CN103540889A - Method for preparing boron carbide coating through low-pressure plasma spraying technology - Google Patents
Method for preparing boron carbide coating through low-pressure plasma spraying technology Download PDFInfo
- Publication number
- CN103540889A CN103540889A CN201210237398.1A CN201210237398A CN103540889A CN 103540889 A CN103540889 A CN 103540889A CN 201210237398 A CN201210237398 A CN 201210237398A CN 103540889 A CN103540889 A CN 103540889A
- Authority
- CN
- China
- Prior art keywords
- boron carbide
- plasma spraying
- low
- wall
- vacuum
- 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.)
- Pending
Links
Images
Abstract
The invention relates to the technical field of anticorrosive treatment of inner surface of an etching process chamber in semiconductor equipment, in particular to a method for preparing boron carbide coating through low-pressure plasma spraying technology. The method comprises the following steps: (1) selecting boron carbide powder and conveying the boron carbide powder into vacuum plasma spraying equipment; (2) pre-treating the inner wall of an etching process chamber of an aluminum base material to be sprayed; and (3) before plasma spraying the inner wall of the etching process chamber through the vacuum plasma spraying equipment, firstly, vacuumizing the vacuum spraying chamber of the vacuum plasma spraying equipment to 1-10 Pa, and then, carrying out the plasma spraying work to prepare the boron carbide coating on the inner wall of the etching process chamber. According to the method provided by the invention, the boron carbide coating is prepared under a low pressure condition, the boron carbide coating prepared by the method provided by the invention is very dense and the porosity is low; the coating stress is small and the bonding strength with the matrix is small; and the coating is high in hardness and good in toughness.
Description
Technical field
The present invention relates to etching technics chamber inner surface corrosion protection processing technology field in semiconductor devices, be specifically related to a kind of method that low-voltage plasma spraying technology is prepared boron carbide coating.
Background technology
At present, low-temperature plasma fine machining method is the gordian technique of material micro-nano processing, it is the basis of the technologies of preparing such as microelectronics, photoelectron, micromechanics, micro-optic, particularly in super large-scale integration manufacturing process, there is nearly 1/3rd operation to complete by means of plasma process, as plasma foil deposition, plasma etching and removing of photoresist by plasma etc.One of technical process that wherein plasma etching is most critical is that the Micropicture of realizing in super large-scale integration production is with high fidelity transferred to the irreplaceable technique silicon chip from Lithographic template.
In etching process, owing to existing a large amount of living radicals with severe corrosive (as Cl
*, Cl
2 *, F
*, CF
*deng), the internal surface in their article on plasma etching technics chambeies also can produce corrosive nature, causes pollution, affects etching effect, and can make etching technics chamber lose efficacy.The plasma etching equipment of the early stage nineties in the situation that of smaller power and single plasma-generating source, adds Al on aluminum substrate layer
2o
3coating just can meet the etch damage of plasma body to etching technics chamber.Enter into 300mm equipment, along with plasma power is increasing, plasma body is also increasing to the damage of etching technics chamber wall, makes, in the process of etching, following problem easily occurs: (1) particle; (2) process cavity wall disbonding, causes plasma body directly and aluminum substrate is had an effect; (3) Al
2o
3the life-span of component is subject to more high-power restriction.So need to find a kind of new approach, etching technics inner cavity surface is carried out to modification, meet the needs of etching technics.
Research shows, Y
2o
3coating has good provide protection to etching technics chamber.With Al
2o
3compare Y
2o
3chemical property highly stable, there is excellent resistance to plasma etching performance, and and CF be the reaction product YF that gas generates
3steam forces down, and as particle, is difficult to disperse.At present, with Y
2o
3powder, as spray material, utilizes air plasma spraying method, prepares the Y of single structure at etching technics inner cavity surface
2o
3corrosion-resistant finishes is a kind of method generally adopting.
Than Y
2o
3, norbide (B
4c) have more potentiality.There is a series of good physical such as superhard, high-melting-point, density be low.Also have excellent chemical stability simultaneously, can resist acid, caustic corrosion, and do not soak and have an effect with most of molten metals.Therefore norbide is again good corrosion resistant material, for the processing of acid-and base-resisting component.Because the compatibility of boron carbide material and semiconductor technology is good, be therefore suitable as very much the corrosion-resistant finishes of semi-conductor component.
Preparation B
4the main method of C coating has: chemical vapour deposition (CVD), reaction sintering and plasma spraying etc.Air plasma spraying is to use N
2, Ar, H
2and He etc. is as ion-gas, through ionization, produces plasma high temperature and high speed jet, and input material fusing or melting are ejected into the method that working-surface forms coating.Plasma arc extreme temperatures wherein, enough melts all high-melting-point ceramic powder.In air plasma spraying technique, atmosphere surrounding can have impact significantly to the final performance of coating.The selection principle of gas is mainly to consider practicality and economy.Concrete requirement is: (1) stable performance, not with spray material generation adverse reaction; (2) heat content is high, is suitable for refractory material, but should be too high and ablation nozzle; (3) should selection and electrode or nozzle there is not the gas of chemical action; (4) with low cost, supply is convenient.
Plasma spraying, due to the feature such as have that jet temperature is high, coat-thickness is controlled, bonding strength is high and easy to operate, is preparation B
4the effective ways of C coating.But, B
4there is the problems such as high temperature oxidation and gasification in C, air plasma spraying can not be prepared well behaved B in spraying process
4c coating.In prior art, there is a kind of extraordinary resist technology, under protection of inert gas, carry out plasma spraying, although obtained B
4c coating, but in coating, still there is small part oxidation products.Therefore need to find more suitably method prepares B
4the C ceramic coating of resistance to erosion.
Summary of the invention
The object of the present invention is to provide a kind of low-voltage plasma spraying technology to prepare the method for boron carbide coating, can prepare at plasma etching industrial inner cavity surface the corrosion-resistant boron carbide coating of excellent performance.
In order to achieve the above object, the technical solution used in the present invention is:
Low-voltage plasma spraying technology is prepared a method for boron carbide coating, comprises the steps:
Step (1), selects boron carbide powder, and described boron carbide powder is sent into vacuum plasma spray coating equipment;
Step (2), carries out pre-treatment to the etching technics chamber inner wall of aluminium base to be sprayed;
Step (3), at described vacuum plasma spray coating equipment, described etching technics chamber inner wall is carried out before plasma spraying, first the vacuum spraying chamber of described vacuum plasma spray coating equipment is evacuated to 1-10Pa, and then carry out plasma spraying operation, at described etching technics chamber inner wall, prepare boron carbide coating.
In such scheme, the granularity of the boron carbide powder in described step (1) is 5～100 μ m, and has single B
4c-structure.
In such scheme, the etching technics chamber inner wall to aluminium base to be sprayed in described step (2) carries out pre-treatment, specifically comprises the steps: the etching technics chamber inner wall of aluminium base to be sprayed to carry out sandblasting, and cleans with acetone.
In such scheme, the sand-blast material that described sandblasting adopts is white fused alumina, and sand size is 50～100 μ m.
In such scheme, in described step (3) after the vacuum spraying chamber of described vacuum plasma spray coating equipment is evacuated to 1-10Pa, before described plasma spraying operation, also comprise the steps: the etching technics chamber inner wall of aluminium base to be sprayed to adopt plasma transferred arc striking, the etching technics chamber inner wall that is about to described aluminium base connects negative pole, make electronics from the etching technics chamber inner wall surface escaping of described aluminium base, remove surperficial dirt, form surface clean, activation.
In such scheme, the ionized gas that vacuum plasma spray coating equipment described in described step (3) is used is Ar and He, or Ar and H
2.
In such scheme, when described ionized gas is Ar and He, the flow of Ar gas is 40～90L/min, and the flow of He gas is 2～10L/min; When described ionized gas is Ar and H
2time, the flow of Ar gas is 40～90L/min, H
2the flow of gas is 5～20L/min.
In such scheme, described in described step (3), the arc voltage of vacuum plasma spray coating equipment is 40～50V, and flame current is 600～900A, and powder feed rate is 15～100g/min, and spray distance is 200～500mm, and powder feeding angle is 50 °～90 °.
Compare with prior art scheme, the beneficial effect that the technical solution used in the present invention produces is as follows:
The present invention prepares boron carbide coating under low pressure condition, and the boron carbide coating that uses the present invention to prepare is very fine and close, and porosity is low; Coating stress is little, high with the bonding strength of matrix; Coating hardness is high, good toughness.
Accompanying drawing explanation
The low-voltage plasma spraying technology that Fig. 1 provides for the embodiment of the present invention is prepared the schema of the method for boron carbide coating.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is described in detail.
The present invention adopts low-voltage plasma spraying technology to prepare norbide corrosion-resistant finishes at etching technics chamber inner wall.Low-voltage plasma spraying (low pressure plasma spraying) is called again vacuum plasma spray coating (vacuum plasma spraying), it is that plasma gun, workpiece and mechanical manipulator are placed in the sealed chamber of rough vacuum or certain selected controlled atmosphere, by vacuum and filtering system, control the vacuum tightness of chamber, at chamber, control the Technology of Plasma Spraying Process Using outward.
As shown in Figure 1, the embodiment of the present invention provides a kind of low-voltage plasma spraying technology to prepare the method for boron carbide coating, specifically comprises the steps:
(1) select boron carbide powder, size range is 5～100 μ m, and powder should have single B
4c-structure; And the boron carbide powder choosing is sent into vacuum plasma spray coating equipment;
(2) the etching technics cavity wall of aluminium base needs being sprayed carries out sandblasting, and sand-blast material is white fused alumina, and size range is 50～100 μ m, and cleans with acetone;
(3) adopt Sluzer Metco ChamPro LPPS-TF vacuum plasma spray coating equipment to carry out plasma spraying, spray gun type 03CP; Before vacuum plasma spray coating equipment carries out plasma spraying, first the vacuum spraying chamber of vacuum plasma spray coating equipment is evacuated to 1-10Pa, then the etching technics chamber inner wall of aluminium base to be sprayed is adopted to plasma transferred arc striking, the etching technics chamber inner wall that is about to aluminium base connects negative pole, make electronics from the etching technics chamber inner wall surface escaping of aluminium base, remove surperficial dirt, form surface clean, activation; Under Ar and He atmosphere surrounding, spray, the flow of Ar gas is 40～90L/min, the flow of He gas is 2～10L/min, the arc voltage of vacuum plasma spray coating equipment is 40～50V, flame current is 600～900A, powder feed rate is 15～100g/min, and spray distance is 200～500mm, and powder feeding angle is 50 °～90 °; At Ar and H
2under atmosphere surrounding, spray, the flow of Ar gas is 40～90L/min, H
2the flow of gas is 5～20L/min, and under this atmosphere surrounding, the processing parameter of vacuum plasma spray coating equipment is with identical under Ar and He atmosphere surrounding; Finally on etching technics chamber inner wall, complete the preparation of norbide corrosion-resistant finishes.
The Vacuum Plasma Spray Technology that the present invention uses there is following characteristics:
(1) low-voltage plasma jet is long, high-temperature zone field width.Under rough vacuum, plasma arc Shu Changdu is elongated to 20-50cm from the 4-5cm normal pressure, and this has increased dusty spray particle in the intrafascicular flight time of arc, the thawing of can being heated fully.
(2) flight velocity of dusty spray particle is fast.Because the pressure of vacuum chamber is low, the speed of plasma air-flow can be brought up to 3-4 Mach.And the low meeting of pressure reduces the resistance of particle flight greatly, makes particle have very high kinetic energy.
(3) substrate preheating temperature is high.Under the protection of low pressure and controlled atmosphere, workpiece substrate to be sprayed can allow to be heated to higher temperature (generally can reach 700 ℃, some superalloy can reach 900 ℃).This can make matrix surface to be sprayed in better active state, and the temperature difference of coating and matrix is decreased, and reduces the speed of cooling of coating.Thereby reduce the bonding strength of thermal stresses, raising coating and matrix.Fully distortion while simultaneously making molten particles arrive matrix surface, wetting and spreading, eliminating gas, thus porosity reduced.
(4) can carry out surface cleaning processing.Before carrying out plasma spraying, adopt plasma transferred arc striking, be about to workpiece substrate and connect negative pole, electronics is overflowed from matrix surface, remove surperficial dirt, form surface clean, activation, make workpiece process and just can be combined well with coating without surface coarsening.
The boron carbide coating that the present invention uses vacuum plasma spray coating method to prepare is very fine and close, and porosity is low; Coating stress is little, high with the bonding strength of matrix; Coating hardness is high, good toughness.Therefore the boron carbide coating that adopts vacuum plasma spray coating method to prepare has very excellent over-all properties.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. low-voltage plasma spraying technology is prepared a method for boron carbide coating, it is characterized in that, comprises the steps:
Step (1), selects boron carbide powder, and described boron carbide powder is sent into vacuum plasma spray coating equipment;
Step (2), carries out pre-treatment to the etching technics chamber inner wall of aluminium base to be sprayed;
Step (3), at described vacuum plasma spray coating equipment, described etching technics chamber inner wall is carried out before plasma spraying, first the vacuum spraying chamber of described vacuum plasma spray coating equipment is evacuated to 1-10Pa, and then carry out plasma spraying operation, at described etching technics chamber inner wall, prepare boron carbide coating.
2. low-voltage plasma spraying technology as claimed in claim 1 is prepared the method for boron carbide coating, it is characterized in that, the granularity of the boron carbide powder in described step (1) is 5～100 μ m, and has single B
4c-structure.
3. low-voltage plasma spraying technology as claimed in claim 1 is prepared the method for boron carbide coating, it is characterized in that, etching technics chamber inner wall to aluminium base to be sprayed in described step (2) carries out pre-treatment, specifically comprise the steps: the etching technics chamber inner wall of aluminium base to be sprayed to carry out sandblasting, and clean with acetone.
4. low-voltage plasma spraying technology as claimed in claim 3 is prepared the method for boron carbide coating, it is characterized in that, the sand-blast material that described sandblasting adopts is white fused alumina, and sand size is 50～100 μ m.
5. low-voltage plasma spraying technology as claimed in claim 1 is prepared the method for boron carbide coating, it is characterized in that, in described step (3) after the vacuum spraying chamber of described vacuum plasma spray coating equipment is evacuated to 1-10Pa, before described plasma spraying operation, also comprise the steps: the etching technics chamber inner wall of aluminium base to be sprayed to adopt plasma transferred arc striking, the etching technics chamber inner wall that is about to described aluminium base connects negative pole, make electronics from the etching technics chamber inner wall surface escaping of described aluminium base, remove surperficial dirt, form clean, the surface of activation.
6. low-voltage plasma spraying technology as claimed in claim 1 is prepared the method for boron carbide coating, it is characterized in that, the ionized gas that vacuum plasma spray coating equipment described in described step (3) is used is Ar and He, or Ar and H
2.
7. low-voltage plasma spraying technology as claimed in claim 6 is prepared the method for boron carbide coating, it is characterized in that, when described ionized gas is Ar and He, the flow of Ar gas is 40～90L/min, and the flow of He gas is 2～10L/min; When described ionized gas is Ar and H
2time, the flow of Ar gas is 40～90L/min, H
2the flow of gas is 5～20L/min.
8. low-voltage plasma spraying technology as claimed in claim 1 is prepared the method for boron carbide coating, it is characterized in that, described in described step (3), the arc voltage of vacuum plasma spray coating equipment is 40～50V, flame current is 600～900A, powder feed rate is 15～100g/min, spray distance is 200～500mm, and powder feeding angle is 50 °～90 °.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210237398.1A CN103540889A (en) | 2012-07-09 | 2012-07-09 | Method for preparing boron carbide coating through low-pressure plasma spraying technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210237398.1A CN103540889A (en) | 2012-07-09 | 2012-07-09 | Method for preparing boron carbide coating through low-pressure plasma spraying technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103540889A true CN103540889A (en) | 2014-01-29 |
Family
ID=49964730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210237398.1A Pending CN103540889A (en) | 2012-07-09 | 2012-07-09 | Method for preparing boron carbide coating through low-pressure plasma spraying technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103540889A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107858629A (en) * | 2017-05-02 | 2018-03-30 | 武汉华工激光工程有限责任公司 | One kind utilizes ceramic material sealing thermal Sperayed Ceramic Coatings hole technique |
| CN109839208A (en) * | 2017-11-27 | 2019-06-04 | 深圳航发复合材料有限公司 | A kind of method of low-voltage plasma spraying matrix characterization temperature |
| CN110029306A (en) * | 2019-04-23 | 2019-07-19 | 度亘激光技术（苏州）有限公司 | A kind of cleaning method of vacuum coating equipment cavity aluminium alloy element |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6054187A (en) * | 1997-12-15 | 2000-04-25 | Ngk Insulators, Ltd. | Method of manufacturing a boron carbide film on a substrate |
| CN1651603A (en) * | 2005-02-06 | 2005-08-10 | 中国科学院上海硅酸盐研究所 | Method of improving vacuum plasma spray coating boron carbide coating layer strength |
| JP2006157461A (en) * | 2004-11-29 | 2006-06-15 | Yamaha Corp | Diaphragm and its manufacturing method |
| CN101248144A (en) * | 2005-04-21 | 2008-08-20 | 标准航空有限公司 | Wear resistant ceramic composite coatings and process for production thereof |
| CN102272344A (en) * | 2008-11-04 | 2011-12-07 | 普莱克斯技术有限公司 | Thermal spray coatings for semiconductor applications |
-
2012
- 2012-07-09 CN CN201210237398.1A patent/CN103540889A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6054187A (en) * | 1997-12-15 | 2000-04-25 | Ngk Insulators, Ltd. | Method of manufacturing a boron carbide film on a substrate |
| JP2006157461A (en) * | 2004-11-29 | 2006-06-15 | Yamaha Corp | Diaphragm and its manufacturing method |
| CN1651603A (en) * | 2005-02-06 | 2005-08-10 | 中国科学院上海硅酸盐研究所 | Method of improving vacuum plasma spray coating boron carbide coating layer strength |
| CN101248144A (en) * | 2005-04-21 | 2008-08-20 | 标准航空有限公司 | Wear resistant ceramic composite coatings and process for production thereof |
| CN102272344A (en) * | 2008-11-04 | 2011-12-07 | 普莱克斯技术有限公司 | Thermal spray coatings for semiconductor applications |
Non-Patent Citations (3)
| Title |
|---|
| CHUN-MING LIN ET AL.: "Effects of microstructure and properties on parameter optimization of boron carbide coatings prepared using a vacuum plasma-spraying process", 《SURFACE & COATINGS TECHNOLOGY》 * |
| LECH PAWLOWSKI著 李辉等译: "《热喷涂科学与工程》", 31 January 2011, 机械工业出版社 * |
| 陈俊凌等: "聚变装置第一壁真空等离子喷涂B4C涂层研究", 《真空与低温》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107858629A (en) * | 2017-05-02 | 2018-03-30 | 武汉华工激光工程有限责任公司 | One kind utilizes ceramic material sealing thermal Sperayed Ceramic Coatings hole technique |
| CN109839208A (en) * | 2017-11-27 | 2019-06-04 | 深圳航发复合材料有限公司 | A kind of method of low-voltage plasma spraying matrix characterization temperature |
| CN110029306A (en) * | 2019-04-23 | 2019-07-19 | 度亘激光技术（苏州）有限公司 | A kind of cleaning method of vacuum coating equipment cavity aluminium alloy element |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6749238B2 (en) | Enhancement of plasma spray coating using plasma flame heat treatment | |
| CN103194715B (en) | Method for preparing amorphous Y3Al5O12 coating through atmospheric plasma spraying technology | |
| CN103074566A (en) | Method for preparing Y3O3 coating by using supersonic plasma spraying technology | |
| WO2020207089A1 (en) | Method for preparing y2o3 ceramic coating by supersonic flame spraying technology | |
| CN103194714B (en) | A kind of method of Plasma Spray Boron Carbide Coating | |
| CN103540889A (en) | Method for preparing boron carbide coating through low-pressure plasma spraying technology | |
| CN102296263B (en) | Modification treatment method for inner surface of plasma etching process chamber | |
| CN103132007B (en) | A kind of low-voltage plasma spraying technology prepares Y 2o 3the method of ceramic coating | |
| CN100540511C (en) | A kind of compound carbon resisting coating material and on matrix the preparation compound carbon resisting coating method | |
| CN104357785A (en) | Method for rapidly preparing high-purity yttrium oxide coating for plasma etching machine | |
| CN103074563B (en) | A kind of Y2O3The improved method of resistant to corrosion ceramic coating | |
| CN108642435A (en) | A kind of big thickness high-temperature protection coating of turbine outer ring inner wall and preparation method thereof | |
| CN103074564A (en) | Method for preparing Y3O3 coating by using vacuum plasma spraying technology | |
| CN104711503A (en) | Boron carbide gradient coating used in quartz substrate and preparation method thereof | |
| CN103132003B (en) | Black Y in a kind of semiconductor devices 2o 3ceramic coating manufacture method | |
| CN103132002B (en) | Preparation method of black yttrium oxide (Y2O3) ceramic coating | |
| CN105624602B (en) | A kind of Y applied to aluminium base base material3Al5O12The preparation method of coating | |
| CN103194716B (en) | A kind of reaction and plasma spraying is prepared the method for boron carbide coating | |
| CN113584421A (en) | Method for enhancing bonding strength of yttrium oxide coating and substrate surface | |
| CN104711504B (en) | A kind of preparation method of boron carbide coating applied to quartz substrate | |
| CN103132001B (en) | Improvement method for preparing Y2O3 ceramic coating | |
| CN103074568A (en) | Preparation method of Y2O3 erosion-resistant ceramic coating | |
| CN103074567A (en) | Method for preparing Y3O3 coating by using water-stable plasma spraying technology | |
| CN103132006B (en) | Black Y is prepared in the process of a kind of plasma hydrogen 2o 3the method of ceramic coating | |
| CN103540891B (en) | A kind of plasma spraying technology prepares the method for boron carbide coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140129 |
|
| RJ01 | Rejection of invention patent application after publication |