钛表面ALD构建氧化锌纳米薄膜及其性能研究

doi:10.13591/j.cnki.kqyx.2023.02.001

摘要/Abstract

摘要：

目的比较研究原子层沉积法(atomic layer deposition,ALD)不同沉积周期制备氧化锌(ZnO)纳米薄膜的理化特点及其抗菌效应。方法根据不同的沉积周期,将实验分为4组(光滑钛组、300循环组、600循环组、1 200循环组)。以二乙基锌、水为前驱体,在纯钛试件表面利用ALD技术制备氧化锌纳米薄膜。采用扫描电子显微镜(SEM)观察薄膜表面形貌,能谱仪(EDS)和X射线衍射仪(XRD)检测薄膜的元素组成和晶型,水接触角检测仪检测薄膜的亲水性,椭偏仪检测镀膜厚度。通过CCK-8实验、光密度法评估薄膜的细胞毒性及其对金黄色葡萄球菌的体外抗菌效果。结果 SEM结果显示ALD在纯钛表面制备的薄膜均匀致密,晶粒尺寸随着沉积周期增加而增大,EDS、XRD结果显示镀膜主要由Zn、O元素构成,成分为氧化锌晶体。水接触角结果显示薄膜为疏水。椭偏仪结果显示各实验组薄膜厚度为纳米级,与沉积周期之间呈线性关系。各实验组均未表现出细胞毒性,具有体外抗金黄色葡萄球菌效果,1 200循环组在24、48 h表现出最高抗菌率,分别为65.9%和52.3%,效果最佳。结论 ALD法在纯钛表面制备的不同沉积周期的氧化锌纳米薄膜均匀、致密,厚度随沉积周期数增加而增厚,具有良好的生物相容性和体外抗金黄色葡萄球菌效应,且1 200循环组抗菌效果最佳。

关键词: 原子层沉积, 氧化锌, 金黄色葡萄球菌, 抗菌性能, 纳米薄膜

Abstract:

Objective To compare and investigate the physicochemical characteristics and antibacterial effect of ZnO nanofilms prepared by atomic layer deposition(ALD) at different deposition cycles. Methods According to different ALD cycles, four groups were set up (control group, 300, 600 and 1 200 cycles group). Using DEZn and water as precursors, ZnO nanofilms were prepared by ALD on the surface of pure titanium specimens. Surface morphology of the films was observed by scanning electron microscope (SEM); the element composition and crystal type of the films were observed by energy dispersive spectrometer (EDS) and X-Ray Diffraction (XRD); the hydrophilicity and thickness of the films were detected by water contact angle detector and ellipsometer. The cytotoxicity of the films was evaluated by CCK-8 assay. The antibacterial effect against S. aureus in vitro of the films was evaluated by optical density method. Results The surface morphology of the films was uniform and compact as shown through SEM. The grain size increased with the increase of the number of ALD cycles. EDS results showed that the films were mainly composed of Zn and O elements. XRD results confirmed that the composition of the films was ZnO. Results of water contact angle showed that the films were hydrophobic. The thickness of the films was nanoscale and there was a linear relationship between the thickness and ALD cycles. All experimental groups showed no cytotoxicity. The 1 200 cycles group showed the highest antibacterial rate of 65.9% and 52.3% at 24 and 48 hours respectively, which was the best among all experimental groups. Conclusion The ZnO nanofilms prepared by ALD at different cycles on pure titanium surface are uniform and compact. Thickness of the films increases with the increase of ALD cycles. The films have good biocompatibility and anti-S. aureus effect in vitro. The 1 200 cycles group has the best antibacterial effect.

Key words: atomic layer deposition, ZnO, S. aureus, antibacterial effect, nanofilm

中图分类号:

R783.1

孙汪心悦, 舒菲, 张志豪, 陈虹, 敦芷悦, 吕玮瑾, 张青红, 刘梅. 钛表面ALD构建氧化锌纳米薄膜及其性能研究[J]. 口腔医学, 2023, 43(2): 97-103.

SUN Wangxinyue, SHU Fei, ZHANG Zhihao, CHEN Hong, DUN Zhiyue, LYU Weijin, ZHANG Qinghong, LIU Mei. The properties of ZnO nanofilms on titanium surface by atomic layer deposition[J]. Stomatology, 2023, 43(2): 97-103.

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参考文献 31

[1]	Takeuchi Y, Tanaka M, Tanaka J, et al. Fabrication systems for restorations and fixed dental prostheses made of titanium and titanium alloys[J]. J Prosthodont Res, 2020, 64(1):1-5. doi: S1883-1958(19)30291-9 pmid: 31711856
[2]	杨帮成, 周学东, 于海洋, 等. 钛种植体表面改性方法[J]. 华西口腔医学杂志, 2019, 37(2):124-129.
[3]	Koizumi H, Takeuchi Y, Imai H, et al. Application of titanium and titanium alloys to fixed dental prostheses[J]. J Prosthodont Res, 2019, 63(3):266-270. doi: S1883-1958(19)30204-X pmid: 31147298
[4]	Valm AM. Thestructure of dental plaque microbial communities in the transition from health to dental caries and periodontal disease[J]. J Mol Biol, 2019, 431(16):2957-2969. doi: 10.1016/j.jmb.2019.05.016
[5]	Lamont RJ, Koo H, Hajishengallis G. The oral microbiota:Dynamic communities and host interactions[J]. Nat Rev Microbiol, 2018, 16(12):745-759. doi: 10.1038/s41579-018-0089-x
[6]	Yamashita Y, Takeshita T. The oral microbiome and human health[J]. J Oral Sci, 2017, 59(2):201-206. doi: 10.2334/josnusd.16-0856 pmid: 28637979
[7]	Heitz-Mayfield LJA, Salvi GE. Peri-implant mucositis[J]. J Periodontol, 2018, 89(Suppl 1):S257-S266. doi: 10.1002/JPER.16-0488
[8]	Abushaheen MA, Muzaheed, Fatani AJ, et al. Antimicrobial resistance, mechanisms and its clinical significance[J]. Dis Mon, 2020, 66(6):100971. doi: 10.1016/j.disamonth.2020.100971
[9]	Souza JCM, Sordi MB, Kanazawa M, et al. Nano-scale modifica-tion of titanium implant surfaces to enhance osseointegration[J]. Acta Biomater, 2019, 94:112-131. doi: 10.1016/j.actbio.2019.05.045
[10]	Ahn TK, Lee DH, Kim TS, et al. Modification of titanium implant and titanium dioxide for bone tissue engineering[J]. Adv Exp Med Biol, 2018, 1077:355-368.
[11]	Chouirfa H, Bouloussa H, Migonney V, et al. Review of titanium surface modification techniques and coatings for antibacterial applications[J]. Acta Biomater, 2019, 83: 37-54. doi: S1742-7061(18)30635-4 pmid: 30541702
[12]	Jin GD, Qin H, Cao HL, et al. Synergistic effects of dual Zn/Ag ion implantation in osteogenic activity and antibacterial ability of titanium[J]. Biomaterials, 2014, 35(27):7699-7713. doi: 10.1016/j.biomaterials.2014.05.074 pmid: 24947228
[13]	Wang LY, Luo QM, Zhang XM, et al. Co-implantation of magnesium and zinc ions into titanium regulates the behaviors of human gingival fibroblasts[J]. Bioact Mater, 2020, 6(1):64-74.
[14]	Shimabukuro M. Antibacterialproperty and biocompatibility of silver, copper, and zinc in titanium dioxide layers incorporated by one-step micro-arc oxidation: A review[J]. Antibiotics (Basel), 2020, 9(10):716.
[15]	Li YC, Liao CZ, Tjong SC. Recent advances in zinc oxide nanostructures with antimicrobial activities[J]. Int J Mol Sci, 2020, 21(22):8836. doi: 10.3390/ijms21228836
[16]	Sirelkhatim A, Mahmud S, Seeni A, et al. Review on zinc oxide nanoparticles: Antibacterial activity and toxicity mechanism[J]. Nanomicro Lett, 2015, 7(3):219-242.
[17]	Król A, Pomastowski P, Rafińska K, et al. Zinc oxide nanoparticles: Synthesis, antiseptic activity and toxicity mechanism[J]. Adv Colloid Interface Sci, 2017, 249: 37-52. doi: 10.1016/j.cis.2017.07.033
[18]	Wang Z, Wang XJ, Wang YR, et al. NanoZnO-modified titanium implants for enhanced anti-bacterial activity, osteogenesis and corrosion resistance[J]. J Nanobiotechnology, 2021, 19(1):353. doi: 10.1186/s12951-021-01099-6
[19]	Hashemi Astaneh S, Faverani LP, Sukotjo C, et al. Atomic layer deposition on dental materials: Processing conditions and surface functionalization to improve physical, chemical, and clinical properties-A review[J]. Acta Biomater, 2021, 121: 103-118. doi: 10.1016/j.actbio.2020.11.024 pmid: 33227485
[20]	Liu LT, Bhatia R, Webster TJ. Atomic layer deposition of nano-TiO₂ thin films with enhanced biocompatibility and antimicrobial activity for orthopedic implants[J]. Int J Nanomedicine, 2017, 12: 8711-8723. doi: 10.2147/IJN
[21]	Coutancier D, Zhang ST, Bernardini S, et al. ALD of ZnO: Ti: Growth mechanism and application as an efficient transparent conductive oxide in silicon nanowire solar cells[J]. ACS Appl Mater Interfaces, 2020, 12(18):21036-21044. doi: 10.1021/acsami.9b22973
[22]	Aa EZ, Sadiku ER, Kupolati WK, et al. Wet ball milling of niobium by using ethanol, determination of the crystallite size and microstructures[J]. Sci Rep, 2021, 11(1):22422. doi: 10.1038/s41598-021-01916-w pmid: 34789854
[23]	Guziewicz E, Kowalik IA, Godlewski M, et al. Extremely low temperature growth of ZnO by atomic layer deposition[J]. J Appl Phys, 2008, 103(3):033515. doi: 10.1063/1.2836819
[24]	Song F, Koo H, Ren D. Effects ofmaterial properties on bacterial adhesion and biofilm formation[J]. J Dent Res, 2015, 94(8):1027-1034. doi: 10.1177/0022034515587690 pmid: 26001706
[25]	Bae J, Samek IA, Stair PC, et al. Investigation of the hydrophobic nature of metal oxide surfaces created by atomic layer deposition[J]. Langmuir, 2019, 35(17):5762-5769. doi: 10.1021/acs.langmuir.9b00577 pmid: 30970206
[26]	Eriksson C, Nygren H, Ohlson K. Implantation of hydrophilic and hydrophobic titanium discs in ratTibia: Cellular reactions on the surfaces during the first 3 weeks in bone[J]. Biomaterials, 2004, 25(19):4759-4766. doi: 10.1016/j.biomaterials.2003.12.006 pmid: 15120522
[27]	Bornstein MM, Valderrama P, Jones AA, et al. Bone apposition around two different sandblasted and acid-etched titanium implant surfaces: A histomorphometric study in canine mandibles[J]. Clin Oral Implants Res, 2008, 19(3):233-241. doi: 10.1111/clr.2008.19.issue-3
[28]	Gittens RA, Scheideler L, Rupp F, et al. A review on the wettability of dental implant surfaces II: Biological and clinical aspects[J]. Acta Biomater, 2014, 10(7):2907-2918. doi: 10.1016/j.actbio.2014.03.032 pmid: 24709541
[29]	Rupp F, Scheideler L, Eichler M, et al. Wetting behavior of dental implants[J]. Int J Oral Maxillofac Implants, 2011, 26(6):1256-1266. pmid: 22167431
[30]	Jiang SJ, Lin KL, Cai M. ZnO nanomaterials: Current advancements in antibacterial mechanisms and applications[J]. Front Chem, 2020, 8: 580. doi: 10.3389/fchem.2020.00580 pmid: 32793554
[31]	Joe A, Park SH, Shim KD, et al. Antibacterial mechanism of ZnO nanoparticles under dark conditions[J]. J Ind Eng Chem, 2017, 45: 430-439. doi: 10.1016/j.jiec.2016.10.013