having a combined electrode that serves as both an electrode for sputtering and an electrode for plasma polymerization. In the film forming apparatus, first, an inert gas is introduced into the chamber, and then DC or RF is applied to the combined electrode to perform sputtering, and then a monomer gas such as HMDSO is introduced into the chamber, and RF voltage is applied to the combined electrode. The plasma is polymerized to form a film.

[先前技術文獻][Previous Technical Literature] [專利文獻][Patent Literature]

[專利文獻1]日本專利特開2011-58048號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-58048

[專利文獻2]日本專利特開平10-195651號公報[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-195651

根據專利文獻1所記載的成膜裝置,可於同一腔室內執行濺鍍成膜與複合成膜或聚合成膜。然而,存在如下問題,即,因濺鍍成膜與複合成膜或聚合成膜分別是於不同位置上執行,故腔室的尺寸大型化,裝置成本上升,不僅如此,腔室內的減壓、氣體交換亦耗費時間。According to the film forming apparatus described in Patent Document 1, it is possible to perform sputtering film formation, composite film formation, or polymerization film formation in the same chamber. However, there is a problem in that the sputtering film formation and the composite film formation or the polymerization film formation are performed at different positions, so that the size of the chamber is increased, the device cost is increased, and not only the pressure reduction in the chamber, Gas exchange also takes time.

另一方面,根據專利文獻2所記載的成膜裝置,由於可使裝置小型化,故可實現裝置成本下降及成膜處理的效率化,但另一方面,濺鍍成膜後執行電漿聚合成膜時,產生電極被聚合堆積物污染的問題。當產生此種聚合堆積物的污染時,會在下一次濺鍍成膜時,產生濺鍍成膜的性能下降的問題。因此,於專利文獻2所記載的成膜裝置中,存在如下問題,即,於執行電漿聚合成膜之後、執行利用直流的濺鍍成膜之前,必須藉由執行射頻濺鍍法等而清潔電極表面。On the other hand, according to the film forming apparatus described in Patent Document 2, since the apparatus can be downsized, the cost of the apparatus can be reduced and the efficiency of the film forming process can be improved. On the other hand, plasma polymerization is performed after the film is formed by sputtering. At the time of film formation, there is a problem that the electrode is contaminated by the polymerization deposit. When such contamination of the polymerization deposit occurs, there is a problem that the performance of the sputtering film formation is lowered when the next sputtering film is formed. Therefore, in the film forming apparatus described in Patent Document 2, there is a problem that it is necessary to perform cleaning by performing RF sputtering or the like after performing plasma polymerization film formation and performing sputtering film formation by direct current. Electrode surface.

本發明是為了解決上述問題研究而成者,其目的在於提供一種成膜裝置,即便於同一腔室內使用同一電極來執行濺鍍成膜與電漿CVD成膜的情形時,亦可不污染電極而有效執行濺鍍成膜與電漿CVD成膜。The present invention has been made to solve the above problems, and an object of the invention is to provide a film forming apparatus which can prevent contamination of an electrode even when a film is formed by sputtering and plasma CVD using the same electrode in the same chamber. Effectively performing sputtering film formation and plasma CVD film formation.

技術方案1所記載的發明是一種成膜裝置,於單一的腔室內對工件執行濺鍍成膜與電漿CVD成膜,其特徵在於包括:電極,具備靶材材料;射頻電源,對上述電極施 加射頻電壓;惰性氣體供給部,向上述腔室內供給惰性氣體;原料氣體供給部,向上述腔室內供給原料氣體;減壓單元,對上述腔室內進行減壓;以及擋板機構,具備擋板,該擋板可於與上述靶材材料接觸的狀態下,在覆蓋該靶材材料的狀態、及開放上述靶材材料的狀態之間切換;於上述濺鍍成膜時開放上述擋板,於上述電漿CVD成膜時藉由上述擋板而覆蓋上述靶材材料。The invention described in claim 1 is a film forming apparatus which performs sputtering film formation and plasma CVD film formation on a workpiece in a single chamber, and is characterized by comprising: an electrode having a target material; a radio frequency power source, the electrode Shi a radio frequency voltage; an inert gas supply unit that supplies an inert gas to the chamber; a material gas supply unit that supplies a material gas into the chamber; a decompression unit that decompresses the chamber; and a baffle mechanism that includes a baffle The baffle is switchable between a state in which the target material is covered and a state in which the target material is opened in a state of being in contact with the target material; and the baffle is opened when the sputtering is performed. When the plasma CVD film is formed, the target material is covered by the baffle.

技術方案2所述的發明是如技術方案1所述的發明,其中上述電極為磁控管(magnetron)電極。The invention of claim 2 is the invention of claim 1, wherein the electrode is a magnetron electrode.

技術方案3所述的發明是如技術方案2所述的發明,其中上述擋板主要由傳導體構成。The invention according to claim 3 is the invention of claim 2, wherein the baffle plate is mainly composed of a conductor.

技術方案4所述的發明是如技術方案1或2所述的發明,其中上述擋板主要是由具有與上述CVD成膜形成的膜共通的元素的材質構成。The invention according to claim 4 is the invention according to claim 1 or 2, wherein the baffle is mainly composed of a material having an element common to the film formed by the CVD film formation.

技術方案5所述的發明是如技術方案1或2所述的發明,其中上述擋板主要是由傳導體、以及形成於上述傳導體的上述工件側的表面且具有與上述CVD成膜形成的膜共通的元素的材質構成。The invention according to claim 1 or 2, wherein the baffle plate is mainly formed of a conductor and a surface formed on the workpiece side of the conductor and having a film formed by the CVD. The material of the elements common to the film.

技術方案6所述的發明是如技術方案1至5中任一所述的發明,其中上述擋板主要由非磁性體構成。The invention of claim 6 is the invention according to any one of claims 1 to 5, wherein the baffle plate is mainly composed of a non-magnetic body.

技術方案7所述的發明是如技術方案1至5中任一所述的發明,其中上述擋板的至少一部分主要由磁性體構成。The invention of claim 7 is the invention according to any one of claims 1 to 5, wherein at least a part of the baffle plate is mainly composed of a magnetic body.

技術方案8所述的發明是如技術方案1至5中任一所述的發明,更具備直流電源,該直流電源對上述電極施加 直流電壓。The invention of claim 8 is the invention according to any one of claims 1 to 5, further comprising a direct current power source that applies the electrode to the electrode DC voltage.

技術方案9所述的發明是如技術方案1至8中任一所述的發明,其中上述擋板機構具備一對擋板、及以將該一對擋板連結於腔室的擺動軸為中心而擺動的臂狀物,且具有藉由使上述一對擋板自中央朝兩側向彼此不同的方向擺動而變成開放狀態的構造。The invention according to any one of claims 1 to 8, wherein the shutter mechanism includes a pair of shutters and a swing shaft that connects the pair of shutters to the chamber The oscillating arm has a structure in which the pair of baffles are opened in a direction in which they are different from each other in the direction from the center to the both sides.

技術方案10所述的發明是如技術方案9所述的發明,其中上述一對擋板的前端部是於面朝與自上述電極朝上述工件的方向交叉的方向的抵接面上相互抵接。The invention according to claim 9 is characterized in that the front end portions of the pair of baffles are in contact with each other on an abutting surface facing a direction intersecting the electrode from the direction of the workpiece. .

技術方案11所述的發明是如技術方案1至8中任一所述的發明,其中上述擋板機構具備臂狀物,此臂狀物以將上述擋板連結於腔室的擺動軸為中心而擺動,且上述擋板配設為可相對於上述臂狀物而擺動。The invention according to any one of claims 1 to 8, wherein the shutter mechanism is provided with an arm that is centered on a swing axis that connects the shutter to the chamber. While swinging, the baffle is configured to swing relative to the arm.

技術方案12所述的發明是如技術方案11所述的發明,其中上述臂狀物具備一對臂構件及一對板簧(plate spring),上述一對臂構件以與上述擺動軸平行地延伸的軸為中心而可相互擺動(swing),上述一對板簧是附設於上述一對臂構件中的其中一臂構件上,且夾持另一臂構件,以便使上述一對臂構件的姿勢為直線狀。The invention of claim 12 is the invention according to claim 11, wherein the arm member includes a pair of arm members and a pair of plate springs, and the pair of arm members extend in parallel with the swing axis The shafts are pivotable to each other, and the pair of leaf springs are attached to one of the pair of arm members, and the other arm member is clamped to position the pair of arm members It is linear.

技術方案13所述的發明是如技術方案1至8中任一所述的發明,其中上述擋板機構具備以將上述擋板連結於腔室的擺動軸為中心而擺動的臂狀物,且於上述臂狀物與上述擋板之間配設有絕緣構件,該絕緣構件形成有於上述濺鍍成膜時用於防止上述臂狀物與上述擋板上亦形成膜的簷 部。The invention according to any one of claims 1 to 8, wherein the shutter mechanism includes an arm that swings around a swing shaft that connects the shutter to a chamber, and An insulating member is disposed between the arm and the baffle, and the insulating member is formed to prevent the arm from forming a film on the baffle and the baffle when the sputter is formed. unit.

[發明的效果][Effects of the Invention]

根據技術方案1所述的發明,即便於同一腔室內使用同一電極來執行濺鍍成膜與電漿CVD成膜的情形時,亦可藉由擋板的作用,不污染電極地有效執行濺鍍成膜與電漿CVD成膜。According to the invention of claim 1, even when the same electrode is used in the same chamber to perform film formation by sputtering and plasma CVD, sputtering can be effectively performed by the action of the baffle without contaminating the electrode. Film formation and plasma CVD film formation.

根據技術方案2所述的發明,藉由採用磁控管電極,將電漿封入靶材附近而提高電漿密度,藉此可提昇濺鍍速度。According to the invention of claim 2, by using a magnetron electrode, the plasma is sealed in the vicinity of the target to increase the plasma density, thereby increasing the sputtering speed.

根據技術方案3所述的發明,由於擋板主要由傳導體構成,因此可使該擋板有效地作為電漿CVD用的電極而發揮功能。According to the invention of claim 3, since the baffle is mainly composed of a conductor, the baffle can be effectively functioned as an electrode for plasma CVD.

根據技術方案4所述的發明,由於擋板主要由具有與CVD成膜形成的膜共通的元素的材質構成,因此於電漿CVD時可防止來自擋板材質的雜質向成膜區域的混入。According to the invention of claim 4, since the baffle is mainly composed of a material having an element common to the film formed by the CVD film formation, it is possible to prevent impurities from the baffle material from entering the film formation region during plasma CVD.

根據技術方案5所述的發明,由於擋板主要由傳導體及具有與CVD成膜形成的膜共通的元素的材質構成,因此可藉由傳導體有效地維持電極功能,並可防止雜質向成膜區域的混入。According to the invention of claim 5, since the baffle is mainly composed of a material of a conductor and an element having a film formed by film formation by CVD, the electrode can be effectively maintained by the conductor, and the impurity can be prevented from being formed. The mixing of the membrane area.

根據技術方案6所述的發明,藉由採用非磁性體的擋板,即便於電漿CVD成膜時,在擋板覆蓋電極的靶材材料的情形時,亦可有效地獲得磁控管電極的磁控管放電作用,從而可提昇電漿CVD的成膜速度。According to the invention of claim 6, by using the non-magnetic baffle, even when the plasma CVD film is formed, the magnetron electrode can be efficiently obtained when the baffle covers the target material of the electrode. The magnetron discharge acts to increase the film formation speed of the plasma CVD.

根據技術方案7所述的發明,由於擋板的至少一部分 主要由磁性體構成,故可控制電漿CVD時的電漿密度或電漿分布,且可增加用於控制電漿CVD成膜的膜厚、膜質的參數。According to the invention of claim 7, due to at least a part of the baffle Mainly composed of a magnetic material, it is possible to control the plasma density or plasma distribution during plasma CVD, and to increase the film thickness and film quality parameters for controlling plasma CVD film formation.

根據技術方案8所述的發明,由於更具備直流電源,因此於使用可進行直流濺鍍的材料的情形時,可更快速地執行濺鍍成膜。According to the invention of claim 8, since the DC power supply is further provided, when a material capable of DC sputtering is used, sputtering film formation can be performed more quickly.

根據技術方案9所述的發明,由於一對擋板採用藉由自中央朝兩側向彼此不同的方向擺動而變成開放狀態的構造,故可減小開閉擋板時所需的佔據空間,從而可實現腔室的小型化。According to the invention of claim 9, since the pair of flaps are configured to be opened by swinging from the center toward the sides in different directions, the space required for opening and closing the flap can be reduced, thereby The miniaturization of the chamber can be achieved.

根據技術方案10所述的發明,一對擋板的前端部於朝向與自電極向工件的方向交叉的方向的抵接面相互抵接,故而於電漿CVD成膜時,可有效防止電極自一對擋板間的間隙被污染。According to the invention of claim 10, the front end portions of the pair of baffles are in contact with each other in abutting direction in a direction intersecting the direction from the electrode to the workpiece, so that the electrode can be effectively prevented from being formed by plasma CVD. The gap between the pair of baffles is contaminated.

根據技術方案11及技術方案12所述的發明,擋板是相對於臂狀物可擺動地配設,故而可使擋板與具備靶材材料的電極全面地密接。因此,可更確實地防止電極的污染,並且可更恰當地使擋板作為電漿CVD用電極而發揮功能。According to the inventions of the eleventh and twelfth aspects, the baffle is swingably disposed with respect to the arm, so that the baffle can be in close contact with the electrode provided with the target material. Therefore, contamination of the electrode can be prevented more reliably, and the baffle can be more appropriately functioned as an electrode for plasma CVD.

根據技術方案13所述的發明,藉由絕緣構件的作用,而可使臂狀物與擋板成為絕緣狀態。而且,藉由絕緣構件的簷部的作用,可防止如下情形,即,於傳導體的成膜時,形成遍及各臂狀物與各擋板的膜,連結於腔室的臂狀物與抵接於電極的擋板導通,導致腔室與電極短路。According to the invention of claim 13, the arm and the shutter can be insulated by the action of the insulating member. Further, by the action of the crotch portion of the insulating member, it is possible to prevent the formation of a film throughout the arm and each of the baffles and the connection of the arms to the chamber during the film formation of the conductor. The baffle connected to the electrode is turned on, causing the chamber to be shorted to the electrode.

以下,基於圖式對本發明的實施形態進行說明。首先,說明應用本發明的成膜裝置1的成膜系統(system)。圖1是應用本發明的成膜裝置的成膜系統的概要圖。Hereinafter, embodiments of the present invention will be described based on the drawings. First, a film forming system to which the film forming apparatus 1 of the present invention is applied will be described. Fig. 1 is a schematic view showing a film forming system to which a film forming apparatus of the present invention is applied.

該成膜系統包括射出成型機2、本發明的成膜裝置1、以及搬送裝置3,搬送裝置3是將工件W自射出成型機2搬送至成膜裝置1。This film forming system includes an injection molding machine 2, a film forming apparatus 1 of the present invention, and a conveying device 3 that conveys the workpiece W from the injection molding machine 2 to the film forming apparatus 1.

工件W由搬送裝置3的機械手(hand)4保持並被搬送至成膜裝置1,此工件W於射出成型機2中經射出成型而形成。成膜裝置1具備腔室10,該腔室10主要由本體11與開閉部12構成。由搬送裝置3所搬送的工件W藉由機械手4而被載置於成膜裝置1的開閉部12上所附設的工件載置部13上。然後,藉由使開閉部12向本體11側移動,而將工件W配置於成膜裝置1的腔室10內。The workpiece W is held by a robot 4 of the conveying device 3 and conveyed to the film forming apparatus 1 which is formed by injection molding in the injection molding machine 2. The film forming apparatus 1 is provided with a chamber 10 mainly composed of a main body 11 and an opening and closing unit 12. The workpiece W conveyed by the conveying device 3 is placed on the workpiece mounting portion 13 attached to the opening and closing portion 12 of the film forming apparatus 1 by the robot 4 . Then, the workpiece W is placed in the chamber 10 of the film forming apparatus 1 by moving the opening and closing unit 12 toward the main body 11 side.

根據此種成膜系統,可將成膜裝置1設置於射出成型機2近前,且可將藉由射出成型機2所射出成型的工件W直接搬入至成膜裝置1。因此,可於射出成型後的工件W上附著水分等的吸附氣體之前,將該工件W搬送至成膜裝置1,從而可省略先前必需的用於除去水分等的吸附氣體的高真空泵。因此,可實現低成本、低能耗,並且可有效地執行成膜作業。According to such a film forming system, the film forming apparatus 1 can be placed in the vicinity of the injection molding machine 2, and the workpiece W that is injection molded by the injection molding machine 2 can be directly carried into the film forming apparatus 1. Therefore, the workpiece W can be transported to the film forming apparatus 1 before the adsorbed gas such as moisture adheres to the workpiece W after the injection molding, and the high vacuum pump for removing the adsorbed gas such as moisture, which is previously necessary, can be omitted. Therefore, low cost, low power consumption, and film forming work can be performed efficiently.

其次,說明本發明的成膜裝置1的具體構成。圖2是本發明的第1實施形態的成膜裝置1的概要圖,圖3是該成膜裝置1的電極20附近的放大圖。Next, a specific configuration of the film forming apparatus 1 of the present invention will be described. FIG. 2 is a schematic view of the film forming apparatus 1 according to the first embodiment of the present invention, and FIG. 3 is an enlarged view of the vicinity of the electrode 20 of the film forming apparatus 1.

如上述般,該成膜裝置1具備主要由本體11與開閉部12構成的腔室10。開閉部12可於搬入工件W的搬入位置、與和本體11之間構成密閉的腔室10的關閉位置之間移動。開閉部12上附設有用於載置工件W的工件載置部13。而且,如圖3所示,該成膜裝置1具備電極20,該電極20主要包含內部具有磁石22的電極部21、及靶材材料23。該電極20介隔絕緣構件14而安裝於腔室的本體11上。此外,構成腔室10的本體11藉由接地部19而接地(earth)。As described above, the film forming apparatus 1 includes the chamber 10 mainly composed of the main body 11 and the opening and closing unit 12. The opening and closing unit 12 is movable between a loading position where the workpiece W is carried in and a closed position of the chamber 10 that is sealed with the main body 11. A workpiece mounting portion 13 on which the workpiece W is placed is attached to the opening and closing portion 12. Further, as shown in FIG. 3, the film forming apparatus 1 includes an electrode 20 mainly including an electrode portion 21 having a magnet 22 therein and a target material 23. The electrode 20 is attached to the body 11 of the chamber by insulating the edge member 14. Further, the body 11 constituting the chamber 10 is grounded by the ground portion 19.

電極20經由開關45而連接於濾波器(Filter,F)42及直流電源(Direct Current,DC)41。而且,電極20經由開關46而與匹配箱(Matching Box,MB)43及射頻電源(radio frequency(RF)generator)44連接。另外,於電極20的靶材材料23的下方,配設有包含一對擋板31的擋板機構。此外,作為射頻電源44,可使用例如產生數十MHz(百萬赫茲(megahertz))左右的射頻。此處,說明書所述的射頻,是指20kHz(千赫茲(kilohertz))以上的頻率。The electrode 20 is connected to a filter (Filter, F) 42 and a direct current (DC) 41 via a switch 45. Further, the electrode 20 is connected to a matching box (MB) 43 and a radio frequency (RF) generator 44 via a switch 46. Further, a shutter mechanism including a pair of shutters 31 is disposed below the target material 23 of the electrode 20. Further, as the radio frequency power source 44, for example, a radio frequency of about several tens of MHz (megahertz) can be used. Here, the radio frequency described in the specification means a frequency of 20 kHz (kilohertz) or more.

圖4是擋板機構的放大圖。Figure 4 is an enlarged view of the shutter mechanism.

該擋板機構中,擋板31是由臂狀物39支持,該臂狀物39以連結於腔室10的本體11的擺動軸15為中心擺動。該臂狀物39具備一對臂構件32、33以及一對板簧35,上述一對臂構件32、33能夠以與擺動軸15平行地延伸的軸34為中心而相互擺動(swing);上述一對板簧35藉由螺 釘37安裝於一對臂構件32、33中其中一臂構件32上,且夾持另一臂構件33,以便使上述一對臂構件32、33的姿勢成為直線狀。臂構件32以連結於本體11的擺動軸15為中心而自由地擺動。此外,該擋板31主要由金屬等傳導體、且非磁性體的材料構成。作為該擋板31的材質,例如可採用鋁。In the shutter mechanism, the shutter 31 is supported by an arm 39 that swings around the swing shaft 15 of the body 11 coupled to the chamber 10. The arm member 39 includes a pair of arm members 32 and 33 and a pair of leaf springs 35, and the pair of arm members 32 and 33 are swingable with respect to a shaft 34 extending parallel to the swing shaft 15; a pair of leaf springs 35 by means of a screw The nail 37 is attached to one of the pair of arm members 32, 33, and the other arm member 33 is clamped so that the posture of the pair of arm members 32, 33 is linear. The arm member 32 swings freely around the swing shaft 15 coupled to the body 11. Further, the baffle 31 is mainly composed of a material such as a metal conductor and a non-magnetic material. As the material of the baffle 31, for example, aluminum can be used.

該擋板機構中,各臂狀物39以擺動軸15為中心擺動,藉此一對擋板31於圖2及圖3中以實線表示的覆蓋電極20的靶材材料23的關閉位置、以及圖2及圖3中以虛擬線表示的開放電極20的靶材材料23的釋放位置之間擺動。即,一對擋板31具有左右對開式的構造,自關閉位置起,上述一對擋板31自中央朝兩側而向彼此不同的方向擺動,藉此變成開放狀態。In the shutter mechanism, each of the arms 39 swings around the swing shaft 15, whereby the pair of shutters 31 are closed positions of the target material 23 covering the electrodes 20, which are indicated by solid lines in FIGS. 2 and 3. And the swing position between the release positions of the target material 23 of the open electrode 20 indicated by a virtual line in FIGS. 2 and 3. In other words, the pair of flaps 31 have a structure of a left-right split type, and the pair of flaps 31 swing from the center toward the both sides from the closed position, thereby being opened.

如圖3中放大後所示,一對擋板31的前端部於抵接面38上相互抵接。在此狀態下,抵接面38朝向與自電極20向工件W的方向正交的方向,且成為與靶材材料23的表面平行的面(即,其表面與自電極20朝工件W的方向正交)。因此,當一對擋板31配置於關閉位置時,可將該等的抵接面38設為完全密接的狀態。藉此,如下述般,於電漿聚合成膜時,可有效防止電極20的靶材材料23因聚合堆積物而被污染的現象。As shown in enlarged view in FIG. 3, the front end portions of the pair of shutters 31 abut each other on the abutting surface 38. In this state, the abutting surface 38 faces a direction orthogonal to the direction from the electrode 20 toward the workpiece W, and becomes a surface parallel to the surface of the target material 23 (that is, a surface thereof and a direction from the electrode 20 toward the workpiece W). Orthogonal). Therefore, when the pair of baffles 31 are disposed at the closed position, the abutting faces 38 can be completely in close contact with each other. Thereby, as described below, when the plasma is formed into a film, the phenomenon that the target material 23 of the electrode 20 is contaminated by the polymerization deposit can be effectively prevented.

而且,該擋板機構中,如上述般,臂狀物39具備可相互擺動的一對臂構件32、33、以及用於使上述一對臂構件32、33的姿勢變成直線狀的一對板簧35。因此,一對擋板 31可以與擺動軸15平行的軸34為中心而向傾斜方向擺動。藉此,即便於電極20的靶材材料23的下表面與擋板31的上表面並非完全平行的情形時,亦可藉由使擋板31擠壓於靶材材料23,擋板31與臂構件33一併抵抗板簧35之力而傾斜,從而可使靶材材料23的下表面與擋板31的上表面完全密接。Further, in the shutter mechanism, as described above, the arm member 39 includes a pair of arm members 32 and 33 that are swingable with each other, and a pair of plates for linearly changing the postures of the pair of arm members 32 and 33. Spring 35. Therefore, a pair of baffles 31 can swing in the oblique direction centering on the shaft 34 parallel to the swing shaft 15. Thereby, even when the lower surface of the target material 23 of the electrode 20 and the upper surface of the baffle 31 are not completely parallel, the baffle 31 and the arm can be pressed by pressing the baffle 31 against the target material 23. The member 33 is inclined together with the force of the leaf spring 35, so that the lower surface of the target material 23 can be completely in close contact with the upper surface of the shutter 31.

另外,於該擋板機構中,在臂構件33與擋板31之間,配設有絕緣構件36,該絕緣構件36用於將臂構件33與擋板31設為絕緣狀態,並且防止於濺鍍成膜時形成遍及臂構件33與擋板31的膜。Further, in the shutter mechanism, between the arm member 33 and the shutter 31, an insulating member 36 for insulating the arm member 33 and the shutter 31 and preventing splashing is disposed. A film extending over the arm member 33 and the baffle 31 is formed when the film is formed.

圖5是擋板機構的絕緣構件36附近的放大圖。Fig. 5 is an enlarged view of the vicinity of the insulating member 36 of the shutter mechanism.

於構成擋板機構的臂狀物39的臂構件33的擋板側的端緣上,附設有絕緣構件36。該絕緣構件36具有兩端形成有簷部48且剖面為大體U字狀的形狀。於電極20與腔室10之間對工件W施加電壓。因此,必須預先將連接於腔室10的本體11的臂狀物39與抵接於電極20的擋板31設為絕緣狀態。An insulating member 36 is attached to the end edge of the arm member 33 of the arm member 39 constituting the shutter mechanism. The insulating member 36 has a shape in which the crotch portion 48 is formed at both ends and has a substantially U-shaped cross section. A voltage is applied to the workpiece W between the electrode 20 and the chamber 10. Therefore, it is necessary to previously insulate the arm 39 connected to the body 11 of the chamber 10 and the baffle 31 abutting against the electrode 20.

此時,於後述濺鍍成膜時,不僅於工件W上,且於擋板31、臂狀物39的表面亦形成包含靶材材料23的膜。於該膜為傳導體的情形時,若該膜遍及臂狀物39的臂構件33與擋板31而形成,則連結於腔室10的臂狀物39與抵接於電極20的擋板31導通,導致腔室10與電極20短路。然而,如圖5所示,由於該絕緣構件36上形成有簷部48,即便於擋板31或臂狀物39的表面形成有包含靶材材料23 的膜100的情形時,簷部48內側的區域A並未形成膜100,從而可有效防止濺鍍成膜時形成遍及臂狀物39與擋板31的膜。At this time, in the case of the sputtering film formation described later, a film including the target material 23 is formed not only on the workpiece W but also on the surfaces of the baffle 31 and the arm 39. When the film is a conductor, if the film is formed over the arm member 33 of the arm 39 and the baffle 31, the arm 39 connected to the chamber 10 and the baffle 31 abutting against the electrode 20 are formed. Turning on causes the chamber 10 to be shorted to the electrode 20. However, as shown in FIG. 5, since the flange portion 48 is formed on the insulating member 36, even if the surface of the shutter 31 or the arm 39 is formed with the target material 23 In the case of the film 100, the film A is not formed in the region A inside the crotch portion 48, so that the film covering the arm 39 and the baffle 31 can be effectively prevented from being formed by sputtering.

再次參照圖2,構成腔室10的本體11經由開閉閥51及流量調整閥52而與氬氣等惰性氣體的供給部53連接。而且,構成腔室10的本體11經由開閉閥54及流量調整閥55而與HMDSO、六甲基二矽烷(hexamethyldisilane,HMDS)等原料氣體的供給部56連接。另外,構成腔室10的本體11與乾式真空泵(dry pump)58及機械式升壓泵(mechanical booster pump)57連接。Referring again to FIG. 2, the body 11 constituting the chamber 10 is connected to the supply portion 53 of an inert gas such as argon gas via the opening and closing valve 51 and the flow rate adjusting valve 52. Further, the main body 11 constituting the chamber 10 is connected to a supply portion 56 of a material gas such as HMDSO or hexamethyldisilane (HMDS) via the opening and closing valve 54 and the flow rate adjusting valve 55. Further, the body 11 constituting the chamber 10 is connected to a dry vacuum pump 58 and a mechanical booster pump 57.

其次,說明具有如上構成的成膜裝置1的成膜動作。當藉由該成膜裝置1執行成膜動作時,如圖1所示,將射出成型機2中經射出成型而形成的工件W藉由搬送裝置3的機械手4予以保持,並載置至附設於成膜裝置1的開閉部12的工件載置部13上。然後,藉由使開閉部12向本體11側移動,將工件W配置於成膜裝置1的腔室10內的與電極20對向的位置上。Next, the film formation operation of the film formation apparatus 1 having the above configuration will be described. When the film forming operation is performed by the film forming apparatus 1, as shown in FIG. 1, the workpiece W formed by injection molding in the injection molding machine 2 is held by the robot 4 of the conveying device 3, and placed thereon. It is attached to the workpiece mounting portion 13 of the opening and closing portion 12 of the film forming apparatus 1. Then, by moving the opening and closing portion 12 toward the main body 11 side, the workpiece W is placed at a position facing the electrode 20 in the chamber 10 of the film forming apparatus 1.

於該狀態下,將腔室10內減壓至0.1帕(PASCAL)至5帕左右為止。此時,首先利用乾式真空泵58快速地使腔室10內減壓之後,使用機械式升壓泵57將腔室10內設為高真空。然後,藉由擋板機構,將一對擋板31配置於圖2及圖3中以虛擬線表示的釋放位置。此外,於藉由乾式真空泵58便可獲得所需真空壓的情形時,亦可省略機械式升壓泵57。In this state, the pressure in the chamber 10 is reduced to 0.1 Pa (PASCAL) to about 5 Pa. At this time, first, the inside of the chamber 10 is quickly depressurized by the dry vacuum pump 58, and the inside of the chamber 10 is set to a high vacuum using a mechanical booster pump 57. Then, the pair of baffles 31 are disposed in the release position indicated by the virtual lines in FIGS. 2 and 3 by the shutter mechanism. Further, when the required vacuum pressure is obtained by the dry vacuum pump 58, the mechanical booster pump 57 may be omitted.

其次,藉由開放開閉閥51,自惰性氣體的供給部53向腔室10內供給氬氣等惰性氣體,以腔室10內的真空度變成0.1帕~5帕的方式,使腔室10內充滿惰性氣體。接著,藉由關閉開關45,經由濾波器42而自直流電源41對電極20施加直流電壓;或者藉由關閉開關46,經由匹配箱43而自射頻電源44對電極20施加射頻電壓。藉此,利用濺鍍現象而於工件W表面形成靶材材料23的薄膜。Then, by opening the on-off valve 51, an inert gas such as argon gas is supplied from the supply portion 53 of the inert gas into the chamber 10, and the degree of vacuum in the chamber 10 is 0.1 Pa to 5 Pa, so that the chamber 10 is inside. Filled with inert gas. Next, a DC voltage is applied to the electrode 20 from the DC power source 41 via the filter 42 by turning off the switch 45; or a RF voltage is applied to the electrode 20 from the RF power source 44 via the matching box 43 by turning off the switch 46. Thereby, a thin film of the target material 23 is formed on the surface of the workpiece W by sputtering.

此外,於對電極20施加直流電壓的情形時,當靶材材料23使用可進行直流濺鍍的材質時,可更快速地執行濺鍍成膜。然而,亦可省略該直流電源41與濾波器42,僅利用射頻電源44執行濺鍍。Further, in the case where a DC voltage is applied to the electrode 20, when the target material 23 is made of a material capable of DC sputtering, sputtering film formation can be performed more quickly. However, the DC power source 41 and the filter 42 may be omitted, and sputtering may be performed only by the RF power source 44.

此時,於本發明的成膜裝置1中,藉由採用於電極20內配設有磁石22的磁控管電極,將電漿封入靶材材料23附近而提高電漿密度,藉此可提昇濺鍍速度。At this time, in the film forming apparatus 1 of the present invention, by using a magnetron electrode in which the magnet 22 is disposed in the electrode 20, the plasma is sealed in the vicinity of the target material 23 to increase the plasma density, thereby improving the plasma density. Sputtering speed.

若藉由以上步驟而結束濺鍍成膜,則繼而執行電漿聚合成膜。該電漿聚合是電漿CVD(Chemical Vapor Deposition)的一種。於執行電漿聚合的情形時,將腔室10內減壓至0.1帕至5帕左右為止。然後,藉由擋板機構,將一對擋板31配置於圖2及圖3中以實線表示的關閉位置。When the sputtering film formation is completed by the above steps, plasma polymerization is performed to form a film. The plasma polymerization is one of chemical vapor CVD (Chemical Vapor Deposition). In the case of performing plasma polymerization, the inside of the chamber 10 is depressurized to about 0.1 Pa to 5 Pa. Then, the pair of baffles 31 are disposed in the closed position indicated by the solid lines in FIGS. 2 and 3 by the shutter mechanism.

其次,藉由開放開閉閥54,自原料氣體的供給部56向腔室10內供給原料氣體,以腔室10內的真空度變成0.1帕~10帕的方式,使腔室10內充滿原料氣體。接著,藉由關閉開關46,經由匹配箱43而自射頻電源44對電極20 施加射頻電壓。此時,使擋板31與電極20一併作為電漿聚合用的電極發揮功能,執行電漿聚合成膜。藉此,利用電漿聚合反應而於工件W表面堆積原料氣體的薄膜。Then, the raw material gas is supplied from the supply unit 56 of the raw material gas into the chamber 10 by the open/close valve 54, and the chamber 10 is filled with the material gas so that the degree of vacuum in the chamber 10 becomes 0.1 Pa to 10 Pa. . Next, the electrode 20 is connected from the RF power source 44 via the matching box 43 by closing the switch 46. Apply RF voltage. At this time, the baffle 31 and the electrode 20 function together as an electrode for plasma polymerization, and plasma polymerization is performed to form a film. Thereby, a film of the material gas is deposited on the surface of the workpiece W by plasma polymerization.

此時,於本發明的成膜裝置1中,藉由採用非磁性體的擋板31,即便於電漿聚合成膜時因擋板31而覆蓋電極20的靶材材料23的情形時,亦可獲得磁石22的磁控管放電作用。因此,即便於電漿聚合成膜時,亦可提昇其成膜速度。In this case, in the film forming apparatus 1 of the present invention, by using the non-magnetic baffle 31, even when the target material 23 of the electrode 20 is covered by the baffle 31 at the time of plasma polymerization film formation, The magnetron discharge of the magnet 22 can be obtained. Therefore, even when the plasma is polymerized into a film, the film formation speed can be increased.

而且,於本發明的成膜裝置1中,如上述般,採用使利用板簧35的靶材材料23的下表面與包含傳導體的擋板31的上表面完全密接的構成,因此可使擋板31與電極20一體化而有效地作為電漿聚合用的電極發揮功能,並且將電極20的靶材材料23完全關閉而可有效防止其污染。而且,由於擋板31是傳導體,因此即便因持續執行濺鍍成膜而使得靶材材料23減少,亦可將聚合成膜狀態維持為固定。即,於此種情形時,無論靶材材料23是否為金屬等導電性材料,只要擋板31是傳導體,則與擋板31與靶材材料23以完全密接的狀態接觸相輔,可使表面側(工件W側)的電壓一致,從而可將成膜狀態維持為固定。Further, in the film forming apparatus 1 of the present invention, as described above, the lower surface of the target material 23 by the leaf spring 35 is completely in close contact with the upper surface of the baffle 31 including the conductor, so that the film can be blocked. The plate 31 is integrated with the electrode 20 to effectively function as an electrode for plasma polymerization, and the target material 23 of the electrode 20 is completely closed, thereby effectively preventing contamination thereof. Further, since the baffle 31 is a conductor, even if the target material 23 is reduced by continuously performing sputtering film formation, the state of the polymerization film formation can be maintained constant. In other words, in this case, regardless of whether or not the target material 23 is a conductive material such as a metal, as long as the baffle 31 is a conductor, the baffle 31 and the target material 23 are in contact with each other in a completely close contact state. The voltage on the surface side (the side of the workpiece W) is uniform, so that the film formation state can be maintained constant.

而且,於該成膜裝置1中,在臂構件33與擋板31之間,配設有絕緣構件36,該絕緣構件36用於防止濺鍍成膜時形成遍及臂構件33與擋板31的膜100,因此可防止因連結於腔室10的臂狀物39與抵接於電極20的擋板31導通,而導致腔室10與電極20短路。Further, in the film forming apparatus 1, between the arm member 33 and the baffle 31, an insulating member 36 for preventing formation of the entire member 33 and the baffle 31 during sputtering is prevented. The film 100 can prevent the chamber 10 and the electrode 20 from being short-circuited by the conduction of the arm 39 connected to the chamber 10 and the shutter 31 abutting against the electrode 20.

另外,於該成膜裝置1中,如上述般,一對擋板31的前端部是於抵接面38上相互抵接,該抵接面38是朝向與自電極20向工件W的方向正交的方向。因此,將一對擋板31配置於關閉位置時,可實現該等的抵接面38完全密接的狀態。藉此,於電漿聚合成膜時,可有效地防止電極20的靶材材料23因聚合堆積物而污染的現象。Further, in the film forming apparatus 1, as described above, the front end portions of the pair of shutters 31 are in contact with each other on the abutting surface 38, and the abutting surface 38 is oriented in the direction from the electrode 20 toward the workpiece W. The direction of the handover. Therefore, when the pair of flaps 31 are disposed at the closed position, the abutting surfaces 38 can be completely in close contact with each other. Thereby, when the plasma is formed into a film, the phenomenon that the target material 23 of the electrode 20 is contaminated by the polymerization deposit can be effectively prevented.

圖6(a)~圖6(d)是表示擋板31的各種前端形狀的說明圖。6(a) to 6(d) are explanatory views showing various front end shapes of the baffle 31.

如圖6(a)所示,於一對擋板31的前端部朝向自電極20向工件W的方向的情形時,使擋板31自關閉位置移動至釋放位置時,為了避免兩方的擋板31的干涉,必須於兩擋板31間設置間隙。因此,由於該間隙,電漿聚合成膜時,會產生電極20的靶材材料23因聚合堆積物而污染的現象。As shown in FIG. 6(a), when the front end portion of the pair of shutters 31 faces the direction from the electrode 20 toward the workpiece W, when the shutter 31 is moved from the closed position to the release position, in order to avoid both of the stops For the interference of the plate 31, a gap must be provided between the two baffles 31. Therefore, due to this gap, when the plasma is polymerized into a film, the target material 23 of the electrode 20 is contaminated by the polymerization deposit.

相對於此,如圖3及圖6(b)所示,於一對擋板31的前端部在朝向與自電極20向工件W的方向正交的方向的抵接面38上相互抵接的情形時,可防止此種間隙的產生。On the other hand, as shown in FIG. 3 and FIG. 6( b ), the distal end portions of the pair of baffles 31 abut each other on the abutting surface 38 in a direction orthogonal to the direction from the electrode 20 toward the workpiece W. In the case of this, the occurrence of such a gap can be prevented.

此外,如圖6(c)所示,亦可採用如下構成,即,其中一擋板31的前端部具有覆蓋另一擋板31的形狀,且該等擋板31的前端部於朝向與自電極20向工件W的方向正交的方向的抵接面上相互抵接。另外,如圖6(d)所示,於採用如下構成的情形時亦可同樣地防止間隙產生,即,一對擋板31的前端部於朝向與自電極20向工件W的方向 交叉的方向傾斜的抵接面上相互抵接。Further, as shown in FIG. 6(c), a configuration may be adopted in which the front end portion of one of the shutters 31 has a shape covering the other shutter 31, and the front end portions of the shutters 31 are oriented toward each other. The electrodes 20 are in contact with each other on the abutting faces in the direction orthogonal to the direction of the workpiece W. Further, as shown in FIG. 6(d), the gap can be similarly prevented in the case where the following configuration is employed, that is, the tip end portion of the pair of shutters 31 faces in the direction from the electrode 20 toward the workpiece W. The abutting faces that are inclined in the direction of intersection abut each other.

此外,於上述實施形態中,擋板31的材質是採用傳導體。然而,擋板31的材質亦可採用傳導體以外者。即便於採用此種材質的情形時,亦可執行濺鍍成膜與電漿CVD成膜。Further, in the above embodiment, the material of the baffle 31 is a conductor. However, the material of the baffle 31 may be other than a conductor. In the case where it is convenient to use such a material, it is also possible to perform film formation by sputtering and plasma CVD.

而且,擋板31的材質亦可採用具有與利用電漿聚合成膜形成的膜共通的元素的材質。如此,於使用與藉由電漿聚合成膜形成的膜組成相近的材質的情形時,可防止電漿聚合時來自擋板31的材質的雜質向成膜區域混入的狀況。該情形時,例如於使用HMDSO或HMDS作為原料氣體而使氧化矽膜成膜的情形時,使用矽氧化物作為擋板31便可。而且,例如使類金剛石碳(diamond-like carbon,DLC)成膜的情形時,使用碳材料作為擋板31便可。該情形時,由於擋板31與靶材材料23以完全密接的狀態接觸,故可較佳防止靶材材料23的污染。Further, the material of the baffle 31 may be a material having an element common to a film formed by plasma polymerization film formation. As described above, when a material having a film composition similar to that formed by plasma polymerization is used, it is possible to prevent impurities from the material of the baffle 31 from being mixed into the film formation region during plasma polymerization. In this case, for example, when HMDSO or HMDS is used as a material gas to form a ruthenium oxide film, ruthenium oxide may be used as the baffle 31. Further, for example, in the case of forming a diamond-like carbon (DLC) film, a carbon material may be used as the baffle 31. In this case, since the shutter 31 and the target material 23 are in contact with each other in a completely close contact state, contamination of the target material 23 can be preferably prevented.

另外,作為擋板31,是採用包含傳導體、以及形成於該傳導體的工件W側的表面且具有與利用CVD成膜形成的膜共通的元素的材質此兩者而成者。圖7是表示此種實施形態的擋板31的構成的說明圖。In addition, the baffle 31 is formed of a material including a conductor and a surface formed on the surface of the workpiece W on the workpiece W and having an element common to the film formed by CVD. Fig. 7 is an explanatory view showing a configuration of a baffle 31 of the embodiment.

圖7所示的擋板31包含傳導體31a以及材質31b,材質31b形成於該傳導體31a下表面(工件W側的表面)且具有與利用CVD成膜形成的膜共通的元素。於採用此種構成的情形時,可藉由傳導體31a有效地維持電極功能,並且可防止雜質向成膜區域的混入。The baffle 31 shown in FIG. 7 includes a conductor 31a and a material 31b. The material 31b is formed on the lower surface of the conductor 31a (the surface on the workpiece W side) and has an element common to the film formed by CVD. In the case of adopting such a configuration, the electrode function can be effectively maintained by the conductor 31a, and the incorporation of impurities into the film formation region can be prevented.

另外,於上述實施形態中,作為擋板31是使用包含非磁性體的物件,但作為擋板31亦可採用其一部分或全部為磁性體的物件。圖8(a)~圖8(b)是表示此種實施形態的擋板31的構成的說明圖。Further, in the above-described embodiment, the object including the non-magnetic material is used as the baffle 31. However, as the baffle 31, an object in which a part or all of the material is a magnetic body may be used. 8(a) to 8(b) are explanatory views showing the configuration of the baffle 31 of the embodiment.

圖8(a)所示的擋板31的全體主要由磁性體構成。於採用此種構成的情形時,藉由調整構成擋板31的磁性體的厚度等,而可調整磁石22的磁控管放電的作用。而且,圖8(b)所示的擋板31具有於非磁性體31c的下表面附設有磁性體31d的構成。於採用此種構成的情形時,藉由調整磁性體31d的厚度、形狀、配置等,而可調整磁場分布。The entire baffle 31 shown in Fig. 8(a) is mainly composed of a magnetic body. In the case of such a configuration, the effect of the magnetron discharge of the magnet 22 can be adjusted by adjusting the thickness of the magnetic body constituting the baffle 31 or the like. Further, the baffle 31 shown in FIG. 8(b) has a configuration in which a magnetic body 31d is attached to the lower surface of the non-magnetic body 31c. In the case of adopting such a configuration, the magnetic field distribution can be adjusted by adjusting the thickness, shape, arrangement, and the like of the magnetic body 31d.

於圖8(a)、圖8(b)的任意情形時,藉由控制磁場的影響而可控制電漿聚合時的電漿密度及電漿分布,從而可增加用於控制電漿聚合成膜的聚合膜的膜厚、膜質的參數。In any case of FIG. 8(a) and FIG. 8(b), the plasma density and the plasma distribution during plasma polymerization can be controlled by controlling the influence of the magnetic field, thereby increasing the film formation for controlling plasma polymerization. The film thickness of the polymer film and the parameters of the film quality.

其次,說明本發明的其他實施形態。圖9是本發明的第2實施形態的成膜裝置1的電極20a、20b附近的放大圖。此外,對於與上述第1實施形態相同的構件,附加相同符號且省略詳細說明。Next, other embodiments of the present invention will be described. FIG. 9 is an enlarged view of the vicinity of the electrodes 20a and 20b of the film forming apparatus 1 according to the second embodiment of the present invention. It is to be noted that the same members as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.

於該實施形態中具有如下構成,即,將具有與第1實施形態的電極20相同的構成的一對電極20a、20b配設於腔室10的本體11上部,並將該等電極20a、20b連接於LF電源49。此處,LF電源49是射頻電源的一種,例如產生20kHz至100kHz的頻率的射頻。In this embodiment, a pair of electrodes 20a and 20b having the same configuration as that of the electrode 20 of the first embodiment are disposed on the upper portion of the body 11 of the chamber 10, and the electrodes 20a and 20b are disposed. Connected to the LF power supply 49. Here, the LF power source 49 is one type of radio frequency power source, for example, a radio frequency that generates a frequency of 20 kHz to 100 kHz.

於該第2實施形態的成膜裝置1中執行濺鍍成膜時,與第1實施形態同樣地,將一對擋板31配置於圖9中以虛擬線表示的釋放位置上。而且,與第1實施形態同樣地,使腔室10內充滿氬氣等惰性氣體。接著,藉由LF電源49對一對電極20a、20b交替施加相位彼此相反的電壓。由於電漿中的氬離子為陽離子,因此負電位的靶材材料被濺射。即,電極20a與電極20b交替發生濺射現象。When the sputtering film formation is performed in the film formation apparatus 1 of the second embodiment, the pair of shutters 31 are disposed at the release position indicated by the imaginary line in FIG. 9 as in the first embodiment. Further, in the same manner as in the first embodiment, the chamber 10 is filled with an inert gas such as argon gas. Next, a voltage having a phase opposite to each other is alternately applied to the pair of electrodes 20a and 20b by the LF power source 49. Since the argon ions in the plasma are cations, the target material of the negative potential is sputtered. That is, the sputtering phenomenon occurs alternately between the electrode 20a and the electrode 20b.

另一方面,於該第2實施形態的成膜裝置1中執行電漿聚合成膜時,與第1實施形態同樣地,將一對擋板31配置於圖9中以實線表示的關閉位置上。而且,使腔室10內充滿原料氣體。接著,藉由LF電源49對一對電極20a、20b施加電壓。藉此,使擋板31與電極20a、20b一併作為電漿聚合用的電極發揮功能,而可執行電漿聚合成膜。On the other hand, when the plasma deposition film formation is performed in the film forming apparatus 1 of the second embodiment, the pair of shutters 31 are disposed in the closed position indicated by the solid line in FIG. 9 as in the first embodiment. on. Further, the chamber 10 is filled with the material gas. Next, a voltage is applied to the pair of electrodes 20a and 20b by the LF power source 49. Thereby, the baffle 31 and the electrodes 20a and 20b function together as an electrode for plasma polymerization, and plasma polymerization can be performed to form a film.

於該第2實施形態的成膜裝置1中,僅使用LF電源49,無需使用射頻電源44、匹配箱43,故而可廉價地製造裝置。而且,即便於靶材材料23上附著有聚合堆積物的情形時,使用LF電源49執行濺鍍成膜時,於濺射的同時可實現靶材材料的清潔效果。In the film forming apparatus 1 of the second embodiment, only the LF power source 49 is used, and it is not necessary to use the RF power source 44 and the matching box 43, so that the apparatus can be manufactured at low cost. Further, even when a polymerized deposit adheres to the target material 23, when the sputtering is performed using the LF power source 49, the cleaning effect of the target material can be achieved while sputtering.

1‧‧‧成膜裝置1‧‧‧ film forming device

2‧‧‧射出成型機2‧‧‧Injection molding machine

3‧‧‧搬送裝置3‧‧‧Transporting device

4‧‧‧機械手4‧‧‧ Robot

10‧‧‧腔室10‧‧‧ chamber

11‧‧‧本體11‧‧‧Ontology

12‧‧‧開閉部12‧‧‧Opening and closing department

13‧‧‧工件載置部13‧‧‧ workpiece placement

14、36‧‧‧絕緣構件14, 36‧‧‧Insulating components

15‧‧‧擺動軸15‧‧‧Swing axis

19‧‧‧接地部19‧‧‧ Grounding Department

20、20a、20b‧‧‧電極20, 20a, 20b‧‧‧ electrodes

21‧‧‧電極部21‧‧‧Electrode

22‧‧‧磁石22‧‧‧ Magnet

23‧‧‧靶材材料23‧‧‧ Target material

31‧‧‧擋板31‧‧‧Baffle

31a‧‧‧傳導體31a‧‧‧ Conductor

31b‧‧‧材質31b‧‧‧Material

31c‧‧‧非磁性體31c‧‧‧Non-magnetic body

31d‧‧‧磁性體31d‧‧‧Magnetic body

32、33‧‧‧臂構件32, 33‧‧‧ arm components

34‧‧‧軸34‧‧‧Axis

35‧‧‧板簧35‧‧‧ leaf spring

37‧‧‧螺釘37‧‧‧ screws

38‧‧‧抵接面38‧‧‧Abutment

39‧‧‧臂狀物39‧‧‧arm

41‧‧‧直流電源41‧‧‧DC power supply

42‧‧‧濾波器42‧‧‧ filter

43‧‧‧匹配箱43‧‧‧match box

44‧‧‧射頻電源44‧‧‧RF power supply

45、46‧‧‧開關45, 46‧‧‧ switch

48‧‧‧簷部48‧‧‧檐

49‧‧‧LF電源49‧‧‧LF power supply

51、54‧‧‧開閉閥51, 54‧‧‧Opening and closing valve

52、55‧‧‧流量調整閥52, 55‧‧‧ flow adjustment valve

53‧‧‧惰性氣體的供給部53‧‧‧Supply of inert gas

56‧‧‧原料氣體的供給部56‧‧‧Material gas supply department

57‧‧‧機械式升壓泵57‧‧‧Mechanical booster pump

58‧‧‧乾式真空泵58‧‧‧Dry vacuum pump

100‧‧‧膜100‧‧‧ film

A‧‧‧區域A‧‧‧ area

W‧‧‧工件W‧‧‧Workpiece

圖1是應用本發明的成膜裝置1的成膜系統的概要圖。Fig. 1 is a schematic view showing a film formation system of a film formation apparatus 1 to which the present invention is applied.

圖2是本發明的第1實施形態的成膜裝置1的概要圖。FIG. 2 is a schematic view of the film formation apparatus 1 according to the first embodiment of the present invention.

圖3是本發明的第1實施形態的成膜裝置1的電極20附近的放大圖。3 is an enlarged view of the vicinity of the electrode 20 of the film forming apparatus 1 according to the first embodiment of the present invention.

圖4是擋板機構的放大圖。Figure 4 is an enlarged view of the shutter mechanism.

圖5是擋板機構的絕緣構件36附近的放大圖。Fig. 5 is an enlarged view of the vicinity of the insulating member 36 of the shutter mechanism.

圖6(a)~圖6(d)是表示擋板31的各種前端形狀的說明圖。6(a) to 6(d) are explanatory views showing various front end shapes of the baffle 31.

圖7是表示其他實施形態的擋板31的構成的說明圖。Fig. 7 is an explanatory view showing a configuration of a baffle 31 of another embodiment.

圖8(a)~圖8(b)是表示其他實施形態的擋板31的構成的說明圖。8(a) to 8(b) are explanatory views showing the configuration of the baffle 31 of another embodiment.

圖9是本發明的第2實施形態的成膜裝置1的電極20a、20b附近的放大圖。FIG. 9 is an enlarged view of the vicinity of the electrodes 20a and 20b of the film forming apparatus 1 according to the second embodiment of the present invention.

11‧‧‧本體11‧‧‧Ontology

14‧‧‧絕緣構件14‧‧‧Insulating components

15‧‧‧擺動軸15‧‧‧Swing axis

20‧‧‧電極20‧‧‧ electrodes

21‧‧‧電極部21‧‧‧Electrode

22‧‧‧磁石22‧‧‧ Magnet

23‧‧‧靶材材料23‧‧‧ Target material

31‧‧‧擋板31‧‧‧Baffle

32、33‧‧‧臂構件32, 33‧‧‧ arm components

34‧‧‧軸34‧‧‧Axis

35‧‧‧板簧35‧‧‧ leaf spring

36‧‧‧絕緣構件36‧‧‧Insulating components

38‧‧‧抵接面38‧‧‧Abutment

39‧‧‧臂狀物39‧‧‧arm

41‧‧‧直流電源41‧‧‧DC power supply

42‧‧‧濾波器42‧‧‧ filter

43‧‧‧匹配箱43‧‧‧match box

44‧‧‧射頻電源44‧‧‧RF power supply

45、46‧‧‧開關45, 46‧‧‧ switch

Claims (13)

一種成膜裝置,於單一的腔室內對工件執行濺鍍成膜與電漿化學氣相沈積成膜,其特徵在於包括:電極,具備靶材材料;射頻電源,對上述電極施加射頻電壓;惰性氣體供給部,向上述腔室內供給惰性氣體;原料氣體供給部,向上述腔室內供給原料氣體;減壓單元,對上述腔室內進行減壓;以及擋板機構,具備擋板,上述擋板可於與上述靶材材料接觸的狀態下,在覆蓋上述靶材材料的狀態以及開放上述靶材材料的狀態之間切換;其中,當上述濺鍍成膜時使上述擋板開放,當上述電漿化學氣相沈積成膜時藉由上述擋板覆蓋上述靶材材料。 A film forming device for performing sputtering film formation and plasma chemical vapor deposition on a workpiece in a single chamber, comprising: an electrode having a target material; a radio frequency power source applying a radio frequency voltage to the electrode; inert a gas supply unit that supplies an inert gas to the chamber; a material gas supply unit that supplies a material gas into the chamber; a pressure reduction unit that decompresses the chamber; and a shutter mechanism that includes a shutter that can be used Switching between the state of covering the target material and the state of opening the target material in a state of being in contact with the target material; wherein the baffle is opened when the sputtering film is formed, when the plasma is The target material is covered by the baffle plate during chemical vapor deposition. 如申請專利範圍第1項所述之成膜裝置,其中上述電極是磁控管電極。 The film forming apparatus of claim 1, wherein the electrode is a magnetron electrode. 如申請專利範圍第2項所述之成膜裝置,其中上述擋板主要由傳導體構成。 The film forming apparatus of claim 2, wherein the baffle plate is mainly composed of a conductor. 如申請專利範圍第1項所述之成膜裝置,其中上述擋板主要由具有與利用上述化學氣相沈積成膜形成的膜共通的元素的材質構成。 The film forming apparatus according to claim 1, wherein the baffle plate is mainly composed of a material having an element common to a film formed by the chemical vapor deposition film formation. 如申請專利範圍第1項所述之成膜裝置,其中上述擋板主要由傳導體以及材質構成,上述材質形成於上述傳導體的上述工件側表面且具有與利用上述化學氣相沈積成膜形成的膜共通的元素。 The film forming apparatus according to claim 1, wherein the baffle plate is mainly composed of a conductor and a material, and the material is formed on the workpiece side surface of the conductor and has a film formed by the chemical vapor deposition. The common elements of the membrane. 如申請專利範圍第1項所述之成膜裝置,其中上述擋板主要由非磁性體構成。 The film forming apparatus of claim 1, wherein the baffle plate is mainly composed of a non-magnetic material. 如申請專利範圍第1項所述之成膜裝置,其中上述擋板的至少一部分主要由磁性體構成。 The film forming apparatus of claim 1, wherein at least a part of the baffle is mainly composed of a magnetic body. 如申請專利範圍第1項所述之成膜裝置,更包括:直流電源,對上述電極施加直流電壓。 The film forming apparatus of claim 1, further comprising: a direct current power source for applying a direct current voltage to the electrodes. 如申請專利範圍第1項所述之成膜裝置,其中上述擋板機構具備一對擋板、及以將上述一對擋板連結於上述腔室的擺動軸為中心而擺動的臂狀物,且具有藉由使上述一對擋板自中央朝兩側而向彼此不同的方向擺動,而變成開放狀態的構造。 The film forming apparatus according to claim 1, wherein the shutter mechanism includes a pair of baffles and an arm that swings around the swing shaft that connects the pair of baffles to the chamber. Further, the pair of baffles are configured to be in an open state by swinging the pair of baffles in directions different from each other from the center toward the both sides. 如申請專利範圍第9項所述之成膜裝置,其中上述一對擋板的前端部於抵接面上相互抵接,上述抵接面朝向與自上述電極向上述工件的方向交叉的方向。 The film forming apparatus according to claim 9, wherein the front end portions of the pair of baffles are in contact with each other on the abutting surface, and the abutting surface faces a direction intersecting the direction from the electrode toward the workpiece. 如申請專利範圍第1項所述之成膜裝置,其中上述擋板機構包括臂狀物,上述臂狀物以將上述擋板連結於上述腔室的擺動軸為中心而擺動,且上述擋板相對於上述的臂狀物而可擺動地配設。 The film forming apparatus according to claim 1, wherein the shutter mechanism includes an arm, and the arm swings around a swing shaft that connects the shutter to the chamber, and the shutter It is swingably arranged with respect to the above-described arm. 如申請專利範圍第11項所述之成膜裝置,其中上述臂狀物包括一對臂構件及一對板簧,上述一對臂構件以與上述擺動軸平行地延伸的軸為中心而可相互擺動,上述一對板簧附設於上述一對臂構件中的其中一臂構件上,且夾持另一臂構件,以便使上述一對臂構件的姿勢成為直線狀。 The film forming apparatus according to claim 11, wherein the arm member includes a pair of arm members and a pair of leaf springs, and the pair of arm members are centered on an axis extending parallel to the swing axis The pair of leaf springs are attached to one of the pair of arm members, and the other arm member is clamped so that the posture of the pair of arm members is linear. 如申請專利範圍第1項所述之成膜裝置,其中上述擋板機構包括臂狀物,上述臂狀物以將上述擋板連結於上述腔室的擺動軸為中心擺動,且於上述臂狀物與上述擋板之間,配設有絕緣構件,上述絕緣構件形成有於上述濺鍍成膜時用於防止形成遍及上述臂狀物與上述擋板的膜的簷部。 The film forming apparatus according to claim 1, wherein the shutter mechanism includes an arm, and the arm swings around a swing axis connecting the shutter to the chamber, and is in the arm shape An insulating member is disposed between the object and the baffle, and the insulating member is formed with a crotch portion for preventing formation of a film extending over the arm and the baffle when the sputtering is performed.
TW101150225A 2012-03-16 2012-12-26 Film formation apparatus TWI460300B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0665738A (en) * 1992-08-25 1994-03-08 Matsushita Electric Works Ltd Device for film formation and method therefor
JPH10195651A (en) * 1997-01-09 1998-07-28 Shin Meiwa Ind Co Ltd Film forming device and its method
JP2004300465A (en) * 2003-03-28 2004-10-28 Matsushita Electric Ind Co Ltd Sputtering apparatus
JP2010163662A (en) * 2009-01-16 2010-07-29 National Institute For Materials Science Dry process apparatus
JP2011058048A (en) * 2009-09-10 2011-03-24 Nikuni:Kk Vacuum film deposition method and device therefor

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10195661A (en) * 1997-01-08 1998-07-28 Ebara Corp Vapor growth device
JP2012177191A (en) * 2011-02-03 2012-09-13 Canon Inc Film-forming apparatus and film-forming method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0665738A (en) * 1992-08-25 1994-03-08 Matsushita Electric Works Ltd Device for film formation and method therefor
JPH10195651A (en) * 1997-01-09 1998-07-28 Shin Meiwa Ind Co Ltd Film forming device and its method
JP2004300465A (en) * 2003-03-28 2004-10-28 Matsushita Electric Ind Co Ltd Sputtering apparatus
JP2010163662A (en) * 2009-01-16 2010-07-29 National Institute For Materials Science Dry process apparatus
JP2011058048A (en) * 2009-09-10 2011-03-24 Nikuni:Kk Vacuum film deposition method and device therefor

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