CN111101102B - 一种MoON涂层及其制备方法和应用 - Google Patents
一种MoON涂层及其制备方法和应用 Download PDFInfo
- Publication number
- CN111101102B CN111101102B CN201911148557.9A CN201911148557A CN111101102B CN 111101102 B CN111101102 B CN 111101102B CN 201911148557 A CN201911148557 A CN 201911148557A CN 111101102 B CN111101102 B CN 111101102B
- Authority
- CN
- China
- Prior art keywords
- coating
- moon
- adjusting
- opening
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910015659 MoON Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 238000000151 deposition Methods 0.000 claims abstract description 35
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 239000013077 target material Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 15
- 239000010409 thin film Substances 0.000 abstract description 11
- 238000004146 energy storage Methods 0.000 abstract description 7
- 239000011253 protective coating Substances 0.000 abstract description 3
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003623 transition metal compounds Chemical class 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- -1 transition metal nitride Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3485—Sputtering using pulsed power to the target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physical Vapour Deposition (AREA)
Abstract
本发明属于薄膜电极和表面防护涂层的技术领域，公开了一种MoON涂层及其制备方法和应用。所述MoON涂层采用脉冲磁控溅射沉积法制备，该层各元素的原子百分比含量：Mo：26～41at.％，O：24～64at.％，N：9～36at.％。本发明采用脉冲磁控溅射沉积法，通过结合了氮化钼和氧化钼的优点，制备的电化学性能优异的MoON涂层，具有膜基结合力好，电容值高，循环寿命长等特点，显著提高了过渡金属化合物薄膜电极的性能，而且可沉积在柔性基体上作为电极，使其在柔性储能器件上有广泛应用前景。
Description
技术领域
本发明属于薄膜电极和表面防护涂层制备技术领域，更具体地，涉及一种MoON涂层及其制备方法和应用。
背景技术
目前应用在超级电容器电极方面的过渡金属化合物大多是氧化物和氮化物。过渡金属氧化物具有高的理论电容值，可发生氧化还原反应进行化学储能，但是导电性较差，电荷转移电阻较大，且电化学充放电过程中晶体结构易被破坏，影响循环寿命；而过渡金属氮化物导电性较好，化学稳定性高，但由于其只有双电层物理吸/脱附储能，理论电容值较低。将氧化物和氮化物结合起来制成氮氧化物，可综合氮化物和氧化物的优点，制备出电阻率较小、电容值大且循环寿命良好的超级电容器电极。
目前，产业上应用的金属化合物储能电极多为粉末材料，需要借助粘合剂涂覆在集电器基体表面。这种方法有两个缺点：一是粘合剂会阻止电极的部分活性表面与电解液接触，降低电极有效比表面积，而且还会增加电极的内阻，影响电极的电化学电极储能性能；二是使用粘结剂做的电极结合力不高，充放电过程中粉体脱落或与集电器脱离都会造成电极循环寿命的显著下降。通过水热法等化学方法将活性材料在泡沫金属集电器上生长的电极可以免除使用粘合剂，但此类电极柔性差，很难做成柔性电极及柔性储能器件。本发明中使用采用脉冲磁控溅射沉积法，原位沉积电极材料在集电基体上，可以很好解决上述问题。沉积薄膜电极不仅具有很强的膜/基结合力，改善活性电极材料与集电基体界面电学接触，且可自由选择柔性基体制备柔性电极及柔性器件。在薄膜沉积过程中，还可通过调整反应气体流量比，靶功率，沉积温度和气压等多个参数，精确控制薄膜电极成分和结构，获得电化学综合性能优异的电极薄膜，在规模化电极生产具有良好应用前途，特别适用于制备柔性超级电容器和芯片级储能器件。
发明内容
为了解决上述现有技术存在的不足和缺点，本发明的目的在于提供了一种MoON涂层，可以进一步提高电极材料的物理，化学，电学性能，更好地满足现代化快速充放电的要求。
本发明另一目的在于提供了上述MoON涂层的制备方法。
本发明再一目的在于提供了上述MoON涂层的应用。
本发明的目的通过以下技术方案来实现：
一种MoON涂层，所述MoON涂层采用脉冲磁控溅射沉积法制备，该层各元素的原子百分比含量：Mo：26～41at.％，O：24～64at.％，N：9～36at.％。
优选地，所述MoON涂层的厚度为3～4μm。
所述的MoON涂层的制备方法，包括如下具体步骤：
S1.将经预处理后的衬底基体固定在镀膜腔室内的工件转架上，使基体正对Mo靶材表面，调节转架自转速度5～10rpm，公转速度0～15rpm，打开加热器升温至100～300℃，预抽本底真空至3～5×10-3Pa；
S2.打开Ar气流量阀，调节气压至0.3～1.2Pa，开启直流脉冲偏压电源，调节基体偏压，占空比和频率，打开阳极层离子源调节电流3～10A对腔体进行离子源刻蚀清洗；
S3.降低基体偏压至0～-150V，打开Ar、N2气流量阀，调节Ar/N2流量比1：4，调节总气压至0.3～1.2Pa，打开Cr电弧靶，调节靶电流40～80A，进行沉积，得到CrN过渡层；
S4.关闭Cr电弧靶，打开Ar、N2、O2气流量阀，调节Ar、N2、O2流量，调节总气压至0.5～1.5Pa，基体偏压0～-200V，打开脉冲磁控溅射的Mo靶，调节靶功率0.8～2kW，频率20～40kHz，进行沉积，在CrN过渡层上得到MoON涂层。
优选地，步骤S1中所述衬底基体为P掺杂导电硅或柔性石墨膜基体。
优选地，步骤S2中所述刻蚀清洗的时间为5～30min。
优选地，步骤S2中所述基体偏压为0～-600V，占空比为30～70％，频率为20～40kHz。
优选地，步骤S3中所述沉积的时间为5～30min。
优选地，，步骤S4中所述Ar、N2、O2流量比为48：(8～11)：(1～4)。
优选地，步骤S4中所述沉积的时间为100～130min。
所述的MoON涂层在超级电容器或表面防护涂层领域中的应用。
与现有技术相比，本发明具有以下有益效果：
1.本发明的MoON涂层具有沉积速率高，结构致密，膜基结合力好和弯折柔性好等优点，可以应用在超级电容器电极的大规模工业化生产及柔性储能器件的制备领域。
2.本发明制备的MoON涂层结合了氮化钼和氧化钼的电学、电化学性能优点，该涂层制备的电极既具有良好的导电性，高电容，高化学稳定性和良好循环寿命，通过优化得到的MoON涂层作为薄膜电极的电容值较MoN涂层作为薄膜电极的电容值升高了57.5％，此种设计还可应用于其他过渡金属氮氧化物薄膜电极。
3.本发明采用脉冲磁控溅射沉积法，原位沉积电极材料在集电基体上，沉积膜电极不仅具有很强的膜/基结合力，改善活性电极材料与集电基体界面电学接触，且可自由选择柔性基体制备柔性电极及柔性器件。在沉积过程中，还可通过调整反应气体流量比，靶功率，沉积温度和气压等多个参数，精确控制薄膜电极成分和结构，获得电化学综合性能优异的电极薄膜。
附图说明
图1为实施例1中MoON涂层的表面SEM图；
图2为实施例1中MoON涂层的截面SEM图；
图3为实施例2中MoON涂层的表面SEM图；
图4为实施例2中MoON涂层的截面SEM图；
图5为对比例1中的MoN与实施例1和2中MoON涂层作为电极材料的XRD图谱对比；
图6为对比例1中的MoN及实施例1和2中MoON涂层作为电极的充放电性能对比；
图7为对比例1中的MoN及实施例1和2中MoON涂层作为电极的单位面积电容值对比；
图8为实施例1中MoON涂层沉积在石墨片上制备出柔性的薄膜电极的实物照片。
图9为实施例1中MoON柔性薄膜电极设计思路图。
具体实施方式
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.将经预处理后的P掺杂导电硅或柔性石墨膜基体固定在镀膜腔室内的工件转架上，使基体正对钼靶表面，靶基距26cm，调节转架自转速度10rpm，公转速度0rpm，打开加热器升温至300℃，预抽本底真空至5.0×10-3Pa；
2.打开Ar气流量阀，调节气压至0.5Pa，开启直流脉冲偏压电源，调节基体偏压至-600V，占空比30％，频率40kHz，打开阳极层离子源调节电流5A对腔体进行离子源刻蚀清洗5min；
3.降低基体偏压至-150V，打开Ar、N2气流量阀，调节Ar/N2流量比1:4，调节总气压至0.9Pa，打开Cr电弧靶，调节靶电流80A，沉积5min，得到300～400nm厚得CrN过渡层，以提高涂层的膜基结合力和韧性；
4.关闭Cr电弧靶，打开Ar、N2、O2气流量阀，调节Ar/N2/O2流量比为240:50:20，调节总气压至0.8Pa，基体偏压-100V，打开脉冲磁控溅射的Mo靶，调节靶功率1.5kW，频率20kHz，沉积120min，沉积结束后，关闭靶电源以及偏压电源，关闭Ar，N2和O2气流量阀，待腔室温度降至室温后即可开炉门取出样品，完成镀膜，得到3～4μm厚MoON涂层。
本实施例制备的MoON涂层中各元素的原子百分比含量为：Mo：26.66at.％，O：63.64at.％，N：9.70at.％。图1和2分别为MoON涂层的表面形貌和截面形貌；发现掺氧之后图层的晶粒细化，表面更加平整，这也在图5的XRD图谱中得到了进一步印证，发现掺氧之后MoN的峰强度变低，说明晶粒得到了细化。图6为对比例1中的MoN及实施例1和2中MoON涂层作为薄膜电极的充放电性能对比，其中，0，5sccm，10sccm，15sccm，20sccm分别代表制备MoON涂层时通入氧气的流量；图7为对比例1中的MoN及实施例1和2中MoON涂层作为薄膜电极的单位面积电容值对比，其中，0，5sccm，10sccm，15sccm，20sccm分别代表制备MoON涂层时通入氧气的流量。从图6和图7中不同氧含量MoON涂层作为薄膜电极与MoN涂层作为电极的电化学性能对比，可以看出，当氧含量较低时，MoON薄膜电极的电化学性能得到了显著的提升。图8为实施例1中MoON沉积在石墨片上制备出柔性的薄膜电极的实物照片。证明了MoON涂层作为柔性电极的可行性。图9为MoON柔性薄膜电极的设计思路，结合物理气相沉积和柔性基体石墨制备出具有良好力学性能和电化学性能的柔性电极。
对比例1
1.将经预处理后的P掺杂导电硅或柔性石墨膜基体固定在镀膜腔室内的工件转架上，使基体正对钼靶表面，靶基距26cm，调节转架自转速度10rpm，公转速度0rpm，打开加热器升温至300℃，预抽本底真空至5.0×10-3Pa；
2.打开Ar气流量阀，调节气压至0.5Pa，开启直流脉冲偏压电源，调节基体偏压至-600V，占空比30％，频率40kHz，打开阳极层离子源调节电流5A对腔体进行离子源刻蚀清洗5min；
3.降低基体偏压至-150V，打开Ar、N2气流量阀，调节Ar/N2流量比1:4，调节总气压至0.9Pa，打开Cr电弧靶，调节靶电流80A，沉积5min，得到300～400nm厚CrN过渡层，以提高涂层的膜基结合力和韧性；
4.关闭Cr电弧靶，打开Ar和N2气流量阀，调节Ar/N2流量比为240:60，调节总气压至0.8Pa，基体偏压-100V，打开脉冲磁控溅射的Mo靶，调节靶功率1.5kW，频率20kHz，沉积120min，沉积结束后，关闭靶电源以及偏压电源，关闭Ar和N2气流量阀，待腔室温度降至室温后即可开炉门取出样品，完成镀膜，得到3～4μm厚MoN涂层。
本实施例制备的MoN涂层中各元素的原子百分比含量为：Mo：50.37at.％，N：49.63at.％。
实施例2
1.将经预处理后的P掺杂导电硅或柔性石墨膜基体固定在镀膜腔室内的工件转架上，使基体正对钼靶表面，靶基距26cm，调节转架自转速度10rpm，公转速度0rpm，打开加热器升温至300℃，预抽本底真空至5.0×10-3Pa；
2.打开Ar气流量阀，调节气压至0.5Pa，开启直流脉冲偏压电源，调节基体偏压至-600V，占空比30％，频率40kHz，打开阳极层离子源调节电流5A对腔体进行离子源刻蚀清洗5min；
3.降低基体偏压至-150V，打开Ar、N2气流量阀，调节Ar/N2流量比1:4，调节总气压至0.9Pa，打开Cr电弧靶，调节靶电流80A，沉积5min，得到300～400nm厚CrN过渡层，以提高涂层的膜基结合力和韧性；
4.关闭Cr电弧靶，打开Ar、N2、O2气流量阀，调节Ar/N2/O2流量比为240:55:5，调节总气压至0.8Pa，基体偏压-100V，打开脉冲磁控溅射的Mo靶，调节靶功率1.5kW，频率20kHz，沉积120min，沉积结束后，关闭靶电源以及偏压电源，关闭Ar，N2和O2气流量阀，待腔室温度降至室温后即可开炉门取出样品，完成镀膜，得到3～4μm厚MoON涂层。
本实施例中制备的MoON涂层中各元素的原子百分比含量为：Mo：35.35at.％，O：40.55at.％，N：24.10at.％。图3为实施例2中MoON涂层的表面SEM图；图4为实施例2中MoON涂层的截面SEM图；从图3和4中可知，当MoON薄膜中氧含量降低时，柱状晶变得更加明显，微观结构越接近MoN的结构。
实施例3
采用实施例1的脉冲磁控溅射沉积法制得MoON涂层，该层各元素的原子百分比含量：Mo：26at.％，O：40at.％，N：34at.％。
实施例4
采用实施例1的脉冲磁控溅射沉积法制得MoON涂层，该层各元素的原子百分比含量：Mo：41at.％，O：24at.％，N：35at.％。
实施例5
采用实施例1的脉冲磁控溅射沉积法制得MoON涂层，该层各元素的原子百分比含量：Mo：41at.％，O：39at.％，N：20at.％。
实施例6
采用实施例1的脉冲磁控溅射沉积法制得MoON涂层，该层各元素的原子百分比含量：Mo：31at.％，O：60at.％，N：9at.％。
实施例7
采用实施例1的脉冲磁控溅射沉积法制得MoON涂层，该层各元素的原子百分比含量：Mo：40at.％，O：24at.％，N：36at.％。
实施例8
采用实施例1的脉冲磁控溅射沉积法制得MoON涂层，该层各元素的原子百分比含量：Mo：30at.％，O：50at.％，N：30at.％。
实施例9
采用实施例1的脉冲磁控溅射沉积法制得MoON涂层，该层各元素的原子百分比含量：Mo：35at.％，O：38at.％，N：27at.％。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (6)
1.一种MoON涂层的制备方法，其特征在于，包括如下具体步骤：
S1. 将经预处理后的衬底基体固定在镀膜腔室内的工件转架上，使基体正对Mo靶材表面，调节转架自转速度5~10 rpm，公转速度0~15 rpm，打开加热器升温至100~300℃，预抽本底真空至3~5×10-3 Pa；所述衬底基体为柔性石墨膜基体；
S2. 打开Ar气流量阀，调节气压至0.3~1.2 Pa，开启直流脉冲偏压电源，调节基体偏压，占空比和频率，打开阳极层离子源调节电流3~10A对腔体进行离子源刻蚀清洗；所述基体偏压为0~ -600 V，占空比为30~70%，频率为20~40 kHz；
S3. 降低基体偏压至0~ -150 V，打开Ar、N2气流量阀，调节Ar/N2流量比1：4，调节总气压至0.3~1.2 Pa，打开Cr电弧靶，调节靶电流40~80 A，进行沉积，得到CrN过渡层；
S4. 关闭Cr电弧靶，打开Ar、N2、O2气流量阀，调节Ar、N2、O2流量，调节总气压至0.5~1.5Pa，基体偏压 0~-200 V，打开脉冲磁控溅射的Mo靶，调节靶功率0.8~2 kW，频率20~40 kHz，进行沉积，在CrN过渡层上得到MoON涂层；所述Ar、N2、O2流量比为48 ：（8~11）：（1~4）；该层各元素的原子百分比含量：Mo：26 .66~ 35.35 at.%，O：40.55 ~ 63.64 at.%，N：9.7 ~24.1at.%，所述MoON涂层的厚度为3~ 4μm。
2.根据权利要求1所述的MoON涂层的制备方法，其特征在于，步骤S2中所述刻蚀清洗的时间为5~30 min。
3.根据权利要求1所述的MoON涂层的制备方法，其特征在于，步骤S3中所述沉积的时间为5~30min。
4.根据权利要求1所述的MoON涂层的制备方法，其特征在于，步骤S4中所述沉积的时间为100~130min。
5.一种MoON涂层，其特征在于，所述MoON涂层是由权利要求1-4任一项所述方法制备得到。
6.权利要求5所述的MoON涂层在超级电容器领域中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911148557.9A CN111101102B (zh) | 2019-11-21 | 2019-11-21 | 一种MoON涂层及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911148557.9A CN111101102B (zh) | 2019-11-21 | 2019-11-21 | 一种MoON涂层及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111101102A CN111101102A (zh) | 2020-05-05 |
| CN111101102B true CN111101102B (zh) | 2022-03-25 |
Family
ID=70420987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911148557.9A Active CN111101102B (zh) | 2019-11-21 | 2019-11-21 | 一种MoON涂层及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111101102B (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5955016A (ja) * | 1982-09-22 | 1984-03-29 | Fujitsu Ltd | 高融点金属窒化膜の形成方法 |
| CN104471101A (zh) * | 2012-03-12 | 2015-03-25 | 欧瑞康贸易股份公司(特吕巴赫) | 具有增强的滑动性质的涂层 |
| CN106048528A (zh) * | 2016-07-07 | 2016-10-26 | 哈尔滨工业大学深圳研究生院 | 一种薄膜电极制备工艺的方法及装置 |
-
2019
- 2019-11-21 CN CN201911148557.9A patent/CN111101102B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5955016A (ja) * | 1982-09-22 | 1984-03-29 | Fujitsu Ltd | 高融点金属窒化膜の形成方法 |
| CN104471101A (zh) * | 2012-03-12 | 2015-03-25 | 欧瑞康贸易股份公司(特吕巴赫) | 具有增强的滑动性质的涂层 |
| CN106048528A (zh) * | 2016-07-07 | 2016-10-26 | 哈尔滨工业大学深圳研究生院 | 一种薄膜电极制备工艺的方法及装置 |
Non-Patent Citations (5)
| Title |
|---|
| Effect of thermal treatments on the structure of MoNxOy thin films;Cunha,L,et al.;《Vacuum》;20081231;第82卷(第12期);第1-2页 * |
| Surface Characterization of Mo oxynitride films Obtained by RF Sputtering at Various N2 Ratios;Juyun Park,et al.;《Met.Mater.Int.》;20131231;第19卷(第1期);第55页 * |
| The Development of Pseudocapacitive Molybdenum Oxynitride Electrodes for Supercapacitors;Haoran Wu,et al.;《ECS Transactions》;20141231;第58卷(第10期);第67页 * |
| TiAlON硬质膜的制备工艺与性能研究;蔡佳婧;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20150415(第4期);第49页 * |
| 磁控溅射技术新进展及应用;张继成 等;《材料导报》;20040430;第18卷(第4期);第57页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111101102A (zh) | 2020-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020019693A1 (zh) | 一种用于燃料电池金属双极板的石墨微晶碳涂层及应用 | |
| WO2020042535A1 (zh) | 一种燃料电池金属双极板用导电耐蚀涂层 | |
| CN104766980B (zh) | 一种酸性介质燃料电池双极板防护涂层及其制备方法 | |
| CN105226258B (zh) | 一种锂离子电池负极复合薄膜材料及其制备方法 | |
| CN104141109B (zh) | 钛金属表面原位合成TiC‑DLC复合涂层的方法 | |
| CN207313693U (zh) | 基于类金刚石薄膜的复合厚膜 | |
| CN106129422B (zh) | 提高燃料电池金属双极板表面镀层致密和耐腐蚀的方法 | |
| CN112909281A (zh) | 不锈钢金属双极板及其制备方法和燃料电池 | |
| CN107338409B (zh) | 可调控磁场电弧离子镀制备氮基硬质涂层的工艺方法 | |
| CN109972082A (zh) | 采用闭合场-磁控溅射沉积技术制备碳基多层薄膜的方法 | |
| WO2023197469A1 (zh) | 高导电耐蚀非晶/纳米晶复合共存的涂层及其制法与应用 | |
| CN105002467B (zh) | 一种Cu‑Ti非晶合金薄膜及其制备方法 | |
| CN103266306A (zh) | 一种用pvd技术制备石墨烯或超薄碳膜的方法 | |
| CN111101102B (zh) | 一种MoON涂层及其制备方法和应用 | |
| CN106684352A (zh) | 一种锂电用二氧化钛纳米管阵列固载球状二硫化钼负极材料的制备方法 | |
| CN203700496U (zh) | 类金刚石膜涂层设备 | |
| CN110137428B (zh) | 用于全固态锂离子电池的超薄锂负极膜的制备工艺 | |
| CN101148102B (zh) | 一种碳基钨涂层及其制备方法 | |
| CN102157262B (zh) | 一种以Ta2O5薄膜为电介质膜的电容器制备方法 | |
| CN116288201A (zh) | 一种铁碳合金靶材及其薄膜制备方法 | |
| CN108831754B (zh) | 一种高比表面积的MeN涂层及其制备方法和超级电容器 | |
| CN108642446B (zh) | 一种多孔CrN涂层及其制备方法和一种超级电容器 | |
| CN109457227A (zh) | 一种直流磁控溅射法制备光电催化氧化钛电极的方法 | |
| CN115522169A (zh) | 氧化物硬质涂层的复合沉积方法及涂层刀具 | |
| CN115044869A (zh) | 一种Cr掺杂ta-C导电耐蚀碳基薄膜及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |