13799.13 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，特別是指一種製傷氮 化銘鈦膜之綠，其製_單料且成本低廉。 【先前技術】13799.13 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a vacuum film forming technique, and more particularly to a green color of a titanium oxide film made of nitrile, which is made of a single material and is inexpensive. [Prior Art]
按，氮化減（TiA1N)為常見的硬質膜材料且有高 機械強度、耐磨耗、耐腐料龍，紅#上有廣泛的應 用，例如：將氮化減鑛著於刀具表層，能降低刀且磨耗， 增加刀具壽命，在電子H氮化缺雜作為擴散阻 陸屉。 、 阻率 習知形成氮化贿狀方法，係_物理氣相沈積法 (PVD) ’在高真空度之環境下，以氬氣作為_氣體以 氮氣作為反應氣體，高壓直流或交流（如射頻）電源 產生親並絲減合錄材，由婦絲出來之欽原^ 與紹原子與氮氣反應結合，即可於—基材上沈積形成 化銘鈦薄膜’改變腔體中氮氣分壓可進一步控制_之電 將氬氣與氮氣通入密閉腔體之前，需先去除密閉妒體 内之空氣，一般需達U3X# Pa之背景壓力值，需^ 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。 【發明内容】 本發明之一目的在於提供一種製傷氮化減膜之方 去，其製程所需設備簡易，原料成本低廉。 本發明之另-目的在於提供一種製備氮化雛膜之方 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，以及一銘鈦合 =材作為陰極，以空氣作為反應㈣，將空氣與氬氣依 瓜量比5 . 1GG〜5G : 1GG通人該密閉腔體中，並控制密閉 腔體之工作壓力於6 65 x】〇-2 pa〜6 65 pa，利用物理氣相沈 ，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，騎景真线之要求較習知方法為低，使本 發月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； 析圖第二圖係本發明一較佳實施例所製成品之X光繞射分 照片第二圖係本發明一較佳實施例所製成品之電子顯微鏡 凊參閱第一圖’本發明一較佳實施例所提供之製備氮 13799.13 化紹鈦膜之方法係利用直流磁控滅鑛系统j 〇，於一密閉腔 體11内置入-基材12作為陽極，以及一銘鈦合金乾材14 作為陰極’該紐12係-P财晶片（削）置於她材14 下方，該減合錄材14置於一磁鐵13下方，該把材Μ 中鈦、IS之原子比例為1:卜在室溫下先啟動二括氣栗浦 15將该岔閉腔體11之背景壓力抽至丨33xl〇_2pa，抽氣時 間僅需約2〜3分鐘。接著，以空氣作為反應氣體，將空氣 • 16與氬氣18分別以—氣體流1：質量計20控制依流量比 17.5: 100〜25: 100流經氣體混合$ 22後通入該密閉腔體 11中’並以二抽氣果浦15控制密閉腔體u之工作壓力於 0.23 Pa’並利用-電源供應器24以獅w之輸出功率施 加直流電該陽極與該陰極，並對該基材12施加偏壓 -50V，藉此，氬氣可於該陽、陰極之間產生錢並受電 場作用而絲該無材14，被轟擊出來之铭原子與欽原子將 與腔體内之n氣結合’形錢化域，並沈積於該基材12 # 纟面’約25分鐘即可在該基材U表面形成-氮化紹鈦 (TiAIN)膜 26。 根據文獻記載，氮化銘鈦為銀灰色或灰黑色硬度約 28〜38 GPa，電阻率範圍為8 6χ1〇2〜5χΐ〇4阳韻，且橫戴 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/氮氣比例為 1 曰7.5/10G條件下，所形成之薄膜呈銀灰色以奈米壓痕儀 量測其硬度為刺.04 Gpa，以四點探針量測其電阻率則為 2211 μΩ,，符合氮化減之特徵，可見在適當之空氣/ 5 1379913 氬氣比例下空氣中主要以氮氣參與反應，其餘空氣/氮氣比 例條件下所形成之薄膜亦符合前述特徵。 表一 氣體比例 空氣/氬氣 色澤 硬度 (GPa) 電阻率 (μΩ-cm) 17.5/100 銀灰 39 士 1.04 2211 20/100 銀灰 36 士 3,6 3286 25 / 100 黑灰 33.8±0.9 23451 接著，再以X光繞射儀分析該薄骐26，結果如第二圖 所示，其中，曲線(a)係針對空氣/氬氣比例為17 5/1〇〇條件 φ 下所形成薄膜之分析結果，曲線(b)係針對空氣/氬氣比例為 20/100條件下所形成薄膜之分析結果，曲線⑷係針對空氣 /氬氣比例為25/100條件下所形成薄膜之分析結果與 JCPDS資料庫中™ (卡號：38-1420)比對，各曲線之繞 射峰均稍向高角度位移，乃是因為Ti N結構中部份τ丨原子 被A1原子所置換，且Αι原子半徑小於Ώ原子，故其晶格 常數降低使繞射峰朝高角度位移，χ光繞射儀分析結果證 實該薄臈26為氮化鋁鈦。 鲁 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，其卜照片⑻係空氣/氯 氣比例為17.5/100條件下所形成之薄膜，照片（b)係空氣/ 氣氣比例為2G/1GG條件下所形成之賴u(e)係空氣/ 鼠氣比例為22.5/100條件下所形成之薄膜，照片⑷係空氣 /氮氣比例為25/100條件下所形成之薄膜，均可見柱狀晶社 構，符合氮化減之待徵。综合上述分析結果，可證實由 6 (8) 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f知方法中密 腔體之背景壓力為U3xl(r4pa)，僅需抽至約133_才2According to the nitriding reduction (TiA1N), it is a common hard film material and has high mechanical strength, wear resistance, and anti-corrosion material. The red # has a wide range of applications, for example, the nitriding is reduced on the surface of the tool. Reduce the knife and wear, increase the tool life, and use the electronic H-nitride as a diffusion barrier. The resistivity is known to form a method of nitriding brittle, _Physical Vapor Deposition (PVD) 'In a high vacuum environment, argon is used as the gas, nitrogen is used as the reaction gas, high voltage DC or AC (such as RF) The power source produces the affinity silk reduction recording material, and the Qinyuan from the pupae is combined with the nitrogen atom and the nitrogen reaction, and the titanium film can be deposited on the substrate to change the nitrogen partial pressure in the cavity. Control_Electrical electricity Before argon gas and nitrogen gas are introduced into the closed cavity, the air in the sealed crucible body must be removed first. Generally, the background pressure value of U3X# Pa is required, and the cavity and pumping equipment of the level are required, and the cost is For a long period of time (about 2 to 3 hours), the vacuum is applied, and the nitrogen gas must be purified from the air to obtain the conventional equipment. The equipment cost and the raw material cost are high, and the process steps are complicated. SUMMARY OF THE INVENTION One object of the present invention is to provide a method for producing a nitride-reducing film, which is simple in equipment and low in raw material cost. Another object of the present invention is to provide a method for preparing a nitrided film which has a simple and rapid process. In order to achieve the foregoing object, the present invention provides a method for preparing a nitride-reducing film by using a built-in human-substrate as an anode, and a titanium alloy as a cathode, and air as a reaction (IV), and air. The ratio of argon gas to melon is 5.3 GG~5G: 1 GG is in the closed cavity, and the working pressure of the closed cavity is controlled at 6 65 x 〇-2 pa~6 65 pa, using physical vapor deposition, It is possible to form a nitride-reducing film on the surface of the substrate. Since the air is extremely convenient to obtain, the requirement for riding the real line is lower than the conventional method, so that the method provided by the present month has the advantages of simple equipment, fast process, and low cost. Low cost and other advantages. 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 illustrated as follows: FIG. 1 is a schematic diagram of a device used in a preferred embodiment of the present invention; 2 is an X-ray diffraction sub-photograph of a preferred embodiment of the present invention. FIG. 2 is an electron microscope of a preferred embodiment of the present invention. Referring to FIG. 1 'a preferred embodiment of the present invention The method for preparing nitrogen 13799.13 for the preparation of titanium film is performed by using a DC magnetron destruction system j 〇, a substrate 12 is embedded in the closed cavity 11 as an anode, and a titanium alloy dry material 14 is used as a cathode. The New 12 Series-P chip is cut under the material 14, and the reduced recording material 14 is placed under a magnet 13. The atomic ratio of titanium and IS in the material is 1: 1 at room temperature. The second air pressure pump 15 is started to pump the background pressure of the closed cavity 11 to 丨33xl〇_2pa, 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 the gas flow 1: mass meter 20 according to the flow ratio of 17.5: 100 to 25: 100, and the gas is mixed by $22 and then introduced into the closed cavity. 11" and control the working pressure of the closed cavity u at 0.23 Pa' with two pumping fruit pumps 15 and apply the direct current to the cathode with the power supply 24 at the output power of the lion w, and the substrate 12 Applying a bias voltage of -50V, whereby argon gas can generate money between the anode and cathode and be subjected to an electric field to wire the material 14. The bombarded atom and the atom will combine with the gas in the chamber. A Titan film 26 can be formed on the surface of the substrate U in a form of a "deposited area" and deposited on the substrate 12# facet for about 25 minutes. According to the literature, nitriding titanium has a silver-gray or gray-black hardness of about 28 to 38 GPa, a resistivity range of 8 6 χ 1 〇 2 to 5 χΐ〇 4 yang, and a transverse crystal structure having a columnar crystal structure. The film 26 formed on the surface of the substrate 12 of the present invention has various characteristics as shown in Table 1. The air/nitrogen ratio is 1 曰7.5/10 G, and the formed film is silver-gray in nanoindenter. The hardness of the test is puncturing. 04 Gpa, and the resistivity measured by the four-point probe is 2211 μΩ, which is consistent with the characteristics of nitriding reduction. It can be seen that the air is mainly nitrogen in the appropriate air / 5 1379913 argon ratio. Participating in the reaction, the film formed under the remaining air/nitrogen ratio conditions also conforms to the aforementioned characteristics. Table 1 Gas ratio Air/argon color hardness (GPa) Resistivity (μΩ-cm) 17.5/100 Silver ash 39 ± 1.04 2211 20/100 Silver ash 36 ± 3,6 3286 25 / 100 Black ash 33.8 ± 0.9 23451 Next, The thin crucible 26 was analyzed by an X-ray diffractometer, and the result is shown in the second figure, wherein the curve (a) is an analysis result of a film formed under the condition of air/argon of 17 5/1 〇〇 condition φ, Curve (b) is the analysis result of the film formed under the air/argon ratio of 20/100, and curve (4) is the analysis result of the film formed under the air/argon ratio of 25/100 and the JCPDS database. TM (card number: 38-1420), the diffraction peaks of each curve are slightly shifted to a high angle, because some of the τ 丨 atoms in the Ti N structure are replaced by A1 atoms, and the radius of Αι atoms is smaller than Ώ atoms. Therefore, the lowering of the lattice constant causes the diffraction peak to shift toward a high angle, and the analysis of the diffractometer confirms that the thin crucible 26 is aluminum titanium nitride. Lu, the cross section of the film 26 was observed by a field emission scanning electron microscope (FE_SEM). As shown in the third figure, the photo (8) is a film formed under the condition of air/chlorine ratio of 17.5/100. Photo (b) is a film formed under the condition of air/air gas ratio of 2G/1GG, which is formed under the condition of air/mouse ratio of 22.5/100. Photograph (4) is air/nitrogen ratio of 25 The film formed under the condition of /100 can be seen as a columnar crystal structure, which is consistent with the nitriding reduction. Based on the above analysis results, it was confirmed that the film formed by the method of 6 (8) was indeed an aluminum nitride titanium film. The method provided by the invention introduces air and argon into the closed cavity. Therefore, it is not necessary to pump the closed cavity to a high vacuum degree (for example, the background pressure of the dense cavity in the method is U3xl (r4pa), only need to be pumped To about 133_only 2
Pa’化費時間僅約2〜3分鐘’可大幅縮短製程所需之時間， 且無需高級之腔體與抽氣設備，製程設備較f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 如習知方法般由空氣巾純化出減，可簡化製程步驟，^ 時降低原瓶體之成本^財之，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紹 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，亦可快速 形成氮化鋁鈦膜，例如：將密閉腔體之背景壓力抽至 1.33xl0_4pa，電源供應器之輸出功率為3〇〇 w，並對基材 表二 氣體比例 空氣/氬氣 色澤 硬度 (GPa) 電阻率 (μΩ-cm) 17.5/100 銀灰 41.5±1.6 1286^~~ 20/100 銀灰 37.2±3.3 142^ 22.5/100 黑灰 ^Τ5.8±4.5 h 22¾^ 25 / 100 黑灰 33.4 士 2.2 9886 事實上，進一步實驗數據顯示，陰極可以—鋁鈀材與 施加偏壓_5GV’在不同之空氣/氬氣比例條件下，所形成薄 膜之各項特徵如表二所列，亦符合氮化鋁鈦之特徵。 一鈦鈀材替代鋁鈦合金鈀材，密閉腔體之背景壓力於 1.33ΧΗΓ4 Pa〜1.33 Pa(以 i.33xl〇-3 pa〜1.33x10·丨 Pa 為宜；）， 1379913 工作麼力介於6.65χ10_2 pa〜6.65 Pa(以0.1 Pa〜1 pa為宜）， 空氣/氬氣之流量比介於5:100〜50:100，電源供應器之輸出 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°C，於基材施加偏壓〇〜_3〇〇v (以 •20〜-100 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，甚至利用濺鍍 法外之其他物理氣相沈積法，亦可形成氮化鋁鈦膜。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。 13799.13 【圖式簡單說明】 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； 第三圖係本發明一較佳實施例所製成品之電子顯微鏡 照片。 【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Pa's time is only about 2~3 minutes', which can greatly shorten the time required for the process, and does not require advanced cavities and pumping equipment. The cost of the process equipment is lower than that of the method. Furthermore, the method uses The air can be obtained anywhere, without the need to purify and reduce the air towel as in the conventional method, which simplifies the process steps and reduces the cost of the original bottle body. The method provided by the invention can be simpler and cheaper. The cost, more rapid production of titanium nitride film, can improve the lack of conventional methods, and has great market potential. According to the spirit of the present invention, the aluminum nitride titanium film can be rapidly formed by changing various parameters in the process, for example, the background pressure of the closed cavity is pumped to 1.33×10 −4 pa, and the output power of the power supply is 3 〇〇w, and Table 2 gas ratio Air/argon color hardness (GPa) Resistivity (μΩ-cm) 17.5/100 Silver ash 41.5±1.6 1286^~~ 20/100 Silver ash 37.2±3.3 142^ 22.5/100 Black ash^Τ5 .8±4.5 h 223⁄4^ 25 / 100 black ash 33.4 ± 2.2 9886 In fact, further experimental data show that the cathode can be formed by aluminum-palladium and bias _5GV' at different air/argon ratios. The characteristics of the film are listed in Table 2, and also meet the characteristics of aluminum nitride. A titanium-palladium material replaces the aluminum-titanium alloy palladium material, and the background pressure of the closed cavity is 1.33ΧΗΓ4 Pa~1.33 Pa (I.33xl〇-3 pa~1.33x10·丨Pa is appropriate;), 1379913 6.65χ10_2 pa~6.65 Pa (0.1 Pa~1 pa is preferred), the air/argon flow ratio is between 5:100 and 50:100, and the power supply output is between 50 and 5 〇〇〇w. DC or AC (RF) power supply can be used, the cavity temperature is maintained at 20~300 °C, and the substrate is biased 〇~_3〇〇v (preferably from 20~-100 V), even without bias Under the pressure condition, a titanium aluminum nitride film can be formed in 60 to 7200 seconds, and even a physical vapor deposition method other than the sputtering method can be used to form an aluminum nitride titanium film. Therefore, any changes in process parameters that are easy to think of should be covered by the scope of the patent application. 13799.13 BRIEF DESCRIPTION OF THE DRAWINGS The first drawing is a schematic diagram of an apparatus used in a preferred embodiment of the present invention; the second drawing is an X-ray diffraction analysis diagram of a finished product according to a preferred embodiment of the present invention; An electron micrograph of a product made in accordance with a preferred embodiment of the present invention. [Main component symbol description] 10 DC magnetron sputtering system 11 closed cavity 12 substrate 13 magnet 14 target 15 pumping pump 16 air 18 argon gas gas flow mass meter 22 gas mixer 24 power supply 26 nitrogen Aluminum titanium film