射频溅射功率对Mn-Co-Ni-O薄膜结构与性能的影响

摘要/Abstract

摘要： 采用射频磁控溅射技术在硅衬底上制备了锰钴镍氧(Mn-Co-Ni-O, MCNO)薄膜并进行了后退火处理。利用X射线衍射、扫描电子显微镜、光学测试仪器等测试手段对晶体结构、表面形貌及光学性能进行表征。分析了不同射频溅射功率(60~100 W)对MCNO薄膜表面微观形貌、晶体结构和光学性能的影响。结果表明,在60~90 W下获得的薄膜表面致密且均匀,但在100 W下获得的MCNO薄膜表面晶粒尺寸显著增大。物相分析表明,采用射频磁控溅射沉积的MCNO薄膜主要为尖晶石结构,溅射功率对薄膜结晶质量和择优取向具有显著影响,在80 W下获得的MCNO薄膜结晶质量最佳。同时,拉曼光谱测试也表明该MCNO薄膜表现出最强的Mn⁴⁺—O对称弯曲振动和最小的压应力。紫外-可见-近红外光谱分析表明,MCNO薄膜的吸光范围主要在可见光-近红外波段,在80~90 W溅射功率下获得的MCNO薄膜在近红外波段表现出更强的吸收峰。射频溅射功率的改变会影响薄膜的厚度和结晶质量,从而对薄膜的光学带隙起到调控作用。光致发光光谱测试不同溅射功率下薄膜的缺陷峰发光强度,且在功率为80 W时沉积的薄膜具有最强紫外发射峰,表明改变溅射功率能够有效改善薄膜缺陷及提高晶体质量。

关键词: 锰钴镍氧薄膜, 射频磁控溅射, 后退火, 溅射功率, 结构性能, 光学性能

Abstract: In this study, manganese-cobalt-nickel-oxide (Mn-Co-Ni-O, MCNO) thin films were prepared on silicon substrates by radio frequency (RF) magnetron sputtering and post-annealing. The crystal structure and surface morphology of the thin films were characterized by X-ray diffraction and scanning electron microscopy, and their optical properties were tested and analyzed by optical testing instruments. The effect of RF sputtering power (60~100 W) on the surface morphology, crystal structure and optical properties of MCNO thin films were analyzed. The surfaces of the films obtained under 60~90 W were dense and uniform, but the surface grain size of the MCNO thin films obtained under 100 W increases significantly. The phase analysis shows that the MCNO thin films deposited by RF magnetron sputtering are mainly spinel structures, and the sputtering power has a significant effect on the crystal quality and preferred orientation of thin films. The crystal quality of the MCNO thin films obtained under 80 W is the best. At the same time, the Raman spectroscopy test also shows that the MCNO thin film exhibits the strongest Mn⁴⁺-O symmetrical bending vibration and the smallest compressive stress. Ultraviolet-visible-near-infrared spectroscopy analysis show that the absorption range of MCNO thin films is mainly in the visible-near-infrared band, and the MCNO thin films obtained under the sputtering power of 80~90 W show stronger absorption peaks in the near-infrared band. The change of the RF sputtering power can affect the thickness and crystalline quality of the thin film, thereby regulating the optical band gap of the thin film. The luminescence of the defect peaks at different sputtering powers was measured by photoluminescence spectroscopy, and the thin films deposited at 80 W have the strongest UV emission peaks, demonstrating that varying the sputtering power can effectively improve the defects and crystal quality.

Key words: manganese cobalt nickel oxide thin film, radio frequency magnetron sputtering, post-annealing, sputtering power, structural property, optical propery

中图分类号:

刘丽华, 赵晶晶, 秦彬皓, 杨为家, 王海燕. 射频溅射功率对Mn-Co-Ni-O薄膜结构与性能的影响[J]. 人工晶体学报, 2022, 51(8): 1361-1369.

LIU Lihua, ZHAO Jingjing, QIN Binhao, YANG Weijia, WANG Haiyan. Effect of Radio Frequency Sputtering Power on the Structure and Properties of Mn-Co-Ni-O Thin Films[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(8): 1361-1369.

参考文献

[1] JAYAWEERA P V V, MATSIK S G, PERERA A G U, et al. Uncooled infrared detectors for 3-5 μm and beyond[J]. Applied Physics Letters, 2008, 93(2): 021105.
[2] AHN M, HAN Y H, MOON S. A novel infrared absorbing structure for uncooled infrared detector[J]. Current Applied Physics, 2007, 7(6): 617-621.
[3] YIN Y M, ZHOU W, JIANG L, et al. Enhanced performance of Mn-Co-Ni-O thermosensitive material by Cu and Sc co-dopants for uncooled infrared detector[J]. Journal of Alloys and Compounds, 2021, 881: 159857.
[4] CHENG O Y, ZHOU W, WU J, et al. Fabrication and characterization of back-incident optically immersed bolometer based on Mn-Co-Ni-O thin films for infrared detection[J]. Sensors and Actuators A: Physical, 2015, 233: 442-450.
[5] WU C Y, ZHOU W, YIN Y M, et al. Long wavelength infrared detection based on Mn-Co-Ni-O thin films with dielectric-metal-dielectric absorptive structures[J]. Infrared Physics & Technology, 2019, 102: 102987.
[6] CHEN W P, WANG X X, WANG J, et al. Hydrogen-induced degradation in Mn-Co-Ni-O negative-temperature-coefficient thermistors[J]. Japanese Journal of Applied Physics, 2003, 42(Part 1, No. 10): 6621-6622.
[7] HE L, LING Z Y. Electrical conduction of intrinsic grain and grain boundary in Mn-Co-Ni-O thin film thermistors: grain size influence[J]. Journal of Applied Physics, 2011, 110(9): 093708.
[8] ZHANG F, HUANG Z M. Spectroscopic ellipsometric properties of annealed Mn_1.95Co_0.77Ni_0.28O₄ thin films[J]. Optics Letters, 2017, 42(19): 3836-3839.
[9] KONG W W, WEI W, GAO B, et al. A study on the electrical properties of Mn-Co-Ni-O thin films grown by radio frequency magnetron sputtering with different thicknesses[J]. Applied Surface Science, 2017, 423: 1012-1018.
[10] HE L, LING Z Y, LING D X, et al. Role of film thickness on the microstructure and electrical properties of Mn-Co-Ni-O thin film thermistors[J]. Materials Science and Engineering: B, 2015, 198: 20-24.
[11] HE L, LING Z Y, HUANG Y T, et al. Effects of annealing temperature on microstructure and electrical properties of Mn-Co-Ni-O thin films[J]. Materials Letters, 2011, 65(11): 1632-1635.
[12] 谢伟,梁枫,邹长伟,等.射频磁控溅射制备铝酸锶长余辉发光薄膜[J].材料研究与应用,2013,7(3):188-192.
XIE W, LIANG F, ZOU C W, et al. Long-persistent luminescence of strontium aluminate thin films fabricated by radio frequency magnetron sputtering[J]. Materials Research and Application, 2013, 7(3): 188-192(in Chinese).
[13] HE L, LING Z Y. Studies of temperature dependent ac impedance of a negative temperature coefficient Mn-Co-Ni-O thin film thermistor[J]. Applied Physics Letters, 2011, 98(24): 242112.
[14] 林松盛,高迪,苏一凡,等.偏压对高功率脉冲磁控溅射DLC膜层结构及性能的影响[J].材料研究与应用,2020,14(1):1-8.
LIN S S, GAO D, SU Y F, et al. Effect of biasvoltage on structure and properties of DLC films deposited by high power pulse magnetron sputtering[J]. Materials Research and Application, 2020, 14(1): 1-8(in Chinese).
[15] 唐鹏,王启民,林松盛,等.基体偏压对高功率脉冲磁控溅射AlCrN涂层结构及其性能的影响[J].材料研究与应用,2019,13(4):257-262.
TANG P, WANG Q M, LIN S S, et al. Influence of substrate bias on the structure and properties of AlCrN coatings deposited by high power impulse magnetron sputtering[J]. Materials Research and Application, 2019, 13(4): 257-262(in Chinese).
[16] ZHANG X B, REN W, KONG W W, et al. Effect of sputtering power on structural, cationic distribution and optical properties of Mn₂Zn_0.25Ni_0.75O₄ thin films[J]. Applied Surface Science, 2018, 435: 815-821.
[17] BABU K R, SINGH R. Effect of RF power on structural, magnetic, and optical properties of CoFe₂O₄ thin films[J]. Journal of Superconductivity and Novel Magnetism, 2018, 31(12): 4029-4037.
[18] AL-BARADI A M, EL-NAHASS M M, HASSANIEN A M, et al. Influence of RF sputtering power on structural and optical properties of Nb₂O₅ thin films[J]. Optik, 2018, 168: 853-863.
[19] CHENG O Y, ZHOU W, WU J, et al. Uncooled bolometer based on Mn_1.56Co_0.96Ni_0.48O₄ thin films for infrared detection and thermal imaging[J]. Applied Physics Letters, 2014, 105(2): 022105.
[20] 姬凯迪,高灿灿,杨发顺,等.后退火气氛对磁控溅射制备β-Ga₂O₃薄膜材料的影响[J].人工晶体学报,2021,50(6):1056-1061.
JI K D, GAO C C, YANG F S, et al. Effect of post annealing atmosphere on β-Ga₂O₃ thin films prepared by magnetron sputtering[J]. Journal of Synthetic Crystals, 2021, 50(6): 1056-1061(in Chinese).
[21] LI R F, FU Q Y, ZOU X H, et al. Mn-Co-Ni-O thin films prepared by sputtering with alloy target[J]. Journal of Advanced Ceramics, 2020, 9(1): 64-71.
[22] SAKTHIVEL P, MURUGAN R, ASAITHAMBI S, et al. Radio frequency power induced changes of structural, morphological, optical and electrical properties of sputtered cadmium oxide thin films[J]. Thin Solid Films, 2018, 654: 85-92.
[23] ASGARY S, VAGHRI E, DAEMI M, et al. Magnetron sputtering technique for analyzing the influence of RF sputtering power on microstructural surface morphology of aluminum thin films deposited on SiO₂/Si substrates[J]. Applied Physics A, 2021, 127(10): 1-7.
[24] ZHANG R G, WANG B Y, WEI L. Influence of RF power on the structure of ZnS thin films grown by sulfurizing RF sputter deposited ZnO[J]. Materials Chemistry and Physics, 2008, 112(2): 557-561.
[25] SHI Q, REN W, KONG W W, et al. Oxidation mode on charge transfer mechanism in formation of Mn-Co-Ni-O spinel films by RF sputtering[J]. Journal of Materials Science: Materials in Electronics, 2017, 28(18): 13659-13664.
[26] ZHOU W, WU C Y, YIN Y M, et al. Thickness dependence of structural, morphological and optical properties of MnCoNiO thin films grown by chemical solution deposition on SiO₂/Si(1 0 0) substrate[J]. Applied Surface Science, 2019, 476: 369-373.
[27] YIN Y M, WU J, ZHOU W, et al. Post annealing effects on low temperature deposited Mn-Co-Ni-O films by radio frequency magnetron sputtering[J]. Materials Letters, 2019, 235: 172-175.
[28] PONMUDI S, SIVAKUMAR R, SANJEEVIRAJA C, et al. Influences of sputtering power and annealing temperature on the structural and optical properties of Al₂O₃∶CuO thin films fabricated by radio frequency magnetron sputtering technique[J]. Journal of Materials Science: Materials in Electronics, 2019, 30(20): 18315-18327.
[29] CHEN L, KONG W W, YAO J C, et al. Synthesis and characterization of Mn-Co-Ni-O ceramic nanoparticles by reverse microemulsion method[J]. Ceramics International, 2015, 41(2): 2847-2851.
[30] ZHANG F, HUANG Z M. Study on the optical properties of Mn-Co-Ni-O thin films deposited by magnetron sputtering[J]. Optical Materials Express, 2018, 8(9): 2815.
[31] CARDENAS FLECHAS L J, XURIGUERA MARTÍN E, PADILLA SANCHEZ J A, et al. Experimental comparison of the effect of temperature on the vibrational and morphological properties of Ni_xCo_3-xO₄ nanostructures[J]. Materials Letters, 2021, 303: 130477.
[32] LARBI T, SAID L B, DALY A B, et al. Ethanol sensing properties and photocatalytic degradation of methylene blue by Mn₃O₄, NiMn₂O₄ and alloys of Ni-manganates thin films[J]. Journal of Alloys and Compounds, 2016, 686: 168-175.
[33] MA C, REN W, WANG L, et al. Effects of cation distribution on optical properties of Mn-Co-Ni-O films[J]. Materials Letters, 2015, 153: 162-164.
[34] ZHANG F, HUANG Z M. Interface electrical properties between MCNO thin film and organic compounds[J]. Applied Physics Letters, 2018, 113(6): 061601.
[35] WANG J W, ZHANG W K, ZHANG X B, et al. Enhanced photocatalytic ability and easy retrievable photocatalysts of Bi₂WO₆ quantum dots decorated magnetic carbon nano-Onions[J]. Journal of Alloys and Compounds, 2020, 826: 154217.
[36] SARAVANAKUMAR K, SAKTHIVEL P, SANKARANARAYANAN R K. Influence of Sn⁴⁺ ion on band gap tailoring, optical, structural and dielectric behaviors of ZnO nanoparticles[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2022, 267: 120487.
[37] SAKTHIVEL P, RASU K K, SIVAKAMI A, et al. Band gap tailoring, structural and optical features of MgS nanoparticles: influence of Ag⁺ ions[J]. Optik, 2021, 236: 166544.
[38] SINGH J, VERMA V, KUMAR R, et al. Influence of Mg²⁺-substitution on the optical band gap energy of Cr_2-xMg_xO₃ nanoparticles[J]. Results in Physics, 2019, 13: 102106.
[39] SHI Q, WANG Q R, ZHANG D, et al. Structural, optical and photoluminescence properties of Ga₂O₃ thin films deposited by vacuum thermal evaporation[J]. Journal of Luminescence, 2019, 206: 53-58.
[40] SHKIR M, KHAN Z R, KHAN A, et al. A comprehensive study on structure, opto-nonlinear and photoluminescence properties of Co₃O₄ nanostructured thin films: an effect of Gd doping concentrations[J]. Ceramics International, 2022, 48(10): 14550-14559.
[41] OUAREZ L, CHELOUCHE A, TOUAM T, et al. Au-doped ZnO sol-gel thin films: an experimental investigation on physical and photoluminescence properties[J]. Journal of Luminescence, 2018, 203: 222-229.
[42] ANSHUL A, KUMAR M, RAJ A. Raman and photoluminescence spectral studies in double perovskite epitaxial Nd₂CoMnO₆ thin films deposited by pulse laser deposition[J]. Optik, 2020, 212: 164749.
[43] GOBBINER C R, DILLIP G R, JOO S W, et al. Heterogeneity of photoluminescence properties and electronic transitions in copper oxide thin films: a thickness dependent structural and optical study[J]. Ceramics International, 2018, 44(14): 16984-16991.