金屬合金材料的發展一直以來不但對於工業需求以及人類的生活品質都有著顯著的影響，至今為止人類已經發展出許多實用的合金系統，每一合金系統皆具有其獨有的優勢，而傳統合金主要的概念是利用單一主要元素，加入其他少量不同的元素且不同的比例，製備所期待特性的合金材料，但傳統合金在形成過程之中，易產生許多複雜的介金屬化合物(Intermetallic compound)，導致材料產生脆化(brittle)的現象，也使得人們難以分析，2004年葉教授提出高熵合金觀念後，發現其具有相當優異的機械性質，而由高熵合金衍生出來的高熵陶瓷材料以及非等比例多元金屬氧化物，因為多元素的混合效應，抑制介金屬化合物的形成，得到更佳的機械性質。
在本研究中，我們使用真空磁控濺鍍的方式在矽基板上沉積多個系列的多元金屬氧化物薄膜，從一元氧化鋅開始，逐步地加入其他元素製備多元金屬氧化物包含(ZnNiMgCoFeTi)O、(ZnNiMgMnFe)O、(ZnNiMgAlFe)O，我們呈現了每一系列多元氧化物的結構與機械性質，並分析每一個元素對於晶體結構以及機械性質所造成的影響，同時也利用多元素的混合效應，抑制介金屬化合物的生成，使其機械性質得以改善。我們利用SEM量測薄膜的厚度，EPMA分析薄膜的元素組成，表面粗度儀量測薄膜的表面粗糙度，以及利用XRD、TEM分析薄膜的微結構，最後使用奈米壓痕儀以及磨耗試驗儀量測薄膜的機械性質。

Series of multi-elements oxide thin film coatings were deposited on silicon substrate by using RF/DC reactive magnetron co-sputtering techniques.In this work,we deposited unary element metal oxide thin film first,then adding element step by step to make three series of multi element oxide. From the binary oxides to quinary oxides, they are all remained single-phase rock salt structures without the existence of second phase like intermetallic compounds.Our goal is to investigate the influence of each element on structure,mechanical properties,and improve the mechanical properties of the multi-elements oxide thin film by using the high entropy effect.

1. R. S. Rana, Rajesh Purohit, and S Das.,“Reviews on the Influences of Alloying elements on the Microstructure and Mechanical Properties of Aluminum Alloys and Aluminum Alloy Composites”,International Journal of Scientific and Research Publications, Vol.2, Issue 6,June, 2012
2. C.N.Panagopoulos,E.P.Georgiou,P.E.Agathocleous,K.I.Giannakopoulos,“Mechanical behaviour of Zn–Fe alloy coated mild steel”, Materials and Design ,Vol.30,pp4267–4272,2009
3. Jing Zhang, Z.X. Guo,Fusheng Pan,Zhongsheng Li, Xiaodong Luo,“Effect of composition on the microstructure and mechanical properties of Mg–Zn–Al alloys”,Materials Science and Engineering A,Vol.456,pp43–51,2007
4. Jien-wei Yei,Swe-Kai Chen,Su-Jien Lin,Jon-Yiew Gan,Tsung-Shune Chin,Tao-Tsung Shun,Chun-Huei Tsau,and Shou-Yi Chang. “Nanostructured High-Entropy Alloys with multiple principal Elements: Novel Alloy Design Concept an Outcomes”,Advanced engineering materials,Vol.6,No.5,2004
5. AF Research Laboratory “A critical review of high entropy alloys and related concept”,Acta Materialia ,Vol.122 ,pp448-511, 2017
6. Hui Zhang,Yi-Zhu He,Ye Pan,and Sheng Guo,“Thermally stable laser cladded CoCrCuFeNi high-entropy alloy coating with low stacking fault energy”, Journal of Alloys and Compounds,Vol.600 ,pp210–214,2014
7. Ya-Chu Hsu, Chia-Lin Li and Chun-Hway Hsueh.“Effects of Al Addition on Microstructures and Mechanical Properties of CoCrFeMnNiAlx High Entropy Alloy Films”, Entropy,Vol.22,No. 2,2020
8. Marco Gabriele Poletti, Gianluca Fiore, Flavia Gili, Davide Mangherini,and Livio Battezzati,“Development of a new high entropy alloy for wear resistance:FeCoCrNiW0.3 and FeCoCrNiW0.3+5at.% of C”,Materials and Design ,Vol.115 pp247–254,2017
9. Xiaofu Zhang,Natascha Winter, Catherine Witteveen , Thomas Moehl, Yuan Xiao, Fabio Krogh, Andreas Schilling,and Fabian von Rohr,“Preparation and characterization of high-entropy alloy (TaNb)1−x(ZrHfTi)x superconducting films”,physical review reaserch,Vol.2,p013375,2020
10. G.J. Zhang, Q.W. Tian, K.X. Yin, S.Q. Niu, M.H. Wu, W.W. Wang, Y.N. Wang,and J.C. Huang,“ Effect of Fe on microstructure and properties of AlCoCrFexNi (x=1.5,2.5)high entropy alloy coatings prepared by laser cladding”,Intermetallic,Vol.119, p106722,2020
11. L.M. Wang, C.C. Chen,J.W. Yeh,and S.T. Ke,“The microstructure and strengthening mechanism of thermal spray coating NixCo0.6Fe0.2CrySizAlTi0.2 high-entropy alloys”,Materials Chemistry and Physics,Vol.126, pp880–885,2011
12. Tian-Wei Lu, Chuang-Shi Feng, Zheng Wang, Kai-Wen Liao, Zhi-Yuan Liu, Yi-Zhu Xie, Ju-Guang Hu,Wei-Bing Liao,“Microstructures and mechanical properties of CoCrFeNiAl0.3 high-entropy alloy thin films by pulsed laser deposition”,Applied Surface Science,Vol.494,pp72–79, 2019
13. Weibing Liao, Si Lan, Libo Gao, Hongti Zhang , Shang Xu, Jian Song, XunliWang, Yang Lu,“Nanocrystalline high-entropy alloy (CoCrFeNiAl0.3) thin-film coating by magnetron sputtering”, Thin Solid Films ,Vol.638,pp383–388, 2017
14. W. J. Shen,M. H. Tsai, K. Y. Tsai, C. C. Juan,C.W.Tsai, J. W. Yeh, and Y. S. Chang,“Superior Oxidation Resistance of (Al0.34Cr0.22Nb0.11Si0.11Ti0.22)50N50 High-Entropy Nitride”, Journal of The Electrochemical Society,Vol.160 ,ppC531-C535,2013
15. Shou-Yi Chang,Ming-Ku Chen, and Dao-Sheng Chen, “Multiprincipal-Element AlCrTaTiZr-Nitride Nanocomposite Film of Extremely High Thermal Stability as Diffusion Barrier for Cu Metallization”, Journal of The Electrochemical Society,Vol.156,ppG37-G42,2009
16. Keng-Hao Cheng, Chia-Han Lai, Su-Jien Lin, Jien-Wei Yeh,“Structural and mechanical properties of multi-element (AlCrMoTaTiZr)Nx coatings by reactive magnetron sputtering”,Thin Solid Films,Vol.519, pp3185–3190, 2011
17. Chuhan Shaa,Zhifeng houb,Zonghan Xiec,and Paul Munroea,“FeMnNiCoCr-based high entropy alloy coatings: Effect of nitrogen additions on microstructural development, mechanical properties and tribological performance” , Applied Surface Science,Vol.507, p145101,2020
18. Christina M. Rost, Edward Sachet, Trent Borman, Ali Moballegh, Elizabeth C. Dickey, Dong Hou,Jacob L. Jones, Stefano Curtarolo & Jon-Paul Maria,“Entropy-stabilized oxides”, Nature communications, vol.6, p.8485, 2015.
19. Nan Qiu,Hong Chen,Zhaoming Yang,Sen Sun,Yuan Wang ,Yanhua Cui,“A high entropy oxide (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O) with superior lithium storage performance”, Journal of Alloys and Compounds,Vol.777,pp767-774, 2019
20. Dongdong Wang, Zhijuan Liu,Shiqian Du, Yiqiong Zhang, Hao Li, Zhaohui Xiao,Wei Chen, Ru Chen,Yanyong Wang, Yuqin Zou and Shuangyin Wang ,“Low-temperature synthesis of small-sized highentropy oxides for water oxidation”, Journal of Materials Chemistry A.,Vol.7,pp24211–24216, 2019
21. David Bérardan,Sylvain Franger,Diana Dragoe,Arun Kumar Meena, and Nita Dragoe,“Colossal dielectric constant in high entropy oxides”, Phys. Status Solidi RRL,Vol.10, No.4,pp 328–333,2016
22. Miao-I. Lin, Ming-Hung Tsai,Wan-Jui Shen,Jien-Wei Yeh,“Evolution of structure and properties of multi-component(AlCrTaTiZr)Ox films”,Thin Solid Films ,Vol.518,pp2732–2737, 2010
23. Yuan-Sheng Huang, Ling Chen,Hong-Wei Lui,Ming-Hong Cai, Jien-Wei Yeh,“Microstructure, hardness, resistivity and thermal stability of sputtered oxide films of AlCoCrCu0.5NiFe high-entropy alloy”,Materials Science and Engineering A,Vol.457,pp77–83,2007
24. Alexander Kirnbauera, Christoph Spadta, Christian M. Kollera,b, Szilard Kolozsváric,Paul H. Mayrhofer, “High-entropy oxide thin films based on Al–Cr–Nb–Ta–Ti”, Vacuum,Vol.168,pp108850,2019
25. Chun Wu,Junjie Cai,Qiaobao Zhang,Xiang Zhou,Ying Zhu,Pei Kang She,and Kaili Zhang,“Hierarchical Mesoporous Zinc−Nickel−Cobalt Ternary Oxide Nanowire Arrays on Nickel Foam as High-Performance Electrodes for Supercapacitors”, ACS Appl. Mater. Interfaces ,Vol.7,pp26512−26521,2015
26. H. Kang,Z.Lu,Z. Zhong,J. Gu,“Structural, optical and electrical characterization of Ga-Mg co-doped ZnO transparent conductive films”, Materials Letters,Vol.215pp102–105,2018
27. Nupur Bahadur,A.K. Srivastava,Sushil Kumar,M. Deepa,Bhavya Nag, “Influence of cobalt doping on the crystalline structure, optical and mechanical properties of ZnO thin films”,Thin Solid Films ,Vol.518,pp5257–5264,2010
28. R.Siddheswaran,R.V.Mangalaraja,RicardoE.Avila,D.Manikandan,C.EstherJeyanthi, S. Ananthakumar, “Evaluation of mechanical hardness and fracture toughness of Co and Al co-doped ZnO”,Material Science Engineering A,Vol.558,pp456-461,2012
29. Ta-Kun Chen, Ming-Show Wong, “Thermal stability of hard transparent AlxCoCrCuFeNi oxide thin films”,Surface&Coatings Technology,Vol.203,pp495–500,2008.
30. Yuchen Liua, Dechang Jiaa,Yu Zhoua,Yanchun Zhouc, Juanli Zhaob, Hongqiang Niand,Bin Liu,“Zn0.1Ca0.1Sr0.4Ba0.4ZrO3: A non-equimolar multicomponent perovskite ceramic with low thermal conductivity”, Journal of the European Ceramic Society,Vol.40,pp6272–6277,2020
31. J. E. Greene, “Review Article: Tracing the recorded history of thin-film sputter deposition: From the 1800s to 2017”, J. Vac. Sci. Technol. A,Vol.35, 2017
32. John A.Thornton, “Influence of apparatus geometry and deposition conditions on the structure and topography of thick sputtered coatings”, J. Vac. Sci. Technol., Vol.11,1974
33. Chapman,B.N,Glow discharge processes:sputtering and plasma etching.1980:Wiley
34. K.C.Sekar,S.Levichev,KoppoleKamakshi,S.Doyle,A.Chahboun,M.J.M.Gomes“Effect of rapid thermal annealing on texure and properties of pulsed laser depositied zinc oxide thin film”,Materials Letters,Vol.98,pp149-152,2013
35. Ahmed H. Hammad ,M. Sh. Abdel-wahab,Sajith Vattamkandathil,Akhalakur Rahman Ansari,“Structural and optical properties of ZnO thin films prepared by RF sputtering at different thicknesses”,Physica : Condensed Matter,Vol.540,pp1-8,2018
36. Debajyoti Das,and Praloy Mondal,“Photoluminescence phenomena prevailing in c-axis oriented intrinsic ZnO thin films prepared by RF magnetron sputtering”, RSC Advances, Vol.4,pp35735–35743,2014
37. J. Mohapatra,D. K. Mishra,S.K.Kamilla1,V.R.R.Medicherla1,D.M. Phase, V.Berma,andS. K. Singh,“Ni-doped ZnO: Studies on structural and magnetic properties”, Phys. Status Solid,Vol.248,pp1352–1359,2011
38. U. C. Oh and Jung Ho Je, “Effects of strain energy on the preferred orientation of TIN thin films”, J. Appl. Phys., Vol. 74,1993
39. OSHUA PELLEG,L.Z.ZEVIN and S. LUNGO,“Reactive-sputter-deposited tin films on glass substrates” , Thin Solid Films,Vol.197,pp 117-128,1991
40. Hak Ki Yu and Jong-Lam Lee,“Understanding of Preferred Orientation Formation in Rock-Salt Materials: The Case of MgO”, Cryst. Growth Des.,Vol.16,pp1978−1983,2016
41. Kyung Ho Kim, Mei Kahuku,Yoshio Abe, Midori Kawamura,Takayuki Kiba, “Improved Electrochromic Performance in Nickel Oxide Thin Film by Zn Doping”, Int. J. Electrochem. Sci.,Vol.15,pp4065 – 4071,2020
42. Yan Zhao,Linfeng Hu,Shangpeng Gao,Meiyong Liao,Liwen Sang , and Limin Wu, “One-Step Self-Assembly Fabrication of High Quality Ni x Mg 1 -x O Bowl-Shaped Array Film and Its Enhanced Photocurrent by Mg2+ Doping”, Adv. Funct. Mater.,Vol.25,pp3256–3263,2015
43. Ksenia Fominykh,Gulen Ceren Tok, Patrick Zeller, Hamidreza Hajiyani, Thomas Miller,Markus Doblinger, Rossitza Pentcheva, Thomas Bein,and Dina Fattakhova-Rohlfing,“Rock Salt Ni/Co Oxides with Unusual Nanoscale-Stabilized Composition as Water Splitting Electrocatalysts”, Adv. Funct. Mater.,Vol.27,pp1605121,2017
44. P.A. Sheena,H. Hithac,A. Sreedevic,Thomas Varghesec, “Microstructural characterization and modified spectral response of cobalt doped NiO nanoparticles”, Materials Chemistry and Physics,Vol.229 ,pp412–420,2019
45. Guang Liu, Xusheng Gao, Kaifang Wang, Dongying He, and Jinping Li,“Mesoporous nickel–iron binary oxide nanorods for efficient electrocatalytic water oxidation”, Nano Research,Vol.10,pp2096–2105, 2017
46. Ruhul Amin, Prashant Mishra, Nasima Khatun, Saniya Ayaz, Tulika Srivastava,Somaditya Sen, “Effect of Titanium on the Structural and Optical Property of NiO Nano Powders”, AIP Conference Proceedings,Vol.1953,pp030129,2018
47. Ganesh Kumar Mani, John Bosco Balaguru Rayappan,“Selective detection of ammonia using spray pyrolysis deposited pureand nickel doped ZnO thin films”, Applied Surface Science ,Vol.311,pp405–412,2014
48. R. Lontio Fomekong, H.M. Tedjieukeng Kamta, J. Ngolui Lambi,D. Lahem,P. Eloy,M. Debliquy, A. Delcorte “A sub-ppm level formaldehyde gas sensor based on Zn-doped NiO prepared by a co-precipitation route” ,Journal of Alloys and Compounds ,Vol.731, pp1188-1196
49. M. BenAmor,A.Boukhachem,K.Boubaker, M.Amlouk, “Structural, optical and electrical studies on Mg-doped NiO thin films for sensitivity applications”,Materials Sciencein Semiconductor Processing,Vol.27,pp994–1006,2014
50. Fan Yang, Xinghao Zhou, Noah T. Plymale, Ke Sun and Nathan S. Lewis ,“Evaluation of sputtered nickel oxide, cobalt oxide and nickel–cobalt oxide on n-type silicon photoanodes for solar-driven O2(g) evolution from water”, J. Mater. Chem. A,Vol.8,pp13955–13963, 2020
51. Mohd. Shkir,Mohd. Arif,V. Ganesh,Arun Singh,H. Algarni, I. S. Yahia,S. AlFaify,“An effect of Fe on physical properties of nanostructured NiO thin films for nonlinear optoelectronic applications”, Applied Physics A,Vol.126, 2020
52. Dongmei Dong, Wenwen Wang, Guobo Dong, Fan Zhang, Hang Yu, Yingchun He and Xungang Diao,“Improved performance of co-sputtered Ni–Ti oxide films for all-solid-state electrochromic devices, RSC Adv.,Vol.6, pp111148–111160,2016
53. Kiran N. Patel,M.P. Deshpande,Krishna Chauhan,Piyush Rajput,Vivek P. Gujarati,Swati Pandya,Vasant Sathe,S.H. Chaki,“Effect of Mn doping concentration on structural, vibrational and magnetic properties of NiO nanoparticles”, Advanced Powder Technology,Vol.29,pp 2394–2403,2018
54. Kiran N. Patel, M.P. Deshpande,Krishna Chauhan,Piyush Rajput,Vivek P. Gujarati ,Swati Pandya,Vasant Sathe, S.H. Chaki, “Effect of Mn doping concentration on structural, vibrational and magnetic properties of NiO nanoparticles”, Advanced Powder Technology,Vol.29,pp2394–2403,2018
55. M. H. Mamat,N. Parimon,A. S. Ismail,I. B. Shameem Banu,S. Sathik Basha,G. V. Vijayaraghavan,M. K. Yaakob,A. B. Suriani,M. K. Ahmad,M. Rusop,“Structural, optical, and electrical evolution of sol–gel‑immersion grown nickel oxide nanosheet array films on aluminium doping”, Journal of Materials Science: Materials in Electronics,Vol.30, pp9916–9930,2019
56. M.H. Mamat, M.Z. Sahdan,Z. Khusaimi,A. Zain Ahmed,S. Abdullah,M. Rusop, “ Influence of doping concentrations on the aluminum doped zinc oxide thin films properties for ultraviolet photoconductive sensor applications”, Optical Materials,Vol.32,pp696–699,2010
57. Kyung-Jun Ahn,Ji-Hyeon Parkb, Beom-Ki Shin,Woong Lee,Geun Young Yeom, Jae-Min Myoung,“Effect of sputtering power on the properties of ZnO:Ga transparent conductive oxide films deposited by pulsed DC magnetron sputtering with a rotating cylindrical target”, Applied Surface Science ,Vol.271,pp216–222, 2013