CN113584417B - Rare earth metal salt ceramic composite coating and preparation method and application thereof - Google Patents
Rare earth metal salt ceramic composite coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN113584417B CN113584417B CN202110881661.XA CN202110881661A CN113584417B CN 113584417 B CN113584417 B CN 113584417B CN 202110881661 A CN202110881661 A CN 202110881661A CN 113584417 B CN113584417 B CN 113584417B
- Authority
- CN
- China
- Prior art keywords
- sio
- composite coating
- plasma
- rare earth
- earth metal
- 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 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- -1 Rare earth metal salt Chemical class 0.000 title claims abstract description 13
- 239000000919 ceramic Substances 0.000 title claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000011812 mixed powder Substances 0.000 claims abstract description 18
- 238000001020 plasma etching Methods 0.000 claims abstract description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
- 238000007750 plasma spraying Methods 0.000 claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001307 helium Substances 0.000 claims description 10
- 229910052734 helium Inorganic materials 0.000 claims description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000011253 protective coating Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000005488 sandblasting Methods 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000007788 roughening Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007751 thermal spraying Methods 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32458—Vessel
- H01J37/32477—Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
本发明涉及一种稀土金属盐类陶瓷复合涂层及其制备方法与应用，属于等离子喷涂技术领域。将Y2O3、Al2O3和SiO2粉末，混合，制备Y2SiO5和Y3Al5O12的混合粉末，混合粉末等离子喷涂在经预处理的基材表面，制得Y2SiO5‑Y3Al5O12复合涂层。复合涂层中Y2SiO5为非晶Y2SiO5结构且质量分数为60‑75％，Y3Al5O12为立方晶体结构。非晶Y2SiO5作为一种非晶材料在结构和组成上更加均匀，立方晶体结构的Y3Al5O12耐腐蚀性能优异。Y2SiO5‑Y3Al5O12复合涂层结合了非晶Y2SiO5和Y3Al5O12的优点，具更好的耐等离子刻蚀性能和更长的使用寿命。
The invention relates to a rare earth metal salt ceramic composite coating, a preparation method and application thereof, and belongs to the technical field of plasma spraying. Y 2 O 3 , Al 2 O 3 and SiO 2 powder were mixed to prepare the mixed powder of Y 2 SiO 5 and Y 3 Al 5 O 12 , and the mixed powder was plasma sprayed on the surface of the pretreated substrate to obtain Y 2 SiO 5 ‑Y 3 Al 5 O 12 composite coating. In the composite coating, Y 2 SiO 5 has an amorphous Y 2 SiO 5 structure with a mass fraction of 60-75%, and Y 3 Al 5 O 12 has a cubic crystal structure. As an amorphous material, amorphous Y 2 SiO 5 is more uniform in structure and composition, and Y 3 Al 5 O 12 with cubic crystal structure has excellent corrosion resistance. Y 2 SiO 5 ‑Y 3 Al 5 O 12 composite coating combines the advantages of amorphous Y 2 SiO 5 and Y 3 Al 5 O 12 , and has better plasma etching resistance and longer service life.
Description
技术领域technical field
本发明属于等离子喷涂技术领域，涉及一种稀土金属盐类陶瓷复合涂层及其制备方法与应用。The invention belongs to the technical field of plasma spraying, and relates to a rare earth metal salt ceramic composite coating and a preparation method and application thereof.
背景技术Background technique
随着半导体器件尺寸的减小、液晶显示器(LCD)和硅晶圆尺寸的增加(由200mm增到300mm)，等离子体刻蚀逐渐成为微米量级的半导体器件制造工艺和微电子制造工艺中广泛应用的刻蚀技术。等离子体刻蚀指利用辉光放电方式，产生包含等离子、电子等带电粒子及具有高度化学活性的中性原子与分子及自由基的等离子，这些活性粒子扩散到需刻蚀的部位与被刻蚀的材料进行反应，形成挥发性生成物而被去除，从而完成图案转印的刻蚀技术，是实现超大规模集成电路生产中的微细图形高保真地从光刻模板转移到晶圆上的不可替代的工艺过程。With the reduction in the size of semiconductor devices and the increase in the size of liquid crystal displays (LCDs) and silicon wafers (from 200mm to 300mm), plasma etching has gradually become a widely used micron-scale semiconductor device manufacturing process and microelectronics manufacturing process. The applied etching technique. Plasma etching refers to the use of glow discharge to generate plasma containing charged particles such as plasma and electrons, as well as highly chemically active neutral atoms, molecules and free radicals. These active particles diffuse to the site to be etched and are etched. The material reacts to form volatile products that are removed, thereby completing the pattern transfer etching technology, which is an irreplaceable alternative to realize the high-fidelity transfer of fine patterns in VLSI production from lithography templates to wafers. process.
等离子体刻蚀用反应气体包括CF4/O2、NF3、Cl2、CH4/Ar等，在等离子体刻蚀过程中，会生成大量的Cl基、F基等活性自由基，它们对半导体器件进行刻蚀时，也会对铝和铝合金制备的等离子刻蚀工艺腔的内表面产生腐蚀作用，这种强烈的侵蚀产生了大量的颗粒不仅导致需要频繁的维护生产设备，严重时甚至会导致刻蚀工艺腔的失效和器件的损坏。The reactive gases used for plasma etching include CF 4 /O 2 , NF 3 , Cl 2 , CH 4 /Ar, etc. During the plasma etching process, a large number of active radicals such as Cl and F radicals will be generated, which are harmful to the plasma etching process. When the semiconductor device is etched, it will also corrode the inner surface of the plasma etching process chamber made of aluminum and aluminum alloys. This strong erosion produces a large number of particles, which not only requires frequent maintenance of production equipment, but even in severe cases. It will lead to the failure of the etching process chamber and the damage of the device.
早期等离子刻蚀防护技术是在铝基材上沉积一层致密的硬质阳极保护层，但由于硬质阳极氧化铝的抗腐蚀能力极其有限，而且硬质阳极氧化铝在沉积过程中会不可避免的出现空隙和局部破损，腐蚀介质将通过这些空隙和破损面渗透到基体表面，造成基材腐蚀。因此需要开发经济实用的抗腐蚀涂层。随着等离子喷涂技术的发展，大气等离子喷涂(APS)Al2O3涂层因其高绝缘性和对等离子体的高耐久性，已被广泛的应用于等离子体刻蚀腔体的防护涂层。随着半导体技术的发展，高纯Al2O3涂层(>99.9％)逐渐用于消除纯度对设备性能的影响，但随着晶圆尺寸的增加，等离子刻蚀工艺腔内径已经由400mm增加到500-600mm，相应的等离子体功率也随之增大，其对刻蚀工艺腔内壁的损伤也加大，使得A12O3涂层在刻蚀的过程容易产生颗粒、涂层与基底脱落等问题。在较高功率的工作条件下，Y2O3涂层，特别是高纯Y2O3涂层由于在Cl基和F基中的稳定性，以及对等离子体的更高耐久性，使其逐渐被应用到等离子体腔室，这种趋势极大的促进了等离子喷涂高纯度陶瓷涂层在等离子体刻蚀腔内侧抗等离子侵蚀上的应用，特别是8英寸以上刻蚀机的优选涂层材料。尽管如此，在高功率等离子侵袭下，现有技术制备的Y2O3涂层的耐等离子刻蚀性能有限，使用寿命较低。The early plasma etching protection technology is to deposit a dense hard anodized protective layer on the aluminum substrate, but the corrosion resistance of hard anodized aluminum is extremely limited, and the hard anodized aluminum will inevitably be in the deposition process. The occurrence of voids and local damage, the corrosive medium will penetrate into the surface of the substrate through these voids and damaged surfaces, causing the substrate to corrode. Therefore, there is a need to develop economical and practical anti-corrosion coatings. With the development of plasma spray technology, atmospheric plasma spray (APS) Al 2 O 3 coatings have been widely used as protective coatings for plasma etching chambers due to their high insulation and high durability to plasma . With the development of semiconductor technology, high-purity Al 2 O 3 coating (>99.9%) is gradually used to eliminate the influence of purity on device performance, but with the increase of wafer size, the inner diameter of the plasma etching process chamber has increased from 400mm To 500-600mm, the corresponding plasma power also increases, and the damage to the inner wall of the etching process chamber also increases, making the A1 2 O 3 coating easy to produce particles, the coating and the substrate during the etching process. And other issues. Under higher power operating conditions, Y2O3 coatings, especially high - purity Y2O3 coatings , make their Gradually applied to the plasma chamber, this trend greatly promotes the application of plasma sprayed high-purity ceramic coatings in the plasma etching resistance of the inner side of the plasma etching chamber, especially the preferred coating material for etching machines above 8 inches . Nevertheless, under high-power plasma attack, the Y 2 O 3 coatings prepared by the prior art have limited plasma etching resistance and low service life.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明的目的之一在于提供一种稀土金属盐类陶瓷复合涂层。In view of this, one of the objectives of the present invention is to provide a rare earth metal salt ceramic composite coating.
本发明的目的之二在于提供一种稀土金属盐类陶瓷复合涂层的制备方法。Another object of the present invention is to provide a method for preparing a rare earth metal salt ceramic composite coating.
本发明的目的之三在于提供一种稀土金属盐类陶瓷复合涂层作为等离子刻蚀工艺腔涂层的应用。The third object of the present invention is to provide an application of a rare earth metal salt ceramic composite coating as a plasma etching process chamber coating.
为达到上述目的，本发明提供如下技术方案：To achieve the above object, the present invention provides the following technical solutions:
1、一种稀土金属盐类陶瓷复合涂层，所述复合涂层为Y2SiO5-Y3Al5O12复合涂层，其中Y2SiO5为非晶Y2SiO5，所述复合涂层中非晶Y2SiO5的质量分数为60-75％。1. A rare earth metal salt ceramic composite coating, the composite coating is a Y 2 SiO 5 -Y 3 Al 5 O 12 composite coating, wherein Y 2 SiO 5 is amorphous Y 2 SiO 5 , and the composite coating is The mass fraction of amorphous Y2SiO5 in the coating is 60-75%.
优选的，所述复合涂层的厚度为100-400μm。Preferably, the thickness of the composite coating is 100-400 μm.
2、一种稀土金属盐类陶瓷复合涂层的制备方法，所述制备方法具体包括如下步骤：2. A preparation method of rare earth metal salt ceramic composite coating, the preparation method specifically comprises the following steps:
(1)取Y2O3、Al2O3和SiO2粉末，混匀后于1500℃下煅烧2-4小时，制得Y2SiO5和Y3Al5O12的混合粉末；(1) Take Y 2 O 3 , Al 2 O 3 and SiO 2 powder, mix well and calcinate at 1500° C. for 2-4 hours to obtain a mixed powder of Y 2 SiO 5 and Y 3 Al 5 O 12 ;
(2)将Y2SiO5和Y3Al5O12的混合粉末等离子喷涂在经预处理的基材表面，即可。(2) Plasma spraying the mixed powder of Y 2 SiO 5 and Y 3 Al 5 O 12 on the surface of the pretreated substrate.
优选的，步骤(1)中，所述Y2O3、Al2O3和SiO2粉末的质量比为60-75：10-15：15-25。Preferably, in step (1), the mass ratio of the Y 2 O 3 , Al 2 O 3 and SiO 2 powders is 60-75:10-15:15-25.
优选的，步骤(1)中，所述Y2O3、Al2O3和SiO2粉末的粒径均为300-600nm。Preferably, in step (1), the particle sizes of the Y 2 O 3 , Al 2 O 3 and SiO 2 powders are all 300-600 nm.
优选的，步骤(1)中，所述混合粉末中Y2SiO5和Y3Al5O12的粒径均为15-65μm。Preferably, in step (1), the particle sizes of Y 2 SiO 5 and Y 3 Al 5 O 12 in the mixed powder are both 15-65 μm.
优选的，步骤(2)中，所述等离子喷涂具体为：在电压为30-60V，电流为800-900A，以10-40g/min的送粉速度，距离90-150mm进行喷涂。Preferably, in step (2), the plasma spraying is specifically: spraying at a voltage of 30-60V, a current of 800-900A, a powder feeding speed of 10-40g/min, and a distance of 90-150mm.
优选的，步骤(2)中，所述等离子喷涂以氩气和氦气、或氩气和氢气为等离子气体，所述氩气的流量为60-90L/min，所述氦气或氢气的流量为10-20L/min。Preferably, in step (2), the plasma spraying uses argon gas and helium gas, or argon gas and hydrogen gas as plasma gases, the flow rate of the argon gas is 60-90L/min, and the flow rate of the helium gas or hydrogen gas is 60-90L/min. 10-20L/min.
优选的，步骤(2)中所述基材的预处理为：将基材清洗、干燥后依次对基材表面进行粗糙化处理和净化处理。Preferably, the pretreatment of the substrate in step (2) is as follows: after the substrate is cleaned and dried, roughening treatment and purification treatment are sequentially performed on the surface of the substrate.
优选的，经粗糙化处理后，基材的表面粗度Ra为4-10μm。Preferably, after roughening treatment, the surface roughness Ra of the substrate is 4-10 μm.
优选的，所述粗糙化处理具体为：对基材表面喷砂，喷砂压力为0.2-0.3Mpa，喷砂高度为300-400mm。Preferably, the roughening treatment is specifically: sandblasting the surface of the substrate, the sandblasting pressure is 0.2-0.3Mpa, and the sandblasting height is 300-400mm.
优选的，所述净化处理为：使用压缩空气对粗糙化处理后的基材喷吹。Preferably, the purification treatment is: using compressed air to spray the roughened substrate.
3、一种稀土金属盐类陶瓷复合涂层作为等离子刻蚀防护涂层的应用3. Application of a rare earth metal salt ceramic composite coating as a protective coating for plasma etching
本发明的有益效果在于：The beneficial effects of the present invention are:
以Y2O3、Al2O3和SiO2粉末为原料制备Y2SiO5和Y3Al5O12，后经等离子喷涂得到的非晶Y2SiO5-Y3Al5O12复合涂层。复合涂层中Y2SiO5为非晶结构，Y3Al5O12为立方晶体结构，其中非晶Y2SiO5作为非晶材料，与晶态材料相比，在组织结构和组成成分上更加均匀，不存在晶界、位错等容易引起局部快速腐蚀的通道，具有极高的强度、韧性和更加优异的耐磨耐腐蚀性能。Y3Al5O12为立方晶体结构、无双折射效应、高温蠕变小，具有优异的耐腐蚀性能。非晶Y2SiO5-Y3Al5O12复合涂层结合了非晶Y2SiO5优异的力学性能和耐腐蚀性能，以及Y3Al5O12高温蠕变小和优异的耐腐蚀性能，在高功率等离子侵袭下，具有比Y2O3涂层更好的耐等离子刻蚀性能和更长的使用寿命。Y 2 SiO 5 and Y 3 Al 5 O 12 were prepared by using Y 2 O 3 , Al 2 O 3 and SiO 2 powder as raw materials, and then the amorphous Y 2 SiO 5 -Y 3 Al 5 O 12 composite coating was obtained by plasma spraying Floor. In the composite coating, Y 2 SiO 5 has an amorphous structure, and Y 3 Al 5 O 12 has a cubic crystal structure. Among them, amorphous Y 2 SiO 5 is an amorphous material. Compared with the crystalline material, in terms of structure and composition It is more uniform, and there are no channels that can easily cause local rapid corrosion such as grain boundaries and dislocations. It has extremely high strength, toughness and more excellent wear resistance and corrosion resistance. Y 3 Al 5 O 12 has cubic crystal structure, no birefringence effect, small high temperature creep, and excellent corrosion resistance. The amorphous Y 2 SiO 5 -Y 3 Al 5 O 12 composite coating combines the excellent mechanical properties and corrosion resistance of amorphous Y 2 SiO 5 with the small high temperature creep and excellent corrosion resistance of Y 3 Al 5 O 12 , which has better plasma etching resistance and longer service life than Y 2 O 3 coating under high power plasma attack.
本发明的其他优点、目标和特征在某种程度上将在随后的说明书中进行阐述，并且在某种程度上，基于对下文的考察研究对本领域技术人员而言将是显而易见的，或者可以从本发明的实践中得到教导。本发明的目标和其他优点可以通过下面的说明书来实现和获得。Other advantages, objects and features of the present invention will be set forth in the description which follows, to the extent that will be apparent to those skilled in the art based on a study of the following, or may be learned from is taught in the practice of the present invention. The objectives and other advantages of the present invention may be realized and attained by the following description.
附图说明Description of drawings
为了使本发明的目的、技术方案和优点更加清楚，下面将结合附图对本发明作优选的详细描述，其中：In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be preferably described in detail below with reference to the accompanying drawings, wherein:
图1为实施例1、2、3、4中涂层的耐腐蚀性能测试结果图。FIG. 1 is a graph showing the test results of the corrosion resistance of the coatings in Examples 1, 2, 3, and 4. FIG.
图2为实施例4中Y2SiO5和Y3Al5O12粉末、复合涂层的XRD图。FIG. 2 is the XRD pattern of Y 2 SiO 5 and Y 3 Al 5 O 12 powder and composite coating in Example 4. FIG.
具体实施方式Detailed ways
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。The embodiments of the present invention are described below through specific specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.
实施例1Example 1
将铝基材进行清洗和干燥，然后在喷砂压力为0.2Mpa，喷砂高度为400mm的条件下对基材表面喷砂处理，得到表面粗度Ra为4μm的基材，再使用压缩空气对喷砂处理后的基材进行喷吹。以60：15：25的质量比取粒径均为300-600nm的Y2O3、Al2O3和SiO2粉末，混匀后于1500℃下煅烧2小时，制得Y2SiO5和Y3Al5O12的混合粉末，制备的混合粉末中Y2SiO5和Y3Al5O12的粒径均为15-65μm。以氩气和氦气为等离子气体，氩气为主气，氦气为次气，其中氩气的流量为60L/min，氦气的流量为20L/min，在电压为30V，电流为800A的条件下，以40g/min的送粉速度，距离基材表面120mm进行等离子喷，得到389μm厚的复合涂层，制得的涂层中Y2SiO5的质量分数为60％。The aluminum substrate was cleaned and dried, and then the surface of the substrate was sandblasted under the conditions of a sandblasting pressure of 0.2Mpa and a sandblasting height of 400mm to obtain a substrate with a surface roughness Ra of 4μm. The sandblasted substrate is sprayed. Y 2 O 3 , Al 2 O 3 and SiO 2 powders with particle diameters of 300-600 nm were taken in a mass ratio of 60:15:25, mixed and calcined at 1500 ° C for 2 hours to obtain Y 2 SiO 5 and The mixed powder of Y 3 Al 5 O 12, the particle size of Y 2 SiO 5 and Y 3 Al 5 O 12 in the prepared mixed powder are both 15-65 μm. Argon and helium are used as plasma gases, argon is the main gas, and helium is the secondary gas. The flow rate of argon gas is 60L/min, the flow rate of helium gas is 20L/min, and the voltage is 30V and the current is 800A. Under the condition of powder feeding speed of 40g/min, plasma spray was carried out at a distance of 120mm from the surface of the substrate to obtain a composite coating with a thickness of 389μm. The mass fraction of Y 2 SiO 5 in the prepared coating was 60%.
实施例2Example 2
将铝基材进行清洗和干燥，然后在喷砂压力为0.3Mpa，喷砂高度为400mm的条件下对基材表面喷砂处理，得到表面粗度Ra为6μm的基材，再使用压缩空气对喷砂处理后的基材进行喷吹。以65：15：20的质量比取粒径均为300-600nm的Y2O3、Al2O3和SiO2粉末，混匀后于1500℃下煅烧2小时，制得Y2SiO5和Y3Al5O12的混合粉末，制备的混合粉末中Y2SiO5和Y3Al5O12的粒径均为15-65μm。以氩气和氢气为等离子气体，氩气为主气，氢气为次气，其中氢气的流量为90L/min，氢气的流量为10L/min，在电压为40V，电流为860A的条件下，以20g/min的送粉速度，距离基材表面150mm进行等离子喷涂，得到194μm厚的复合涂层，制得的涂层中Y2SiO5的质量分数为67％。The aluminum substrate was cleaned and dried, and then the surface of the substrate was sandblasted under the conditions of a sandblasting pressure of 0.3Mpa and a sandblasting height of 400mm to obtain a substrate with a surface roughness Ra of 6μm. The sandblasted substrate is sprayed. Take Y 2 O 3 , Al 2 O 3 and SiO 2 powder with a particle size of 300-600nm in a mass ratio of 65:15:20, mix them, and calcine them at 1500 ° C for 2 hours to obtain Y 2 SiO 5 and The mixed powder of Y 3 Al 5 O 12, the particle size of Y 2 SiO 5 and Y 3 Al 5 O 12 in the prepared mixed powder are both 15-65 μm. Argon and hydrogen are used as plasma gases, argon is the main gas, and hydrogen is the secondary gas. The flow rate of hydrogen is 90L/min, and the flow rate of hydrogen is 10L/min. Under the conditions of a voltage of 40V and a current of 860A, the The powder feeding speed was 20 g/min, and plasma spraying was performed at a distance of 150 mm from the surface of the substrate to obtain a composite coating with a thickness of 194 μm. The mass fraction of Y 2 SiO 5 in the obtained coating was 67%.
实施例3Example 3
将铝基材进行清洗和干燥，然后在喷砂压力为0.3Mpa，喷砂高度为350mm的条件下对基材表面喷砂处理，得到表面粗度Ra为10μm的基材，再使用压缩空气对喷砂处理后的基材进行喷吹。以70：10：20的质量比取粒径均为300-600nm的Y2O3、Al2O3和SiO2粉末，混匀后于1500℃下煅烧3小时，制得Y2SiO5和Y3Al5O12的混合粉末，制备的混合粉末中Y2SiO5和Y3Al5O12的粒径均为15-65μm。以氩气和氢气为等离子气体，氩气为主气，氢气为次气，其中氢气的流量为60L/min，氢气的流量为20L/min，在电压为50V，电流为840A的条件下，以30g/min的送粉速度，距离基材表面140mm进行等离子喷涂，得到306μm厚的复合涂层，制得的涂层中Y2SiO5的质量分数为71％。The aluminum substrate was cleaned and dried, and then the surface of the substrate was sandblasted under the conditions of a sandblasting pressure of 0.3Mpa and a sandblasting height of 350mm to obtain a substrate with a surface roughness Ra of 10μm. The sandblasted substrate is sprayed. Take Y 2 O 3 , Al 2 O 3 and SiO 2 powders with a particle size of 300-600nm in a mass ratio of 70:10:20, mix them, and calcine them at 1500 ° C for 3 hours to obtain Y 2 SiO 5 and The mixed powder of Y 3 Al 5 O 12, the particle size of Y 2 SiO 5 and Y 3 Al 5 O 12 in the prepared mixed powder are both 15-65 μm. Argon and hydrogen are used as plasma gases, argon is the main gas, and hydrogen is the secondary gas. The flow rate of hydrogen is 60L/min, and the flow rate of hydrogen is 20L/min. Under the condition of voltage of 50V and current of 840A, The powder feeding speed was 30 g/min, and the distance from the substrate surface was 140 mm for plasma spraying to obtain a composite coating with a thickness of 306 μm. The mass fraction of Y 2 SiO 5 in the prepared coating was 71%.
实施例4Example 4
将铝基材进行清洗和干燥，然后在喷砂压力为0.3Mpa，喷砂高度为350mm的条件下对基材表面喷砂处理，得到表面粗度Ra为10μm的基材，再使用压缩空气对喷砂处理后的基材进行喷吹。以75：10：15的质量比取粒径均为300-600nm的Y2O3、Al2O3和SiO2粉末，混匀后于1500℃下煅烧4小时，制得Y2SiO5和Y3Al5O12的混合粉末，制备的混合粉末中Y2SiO5和Y3Al5O12的粒径均为15-65μm。以氩气和氦气为等离子气体，氩气为主气，氦气为次气，其中氩气的流量为90L/min，氦气的流量为10L/min，在电压为60V，电流为900A的条件下，以10g/min的送粉速度，距离基材表面90mm进行等离子喷涂，得到110μm厚的复合涂层，制得的涂层中Y2SiO5的质量分数为75％。The aluminum substrate was cleaned and dried, and then the surface of the substrate was sandblasted under the conditions of a sandblasting pressure of 0.3Mpa and a sandblasting height of 350mm to obtain a substrate with a surface roughness Ra of 10μm. The sandblasted substrate is sprayed. Take Y 2 O 3 , Al 2 O 3 and SiO 2 powders with a particle size of 300-600 nm in a mass ratio of 75:10:15, mix them, and calcine them at 1500 ° C for 4 hours to obtain Y 2 SiO 5 and The mixed powder of Y 3 Al 5 O 12, the particle size of Y 2 SiO 5 and Y 3 Al 5 O 12 in the prepared mixed powder are both 15-65 μm. Argon and helium are used as plasma gases, argon is the main gas, and helium is the secondary gas. The flow rate of argon gas is 90L/min, and the flow rate of helium gas is 10L/min. The voltage is 60V and the current is 900A. Plasma spraying was carried out at a powder feeding speed of 10 g/min and a distance of 90 mm from the surface of the substrate under the conditions of 110 μm thick composite coating. The mass fraction of Y 2 SiO 5 in the prepared coating was 75%.
将实施例1-4中的复合涂层分别在浓度为7％的HCl溶液中腐蚀，记录各复合涂层发生剥落的时间，测试结果见图1，由图1可知，实施例1-4中复合涂层发生剥落的时间依次为：184min、195min、217min、238min。取常规工艺制备的Y2O3等离子喷涂涂层在浓度为7％的HCl溶液中腐蚀，其发生剥落的时间为45min，由此可知，本发明制备的涂层较常规工艺制备的Y2O3等离子喷涂涂层的耐蚀性能更优。The composite coatings in Examples 1-4 were corroded in a 7% HCl solution, and the time when each composite coating peeled off was recorded. The test results are shown in Figure 1. It can be seen from Figure 1 that in Examples 1-4 The time for the composite coating to peel off is: 184min, 195min, 217min, 238min. The Y 2 O 3 plasma spray coating prepared by the conventional process was corroded in the HCl solution with a concentration of 7%, and the time for peeling off was 45 min. It can be seen that the coating prepared by the present invention is more than the Y 2 O prepared by the conventional process. 3 The corrosion resistance of plasma sprayed coating is better.
取实施例4条件下制备的Y2SiO5和Y3Al5O12粉末、复合涂层分别进行XRD成分分析，分析结果见图2。由图2可知，复合涂层XRD图谱有显著弥散宽化的非晶散射特征，对应混合粉末中Y2SiO5的位置，说明Y2SiO5经熔射后在复合涂层中为非晶Y2SiO5，而Y3Al5O12对应位置的特征都是晶态试样衍射，说明复合涂层中的Y3Al5O12为晶态结构，由此可见本发明制备得到非晶Y2SiO5-Y3Al5O12复合涂层。The powders of Y 2 SiO 5 and Y 3 Al 5 O 12 and the composite coating prepared under the conditions of Example 4 were respectively subjected to XRD component analysis, and the analysis results are shown in Figure 2 . It can be seen from Figure 2 that the XRD pattern of the composite coating has the characteristics of amorphous scattering with significant dispersion broadening, which corresponds to the position of Y 2 SiO 5 in the mixed powder, indicating that Y 2 SiO 5 is amorphous Y in the composite coating after thermal spraying. 2 SiO 5 , and the characteristics of the corresponding position of Y 3 Al 5 O 12 are all diffraction of the crystalline sample, indicating that the Y 3 Al 5 O 12 in the composite coating is a crystalline structure, and it can be seen that the amorphous Y prepared by the present invention is 2 SiO 5 -Y 3 Al 5 O 12 composite coating.
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be Modifications or equivalent replacements, without departing from the spirit and scope of the technical solution, should all be included in the scope of the claims of the present invention.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110881661.XA CN113584417B (en) | 2021-08-02 | 2021-08-02 | Rare earth metal salt ceramic composite coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110881661.XA CN113584417B (en) | 2021-08-02 | 2021-08-02 | Rare earth metal salt ceramic composite coating and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113584417A CN113584417A (en) | 2021-11-02 |
| CN113584417B true CN113584417B (en) | 2022-08-02 |
Family
ID=78253882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110881661.XA Active CN113584417B (en) | 2021-08-02 | 2021-08-02 | Rare earth metal salt ceramic composite coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113584417B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030134134A1 (en) * | 2002-01-11 | 2003-07-17 | Saint-Gobain Ceramics & Plastics, Inc. | Method for forming ceramic layer having garnet crystal structure phase and article made thereby |
| CN103194715A (en) * | 2012-01-05 | 2013-07-10 | 中国科学院微电子研究所 | Preparation of amorphous Y by atmospheric plasma spraying technology3Al5O12Method for coating |
| CN105648386A (en) * | 2016-02-18 | 2016-06-08 | 中国科学院上海硅酸盐研究所 | Thermal spraying aluminum oxide-yttrium oxide composite ceramic coating and preparing method thereof |
| KR102259919B1 (en) * | 2020-03-06 | 2021-06-07 | 주식회사 그린리소스 | Coating member of a chamber and method for manufacturing the same |
-
2021
- 2021-08-02 CN CN202110881661.XA patent/CN113584417B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030134134A1 (en) * | 2002-01-11 | 2003-07-17 | Saint-Gobain Ceramics & Plastics, Inc. | Method for forming ceramic layer having garnet crystal structure phase and article made thereby |
| CN103194715A (en) * | 2012-01-05 | 2013-07-10 | 中国科学院微电子研究所 | Preparation of amorphous Y by atmospheric plasma spraying technology3Al5O12Method for coating |
| CN105648386A (en) * | 2016-02-18 | 2016-06-08 | 中国科学院上海硅酸盐研究所 | Thermal spraying aluminum oxide-yttrium oxide composite ceramic coating and preparing method thereof |
| KR102259919B1 (en) * | 2020-03-06 | 2021-06-07 | 주식회사 그린리소스 | Coating member of a chamber and method for manufacturing the same |
Non-Patent Citations (1)
| Title |
|---|
| "等离子喷涂法制备炭/炭复合材料硅酸钇涂层研究";黄敏等;《新型炭材料》;20100630;第25卷(第3期);第187-191页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113584417A (en) | 2021-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107287545B (en) | Yttrium fluoride spray coating, spray material for the same, and corrosion-resistant coating including the spray coating | |
| KR101304082B1 (en) | Corrosion resistant multilayer member | |
| EP1277850B1 (en) | Sprayed film of yttria-alumina complex oxide | |
| CN105385983B (en) | A kind of hard coat preparation method of thermal diffusion using nano-carbon material as pretreatment | |
| JP2017512375A (en) | Chamber coating | |
| TW201936389A (en) | Plasma erosion resistant rare-earth oxide based thin film coatings | |
| JPH1180925A (en) | Corrosion resistant member, wafer mounting member, and manufacture of corrosion resistant member | |
| TW200829719A (en) | Thermal spray powder, method for forming thermal spray coating, and plasma resistant member | |
| TW202231899A (en) | Erosion resistant metal fluoride coated articles, methods of preparation and methods of use thereof | |
| CN106283052A (en) | A kind of two-dimensional material regulation and control silicon-carbon composite construction hydrogen resistance coating and preparation method thereof | |
| JP2003212598A (en) | Quartz glass parts, ceramic parts, and methods for producing them | |
| CN113584417B (en) | Rare earth metal salt ceramic composite coating and preparation method and application thereof | |
| US20210403337A1 (en) | Yttrium oxide based coating and bulk compositions | |
| CN111848222B (en) | A kind of gradient environment barrier coating formed on base material and preparation method thereof | |
| CN113584421A (en) | Method for enhancing bonding strength of yttrium oxide coating and substrate surface | |
| TWI779071B (en) | Material for thermal spray, thermal spray coating using the same and manufacture methods thereof | |
| KR101550439B1 (en) | Ceramic heater for semiconductor wafer and manufacturing method thereof | |
| CN113584420A (en) | Amorphous Y2SiO5Method for producing a coating | |
| JP2004002101A (en) | Plasma resistant member and method of manufacturing the same | |
| JP3808245B2 (en) | Chamber component for semiconductor manufacturing | |
| JP3929140B2 (en) | Corrosion resistant member and manufacturing method thereof | |
| CN115961252A (en) | A kind of corrosion-resistant amorphous alloy multilayer film and its preparation method | |
| CN105624602B (en) | Y applied to aluminum-based base material3Al5O12Method for producing a coating | |
| JP2023521164A (en) | Yttrium oxide-based coating composition | |
| CN116003152B (en) | Silicon carbide ceramic connectors resistant to high-temperature water vapor oxidation and their preparation methods and applications |
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 | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 401326 no.66-72, sendi Avenue, Xipeng Town, Jiulongpo District, Chongqing Patentee after: Chongqing Zhenbao Technology Co.,Ltd. Address before: 401326 no.66-72, sendi Avenue, Xipeng Town, Jiulongpo District, Chongqing Patentee before: CHONGQING ZHENBAO INDUSTRIAL Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20241211 Address after: 438000 No.1, Huahai Avenue, Huangzhou District, Huanggang City, Hubei Province Patentee after: Hubei Xinjie Electronic Technology Co.,Ltd. Country or region after: China Address before: 401326 no.66-72, sendi Avenue, Xipeng Town, Jiulongpo District, Chongqing Patentee before: Chongqing Zhenbao Technology Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |