TWI700384B - Method for manufacturing chromium nitride film - Google Patents
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本發明係關於一種薄膜的製造方法，尤其是一種氮化鉻薄膜的製造方法。 The invention relates to a method for manufacturing a thin film, especially a method for manufacturing a chromium nitride thin film.
氮化鉻(CrN、Cr2N)具有很高的硬度、良好的抗氧化、抗腐蝕以及耐疲勞性能，因而被廣泛地應用於製作各種材料、工具及各種機械加工零件的鍍膜層。習知氮化鉻薄膜的製造方法係先以磁控濺鍍法將一鉻金屬薄膜沉積於載玻片上，再對該鉻金屬薄膜進行氮化處理；然而，以磁控濺鍍法成形該鉻金屬薄膜時需要維持環境為真空，因此需要使用一真空設備，導致氮化鉻薄膜的製造成本過高且製造過程費時。 Chromium nitride (CrN, Cr 2 N) has high hardness, good oxidation resistance, corrosion resistance and fatigue resistance, so it is widely used to make coating layers of various materials, tools and various machined parts. The conventional manufacturing method of chromium nitride film is to deposit a chromium metal film on a glass slide by magnetron sputtering method, and then perform nitriding treatment on the chromium metal film; The metal film needs to maintain a vacuum in the environment, so a vacuum device is required, which leads to high manufacturing cost and time-consuming manufacturing process of the chromium nitride film.
有鑑於此，該習知氮化鉻薄膜的製造方法確實仍有加以改善之必要。 In view of this, the conventional manufacturing method of chromium nitride film does still need to be improved.
為解決上述問題，本發明的目的是提供一種氮化鉻薄膜的製造方法，係可以免除該習知氮化鉻薄膜的製造方法中所使用的真空設備者。 In order to solve the above problems, the object of the present invention is to provide a method for manufacturing a chromium nitride film, which can eliminate the vacuum equipment used in the conventional method for manufacturing a chromium nitride film.
本發明的一種氮化鉻薄膜的製造方法，可以包含：使一鉻鹽溶液於一基板上形成一薄膜前驅體；及於1000~1350℃之溫度、800~1100W的功率下，使用一常壓微波電漿，對該薄膜前驅體進行一常壓微波電漿退火 處理3~5分鐘，以形成一氮化鉻薄膜；其中，該常壓微波電漿退火處理係使一電漿氣體轟擊該薄膜前驅體，該電漿氣體包含一中心氣體及一旋進氣體，該中心氣體為氮氣或一氮氫混合氣，該旋進氣體為氮氣，該中心氣體的流量為1SLM，該旋進氣流的流量為9SLM，該電漿氣體係來自一電漿源，該電漿源與該薄膜前驅體之間具有一轟擊距離，該轟擊距離為3~7cm。 The method for manufacturing a chromium nitride film of the present invention may include: forming a film precursor on a substrate with a chromium salt solution; and using a normal pressure at a temperature of 1000~1350°C and a power of 800~1100W Microwave plasma, an atmospheric pressure microwave plasma annealing of the film precursor Process for 3 to 5 minutes to form a chromium nitride film; wherein, the atmospheric pressure microwave plasma annealing process causes a plasma gas to bombard the film precursor, and the plasma gas includes a center gas and a precession gas, The central gas is nitrogen or a nitrogen-hydrogen mixture, the swirling gas is nitrogen, the flow of the central gas is 1 SLM, the flow of the swirling gas is 9 SLM, the plasma gas system comes from a plasma source, and the electric There is a bombardment distance between the slurry source and the film precursor, and the bombardment distance is 3-7 cm.
據此，本發明的氮化鉻薄膜的製造方法，係可以於大氣環境中製造氮化鉻薄膜，因此可以免除習知氮化鉻薄膜的製造方法所使用的真空設備，亦可以減少抽真空所耗費的時間，進而可以達成有效降低製造氮化鉻薄膜的製造成本及製造時間之功效。再且，當該轟擊距離大於7cm時，容易形成氧化物，當該轟擊距離小於3cm時，容易使該基板及已形成於該基板上的氮化鉻薄膜熔化。 Accordingly, the chromium nitride film manufacturing method of the present invention can manufacture chromium nitride film in an atmospheric environment, so the vacuum equipment used in the conventional chromium nitride film manufacturing method can be eliminated, and the vacuum required can be reduced. The time consuming can further effectively reduce the manufacturing cost and manufacturing time of the chromium nitride film. Furthermore, when the bombardment distance is greater than 7 cm, oxides are easily formed, and when the bombardment distance is less than 3 cm, the substrate and the chromium nitride film formed on the substrate are easily melted.
本發明的氮化鉻薄膜的製造方法中，該中心氣體為體積比為9：1的氮氫混合氣。如此，藉由控制該中心氣體及該旋進氣流的總流量，能夠有效控制該氮化鉻薄膜的形成溫度。 In the manufacturing method of the chromium nitride film of the present invention, the center gas is a mixture of nitrogen and hydrogen with a volume ratio of 9:1. In this way, by controlling the total flow of the center gas and the swirling gas flow, the formation temperature of the chromium nitride film can be effectively controlled.
S1:薄膜前驅體成形步驟 S1: Film precursor forming steps
S2:常壓微波電漿退火處理步驟 S2: Atmospheric microwave plasma annealing treatment steps
〔第1圖〕本發明的氮化鉻薄膜的製造方法的一實施例的流程圖。 [Figure 1] A flowchart of an embodiment of the method for manufacturing a chromium nitride thin film of the present invention.
〔第2a圖〕第A1組氮化鉻薄膜的X光繞射分析結果。 [Figure 2a] The X-ray diffraction analysis result of the chromium nitride film of group A1.
〔第2b圖〕第A2組氮化鉻薄膜的X光繞射分析結果。 [Figure 2b] X-ray diffraction analysis results of the chromium nitride film of the group A2.
〔第2c圖〕第A3組氮化鉻薄膜的X光繞射分析結果。 [Figure 2c] X-ray diffraction analysis results of the chromium nitride film of group A3.
〔第2d圖〕第A4組氮化鉻薄膜的X光繞射分析結果。 [Figure 2d] X-ray diffraction analysis results of the A4 group of chromium nitride films.
〔第2e圖〕第A5組氮化鉻薄膜的X光繞射分析結果。 [Figure 2e] X-ray diffraction analysis results of the chromium nitride film of group A5.
為讓本發明之上述及其他目的、特徵及優點能更明顯易懂，下文特舉本發明之較佳實施例，並配合所附圖式，作詳細說明如下：請參照第1圖所示，本發明的氮化鉻薄膜的製造方法的一實施例可以包含：一薄膜前驅體成形步驟S1及一常壓微波電漿退火處理步驟S2，藉由前述步驟即可以於大氣環境中製造一氮化鉻薄膜。 In order to make the above and other objects, features and advantages of the present invention more obvious and understandable, the preferred embodiments of the present invention are described below in detail with the accompanying drawings: Please refer to Figure 1. An embodiment of the method for manufacturing a chromium nitride film of the present invention may include: a thin film precursor forming step S1 and an atmospheric microwave plasma annealing step S2. Through the foregoing steps, a nitride film can be manufactured in an atmospheric environment. Chrome film.
詳而言之，該薄膜前驅體成形步驟S1中，係可以使一鉻鹽溶液於一基板上形成一薄膜前驅體。舉例而言，可以使一鉻鹽溶解於一溶劑中，並於其中加入螯合劑，以共同形成該鉻鹽溶液，該鉻鹽可以為硝酸鉻(chromium(III)nitrate，Cr(NO)3)、醋酸鉻(chromium(III)acetate，Cr(CH3COO)3)、氯化鉻(chromium(III)chloride，CrCl3)或鉻酸銅(copper(II)chromate，CuCrO4)等，該溶劑可以為乙醇，該螯合劑可以為三乙醇胺(triethanolamine)、乙醯丙酮(acetylacetone)或二乙醇胺(diethanolamine)等。於本實施例中，係將硝酸鉻溶於乙醇(0.8M)中，均勻攪拌1小時之後，接著加入三乙醇胺，再持續攪拌3天，即可以形成該鉻鹽溶液。 In detail, in the thin film precursor forming step S1, a chromium salt solution can be used to form a thin film precursor on a substrate. For example, a chromium salt can be dissolved in a solvent, and a chelating agent can be added to it to form the chromium salt solution. The chromium salt can be chromium(III)nitrate (Cr(NO) 3 ) , Chromium (III) acetate (Cr(CH 3 COO) 3 ), chromium (III) chloride (CrCl 3 ) or copper chromate (copper(II) chromate, CuCrO 4 ), etc., the solvent It can be ethanol, and the chelating agent can be triethanolamine, acetylacetone, or diethanolamine. In this embodiment, chromium nitrate is dissolved in ethanol (0.8M) and stirred uniformly for 1 hour, then triethanolamine is added, and the stirring is continued for 3 days to form the chromium salt solution.
接著可以利用浸漬塗佈法(dipping coating)、噴霧法(spraying coating)等各種習知手段，使該鉻鹽溶液能夠於該基板上形成該薄膜前驅體。本實施例中，係以旋轉塗佈法(spinning coating)，將該鉻鹽溶液均勻地塗佈於一石英玻璃基板上(轉速為1500rpm，維持15秒)，在乾燥後即可以形成該薄膜前驅體，惟此為本發明所屬技術領域中的通常知識，於此不加以限制。 Then, various conventional methods such as dipping coating and spraying coating can be used to enable the chromium salt solution to form the thin film precursor on the substrate. In this embodiment, the chromium salt solution is uniformly coated on a quartz glass substrate (rotation speed is 1500 rpm, maintained for 15 seconds) by spinning coating, and the film precursor can be formed after drying However, this is common knowledge in the technical field to which the present invention belongs, and is not limited here.
於常壓微波電漿退火處理步驟S2中，係以一常壓微波電漿(atmospheric pressure microwave plasma，簡稱APMP)對形成於該基板上的薄膜前驅體進行一常壓微波電漿退火處理，此時，來自一電漿源的一電漿氣體即可以轟擊該薄膜前驅體，使該薄膜前驅體可以轉化為該氮化鉻薄膜。 於本實施例中，該常壓微波電漿退火處理係可以於1000~1350℃之溫度、800~1100W的功率下進行。 In the atmospheric pressure microwave plasma annealing treatment step S2, an atmospheric pressure microwave plasma (APMP) is used to perform an atmospheric pressure microwave plasma annealing treatment on the thin film precursor formed on the substrate. At this time, a plasma gas from a plasma source can bombard the film precursor so that the film precursor can be converted into the chromium nitride film. In this embodiment, the atmospheric pressure microwave plasma annealing treatment can be performed at a temperature of 1000 to 1350° C. and a power of 800 to 1100 W.
值得注意的是，該電漿氣體可以包含一中心氣體及一旋進氣體，該中心氣體為氮氣(純度為99.995%以上)或一氮氫混合氣(氮氣與氫氣的體積比為9：1)，且該旋進氣體為氦氣(純度為99.995%以上)。並且，該電漿氣體的總流量為10SLM(standard litre per minute，標準狀態下1L/min的流量)，其中該中心氣體與該旋進氣體的流量比為1：9(即，該中心氣體的流量為1SLM，該旋進氣流的流量為9SLM)。 It is worth noting that the plasma gas may include a center gas and a precession gas. The center gas is nitrogen (purity above 99.995%) or a nitrogen-hydrogen mixture (volume ratio of nitrogen to hydrogen is 9:1) , And the precession gas is helium (purity above 99.995%). In addition, the total flow rate of the plasma gas is 10SLM (standard litre per minute, a flow rate of 1L/min under standard conditions), and the flow ratio of the center gas to the precession gas is 1:9 (that is, the center gas The flow rate is 1 SLM, and the flow rate of the swirling air flow is 9 SLM).
此外，該電漿源與該薄膜前驅體之間具有一轟擊距離，於本實施例中，係控制該轟擊距離為3~7cm。當該轟擊距離大於7cm時，容易形成氧化物，當該轟擊距離小於3cm時，容易使該基板及已形成於該基板上的氮化鉻薄膜熔化。 In addition, there is a bombardment distance between the plasma source and the thin film precursor. In this embodiment, the bombardment distance is controlled to be 3-7 cm. When the bombardment distance is greater than 7 cm, oxides are easily formed, and when the bombardment distance is less than 3 cm, it is easy to melt the substrate and the chromium nitride film formed on the substrate.
為證實以本實施例的氮化鉻薄膜的製造方法確實可以製造出氮化鉻薄膜，遂於該石英玻璃基板上形成該薄膜前驅體後，以如第1表所示的參數進行該常壓微波電漿退火處理步驟S2。 In order to verify that the chromium nitride thin film manufacturing method of this embodiment can indeed produce a chromium nitride thin film, after forming the thin film precursor on the quartz glass substrate, the atmospheric pressure is performed with the parameters shown in Table 1. Microwave plasma annealing treatment step S2.
使用高解析X光繞射儀(High Resolution X-ray Diffractometer)，對以第1表所示的參數所製造出的各組氮化鉻薄膜進行X光繞射分析，並與Cr2N及CrN的JCPDS(joint committee on Poder Diffraction Standards)特徵波峰進行比對，其結果分別如第2a~2e圖所示。其中，第A1~A2組的氮化鉻薄膜的繞射峰與Cr2N及CrN的特徵波峰相符，第A3組的氮化鉻薄膜的繞射峰與Cr2N的特徵波峰相符，第A4~A5組的氮化鉻薄膜的繞射峰與CrN的特徵波峰相符，顯示第A1~A2組的氮化鉻薄膜具有Cr2N及CrN的混合晶相，第A3組的氮化鉻薄膜具有Cr2N的單一晶相，而第A4~A5組的氮化鉻薄膜具有CrN的單一晶相。 Using High Resolution X-ray Diffractometer, X-ray diffraction analysis was performed on each group of chromium nitride films manufactured with the parameters shown in Table 1, and the results were compared with Cr 2 N and CrN The characteristic peaks of JCPDS (joint committee on Poder Diffraction Standards) are compared, and the results are shown in Figures 2a~2e. Among them, the diffraction peaks of the chromium nitride film of the A1~A2 groups are consistent with the characteristic peaks of Cr 2 N and CrN, the diffraction peaks of the chromium nitride film of the A3 group are consistent with the characteristic peaks of Cr 2 N, and the A4 The diffraction peak of the chromium nitride film of group A5 is consistent with the characteristic peak of CrN, indicating that the chromium nitride film of group A1~A2 has a mixed crystal phase of Cr 2 N and CrN, and the chromium nitride film of group A3 has Cr 2 N has a single crystal phase, and the chromium nitride films of the A4 to A5 groups have a single crystal phase of CrN.
綜上所述，本發明的氮化鉻薄膜的製造方法，係可以於大氣環境中製造氮化鉻薄膜，因此可以免除習知氮化鉻薄膜的製造方法所使用的真空設備，亦可以減少抽真空所耗費的時間，進而可以達成有效降低製造氮化鉻薄膜的製造成本及製造時間之功效。 In summary, the chromium nitride film manufacturing method of the present invention can manufacture chromium nitride film in an atmospheric environment, so it can eliminate the vacuum equipment used in the conventional chromium nitride film manufacturing method, and can also reduce pumping The time consumed by the vacuum can further effectively reduce the manufacturing cost and manufacturing time of the chromium nitride film.
雖然本發明已利用上述較佳實施例揭示，然其並非用以限定本發明，任何熟習此技藝者在不脫離本發明之精神和範圍之內，相對上述實施例進行各種更動與修改仍屬本發明所保護之技術範疇，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed using the above-mentioned preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with the art without departing from the spirit and scope of the present invention may make various changes and modifications relative to the above-mentioned embodiments. The technical scope of the invention is protected. Therefore, the scope of protection of the invention shall be subject to the scope of the attached patent application.
S1:薄膜前驅體成形步驟 S1: Film precursor forming steps
S2:常壓微波電漿退火處理步驟 S2: Atmospheric microwave plasma annealing treatment steps
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| 蕭富謙, 陳弘穎, 蔡政賢, "以常壓微波電漿火炬氮化鈦金屬薄膜之研究", 國立高雄應用科技大學, 化學工程系碩士論文, 論文出版年2008, 國家圖書館上架日:2010/03/25, 電子全文共62頁 * |
| 蕭富謙, 陳弘穎, 蔡政賢, "以常壓微波電漿火炬氮化鈦金屬薄膜之研究", 國立高雄應用科技大學, 化學工程系碩士論文, 論文出版年2008, 國家圖書館上架日:2010/03/25, 電子全文共62頁。 |
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