201038755 六、發明說明： 【發明所屬之技術領域】 本發明係與真空成膜技術有關，特別是指一種製備氮 化鋁鈦膜之方法，其製程簡單快速且成本低廉。 【先前技術】 按，氮化鋁鈦（ΤιΑΙΝ)為常見的硬質膜材料，具有高 ❹ 機械強度、耐磨耗、耐腐蝕等特性，在工業上有廣泛的應 用，例如：將氮化鋁鈦鍍著於刀具表層，能降低刀具磨耗， 增加刀具壽命，在電子工業中，氮化銘鈦亦能作為擴散阻 障層。 習知形成氣化銘鈦膜之方法，係利用物理氣相沈積法 (PVD) ’在高真空度之環境下’錢氣作域射氣體，以 氮氣作為反應氣體，利用高壓直流或交流（如射頻）電源 產生電漿並轟擊鋁鈦合金靶材，由靶材轟擊出來之鈦原子 〇 與鋁原子與氮氣反應結合，即可於一基材上沈積形成一氮 化鋁鈦薄膜，改變腔體中氮氣分壓可進一步控制薄膜之電 阻率。 將A氣與氮氣通入密閉腔體之前，需先去除密閉腔體 内之空氣’一般需達1.33xl〇-4 Pa之背景壓力值，需要高 級之腔體與抽氣設備，並花費較長之時間（約2〜3小時） 進行抽真空，且氮氣必須由空氣中純化始能獲得，故習知 方法之設備成本與原料成本均高昂，且製程步驟繁雜。 3 201038755 【發明内容】 .本發月t目的在於提供一種製備氮化紹欽膜之方 法，其製程所需設備簡易，原料成本低廉。 本發明之另一目的在於提供一種製備氮化銘鈦膜之方 法，其製程步驟單純且快速。 為達成前揭目的，本發明所提供製備氮化減膜之方 法係於-密閉腔體内置人—基材作為陽極，以及一減合 材作秘極氣作為反應氣體，毅氣與氮氣依 桃量比5 . 1〇〇〜5〇 : 1〇〇通入該密閉腔體中，並控制密閉 腔體之工作壓力於6 65xlG_2 pa〜6 65 ，利用物理氣相沈 積法即可在該基材表面形成—氮化減膜，由於空氣之取 得極為方便’且背景真空度之要求較f知方法為低，使本 發明所提供之方法具有設備簡單、製程快速、成本低廉等 優點。 【實施方式】 為了更瞭解本發明之特點所在，茲舉以下一較佳實施 例並配合圖式說明如下，其中： 第一圖係本發明一較佳實施例所使用之設備示意圖； 第二圖係本發明一較佳實施例所製成品之X光繞射分 析圖； 第二圖係本發明一較佳實施例所製成品之電子顯微鏡 照片。 ’ 請參閱第一圖，本發明一較佳實施例所提供之製備氣 201038755 化紹鈦膜之方錢利用紐磁控麟系統⑺ ，於一密閉腔 體11内置入一基材12作為陽極 ，以及一鋁鈦合金靶材14 作為陰極’錄材12係_ p财⑸（議）置於該妃材14 下方該銘鈦合金乾材Η置於一磁鐵η下方該纪材Μ 中鈦紹之原子比例為1:卜在室溫下先啟動二抽氣泵浦 15將該密閉腔體11之背景壓力抽至1.33xlG_2Pa，抽氣時 間僅而約2〜3分鐘。接著，以空氣作為反應氣體，將空氣 16 ,、氬氣18分別以一氣體流量質量計2〇控制依流量比201038755 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a vacuum film forming technique, and more particularly to a method for preparing a titanium aluminum nitride film, which is simple, rapid, and inexpensive. [Prior Art] Aluminum titanium nitride (ΤιΑΙΝ) is a common hard film material with high mechanical strength, wear resistance, corrosion resistance, etc. It is widely used in industry, for example: titanium aluminum nitride It is plated on the surface of the tool to reduce tool wear and increase tool life. In the electronics industry, nitriding titanium can also act as a diffusion barrier. It is customary to form a method for gasification of titanium film by physical vapor deposition (PVD) 'in a high vacuum environment', the gas is used as a gas, and nitrogen is used as a reaction gas, using high-voltage direct current or alternating current (such as The radio frequency power source generates plasma and bombards the aluminum-titanium alloy target. The titanium atomic ruthenium bombarded by the target is combined with aluminum atom and nitrogen to deposit a titanium aluminum nitride film on a substrate to change the cavity. The partial pressure of nitrogen can further control the resistivity of the film. Before passing A gas and nitrogen into the closed cavity, the air in the closed cavity must be removed first. Generally, the background pressure of 1.33xl〇-4 Pa is required. It requires advanced cavity and pumping equipment, and it takes a long time. The time (about 2 to 3 hours) is vacuumed, and nitrogen must be obtained by purifying in air. Therefore, the equipment cost and raw material cost of the conventional method are high, and the process steps are complicated. 3 201038755 [Summary of the Invention] The purpose of this month is to provide a method for preparing a nitrided film, which requires simple equipment and low raw material cost. Another object of the present invention is to provide a method for preparing a nitrided titanium film whose process steps are simple and rapid. In order to achieve the foregoing object, the method for preparing a nitride-reducing film is provided in a closed cavity built-in human-substrate as an anode, and a subtractive material as a reactive gas as a reaction gas, and a gas and a nitrogen gas The ratio is 5. 1〇〇~5〇: 1〇〇 is introduced into the closed cavity, and the working pressure of the closed cavity is controlled at 6 65xlG_2 pa~6 65 , and the substrate can be used by physical vapor deposition. Surface formation—nitriding and film-reducing, because air is very convenient to obtain, and the background vacuum degree is lower than that of the method, so that the method provided by the invention has the advantages of simple equipment, fast process and low cost. BRIEF DESCRIPTION OF THE DRAWINGS In order to better understand the features of the present invention, the following description of the preferred embodiments and the accompanying drawings are as follows, wherein: FIG. 1 is a schematic diagram of a device used in a preferred embodiment of the present invention; An X-ray diffraction analysis chart of a product according to a preferred embodiment of the present invention; and a second embodiment is an electron microscope photograph of a product of a preferred embodiment of the present invention. Referring to the first figure, a method for preparing a gas film 201038755 according to a preferred embodiment of the present invention utilizes a new magnetic control system (7), and a substrate 12 is built in a closed cavity 11 as an anode. And an aluminum-titanium alloy target 14 as a cathode 'recording material 12 series _ p Cai (5) (discussion) placed under the coffin 14 the Ming titanium alloy dry material Η placed under a magnet η the Μ Μ Μ 绍The atomic ratio is 1: First, the second pumping pump 15 is started at room temperature to pump the background pressure of the closed chamber 11 to 1.33 x 1 G 2 Pa, and the pumping time is only about 2 to 3 minutes. Then, using air as the reaction gas, the air 16 and the argon gas 18 are respectively controlled by a gas flow mass meter.
17·5. 100〜25: 1〇〇流經氣體混合器22後通入該密閉腔體 11中，並以二抽氣泵浦15控制密閉腔體η之工作壓力於 0.23 Pa’並利用一電源供應器24以3〇〇 w之輸出功率施 加直流電壓於該陽極與該陰極，並_基材12施加偏壓 -50V ’藉此’氬氣可於該陽、陰極之間產生電聚，並受電 場作用而轟擊該乾材14,被轟擊出來之銘原子與鈦原子將 與腔體内之氮氣結合，形錢化減，並沈積於該基材η 表面’約25分鐘即可在該基材12表面形成—氮化紹欽 (TiAIN)膜 26 〇 根據文獻記載，氮化鋁鈦為銀灰色或灰黑色，硬度約 28〜38 GPa ’電阻率範圍為8.6xl〇2〜5xl〇4，且^截 面具有柱狀晶結構。檢視本發明於基材12表面形成之薄膜 26 ’其各項特徵如表一所列，其中，空氣/氣氣比例為 Π.5鳩條件下’所形成之薄膜呈銀灰色，以奈米壓痕儀 量測其硬度為39±1.04 Gpa ’以四點探針量測其電阻率則為 2211 μΩ-cm，符合氮化鋁鈦之特徵，可見在適當之空氣/ 5 201038755 氣體比例 空氣/氬氣」 色澤 硬度 (GPa) 17.5/100 銀灰 39±1.〇4 、 20/100 銀灰 36±3.6 25/100 黑灰 33.8±0.9 ^ , 、26’結果如第二圖 所不，其中，曲線⑻係針對空氣/氬氣比例為17 5胸 下:成薄膜之分析結果，氬氣比例 ⑽條件下所形成_之分析結果，曲線_針對空氣 /風虱比例為25/100條件下所形成薄獏之分析 鱼 JCPDS資料庫巾TiN (卡號：38彻）比對，各曲線之繞 射峰均稱向高角度位移，乃是因為備結構中部份 被入1原子所置f原子半徑小於Ti原子，故其晶格 常數降低使繞射峰朝高肖度位移，X光繞㈣分析結果證 實該薄膜26為氮化鋁鈦。 再者，以場發射掃瞄式電子顯微鏡(FE_SEM)觀察該薄 膜26之橫截面，如第三圖所示，其中，照片⑻係空氣/氬 氣比例為17.5/1〇〇條件下所形成之薄膜，照片（b)係空氣/ 氬氣比例為2G/1GG條件下所形成之薄膜，照片（e)係空氣/ 氬氣比例為22.5/刚條件下所形成之薄膜’照片_空氣 /氬氣比例為25/1GG條件下所形成之薄膜，均可見桂狀晶結 構，符合ll化減之特徵。综合上述分析結果，可證實由 201038755 本發明方法所形成之薄膜確為氮化鋁鈦膜。 本發明所提供之方法係將空氣及氬氣通入密閉腔體 中，故無需將密閉腔體抽至高真空度（如習知方法中密閉 腔體之背景壓力為1.33xl(T4Pa)，僅需抽至約ΐ 33χ1〇_217·5. 100~25: 1〇〇 flows through the gas mixer 22 and then enters the closed cavity 11, and controls the working pressure of the closed cavity η at 0.23 Pa' with two pumping pumps 15 and utilizes one The power supply 24 applies a DC voltage to the anode and the cathode at an output power of 3 〇〇w, and applies a bias voltage of -50 V to the substrate 12, whereby argon gas can generate electropolymerization between the anode and the cathode. And bombarded by the electric field to bombard the dry material 14, the bombarded Ming atom and the titanium atom will be combined with the nitrogen in the cavity, and the shape is reduced and deposited on the surface of the substrate η for about 25 minutes. The surface of the substrate 12 is formed - a nitrided TiAIN film 26 〇 According to the literature, the aluminum nitride titanium is silver gray or grayish black, and the hardness is about 28 to 38 GPa. The resistivity ranges from 8.6 x 1 〇 2 to 5 x 10 , 4, and The cross section has a columnar crystal structure. The film 26' formed on the surface of the substrate 12 of the present invention has various characteristics as listed in Table 1. The air/gas ratio is Π.5鸠, and the film formed is silver-gray, with nanoindentation. The hardness of the instrument is 39±1.04 Gpa. The resistivity measured by the four-point probe is 2211 μΩ-cm, which is consistent with the characteristics of aluminum nitride titanium. It can be seen in the proper air / 5 201038755 gas ratio air / argon Color hardness (GPa) 17.5/100 silver ash 39±1. 〇4, 20/100 silver ash 36±3.6 25/100 black ash 33.8±0.9 ^ , 26' results as shown in the second figure, where curve (8) The air/argon ratio is 17 5 chest: the result of the analysis of the film, the analysis result of the argon gas ratio (10), the curve _ for the air/wind ratio of 25/100 Analyze the fish JCPDS database towel TiN (card number: 38), the diffraction peaks of each curve are said to shift to a high angle, because the part of the preparation structure is divided into 1 atom, the radius of the f atom is smaller than the Ti atom. Therefore, the lattice constant is lowered to make the diffraction peak shift toward the high degree of Xiao, and the X-ray winding (four) analysis results are proved. The film 26 is a titanium aluminum nitride. Further, the cross section of the film 26 was observed by a field emission scanning electron microscope (FE_SEM) as shown in the third figure, wherein the photograph (8) was formed under the condition of an air/argon ratio of 17.5/1 Torr. Film, photo (b) is a film formed under the condition of air/argon ratio of 2G/1GG, and photo (e) is a film formed by air/argon ratio of 22.5/just under the condition 'photo_air/argon The film formed under the condition of 25/1 GG can be seen as a laurel crystal structure, which is consistent with the characteristics of ll reduction. Based on the above analysis results, it was confirmed that the film formed by the method of the present invention of 201038755 was confirmed to be an aluminum nitride titanium film. The method provided by the invention introduces air and argon into the closed cavity, so that it is not necessary to pump the closed cavity to a high vacuum degree (as in the conventional method, the background pressure of the closed cavity is 1.33xl (T4Pa), only need Pumped to approximately 33χ1〇_2
Pa’花費時間僅約2〜3分鐘，可大幅縮短製程所需之時間， 且無需尚級之腔體與抽氣設備，製程設備較習知方法之成 本低廉，再者，本方法所使用之空氣隨處均可取得，無需 〇 如習知方法般由空氣中純化出氮氣，可簡化製程步驟，同 時降低原料氣體之成本。換言之，本發明所提供之方法可 以較簡易之設備與較低廉之成本，更迅速的製造出氮化銥 鈦膜，可改善習知方法之缺失，並極具市場潛力。 依據本發明之精神，改變製程中各項參數，亦可快逮 形成氮化鋁鈦膜，例如：將密閉腔體之背景壓力抽至 1.33x10 4 Pa，電源供應器之輸出功率為3〇〇 w，並對基柯 施加偏壓-50V，在不同之空氣/氬氣比例條件下，所形成薄 〇 膜之各項特徵如表一所列，亦符合氮化紹欽之特徵。 表二 氣體比例 空氣/氬氣 色澤 硬度 (GPa) 電 (μΩ-cm^ 17.5/100 銀灰 41.5±1.6 1286~~~ 20/100 銀灰 37.2±3.3 1425 22.5/100 黑灰1 35.8±4.5 1 2229 25 / 100 黑灰 33.4±2.2 ~9886~^~ 事實上’進-步實驗數據顯示，陰極可以一銘把材輿 一鈦鈀材替代鋁鈦合金鈀材，密閉腔體之背景壓力柃 1.33x10 Pa〜1.33 Pa (以 1·33χ1〇-3 pa〜1 33x10] pa 為宜）， 201038755 工作壓力介於6.65><1〇-2?&〜6.65?3(以0.1?&〜1?&為宜）， 空氣/氬氣之流量比介於5:1〇〇〜5〇:1〇〇，電源供應器之輪出 功率介於50〜5〇〇〇 W，採直流或交流（射頻）電源均可， 腔體溫度維持於20〜300。(：，於基材施加偏壓〇〜-3〇〇v (以 -20〜·1〇〇 v較佳），甚至不施加偏壓之條件下，均可於 60〜7200秒之時間内形成具有氮化鋁鈦膜，甚至利用濺鑛 法外之其他物理氣相沈積法，亦可形成氮化鋁鈦獏。是故， 舉凡此等易於思及之製程參數變化，均應為本發明申請專 利範圍所涵蓋。 201038755 【圖式簡單說明】 第-圖係本發明一較佳實施例所使用之設備示意圖； 第一圖係本發明一較佳實施例所製成品之X光繞射分 析圖； 第二圖係本發明一較佳實施例所製成品之電子顯微鏡 照片。 ❹ 【主要元件符號說明】 10直流磁控濺鍍系統 11密閉腔體 12基材 13磁鐵 14靶材 15抽氣泵浦 16空氣 18氬氣 20氣體流量質量計 22氣體混合器24電源供應器26氮化鋁鈦膜 〇 9Pa' takes only about 2 to 3 minutes, which can greatly shorten the time required for the process, and does not require a cavity and pumping equipment. The cost of the process equipment is lower than that of the conventional method. Moreover, the method uses Air can be obtained anywhere, eliminating the need to purify nitrogen from air as is conventional, simplifying the process steps and reducing the cost of the feed gas. In other words, the method provided by the present invention can produce a titanium nitride nitride film more quickly and at a lower cost, and can improve the lack of conventional methods and has great market potential. According to the spirit of the present invention, by changing various parameters in the process, a titanium aluminum nitride film can be quickly formed, for example, the background pressure of the closed cavity is drawn to 1.33×10 4 Pa, and the output power of the power supply is 3〇〇. w, and biased to Keke -50V, under different air / argon ratio conditions, the characteristics of the thin film formed as shown in Table 1, is also consistent with the characteristics of nitride. Table 2 Gas ratio Air/argon color hardness (GPa) Electricity (μΩ-cm^17.5/100 Silver ash 41.5±1.6 1286~~~ 20/100 Silver ash 37.2±3.3 1425 22.5/100 Black ash 1 35.8±4.5 1 2229 25 / 100 Black ash 33.4±2.2 ~9886~^~ In fact, the experimental data show that the cathode can replace the aluminum-titanium alloy palladium material with a titanium-palladium material, and the background pressure of the closed cavity is 1.33x10 Pa. ~1.33 Pa (1.33χ1〇-3 pa~1 33x10] pa is appropriate), 201038755 Working pressure is 6.65><1〇-2?&~6.65?3 (to 0.1?&~1 ? & is appropriate, the air / argon flow ratio is between 5:1 〇〇 ~ 5 〇: 1 〇〇, the power supply's wheel power is between 50 ~ 5 〇〇〇 W, with DC or AC (RF) power supply can be, the cavity temperature is maintained at 20~300. (:, the substrate is biased 〇~-3〇〇v (preferably -20~·1〇〇v), even without bias Under the condition of pressure, titanium nitride film can be formed in 60~7200 seconds, and even other physical vapor deposition methods other than splashing can be used to form aluminum nitride titanium nitride. So easy to think The process parameters are all covered by the scope of the present invention. 201038755 [Simplified description of the drawings] The first drawing is a schematic diagram of the apparatus used in a preferred embodiment of the present invention. The first drawing is a preferred embodiment of the present invention. The X-ray diffraction analysis chart of the manufactured product; the second figure is an electron microscope photograph of a product manufactured by a preferred embodiment of the present invention. ❹ [Main component symbol description] 10 DC magnetron sputtering system 11 sealed cavity 12 Substrate 13 Magnet 14 Target 15 Pumping Pump 16 Air 18 Argon 20 Gas Flow Meter 22 Gas Mixer 24 Power Supply 26 Aluminum Nitride Film 〇 9