TWI554633B - A diamond-like carbon film and manufacturing method thereof - Google Patents
A diamond-like carbon film and manufacturing method thereof Download PDFInfo
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Description
本發明係關於一種薄膜及其製作方法，特別是關於一種類鑽碳膜及其製作方法。The present invention relates to a film and a method of fabricating the same, and more particularly to a diamond-like carbon film and a method of fabricating the same.
類鑽碳(Diamond-Like Carbon)是指以sp2之石墨結構及sp3之鑽石立方結構所隨機排列混合構成之非晶態碳。Diamond-Like Carbon refers to amorphous carbon composed of a random arrangement of sp 2 graphite structure and sp 3 diamond cubic structure.
由於類鑽碳膜(Diamond-Like Carbon film)具有結構穩定性佳、低導電性、低摩擦係數及質地緻密等優點。因此，常被應用於需具有耐磨耗或抗腐蝕特性之零組件的製作上。例如，切削元件或鑽頭之表面通常將進一步設置該類鑽碳膜，以強化整體硬度及耐磨性。Diamond-Like Carbon film has the advantages of good structural stability, low electrical conductivity, low friction coefficient and dense texture. Therefore, it is often applied to the production of components requiring wear resistance or corrosion resistance. For example, the surface of the cutting element or drill bit will typically be further provided with a diamond-like carbon film to enhance overall hardness and wear resistance.
一般類鑽碳膜通常係以sp2石墨結構及sp3之鑽石立方結構為主要結構。其中，sp3之鑽石立方結構的硬度較高，耐磨性較佳。然而，其相對亦具有較高之內應力，除了結構容易崩壞以外，與工件表面之附著性亦不佳。因此，通常若欲於工件上製作類鑽碳膜，需另於製程進行適當調整以提升該類鑽碳膜之附著性。例如，可選擇將類鑽碳膜製作至較薄之厚度方可達到低內應力之效果，然而一般工業上使用之類鑽碳膜厚度至少需2μm，因此通常係於類鑽碳膜中添加其他金屬元素或另行設置中介層之方式提升附著性。Generally, the diamond-like carbon film is mainly composed of sp 2 graphite structure and sp 3 diamond cubic structure. Among them, the diamond cubic structure of sp 3 has higher hardness and better wear resistance. However, it also has a relatively high internal stress, and the adhesion to the surface of the workpiece is not good except that the structure is easily collapsed. Therefore, if a diamond-like carbon film is to be produced on a workpiece, it is necessary to adjust the process to adjust the adhesion of the carbon film. For example, the diamond-like carbon film can be made to a thinner thickness to achieve a low internal stress. However, the thickness of the drilled carbon film generally used in the industry needs to be at least 2 μm, so it is usually added to the diamond-like carbon film. Adhesion is improved by means of metal elements or by providing an intervening layer.
習用類鑽碳膜之製作方法，係如中華民國公告第372249號「利用非平衡磁控濺鍍設備在鋼材表面蒸鍍含鉻碳氫類鑽膜之方法」專利所述，其主要係透過濺鍍方式，於鋼材表面依序形成鉻層、氮化鉻、氮碳化鉻及碳化鉻等被覆中介層，以降低非晶形含鉻碳氫類鑽膜之內應力。此法主要係於類鑽碳膜中摻雜金屬成分作為中介層，以降低該類鑽碳膜之內應力。The production method of the conventional diamond-like carbon film is as described in the patent of the Republic of China Announcement No. 372249 "Using Unbalanced Magnetron Sputtering Equipment to Evaporate Chromium-Containing Hydrocarbon-Drilling Membrane on Steel Surface", which is mainly through splashing. The plating method forms a coating layer of chromium layer, chromium nitride, chromium carbide and chromium carbide on the surface of the steel to reduce the internal stress of the amorphous chromium-containing hydrocarbon film. This method is mainly used to dope metal components in the diamond-like carbon film as an interposer to reduce the internal stress of the carbon film.
然而，此法需另準備金屬靶材進行摻雜，除了增加整體製程複雜度以外，該金屬靶材之損耗亦將增加製作成本。However, this method requires the preparation of a metal target for doping. In addition to increasing the overall process complexity, the loss of the metal target will also increase the manufacturing cost.
另一習用類鑽碳膜之製作方法，係如中華民國公告第370571號「連續式成長高附著性類碳膜之方法」專利所述，其主要係透過電漿氣相沈積法依序於一基材上沈積一層低應力含矽碳膜作為中介層，進一步於該中介層之表面沈積一層類鑽碳膜。如此，便可透過該中介層減少該類鑽碳膜與該基材間性質的差異，進而提升該類鑽碳膜之附著性。Another conventional method for producing a diamond-like carbon film is as described in the Patent of the Republic of China Bulletin No. 370571, "Method for Continuously Growing Highly Adhesive Carbon Films", which is mainly processed by plasma vapor deposition. A low-stress ruthenium-containing carbon film is deposited on the substrate as an interposer, and a diamond-like carbon film is further deposited on the surface of the interposer. In this way, the intervening layer can reduce the difference in properties between the drilled carbon film and the substrate, thereby improving the adhesion of the drilled carbon film.
然而，該中介層之設置將會造成製程上之複雜度，且通入之氣體除單純的類鑽碳膜所需的含碳氣體以外，需要另加入含矽氣體或者其他氣體，不但增加製程複雜度，亦增加了該類鑽碳膜之製作成本。However, the setting of the interposer will cause complexity in the process, and the gas to be introduced needs to add a helium-containing gas or other gas in addition to the carbon-containing gas required for the pure diamond-like carbon film, which not only increases the complexity of the process. Degree, also increased the production cost of this type of drill carbon film.
此外，請參照第1圖所示，其係出自於「Systematic variation of the Raman spectra of DLC films as a function of sp2:sp3 composition」(S. Prawer等人於1996年提出)論文中。其中，前述兩件前案所使用之濺鍍及電漿氣相沈積法之給予離子的沈積能量(解離能量)較低，其所形成之類鑽碳膜僅落於圖中沈積能量(解離能量)較低的A區中，代表二件前案所形成之類鑽碳膜中所含的sp2結構比例較高，sp3結構比例較低。因此，其所製成之類鑽碳膜之硬度仍嫌不足；且由於沈積能量(解離能量)較低，該類鑽碳膜與基材之結合性亦相對不足。Further, please refer to Fig. 1, which is from the paper "Systematic variation of the Raman spectra of DLC films as a function of sp 2 : sp 3 composition" (S. Prawer et al., 1996). Among them, the sputtering energy and the plasma vapor deposition method used in the two previous cases have lower deposition energy (dissociation energy), and the formed carbon film is only deposited in the figure (dissociation energy). In the lower A zone, the proportion of sp 2 structure contained in the diamond-like carbon film formed by the two previous cases is higher, and the proportion of sp 3 structure is lower. Therefore, the hardness of the carbon film produced by the drilled carbon film is still insufficient; and because the deposition energy (dissociation energy) is low, the bonding of the diamond-like carbon film to the substrate is relatively insufficient.
基於上述原因，其有必要進一步改良上述習用類鑽碳膜及其製作方法。For the above reasons, it is necessary to further improve the conventional diamond-like carbon film and its manufacturing method.
本發明目的乃改良上述缺點，以提供一種類鑽碳膜，不需摻雜或中介層等方式便可提升類鑽碳膜之附著性為目的。The object of the present invention is to improve the above disadvantages, so as to provide a diamond-like carbon film, which can improve the adhesion of the diamond-like carbon film without doping or interposer.
本發明次一目的係提供一種類鑽碳膜之製作方法，透過以高能量離子源提供含碳氣體高解離能量，而形成高附著性及高硬度之類鑽碳膜。A second object of the present invention is to provide a method for producing a diamond-like carbon film by providing a high-energy ion source with a high dissociation energy of a carbon-containing gas to form a carbon film of high adhesion and high hardness.
根據本發明的類鑽碳膜，係包含：一類鑽碳附著層，係設於一基材；及一類鑽碳強化層，係設於該類鑽碳附著層之表面；其中，該類鑽碳附著層之sp2石墨結構所佔之比例係高於該類鑽碳強化層之sp2石墨結構所佔之比例。The diamond-like carbon film according to the present invention comprises: a type of carbon-adhesive layer attached to a substrate; and a type of carbon-strengthening layer disposed on the surface of the carbon-adhesive layer; wherein the carbon-like layer is drilled percentage of proportion of sp 2 graphite structure of the adhesive layer is higher than the proportion of sp 2 graphite structure reinforcement layer of DLC.
根據本發明的類鑽碳膜之製作方法，係包含：一前置步驟，將一基板置於一反應腔體中；一類鑽碳附著層製作步驟，將一含碳氣體通入該反應腔體中，並以一離子源提供能量使該含碳氣體解離，並具備701~3000eV之解離能量，使該含碳氣體於該基板之表面沈積形成一類鑽碳附著層；及一類鑽碳強化層製作步驟，以該離子源使該含碳氣體解離，並具備100~700eV之解離能量，使該含碳氣體進一步於該類鑽碳附著層沈積形成一類鑽碳膜。The method for manufacturing a diamond-like carbon film according to the present invention comprises: a pre-step of placing a substrate in a reaction chamber; and a step of fabricating a carbon-adhesive layer to pass a carbon-containing gas into the reaction chamber Providing energy from an ion source to dissociate the carbon-containing gas and having a dissociation energy of 701 to 3000 eV, so that the carbon-containing gas is deposited on the surface of the substrate to form a type of carbon-adhesive adhesion layer; and a type of carbon-enhanced layer is formed In the step, the carbon-containing gas is dissociated by the ion source, and has a dissociation energy of 100-700 eV, so that the carbon-containing gas is further deposited on the diamond-like carbon adhesion layer to form a diamond-like carbon film.
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2圖所示，本發明之類鑽碳膜之製作方法係包含一前置步驟S1、一類鑽碳附著層製作步驟S2及一類鑽碳強化層製作步驟S3。The above and other objects, features and advantages of the present invention will become more <RTIgt; The method for manufacturing a drilled carbon film of the present invention comprises a pre-step S1, a drilling carbon adhesion layer forming step S2 and a drilling carbon strengthening layer forming step S3.
請參照第3圖所示，本發明之類鑽碳膜之製作方法係利用如第3圖所示之離子源(Ion Beam)裝置進行。該離子源裝置主要係包含一反應腔體1及一設置於該反應腔體1內的離子源產生裝置2。該反應腔體1係設有一反應空間11、一進氣口12及一排氣口13。該反應空間11係形成於該反應腔體1內，該進氣口12及排氣口13係分別穿設於該反應腔體1之壁面；該進氣口12係用以將氣體導入該離子源產生裝置2中；該排氣口13係用以將氣體導出該反應腔體1用。該離子源產生裝置2係透過一電源供應器提供電源，使該離子源產生裝置2形成有一偏壓而可產生離子源。Referring to Fig. 3, the method for producing a drilled carbon film of the present invention is carried out by using an ion source (Ion Beam) apparatus as shown in Fig. 3. The ion source device mainly comprises a reaction chamber 1 and an ion source generating device 2 disposed in the reaction chamber 1. The reaction chamber 1 is provided with a reaction space 11, an air inlet 12 and an exhaust port 13. The reaction space 11 is formed in the reaction chamber 1 , and the air inlet 12 and the exhaust port 13 are respectively disposed on the wall surface of the reaction chamber 1; the air inlet 12 is used to introduce a gas into the ion The source generating device 2 is configured to discharge gas to the reaction chamber 1. The ion source generating device 2 supplies power through a power supply device such that the ion source generating device 2 forms a bias voltage to generate an ion source.
請參照第2圖所示，本發明之前置步驟S1係將一基板3置於該反應腔體1內。更詳言之，此前置步驟S1係先將該基板3置於該反應腔體1之反應空間11內，以供後續於該基板3之表面沈積形成類鑽碳膜。該基板3係可選擇為矽基板、玻璃基板或金屬基板等適當材質製成之基板。其中，該基板3較佳係先經過一表面清潔製程，以去除該基板3表面之雜質。舉例而言，本實施例係選擇以電漿對該基板3之表面進行清潔。於該基板3置入該反應空間11後，透過一抽氣單元連接該排氣口13對該反應腔體進行除氣抽真空至壓力低於3.00×10-5torr，接著由該進氣口12引入氬氣(Ar)12~30sccm，使該反應腔體1內的壓力維持在4.00×10-4~1.54×10-3 torr，接著，啟動該離子源產生裝置2，電壓調至0.5KV~3.0KV，便可產生氬氣電漿對該基板3之表面進行離子轟擊前處理，以清潔該基板3之表面。至此，便完成本發明之前置步驟S1。例如，本實施例之表面清潔製程之氬氣流量係為20sccm，壓力維持在8.00×10-4torr，電壓調為1.5KV以產生電漿清潔該基板3。Referring to FIG. 2, the pre-step S1 of the present invention places a substrate 3 in the reaction chamber 1. In more detail, the step S1 is preceded by placing the substrate 3 in the reaction space 11 of the reaction chamber 1 for subsequent deposition on the surface of the substrate 3 to form a diamond-like carbon film. The substrate 3 may be selected from a substrate made of a suitable material such as a germanium substrate, a glass substrate, or a metal substrate. The substrate 3 is preferably subjected to a surface cleaning process to remove impurities on the surface of the substrate 3. For example, in this embodiment, the surface of the substrate 3 is selected to be cleaned by plasma. After the substrate 3 is placed in the reaction space 11, the reaction chamber is degassed and evacuated through an exhaust unit 13 to a pressure lower than 3.00×10 −5 torr, and then the air inlet is used. 12 introducing argon (Ar) 12~30sccm, maintaining the pressure in the reaction chamber 1 at 4.00×10 -4 ~1.54×10 -3 torr, and then starting the ion source generating device 2, the voltage is adjusted to 0.5KV ~3.0KV, an argon plasma can be generated to perform ion bombardment treatment on the surface of the substrate 3 to clean the surface of the substrate 3. So far, the pre-step S1 of the present invention is completed. For example, the argon gas flow rate of the surface cleaning process of this embodiment is 20 sccm, the pressure is maintained at 8.00 × 10 -4 torr, and the voltage is adjusted to 1.5 kV to cause plasma cleaning of the substrate 3.
請參照第2及4圖所示，本發明之類鑽碳附著層製作步驟S2係將一含碳氣體(例如甲烷、乙烷、丙烷或乙炔等氣體)通入該反應腔體1中，並以一離子源使該含碳氣體解離，並具備701~3000eV之解離能量，使該含碳氣體於該基板3之表面沈積形成一類鑽碳附著層4。更詳言之，為了提升類鑽碳膜於該基材3表面之附著力，請參照第1圖所示，本發明透過使含碳氣體解離，並具備701eV~3000eV之解離能量，參照第1圖中的C區，因而可獲得較高能量之碳離子，因此可提升該類鑽碳膜相對於該基材3表面之附著性。舉例而言，本實施例係將前述之氬氣關閉，且選擇乙炔作為該含碳氣體，乙炔流量控制為21sccm，該反應腔體1之壓力維持在5.0×10-3torr，並使該離子源產生裝置2產生2.6KV之偏壓(相當於使碳離子具1280eV之能量)。如此，便可透過該離子源產生裝置2產生離子源提供能量，使該些含碳氣體產生解離，而於該基板3之表面沈積形成厚度為10～1000nm之類鑽碳附著層4。藉此，該類鑽碳附著層製作步驟S2透過該離子源產生裝置2解離該含碳氣體，使碳離子具備701~3000eV之能量，便可形成sp2結構比例較多之類鑽碳附著層4，使該類鑽碳附著層4之內應力較低。再且，透過高解離能量所製成之類鑽碳附著層4，其與該基板3之表面結合性較強，因此可進一步提升該類鑽碳附著層4之附著性。Referring to Figures 2 and 4, in the step S2 of forming a carbon-adhesive adhesion layer of the present invention, a carbon-containing gas (for example, a gas such as methane, ethane, propane or acetylene) is introduced into the reaction chamber 1, and The carbon-containing gas is dissociated by an ion source and has a dissociation energy of 701 to 3000 eV, so that the carbon-containing gas is deposited on the surface of the substrate 3 to form a diamond-like carbon adhesion layer 4. More specifically, in order to enhance the adhesion of the diamond-like carbon film on the surface of the substrate 3, as shown in Fig. 1, the present invention dissociates the carbon-containing gas and has a dissociation energy of 701 eV to 3000 eV, with reference to the first The C region in the figure, thus obtaining higher energy carbon ions, can enhance the adhesion of the diamond-like carbon film to the surface of the substrate 3. For example, in the present embodiment, the argon gas described above is closed, and acetylene is selected as the carbon-containing gas, the flow rate of acetylene is controlled to 21 sccm, the pressure of the reaction chamber 1 is maintained at 5.0×10 −3 torr, and the ion is maintained. The source generating device 2 generates a bias voltage of 2.6 kV (corresponding to an energy of 1280 eV for carbon ions). In this way, the ion source generating device 2 generates an ion source to supply energy to dissociate the carbon-containing gas, and deposits a diamond-like carbon adhesion layer 4 having a thickness of 10 to 1000 nm on the surface of the substrate 3. Thereby, the carbon-adhesive layer forming step S2 is dissociated from the carbon-containing gas by the ion source generating device 2, so that the carbon ions have an energy of 701 to 3000 eV, thereby forming a diamond-like carbon adhesion layer having a large sp 2 structure ratio. 4. The internal stress of the carbon-adhesive layer 4 is low. Further, the diamond-like carbon adhesion layer 4 formed by the high dissociation energy has a strong bonding property with the surface of the substrate 3, so that the adhesion of the diamond-like carbon adhesion layer 4 can be further improved.
於此步驟中，並不限於以相同解離能量製作該類鑽碳附著層4，僅需於該基板3之表面，以介於701~3000eV之間並逐漸遞減解離偏壓之解離能量製作該類鑽碳附著層4，相同可達到越接近該基板3之類鑽碳附著層4的結構附著力越佳之效果，因而可應用於連續式之生產。In this step, it is not limited to fabricating the diamond-like carbon adhesion layer 4 with the same dissociation energy, and only needs to be made on the surface of the substrate 3 with a dissociation energy of between 701 and 3000 eV and gradually decreasing the dissociation bias. The carbon adhesion layer 4 can be drilled to achieve the same effect of better adhesion to the carbon-adhesive adhesion layer 4 such as the substrate 3, and thus can be applied to continuous production.
例如，此步驟中於該1280eV之解離能量產生沈積形成類鑽碳附著膜後，亦可進一步再將該離子源產生裝置2之偏壓調降至2.0KV(相當於950eV之解離能量)，以連續式沈積出另一sp2結構所佔比例更低之類鑽碳膜(厚度50~1000nm)，如此，便可形成漸層式的類鑽碳附著層4，以提升類鑽碳膜之附著性。For example, in this step, after the dissociation energy of 1280 eV is deposited to form a diamond-like carbon-attached film, the bias of the ion source generating device 2 can be further reduced to 2.0 KV (equivalent to a dissociation energy of 950 eV). Continuously deposit another diamond-like carbon film (thickness 50~1000nm) with a lower proportion of sp 2 structure. Thus, a graded diamond-like carbon adhesion layer 4 can be formed to enhance the adhesion of the diamond-like carbon film. Sex.
請參照第2及5圖所示，本發明之類鑽碳強化層製作步驟S3，係以該離子源使該含碳氣體解離，並使碳離子具備100~700eV之解離能量，使該含碳氣體進一步於該類鑽碳附著層4沈積形成一類鑽碳強化層5。更詳言之，完成前述之類鑽碳附著層4的製作後，僅需對反應條件進行適當調整，便可連續地進行該類鑽碳強化層5之製作。舉例而言，本實施例係選擇將該離子源產生裝置2之偏壓調降至1.0KV(相當於400eV之解離能量)，並將該含碳氣體(乙炔)之流量調整為12sccm，該反應腔體1內之壓力維持在6.0×10-4torr，以繼續透過該離子源產生裝置2所產生之離子源激發該些含碳氣體產生解離，而進一步於該類鑽碳附著層4之表面沈積形成厚度介於50~1000nm的類鑽碳強化層5。如第1圖所示，由於此步驟係將給予含碳氣體之解離能量調降至100~700eV，因此將落於第1圖之B區內，形成包含sp3結構比例較多的類鑽碳強化層5，藉此可提升該類鑽碳強化層5之整體結構硬度，作為該基材3之最表層可提供耐磨耗之作用。當然，此步驟與該類鑽碳附著層製作步驟S2係可選擇以不同之含碳氣體作為反應，以製作具備適當性質之薄膜，且此步驟相同亦可以介於100~700eV之間，並逐漸遞減解離偏壓之解離能量製作該類鑽碳強化層5，以製作越接近表層硬度越高之類鑽碳強化層5。Referring to FIGS. 2 and 5, in the step S3 of forming a carbon-reinforced layer of the present invention, the carbon source is dissociated by the ion source, and the carbon ion is provided with a dissociation energy of 100 to 700 eV to make the carbon-containing carbon. The gas is further deposited on the diamond-like carbon adhesion layer 4 to form a diamond-like carbon strengthening layer 5. More specifically, after the production of the above-described drilled carbon adhesion layer 4 is completed, the production of the carbon-dye-strengthening layer 5 can be continuously performed only by appropriately adjusting the reaction conditions. For example, in this embodiment, the bias of the ion source generating device 2 is adjusted to be reduced to 1.0 kV (corresponding to a dissociation energy of 400 eV), and the flow rate of the carbon-containing gas (acetylene) is adjusted to 12 sccm. The pressure in the cavity 1 is maintained at 6.0×10 −4 torr to continue to excite the carbon-containing gas generated by the ion source generated by the ion source generating device 2 to further dissociate, and further surface of the carbon-adhesive layer 4 A diamond-like carbon strengthening layer 5 having a thickness of 50 to 1000 nm is deposited. As shown in Figure 1, since this step is to reduce the dissociation energy of the carbon-containing gas to 100-700 eV, it will fall in the B zone of Figure 1 to form a diamond-like carbon containing a large proportion of sp 3 structure. The layer 5 is strengthened, whereby the overall structural hardness of the diamond-like carbon strengthening layer 5 can be improved, and the outermost layer of the substrate 3 can provide wear resistance. Of course, this step and the step of forming the carbon-adhesive layer of the diamond-like layer can be selected by reacting different carbon-containing gases to produce a film having suitable properties, and the step can also be between 100 and 700 eV, and gradually The dissociation energy of the de-biasing bias is decremented to produce the carbon-strengthening layer 5, so as to produce a carbon-like strengthening layer 5 which is closer to the hardness of the surface layer.
藉此，本發明之類鑽碳附著層製作步驟S2及類鑽碳強化層製作步驟S3進行時，皆是單純以含碳氣體進行沈積，僅需適當調整該離子源產生裝置2供應之解離能量，以適當形成sp2結構比例較高之類鑽碳附著層4而提升附著性，以及形成sp3結構比例較高之類鑽碳強化層5以提高硬度，而完成兼具有高附著性及高硬度的類鑽碳膜之製作。Therefore, when the carbonaceous carbon adhesion layer forming step S2 and the diamond-like carbon strengthening layer forming step S3 of the present invention are performed, the deposition is performed only by the carbon-containing gas, and only the dissociation energy supplied from the ion source generating device 2 needs to be appropriately adjusted. The carbon-adhesive layer 4 having a higher ratio of the sp 2 structure is appropriately formed to improve the adhesion, and the carbon-reinforced layer 5 having a higher proportion of the sp 3 structure is formed to increase the hardness, and the completion has both high adhesion and The production of high hardness diamond-like carbon film.
再且，由於類鑽碳附著層製作步驟S2及類鑽碳強化層製作步驟S3之進行僅需以遞減之解離能量激發含碳氣體，因此，可應用於連續式製程，且無須進行金屬或其他元素之摻雜，可有效簡化製程。Moreover, since the diamond-like carbon adhesion layer forming step S2 and the diamond-like carbon strengthening layer forming step S3 are performed only by the decomposed energy to excite the carbon-containing gas, the continuous process can be applied without metal or other The doping of the elements can effectively simplify the process.
如此，透過前述之製作方法便可製成本案之類鑽碳膜。請參照第5圖所示，本發明之類鑽碳膜係包含有一類鑽碳附著層4及一類鑽碳強化層5。Thus, the carbon film of the present invention can be produced by the above-described manufacturing method. Referring to FIG. 5, the drilled carbon film of the present invention comprises a type of carbon-adhesive adhesion layer 4 and a diamond-like carbon strengthening layer 5.
該類鑽碳附著層4係如第5圖所示可設置於一基材3之表面，且該類鑽碳附著層4之sp2石墨結構所佔比例高於該類鑽碳強化層5之sp2石墨結構所佔之比例。因此，使得該類鑽碳附著層4對於該基材3具有較高的附著性。其中，如第1圖所示，該類鑽碳附著層4之sp2石墨結構所佔比例較佳係高於0.3(第1圖之C區)，以提升該類鑽碳附著層4相對於該基材3之附著性。若該類鑽碳附著層4之sp2石墨結構所佔比例低於0.3，則將會影響到該類鑽碳附著層4相對於該基材3之附著性。該類鑽碳附著層4之厚度係為10～1000nm。The carbon-adhesive layer 4 can be disposed on the surface of a substrate 3 as shown in FIG. 5, and the proportion of the sp 2 graphite structure of the diamond-like carbon adhesion layer 4 is higher than that of the diamond-like carbon layer 5 The proportion of sp 2 graphite structure. Therefore, the carbon-adhesive layer 4 of this type is made to have high adhesion to the substrate 3. Wherein, as shown in FIG. 1, the proportion of the sp 2 graphite structure of the carbon-like adhesion layer 4 is preferably higher than 0.3 (C area of FIG. 1) to enhance the carbon-like adhesion layer 4 relative to Adhesion of the substrate 3. If the proportion of the sp 2 graphite structure of the carbon-adhesive layer 4 is less than 0.3, the adhesion of the diamond-like carbon adhesion layer 4 to the substrate 3 will be affected. The thickness of the carbon-adhesive layer 4 is 10 to 1000 nm.
該類鑽碳強化層5係如第5圖所示設置於該類鑽碳附著層4之表面，由於該類鑽碳強化層5主要係提供該類鑽碳膜高硬度。因此，如第1圖所示，該類鑽碳強化層5內之sp2石墨結構所佔比例較佳係低於0.3(第1圖之B區)，以相對提昇sp3鑽石立方結構於該類鑽碳強化層5中的比例，進而提升整體類鑽碳膜之硬度。若該類鑽碳強化層5內之sp2石墨結構所佔比例高於0.3，則將降低該類鑽碳強化層5之硬度。該類鑽碳強化層5之厚度係為50~1000nm。The drilled carbon strengthening layer 5 is disposed on the surface of the diamond-like carbon adhesion layer 4 as shown in Fig. 5, and the carbon-reinforced layer 5 mainly provides the high hardness of the diamond-like carbon film. Therefore, as shown in Fig. 1, the proportion of the sp 2 graphite structure in the carbon-like strengthening layer 5 is preferably less than 0.3 (region B of Fig. 1) to relatively enhance the sp 3 diamond cubic structure. The proportion of the diamond-like carbon strengthening layer 5 is increased, thereby increasing the hardness of the overall diamond-like carbon film. If the proportion of the sp 2 graphite structure in the carbon-reinforced layer 5 is higher than 0.3, the hardness of the carbon-reinforced layer 5 will be lowered. The thickness of the carbon-reinforced layer 5 of this type is 50 to 1000 nm.
請參照表一所示，其係為本發明之方法利用不同解離能量所製成之類鑽碳膜之特性。由結果可明顯得知，本發明之解離能量介於100~700eV之類鑽碳強化層5之sp3之結構比例較高，因此硬度亦較解離能量介於701~3000eV之類鑽碳附著層4之硬度來的高，甚至硬度可高達6000Hv以上。而該類鑽碳附著層4相較之下則具有高附著性之優點。Referring to Table 1, it is a characteristic of the diamond-like carbon film produced by the method of the present invention using different dissociation energies. It can be clearly seen from the results that the sp 3 of the carbon-strengthening layer 5 having a dissociation energy of 100 to 700 eV has a higher structural ratio, and thus the hardness is also higher than that of the carbon-bonded layer having a dissociation energy of 701 to 3000 eV. The hardness of 4 is high, and even the hardness can be as high as 6000Hv or more. Compared with the carbon-adhesive layer 4, the carbon-adhesive layer 4 has the advantage of high adhesion.
請再參照第6圖及第7圖所示，其係為本發明之類鑽碳膜於金屬基材上之壓痕測試。第6圖為一般類鑽碳膜直接設置於金屬基材上之壓痕測試結果，可明顯觀察到該習用類鑽碳膜由於內應力過大，附著力不佳，因此於壓痕的周緣皆已產生裂紋。而本發明之製作方法所製作之類鑽碳附著層4之壓痕測試結果如第7圖所示，可明顯觀察得知壓痕周緣仍然保持平整，表示本發明所製作之類鑽碳附著層4確實具有提升附著性之功效。 Please refer to FIG. 6 and FIG. 7 again, which is an indentation test of the carbon film on the metal substrate of the present invention. Figure 6 is the result of the indentation test of the general diamond-like carbon film directly placed on the metal substrate. It can be clearly observed that the conventional diamond-like carbon film has excessive internal stress and poor adhesion, so the periphery of the indentation has been Cracks are generated. The indentation test result of the diamond-like carbon adhesion layer 4 produced by the manufacturing method of the present invention is as shown in Fig. 7, and it can be clearly observed that the periphery of the indentation remains flat, indicating that the carbon-adhesive layer is made of the present invention. 4 does have the effect of improving adhesion.
如上所述，透過本發明之製作方法中的類鑽碳附著層製作步驟S2及類鑽碳強化層製作步驟S3以遞減之解離能量激發含碳氣體產生沈積反應，以形成不同結構組成比例之類鑽碳附著層4及類鑽碳強化層5。便可透過該類鑽碳附著層4提供高附著性，透過該類鑽碳強化層5作為表層提供高硬度。因此，無須摻雜或中介層等方式便可提升類鑽碳膜之附著性。 As described above, the diamond-like carbon adhesion layer forming step S2 and the diamond-like carbon strengthening layer forming step S3 in the manufacturing method of the present invention excite the carbon-containing gas to generate a deposition reaction by decreasing the dissociation energy to form different structural composition ratios and the like. The carbon adhesion layer 4 and the diamond-like carbon strengthening layer 5 are drilled. High adhesion can be provided by the carbon-adhesive layer 4 of this type, and the carbon-reinforced layer 5 is provided as a surface layer to provide high hardness. Therefore, the adhesion of the diamond-like carbon film can be improved without doping or interposer.
本發明係透過高能量離子源提供高解離能量使該含碳氣體解離，而形成高附著性及高硬度之類鑽碳膜。 The present invention provides high dissociation energy through a high energy ion source to dissociate the carbonaceous gas to form a carbon film of high adhesion and high hardness.
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。 While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.
S1‧‧‧前置步驟 S1‧‧‧Pre-steps
S2‧‧‧類鑽碳附著層製作步驟 S2‧‧‧Drilling carbon adhesion layer production steps
S3‧‧‧類鑽碳強化層製作步驟 S3‧‧‧Drilling carbon strengthening layer production steps
1‧‧‧反應腔體 1‧‧‧Reaction chamber
11‧‧‧反應空間 11‧‧‧Reaction space
12‧‧‧進氣口 12‧‧‧air inlet
13‧‧‧排氣口 13‧‧‧Exhaust port
2‧‧‧離子源產生裝置 2‧‧‧Ion source generating device
3‧‧‧基板 3‧‧‧Substrate
4‧‧‧類鑽碳附著層 4‧‧‧Drilling carbon adhesion layer
5‧‧‧類鑽碳強化層 5‧‧‧Drilling carbon strengthening layer
第1圖：sp2比例與解離能量(eV)之相對變化圖。 Figure 1: Relative change pattern of sp 2 ratio and dissociation energy (eV).
第2圖：本發明之類鑽碳膜之製作方法的流程圖。 Fig. 2 is a flow chart showing a method of producing a drilled carbon film of the present invention.
第3圖：本發明之類鑽碳膜之製作方法所使用的裝置示意圖。 Fig. 3 is a schematic view of a device used in a method of producing a carbon-coated carbon film of the present invention.
第4圖：本發明之類鑽碳附著層製作步驟的示意圖。 Fig. 4 is a schematic view showing the steps of producing a carbon-adhesive layer of the present invention.
第5圖：本發明之類鑽碳強化層製作步驟的示意圖。 Fig. 5 is a schematic view showing the steps of producing a carbon-reinforced layer of the present invention.
第6圖：習用類鑽碳膜之壓痕測試結果。 Figure 6: Indentation test results of conventional diamond-like carbon film.
第7圖：本發明之製作方法所製作之類鑽碳膜之壓痕測試結果。 Figure 7: Indentation test results of a diamond-like carbon film produced by the production method of the present invention.
S1．．．前置步驟S1. . . Pre-step
S2．．．類鑽碳附著層製作步驟S2. . . Drilling carbon adhesion layer manufacturing steps
S3．．．類鑽碳強化層製作步驟S3. . . Drilling carbon strengthening layer production steps
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| EP1451118B1 (en) * | 2001-11-28 | 2009-07-08 | Guardian Industries Corp. | Buffing diamond-like carbon (dlc) to improve scratch resistance |
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| CN1487118A (en) * | 2003-08-13 | 2004-04-07 | 复旦大学 | Plasma decomposition method and apparatus for preparing diamond-like film |
| US20100260994A1 (en) * | 2007-12-20 | 2010-10-14 | Roland Groenen | substrate coated with amorphous hydrogenated carbon |
| EP2083095A2 (en) * | 2008-01-21 | 2009-07-29 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Diamond-like carbon film for sliding parts and method for production thereof |
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