CN101104926B - Method for preparing boron phosphite hard coating - Google Patents
Method for preparing boron phosphite hard coating Download PDFInfo
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- CN101104926B CN101104926B CN2007101181413A CN200710118141A CN101104926B CN 101104926 B CN101104926 B CN 101104926B CN 2007101181413 A CN2007101181413 A CN 2007101181413A CN 200710118141 A CN200710118141 A CN 200710118141A CN 101104926 B CN101104926 B CN 101104926B
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Abstract
The invention provides a preparation method of boron phosphide hard coating, which employs the radio frequency plasma-enhanced CVD technique. The method comprises placing a work piece to be protected on a radio-frequency pole plate and heating up to 200-700 DEG C; allowing the deposition of boron phosphide coating by the radio-frequency glow discharge of boron-containing and phosphor-containing gases, wherein the deposition procedure comprises the following two steps: firstly the deposition of boron phosphide coating under a high radio-frequency power and then the deposition under a reduced radio-frequency power; and cooling the work piece down to room temperature under the atmosphere containing a phosphor-containing gas. Compared with the prior art, the invention has the advantages of low temperature, uniform distribution of components of boron phosphide coating, less stress, good adhesion to work piece, high hardness and mechanical strength, and excellent infrared optical property.
Description
Technical field
The invention belongs to the thin film technique field, relate to a kind of preparation method of boron phosphite hard coating, particularly a kind of employing radio-frequency plasma strengthens the CVD technology, prepares the method for boron phosphite hard coating at workpiece surface.
Background technology
In some Application Areas, need workpiece to have high rigidity, characteristics such as wear-resistant, corrosion-resistant, but generally speaking, be subjected to the restriction of material inherent nature, workpiece itself can't satisfy above-mentioned service requirements.At above-mentioned situation, be one of way that addresses this problem in workpiece surface coating hard coating, for example: on cutting tool or mould, apply the single or multiple lift hard coat and can improve its wear resisting property, significantly improve the durability effect; Apply DLC, Ge at optical element such as ZnS window surface
1-xC
xCan improve the ability of its anti-weathering, sand cutting and salt air corrosion Deng hard film layer, thereby guarantee its works better under abominable Working environment.
Boron phosphide BP has high hardness, and Knoop hardness is 4700kg/mm
2Be only second to diamond and cubic boron nitride; have characteristics such as good wear resistance, stable chemical performance, infrared optics excellent property simultaneously, be suitable as the protective film of the wear-resistant coating and the infrared optical element of tool surfaces, its preparation method mainly contains following two classes:
One class is a high temperature CVD method, promptly in an open pipe reactor, workpiece is heated to 900～1100 ℃, feeds boron-containing gas (as B
2H
6, BCl
3, BBr
3) and phosphorous gas (as PH
3, PCl
3, PBr
3) and hydrogen can obtain the boron phosphide BP coating at the matrix surface reactive deposition, the advantage of this method is that the coating machine performance is good, shortcoming is the preparation temperature height.
Another kind of method and the present invention are similar, for radio-frequency plasma strengthens the CVD technology, (U.S.Patent 5 for U.S. patent documents, 007,689 C.J.Kelly, K.L.Lewis) boron phosphide BP that adopted this prepared such as C.J.Kelly and as the protective membrane of infrared optical window in, the workpiece Heating temperature is less than 600 ℃, reactant gases is a phosphine, borine, radio frequency power 10～1000W, the advantage of this method is that Heating temperature is low, but has following shortcoming: the performance of (1) boron phosphide BP is subjected to preparation technology, and particularly the influence of radio frequency power is very big, the poor adhesive force of radio frequency power hour boron phosphide BP and matrix, easily come off, the boron phosphide BP internal stress was big when radio frequency power was big, and growth velocity is little; (2) Zhi Bei boron phosphide BP is a non-stoichiometric, and there is serious mistake phosphorus phenomenon (K.L.Lewis in the surface, C.J.Kelly, and B.C.Monachan, Reccntprogress in the development of boron phosphide as a robustcoating material for infra-red transparencies, SPIE vol.1112,4071989.), and the performance of boron phosphide BP is subjected to the influence of composition very big, so boron phosphide BP uneven components of preparation, unstable properties, preparation technology's poor controllability.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of boron phosphite hard coating, adopt this method to prepare boron phosphide BP, depositing temperature is low, and the coated component of preparation is even, and stress is little, and is good with the sticking power of workpiece.
The object of the present invention is achieved like this:
With boron-containing gas and phosphorous gas is reactant gases, and rare gas element adopts radio-frequency plasma to strengthen the CVD technology and prepares boron phosphite hard coating at workpiece surface for carrying gas, realizes that the concrete steps of present method are as follows:
(1) workpiece is placed on the PECVD equipment radio frequency cathode plate, at first the vacuum chamber vacuum is evacuated to and is higher than 3 * 10
-3Pa is heated to workpiece 200～700 ℃ then;
(2) charge into Ar gas to vacuum chamber, keep vacuum at 1～3Pa, add radio frequency power 1000～1500W, bombardment was cleaned 5～10 minutes to workpiece surface;
(3) feed the mixed gas of rare gas element, boron-containing gas and phosphorous gas in proportion, wherein rare gas element is for carrying gas, boron-containing gas and phosphorous gas are reactant gases, keep vacuum at 1～600Pa, regulate radio frequency power more than 2500W, deposit 1～5 minute, under high radio frequency power, workpiece surface is subjected to high-octane incident ion bombardment, dynamic mixing phenomena will take place with deposition and atomic in the atom that is sputtered at the interface, and the sticking power between coating and the workpiece is increased significantly; Reduce radio frequency power to 50～1500W then and continue deposition until reaching required thickness, under low radio frequency power, sedimentary boron phosphide BP internal stress is little, and subsurface defect is few, the sedimentation rate height;
(4) deposition charges into H to vacuum chamber after finishing in proportion
2With the mixed gas of phosphorous gas composition, keep vacuum at 1～600Pa, workpiece temperature is slowly reduced to room temperature, 30～100 ℃/hour of rate of temperature fall, owing in phosphorous atmosphere, lower the temperature, avoided the volatilization of phosphorus in the boron phosphide BP, guaranteed the even of boron phosphide BP surface and internal component; After dropping to room temperature, charge into nitrogen to vacuum chamber, open vacuum chamber and take out workpiece, preparation process finishes.
Wherein rf frequency is 13.56MHz, by matching impedance and be capacitively coupled on the radio-frequency electrode; Add thermal recovery resistance-type type of heating; Working gas is meant rare gas element such as Ar, He, Ne and mixed gas thereof, and boron-containing gas is meant diborane (B
2H
6But) wait the boron-bearing liquid such as the BCl of boron-containing gas or low pressure gasifying
3, BBr
3, and the mixed gas formed such as above-mentioned substance and hydrogen, rare gas element; Phosphorous gas is meant phosphine (PH
3But) wait the phosphorous liquid such as the PCl of phosphorous gas or low pressure gasifying
3, PBr
3, and the mixed gas formed such as above-mentioned substance and hydrogen, rare gas element;
H
2Scope with gas volume ratio in the mixed gas of phosphorous gas composition: H
2/ (phosphorous gas+H
2) be 0.3～0.8;
In the mixed gas of rare gas element, boron-containing gas and phosphorous gas, the scope of gas volume ratio: boron-containing gas/(phosphorous gas+boron-containing gas) is 0.05～0.5, (phosphorous gas+boron-containing gas)/rare gas element is 0.5～0.95.
The thickness of sedimentary boron phosphide BP is by sedimentation rate and depositing time control; The flow of gas is controlled by mass-flow gas meter, and flow range is all in 5～200sccm scope.
Workpiece to be protected can be made for metal, alloy among the present invention instrument, cutter, mould, or the infrared optical element for being made by ZnS, ZnSe, Ge, Si, quartz etc., its shape can be plate shaped, spherical and other complicated shape.
Compared with prior art, beneficial effect of the present invention is:
Adopt the sedimentary boron phosphide BP coating of the inventive method depositing temperature low, the coated component of preparation is even, and stress is little, and is good with the sticking power of workpiece, has characteristics such as hardness height, physical strength height and infrared optics excellent property.
Description of drawings
Fig. 1 strengthens CVD depositing device sketch for the radio-frequency plasma of preparation boron phosphide BP coating.
Embodiment
As shown in Figure 1: be provided with inlet mouth 5 and vacuum pump 6 in vacuum chamber 4 bottoms, be provided with radio frequency cathode plate 14 in vacuum chamber 4 inside, radio frequency cathode plate 14 inside are provided with well heater, and place work piece 10 on the radio frequency cathode plate 14, and vacuum chamber is provided with radio circuit 15 and vacuumometer 16.
Embodiment 1
(1) the rapid steel workpiece is placed on the PECVD equipment radio frequency cathode plate, at first the vacuum chamber vacuum is evacuated to and is higher than 3 * 10
-3Pa is heated to optical element 600 ℃ then;
(2) charge into Ar gas to vacuum chamber, keep vacuum at 1Pa, add radio frequency power 1500W, bombardment was cleaned 10 minutes to workpiece surface;
(3) gas volume feeds mixed gas than the ratio in borine/(borine+phosphine)=0.3, (borine+phosphine)/Ar=0.5, keep vacuum at 300Pa, regulate radio frequency power more than 2500W, deposit 5 minutes, reducing radio frequency power then continues to deposit until reaching required thickness to 500W
(4) deposition finishes the back gas volume than pressing H
2/ (PH
3+ H
2The ratio of)=0.3 charges into H to vacuum chamber
2With the mixed gas that phosphine is formed, keep vacuum at 300Pa, workpiece temperature is slowly reduced to room temperature, 30～100 ℃/hour of rate of temperature fall.After dropping to room temperature, charge into nitrogen to vacuum chamber, open vacuum chamber and take out workpiece, preparation process finishes.
The boron phosphide BP coat-thickness of preparation adopts the nano-probe pressing in method to test its microhardness greater than 40GPa greater than 10 μ m, adopts scratch method to test its adhesion strength greater than 20N.
Embodiment 2
(1) the germanium polishing workpiece is placed on the PECVD equipment radio frequency cathode plate, at first the vacuum chamber vacuum is evacuated to and is higher than 3 * 10
-3Pa is heated to optical element 400 ℃ then;
(2) charge into Ar gas to vacuum chamber, keep vacuum at 2Pa, add radio frequency power 1500W, bombardment was cleaned 5 minutes to workpiece surface;
(3) gas volume is than feeding mixed gas in borine/(borine+phosphine)=0.1, gas volume than the ratio of (borine+phosphine)/Ar=0.7, keep vacuum at 50Pa, regulate radio frequency power more than 2500W, deposit 5 minutes, reducing radio frequency power then continues to deposit until reaching required thickness to 500W
(4) deposition finishes the back gas volume than pressing H
2/ (PH
3+ H
2The ratio of)=0.1 charges into H to vacuum chamber
2With the mixed gas that phosphine is formed, keep vacuum at 50Pa, workpiece temperature is slowly reduced to room temperature, 30～100 ℃/hour of rate of temperature fall.After dropping to room temperature, charge into nitrogen to vacuum chamber, open vacuum chamber and take out workpiece, preparation process finishes.
The boron phosphide BP coat-thickness of preparation adopts its surface of XPS methods analyst consistent with the boron atom ratio example with inner phosphorus atom greater than 300nm, tests its infrared transmittivity, behind the germanium workpiece single face plating boron phosphide BP, can bring up to 58% by 47% in 3～5 μ m transmitances.
More than a kind of method for preparing boron phosphite hard coating at workpiece surface provided by the present invention is described in detail, used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (11)
1. one kind prepares the method for boron phosphite hard coating at workpiece surface, is to adopt radio-frequency plasma to strengthen the CVD technology, it is characterized in that: realize that the required preparation process of present method may further comprise the steps:
(1) workpiece is placed on the PECVD equipment radio frequency cathode plate, at first the vacuum chamber vacuum is evacuated to and is higher than 3 * 10
-3Pa is heated to optical element 200-700 ℃ then;
(2) charge into Ar gas to vacuum chamber, keep vacuum at 1～3Pa, add radio frequency power 1000～1500W, bombardment was cleaned 5～10 minutes to workpiece surface;
(3) feed the mixed gas of rare gas element, boron-containing gas and phosphorous gas in proportion, wherein rare gas element is for carrying gas, boron-containing gas and phosphorous gas are reactant gases, keep vacuum at 1～600Pa, regulate radio frequency power more than 2500W, deposit 1～5 minute, reduce radio frequency power to 50～1500W then and continue deposition until reaching required thickness;
(4) deposition charges into H to vacuum chamber after finishing in proportion
2With the mixed gas of phosphorous gas composition, keep vacuum at 1～600Pa, workpiece temperature is slowly reduced to room temperature, 30～100 ℃/hour of rate of temperature fall, drop to room temperature after, charge into nitrogen to vacuum chamber, open vacuum chamber and take out workpiece, preparation process finishes.
2. according to claim 1ly prepare the method for boron phosphite hard coating at workpiece surface, it is characterized in that: described rare gas element is meant Ar, He, Ne or its mixed gas.
3. according to claim 1ly prepare the method for boron phosphite hard coating at workpiece surface, it is characterized in that: described boron-containing gas is meant the mixed gas that diborane and hydrogen, rare gas element are formed.
4. according to claim 1ly prepare the method for boron phosphite hard coating at workpiece surface, it is characterized in that: described phosphorous gas is meant the mixed gas that phosphine and hydrogen, rare gas element are formed.
5. according to claim 1ly prepare the method for boron phosphite hard coating, it is characterized in that: described H at workpiece surface
2In the mixed gas of phosphorous gas composition, H
2/ (phosphorous gas+H
2)=0.3～0.8.
6. the method for preparing boron phosphite hard coating at workpiece surface according to claim 1, it is characterized in that: in the mixed gas of described rare gas element, boron-containing gas and phosphorous gas, boron-containing gas/(phosphorous gas+boron-containing gas)=0.05～0.5, (phosphorous gas+boron-containing gas)/rare gas element=0.5～0.95.
7. according to claim 1ly prepare the method for boron phosphite hard coating, it is characterized in that: instrument or the mould of described workpiece for making by alloy at workpiece surface; Or infrared optical element for making by ZnS, ZnSe, Ge, Si or quartz.
8. according to claim 6ly prepare the method for boron phosphite hard coating at workpiece surface, it is characterized in that: being shaped as of described workpiece is plate shaped or spherical.
9. according to claim 1ly prepare the method for boron phosphite hard coating at workpiece surface, it is characterized in that: described radio frequency is by matching impedance and be capacitively coupled on the radio-frequency electrode.
10. according to claim 1ly prepare the method for boron phosphite hard coating at workpiece surface, it is characterized in that: described type of heating is to adopt the resistance-type type of heating.
11. according to claim 1ly prepare the method for boron phosphite hard coating at workpiece surface, it is characterized in that: the flow of gas is controlled by mass-flow gas meter in the described deposition process, flow range is all in 5～200sccm scope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101181413A CN101104926B (en) | 2007-06-29 | 2007-06-29 | Method for preparing boron phosphite hard coating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101181413A CN101104926B (en) | 2007-06-29 | 2007-06-29 | Method for preparing boron phosphite hard coating |
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| Publication Number | Publication Date |
|---|---|
| CN101104926A CN101104926A (en) | 2008-01-16 |
| CN101104926B true CN101104926B (en) | 2010-06-09 |
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|---|---|---|---|
| CN2007101181413A Active CN101104926B (en) | 2007-06-29 | 2007-06-29 | Method for preparing boron phosphite hard coating |
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| CN108046225B (en) * | 2018-01-23 | 2019-08-20 | 信阳师范学院 | A kind of preparation method of boron phosphide monodimension nanometer material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5007689A (en) * | 1988-09-08 | 1991-04-16 | Barr & Stroud | Infra-red transmitting optical components and optical coatings therefor |
| CN1538535A (en) * | 2003-04-16 | 2004-10-20 | 威凯科技股份有限公司 | Heap crystal structured of gallium nitride series compound semiconductor and its manufacturing method |
| CN1938821A (en) * | 2004-03-30 | 2007-03-28 | 昭和电工株式会社 | Compound semiconductor element, manufacturing method of compound semiconductor element, diode element |
-
2007
- 2007-06-29 CN CN2007101181413A patent/CN101104926B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5007689A (en) * | 1988-09-08 | 1991-04-16 | Barr & Stroud | Infra-red transmitting optical components and optical coatings therefor |
| CN1538535A (en) * | 2003-04-16 | 2004-10-20 | 威凯科技股份有限公司 | Heap crystal structured of gallium nitride series compound semiconductor and its manufacturing method |
| CN1938821A (en) * | 2004-03-30 | 2007-03-28 | 昭和电工株式会社 | Compound semiconductor element, manufacturing method of compound semiconductor element, diode element |
Non-Patent Citations (1)
| Title |
|---|
| JP昭57-196710A 1982.12.02 |
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Effective date of registration: 20151208 Address after: Langfang City, Hebei Province, Sanhe Yanjiao 065201 Star Village South Patentee after: GRINM GUOJING ADVANCED MATERIALS CO., LTD. Address before: 100088, No. two, No. 43 middle third ring road, Haidian District, Beijing Patentee before: Beijing Guojing Infrared Optical Technology Co., Ltd. |
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Address after: 065201 Langfang city of Hebei province Sanhe Yanjiao Hing Village South Patentee after: GRINM GUOJING ADVANCED MATERIALS CO., LTD. Address before: Langfang City, Hebei Province, Sanhe Yanjiao 065201 Star Village South Patentee before: GRINM GUOJING ADVANCED MATERIALS CO., LTD. |