TWI395829B - Sputtered copper layer with good properties and method for manufacturing the same - Google Patents
Sputtered copper layer with good properties and method for manufacturing the same Download PDFInfo
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本發明係一種銅鍍層的濺鍍合成方法，尤其是一種濺鍍合成法以製備添加有微量釕之釕鉿氮化物(RuHfNx )以固溶於銅鍍層，藉以提升銅鍍層之附著性、導電性與漏電流性質。The invention relates to a sputtering synthesis method of a copper plating layer, in particular to a sputtering synthesis method for preparing a cerium nitride (RuHfN x ) added with a trace amount of cerium to dissolve in a copper plating layer, thereby improving the adhesion and conductivity of the copper plating layer. Sex and leakage current properties.
由於銅及其合金具有極優良的導電性、熱傳性與良好的常溫機械性質，因而被廣泛地使用，然而銅與銅合金在高溫使用時之機械性質較差，因而這些合金材料有效使用的工作溫度皆不高，以致其良好的導電性、熱傳性無法受到有效運用，使得材料在使用上受到許多限制。近年來，由於銅除了具有極佳的導電性外，尚具有較高的電荷遷移阻力，使得銅導線的元件具有更高的壽命及穩定性，進而取代鋁成為半導體元件中的導電層，因此，使得銅鍍層薄膜在應用上又增添了更有效的利用價值；但不論在製程上或是材料方面，銅導電層在使用上仍有一些限制，如較差的附著性及易與矽產生反應等。然而添加合金元素後，銅的導電性隨即下降並且硬度值提高。因此經由添加不互溶元素應是解決之道，並可由以下相關文獻可得知：如J. P. Chu,C. H. Chung,P. Y. Lee,J. M. Rigsbee,and J. Y. Wang,"Microstructure and Properties of Cu-C Pseudoalloy Films Prepared by Sputter Deposition",Metallurgical and Materials Transactions A,Vol. 29A,p. 647-658,(1998)；J. P. Chu and T. N. Lin,"Deposition,Microstructure and Properties of Sputtered Copper Films Containing Insoluble Molybdenum",Journal of Applied Physics,85,p.6462-6469(1999)；C. H. Lin,J. P. Chu,T. Mahalingam,T. N. Lin and S. F. Wang,"Thermal Stability of Sputtered Copper Films Containing Dilute Insoluble Tungsten:A Thermal Annealing Study,"Journal of Materials Research,Vol. 18,No. 6,p. 1429-1434(2003)；J. P. Chu and C. H. Lin,“Formation of A Reacted Layer at The Barrierless Cu(WN)/Si Interface,”Applied Physics Letters,Vol. 87,No. 21,p. 211902(2005)；S. L. Zhang,J. M. E. Harper and F. M. D'Heurle,"High conductivity copper-boron alloys obtained by low temperature annealing",Journal of Electronic Materials,Vol. 30,p. L1,(2001)；朱瑾、朱閔聖，濺鍍法製作含鉭之銅鍍層以提升鍍層之硬度及導電性質，本國發明專利證書第152100號及朱瑾、林宗新，具高溫穩定性、良好導電性與漏電流性質之銅鍍層及其製作法，本國發明專利證書第1237328號。在銅薄膜所添加之不互溶氮化物(如WNx )，可以有效地使晶粒細化，並且不互溶氮化物之氮於高溫下會於晶界析出，並與矽基板反應形成氮矽化合物(Si3 N4 )以有效降低銅原子之擴散速率並使電阻下降。Copper and its alloys are widely used because of their excellent electrical conductivity, heat transfer and good room temperature mechanical properties. However, copper and copper alloys have poor mechanical properties at high temperatures, so the effective use of these alloy materials The temperature is not so high that its good electrical conductivity and heat transfer property cannot be effectively used, which makes the material subject to many restrictions. In recent years, in addition to excellent electrical conductivity, copper has a high charge-migrating resistance, which makes the components of the copper wire have higher life and stability, and thus replaces aluminum as a conductive layer in a semiconductor element. The copper-plated film has added more effective use value in application; however, there are still some limitations in the use of the copper conductive layer in terms of process or material, such as poor adhesion and easy reaction with ruthenium. However, after the addition of the alloying elements, the conductivity of the copper decreases and the hardness value increases. Therefore, the addition of immiscible elements should be the solution, and can be known from the following related literature: such as JP Chu, CH Chung, PY Lee, JM Rigsbee, and JY Wang, "Microstructure and Properties of Cu-C Pseudoalloy Films Prepared by Sputter Deposition", Metallurgical and Materials Transactions A, Vol. 29A, p. 647-658, (1998); JP Chu and TN Lin, "Deposition, Microstructure and Properties of Sputtered Copper Films Containing Insoluble Molybdenum", Journal of Applied Physics, 85, p.6462-6469 (1999); CH Lin, JP Chu, T. Mahalingam, TN Lin and SF Wang, "Thermal Stability of Sputtered Copper Films Containing Dilute Insoluble Tungsten: A Thermal Annealing Study," Journal of Materials Research, Vol. 18, No. 6, p. 1429-1434 (2003); JP Chu and CH Lin, "Formation of A Reacted Layer at The Barrierless Cu (WN)/Si Interface," Applied Physics Letters, Vol. 87, No 21, p. 211902 (2005); SL Zhang, JME Harper and FM D'Heurle, "High conductivity copper-boron alloys obtained by low temperature annealing", Journal of Electronic Materials, Vol. 30, p. L 1, (2001); Zhu Xi, Zhu Xisheng, sputter plating method to make copper coating with antimony to improve the hardness and electrical conductivity of the coating, national invention patent certificate No. 152100 and Zhu Xi, Lin Zongxin, with high temperature stability, good Copper plating layer with conductivity and leakage current properties and its manufacturing method, National Invention Patent Certificate No. 1237328. The immiscible nitride (such as WN x ) added to the copper film can effectively refine the grain, and the nitrogen of the immiscible nitride precipitates at the grain boundary at a high temperature and reacts with the ruthenium substrate to form a ruthenium compound. (Si 3 N 4 ) is effective in reducing the diffusion rate of copper atoms and lowering the electrical resistance.
運用磁控濺鍍法(Sputter Deposition)製程將完全不互溶的元素或化合物合成製造是以「原子長原子」的成長方式(Atom-by-atom growth)形成「過飽和固溶體」(Supersaturated Solid Solution)，因而不會受限於傳統熱力學如固溶限及相平衡等的限制，進而可輕易合成以往認定為不可能的材料。此種方法所製造出之材料具有之特點為：具有非平衡相(Non-equilibrium)、超微粒顯微組織(Nano-scale microstructure)結構之金屬複合材料、高溫穩定性佳以及機械強度高。The use of the Sputter Deposition process to synthesize completely immiscible elements or compounds to form a "supersaturated solid solution" by "Atom-by-atom growth" (Supersaturated Solid Solution) Therefore, it is not limited by the limitations of traditional thermodynamics such as solid solution limit and phase balance, and it is easy to synthesize materials that have been previously considered impossible. The material produced by this method has the characteristics of a metal composite material having a non-equilibrium phase, a nano-scale microstructure, high temperature stability, and high mechanical strength.
既有在銅薄膜所添加之不互溶氮化物的氮能在高溫下與矽基板反應形成氮矽化合物，作為阻絕層；而本發明人則創新地研發一種能夠自發性生成之阻絕層，而毋須再經由化學氣相沉積(chemical vapor deposition)高溫製程，以大幅降低製程複雜性與製造成本的銅鍍層的濺鍍合成方法。The nitrogen energy of the immiscible nitride added to the copper film reacts with the ruthenium substrate at a high temperature to form a nitrogen ruthenium compound as a barrier layer; and the inventors have innovatively developed a barrier layer capable of spontaneous generation without the need for a barrier layer. The sputtering method of copper plating is further reduced by a chemical vapor deposition high-temperature process to greatly reduce process complexity and manufacturing cost.
本發明之目的係在於提供一種濺鍍合成法以製備添加有微量釕之釕鉿氮化物(RuHfNx )以固溶於銅鍍層，藉以提升銅鍍層之附著性、導電性與漏電流性質。It is an object of the present invention to provide a sputtering synthesis method for preparing a niobium nitride (RuHfN x ) to which a trace amount of niobium is added to dissolve in a copper plating layer, thereby improving the adhesion, conductivity and leakage current properties of the copper plating layer.
為達上述目的，本發明之銅鍍層的濺鍍合成方法，係包括：於真空濺鍍環境中導入微量氮氣與氬氣，於氮氣與氬氣混合狀態下共同濺鍍銅與釕、鉿或其合金，其中真空濺鍍環境的濺鍍功率為100-200瓦(W)，濺鍍壓力為Ix10-2 ～1x10-3 托耳(torr)；以及獲得該銅鍍層。In order to achieve the above object, the method for sputter plating of the copper plating layer of the present invention comprises: introducing a small amount of nitrogen gas and argon gas in a vacuum sputtering environment, and co-sputtering copper and tantalum or niobium or the like under a mixed state of nitrogen gas and argon gas; An alloy in which the sputtering power of the vacuum sputtering environment is 100-200 watts (W), the sputtering pressure is Ix10 -2 to 1 x 10 -3 torr, and the copper plating layer is obtained.
其中，該銅鍍層中的釕、鉿與氮含量皆低於2.0原子百分比。Wherein, the content of lanthanum, cerium and nitrogen in the copper plating layer is less than 2.0 atomic percent.
其中，上述銅與釕鉿合金係以直流磁控濺鍍製程進行共濺鍍。Among them, the above copper and bismuth alloys are co-sputtered by a DC magnetron sputtering process.
其中，該真空濺鍍環境的濺鍍溫度為常溫至I00℃。Wherein, the sputtering temperature of the vacuum sputtering environment is from normal temperature to I00 °C.
其中，該真空濺鍍環境的濺鍍功率為150瓦(W)。Among them, the sputtering power of the vacuum sputtering environment is 150 watts (W).
其中，共同濺鍍銅與釕鉿合金之後係獲得一待處理的銅鍍層，且本發明之合成方法尚包括讓該待處理的銅鍍層進行退火處理製程，其係包括在真空退火壓力為Ix10-6 ～1x10-7 torr的環境中將該待處理的銅鍍層以每分鐘4℃到6℃的加熱速率，且退火溫度範圍於200℃至750℃持溫一小時，以獲得該銅鍍層。Wherein, the copper and the bismuth alloy are co-sputtered to obtain a copper plating layer to be treated, and the synthesis method of the present invention further comprises an annealing treatment process for the copper plating layer to be treated, which is included in the vacuum annealing pressure Ix10 - The copper plating layer to be treated was heated at a heating rate of 4 ° C to 6 ° C per minute in an environment of 6 to 1 x 10 -7 torr, and the annealing temperature was maintained at 200 ° C to 750 ° C for one hour to obtain the copper plating layer.
其中，經由退火後，該銅鍍層有接近純銅鍍層之電阻係數值，其係約為2~3μΩ-cm。Wherein, after annealing, the copper plating layer has a resistivity value close to that of the pure copper plating layer, which is about 2 to 3 μΩ-cm.
其中，經由退火後，該銅鍍層具有低之漏電流性質，其係約為10-10 ~10-9 A/cm2 。Wherein, after annealing, the copper plating layer has low leakage current properties, which is about 10 -10 ~ 10 -9 A/cm 2 .
其中，該銅鍍層具有極佳之附著性質，其接著強度約為10~30Mpa。Among them, the copper plating layer has excellent adhesion properties, and its bonding strength is about 10 to 30 MPa.
其中，該銅鍍層具有極佳之TDDB結果，其係大於約10年的依時性介質崩潰電壓(TDDB)。Among them, the copper plating layer has an excellent TDDB result, which is greater than about 10 years of time-dependent dielectric breakdown voltage (TDDB).
本發明尚關於一種銅鍍層，其包括銅以及選自於由鉿的氮化物、釕的氮化物以及鉿釕的氮化物所組成之群組。The present invention is also directed to a copper plating layer comprising copper and a group selected from the group consisting of nitrides of tantalum, nitrides of tantalum, and nitrides of tantalum.
其中，釕、鉿與氮含量各低於2.0原子百分比。Among them, the lanthanum, cerium and nitrogen contents are each less than 2.0 atomic percent.
本發明的材料是選擇元素釕鉿氮化物(RuHfNx )，主要的目的在於提供銅鍍層中添加微量金屬含量與濺鍍製程，而得到具有細微顯微組織結構、低電阻與低漏電流之優越性質。因此本發明含釕鉿及其氮化物之銅鍍層具有下列之獨創性：The material of the invention is a selective element lanthanum nitride (RuHfN x ), the main purpose of which is to provide a trace metal content and a sputtering process in the copper plating layer, thereby obtaining a superior microstructure, low resistance and low leakage current. nature. Therefore, the copper plating layer containing niobium and its nitride of the present invention has the following originality:
(1)本發明係利用真空潔淨無污染之濺鍍製程，並且在導入微量氮氣與氬氣混合狀態下使銅與釕鉿靶以共同濺鍍的方式，進而控制鍍層中之鉿、釕、或其合金與氮化物的含量；(1) The present invention utilizes a vacuum clean and non-polluting sputtering process, and in the state of introducing a small amount of nitrogen and argon gas, the copper and the ruthenium target are co-sputtered, thereby controlling the ruthenium, ruthenium, or Its alloy and nitride content;
(2)含釕鉿氮化物之銅鍍層於高溫下析出形成之阻絕層(Self-passivation layer)具高溫穩定性及隔絕銅與矽反應之功能外，尚有下列諸多特性：(2) In addition to the high temperature stability and the function of isolating the reaction between copper and bismuth, the copper-plated layer containing cerium nitride precipitated at a high temperature has the following characteristics:
a.阻絕其他氣體進入作為阻絕層(Passivation layer)之用a. Blocking other gases from entering the Passivation layer
b.阻絕銅矽之間的反應作擴散阻絕(diffusion barrier)之用b. Blocking the reaction between the copper mats for diffusion barrier
(3)因本發明能夠自然形成阻絕層，其係一種自發性生成之產物，因此毋須再經由化學氣相沉積(chemical vapor deposition)高溫製程製得阻絕層；故藉由本發明的方法可將銅鍍層與阻絕層兩者合而為一，大幅降低製程複雜性與製造成本。由此可知，本發明所添加之貴金屬氮化物所產生的特點有別於先前不互溶高溫元素之添加，此亦為本發明之獨特之處。(3) Since the present invention can naturally form a barrier layer which is a spontaneously formed product, it is not necessary to obtain a barrier layer by a chemical vapor deposition high temperature process; therefore, copper can be obtained by the method of the present invention. The combination of the plating layer and the barrier layer is one, which greatly reduces the process complexity and manufacturing cost. It can be seen that the noble metal nitride added by the present invention is different from the previously added immiscible high temperature element, which is also unique to the present invention.
(4)銅與釕鉿氮化物(RuHfNx )皆為微量互溶，將這些微量互溶物質導入於銅薄膜中製得含微量互溶物質之銅鍍層且經由退火後鉿氮化物析出形成之界面層具高溫穩定性、附著性佳、較低電阻係數值與漏電流性質，是良好的導電鍍層，適用於半導體、光電與其他相關產業，進而可改善目前之銅製程技術。(4) Both copper and niobium nitride (RuHfN x ) are miscible, and these trace miscible substances are introduced into the copper thin film to prepare a copper plating layer containing a trace amount of miscible substance and formed by annealing the niobium nitride. High temperature stability, good adhesion, low resistivity value and leakage current property, it is a good conductive coating, suitable for semiconductor, optoelectronic and other related industries, and can improve the current copper process technology.
綜上所述，本發明所提出的技術及含釕鉿金屬元素及其氮化物之銅鍍層的合金組成與性質實前所未見，符合新穎首創之要件，且在產業上的利用更具有高度之價值性及應用性。In summary, the technology and the alloy composition and properties of the copper plating layer containing the bismuth metal element and the nitride thereof are unprecedented, conform to the requirements of the novel initiative, and are more highly utilized in the industry. Value and applicability.
本發明之銅鍍層的濺鍍合成方法，係包括於真空濺鍍環境中導入微量氮氣與氬氣，使氮氣與氬氣混合狀態下共同濺鍍銅與釕鉿合金以獲得一待處理的銅鍍層，其中真空濺鍍環境的濺鍍功率為150瓦(W)，濺鍍壓力為I x10-2 ～1x10-3 托耳(torr)，濺鍍溫度為常溫至I00℃；在真空退火壓力為Ix10-6 ～1x10-7 torr的環境中將該待處理的銅鍍層以每分鐘4℃到6℃的加熱速率，且退火溫度範圍於200℃至750℃持溫一小時，以獲得該銅鍍層，該銅鍍層中的釕、鉿與氮含量皆低於2.0原子百分比。The method for sputter synthesis of the copper plating layer of the invention comprises introducing a small amount of nitrogen gas and argon gas in a vacuum sputtering environment, and co-sputtering copper and bismuth alloy in a state of mixing nitrogen gas and argon gas to obtain a copper plating layer to be treated. The sputtering power in the vacuum sputtering environment is 150 watts (W), the sputtering pressure is I x10 -2 to 1 x 10 -3 torr, the sputtering temperature is normal temperature to I00 ° C; the vacuum annealing pressure is Ix10 The copper plating layer to be treated is heated at a heating rate of 4 ° C to 6 ° C per minute in an environment of -6 to 1 x 10 -7 torr, and the annealing temperature is maintained at 200 ° C to 750 ° C for one hour to obtain the copper plating layer. The content of ruthenium, osmium and nitrogen in the copper plating layer is less than 2.0 atomic percent.
實施例Example
壹、本發明含釕鉿氮化物之銅鍍層的濺鍍合成法：溅, the sputtering synthesis method of the copper plating layer containing cerium nitride of the invention:
含釕鉿金屬元素及氮化物之銅鍍層在本發明的實施例中是以直流磁控濺鍍(DC Magnetron Sputter Deposition)製程製得，先將濺鍍真空系統腔體抽至7 x 10-7 torr以下的壓力，再將高純度氬氣(Ar)與微量氮氣(N2 )導入真空系統中，以150W的能量進行濺鍍之工作，且氬氣/氮氣的工作壓力為1*10-2 torr。以純銅及釕鉿金屬元素作為濺鍍靶材之材料，將靶材以共濺鍍(co-sputtering)的方式進行鍍層之工作，銅鍍層中所需要之釕鉿及其氮含量(表一所示)，將靶材置於基材之正下方約20公分處，且面朝上。基材以矽晶片，為求鍍層均勻，濺鍍過程基材以定速作旋轉運動。其它濺鍍製程重要參數詳如表二所示。In the embodiment of the invention, the copper plating layer containing the bismuth metal element and the nitride is prepared by a DC Magnetron Sputter Deposition process, and the sputtering vacuum system cavity is first pumped to 7 x 10 -7. The pressure below torr is then introduced into the vacuum system with high purity argon (Ar) and trace nitrogen (N 2 ), and the sputtering operation is performed at 150 W energy, and the working pressure of argon/nitrogen is 1*10 -2 Torr. Pure copper and bismuth metal elements are used as the material of the sputtering target, and the target is plated by co-sputtering. The ruthenium and nitrogen content required in the copper plating are shown in Table 1. Show), placing the target approximately 20 cm directly below the substrate with the side facing up. The substrate is made of a germanium wafer, and the plating layer is uniform, and the substrate is rotated at a constant speed during the sputtering process. Other important parameters of the sputtering process are shown in Table 2.
貳、銅鍍層中氮和釕鉿金屬元素含量定性、定量與低電阻：Qualitative, quantitative and low resistance of nitrogen and niobium metal elements in tantalum and copper plating:
本發明銅鍍層中之釕鉿與氮含量分別由電子微探針分析儀(EPMA)測得，其組成如表一所示。表三所示為純Cu、Cu(RuHf)與Cu(RuHfNx )鍍層退火前後依ASTM D4541-02測試法量得之附著力量測結果比較，依此結果可知含釕鉿氮化物之銅鍍層均有極佳之附著性質，且Cu(RuHfNx )鍍層於退火前後均具良好之附著力。第一圖所示為未退火Cu(Ru(HfNx))之SIMS圖譜。依此圖可知鍍層中含Cu、Hf、Ru與N元素。第二圖所示為此未退火鍍層之XPS結果。依此圖可知Hf與Ru均與N形成鍵結。第三圖所示為退火前Cu(RuHfN)之XRD與擇區繞設圖，依此二圖皆顯示退火前有Hf4 N3 相形成，此與XPS結果一致。第四圖所示為退火前後之TEM成像。退火前Cu(HfN)之晶粒大小為16±3nm，退火後Cu(HfN)之晶粒大小達110±5nm，退火前後界面處有~2.7nm之native oxide生成，退火後並無銅矽化合物生成於界面。依退火後之擇區繞射圖可知界面有微量之Hf4 N3 ，仍須進一步確認。第五圖所示為Cu(HfN)、Cu(RuHfN)與純銅退火前後之電阻係數比較。依此圖可知Cu(HfN)、Cu(RuHfN)分別於630℃與720℃之電阻值分別為3.0與2.7μΩ-cm，且無銅矽化合物生成。第六圖所示為Cu(RuHfN)、Cu(HfN)與純銅之漏電流、依時性介質崩潰電壓(TDDB)結果比較，依此結果可知加入微量之Ru可降低鍍層之漏電流與可信賴性較佳之TDDB結果。The bismuth and nitrogen contents in the copper plating layer of the present invention were respectively measured by an electronic microprobe analyzer (EPMA), and the composition thereof is shown in Table 1. Table 3 shows the comparison of the adhesion strength measurements of the pure Cu, Cu (RuHf) and Cu (RuHfN x ) coatings before and after annealing according to the ASTM D4541-02 test method. According to the results, the copper coatings containing niobium nitrides are known. It has excellent adhesion properties, and the Cu(RuHfN x ) coating has good adhesion before and after annealing. The first figure shows the SIMS spectrum of unannealed Cu(Ru(HfNx)). According to this figure, it is known that the plating layer contains Cu, Hf, Ru and N elements. The second figure shows the XPS results for this unannealed coating. According to this figure, both Hf and Ru form a bond with N. The third figure shows the XRD and the selected area of the Cu(RuHfN) before annealing. The two figures show that the Hf 4 N 3 phase is formed before annealing, which is consistent with the XPS results. The fourth image shows TEM imaging before and after annealing. The grain size of Cu(HfN) before annealing is 16±3nm, and the grain size of Cu(HfN) after annealing is 110±5nm. There is a native oxide of ~2.7nm at the interface before and after annealing, and there is no copper bismuth compound after annealing. Generated in the interface. According to the diffraction pattern of the selected region after annealing, it is known that there is a trace amount of Hf 4 N 3 at the interface, which needs further confirmation. The fifth figure shows the comparison of the resistivity of Cu(HfN), Cu(RuHfN) and pure copper before and after annealing. According to this figure, the resistance values of Cu (HfN) and Cu (RuHfN) at 630 ° C and 720 ° C were 3.0 and 2.7 μΩ-cm, respectively, and no copper ruthenium compound was formed. The sixth figure shows the leakage current of Cu(RuHfN), Cu(HfN) and pure copper, and the time-dependent dielectric breakdown voltage (TDDB). Based on the results, it can be seen that the addition of a small amount of Ru can reduce the leakage current and reliability of the coating. Better TDDB results.
參、含鉿釕元素及其氮化物之銅鍍層的性質測試：Properties of copper coatings of ginseng, niobium containing elements and their nitrides:
本發明實施例中，主要說明含鉿釕元素及其氮化物之銅鍍層性質。導入氮原子於鍍層中，如上所述可提升銅鍍層之高溫穩定性，並獲低電阻、低漏電流及良好之接著強度。In the examples of the present invention, the copper plating properties of the cerium-containing element and its nitride are mainly described. By introducing a nitrogen atom into the plating layer, as described above, the high temperature stability of the copper plating layer can be improved, and low resistance, low leakage current, and good adhesion strength can be obtained.
由上述實施例可知，本發明之銅鍍層在經由不同退火溫度後，均有接近純銅鍍層之電阻係數值以及低的漏電流性質；且於退火前或經由不同退火溫度後，皆具有極佳之附著性質以及極佳之TDDB結果。It can be seen from the above embodiments that the copper plating layer of the present invention has a resistivity value close to the pure copper plating layer and a low leakage current property after passing through different annealing temperatures; and it is excellent before annealing or after different annealing temperatures. Adhesion properties and excellent TDDB results.
本發明係以較佳的實例之製程及合金組成來說明含釕鉿金屬元素及氮化物之銅鍍層的優異性質，然而其並非用以限定本發明，因比任何學習此項研究，可根據本發明之技術思想做些許更動與改變，來達到等效的目的。因此，本發明之保護範圍應包含本發明濺鍍技術之原則而達到具高溫穩定性且有良好導電性質之含釕鉿金屬元素及氮化物之銅鍍層。The present invention describes the excellent properties of the copper-plated layer containing the bismuth metal element and the nitride by the process of the preferred embodiment and the alloy composition, but it is not intended to limit the present invention, as compared with any study of this study, The technical idea of the invention is to make some changes and changes to achieve the equivalent purpose. Therefore, the scope of protection of the present invention should include the principles of the sputtering technique of the present invention to achieve a copper plating layer containing a ruthenium metal element and a nitride having high temperature stability and good electrical conductivity.
第一圖係顯示本發明實施例中未退火之Cu(RuHfN)薄膜組成之SIMS圖。The first figure shows a SIMS diagram of the composition of an unannealed Cu(RuHfN) film in an embodiment of the present invention.
第二圖係顯示本發明實施例中未退火之Cu(RuHfN)薄膜之XRD與擇區繞射圖。The second graph shows the XRD and selective diffraction patterns of an unannealed Cu(RuHfN) film in an embodiment of the present invention.
第三圖係顯示本發明實施例中Cu(AgNx)經400℃退火一小時之漏電流密度。The third graph shows the leakage current density of Cu (AgNx) annealed at 400 ° C for one hour in the examples of the present invention.
第四圖係顯示本發明實施例中退火前(a)、退火後(b)之Cu(RuHfN)TEM成像與擇區繞射圖(c)。The fourth figure shows Cu (RuHfN) TEM imaging and selective diffraction pattern (c) before (a) annealing and after annealing (b) in the embodiment of the present invention.
第五圖係顯示本發明實施例中Cu(HfN)、Cu(RuHfN)與純銅之電阻係數比較圖。The fifth figure shows a comparison of the resistivity of Cu(HfN), Cu(RuHfN) and pure copper in the embodiment of the present invention.
第六圖係顯示本發明實施例中Cu(HfN)、Cu(RuHfN)與純銅之(a)漏電流密度(b)固定電場強度之應力時間(c)TDDB結果比較圖。Fig. 6 is a graph showing a comparison of stress time (c) TDDB results of (a) leakage current density (b) fixed electric field strength of Cu(HfN), Cu(RuHfN) and pure copper in the embodiment of the present invention.
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| TW200927973A (en) * | 2007-10-24 | 2009-07-01 | Starck H C Inc | Refractory metal-doped sputtering targets, thin films prepared therewith and electronic device elements containing such films |
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| TW200908021A (en) * | 2007-08-03 | 2009-02-16 | Jin Zhu | Conducting material with good thermal stability |
| TW200927973A (en) * | 2007-10-24 | 2009-07-01 | Starck H C Inc | Refractory metal-doped sputtering targets, thin films prepared therewith and electronic device elements containing such films |
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