CN1473952A - Method for treating material surface under nornal temperature with microvave plasma and laser - Google Patents
Method for treating material surface under nornal temperature with microvave plasma and laser Download PDFInfo
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- CN1473952A CN1473952A CNA031418023A CN03141802A CN1473952A CN 1473952 A CN1473952 A CN 1473952A CN A031418023 A CNA031418023 A CN A031418023A CN 03141802 A CN03141802 A CN 03141802A CN 1473952 A CN1473952 A CN 1473952A
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Abstract
The present invention relates to the material surface treating process with microwave plasma and laser under normal temperature. The process includes electronic cyclically resonating and microwave discharge of specific working gas to produce microwave plasma, leading the plasma into material treating chamber, leading laser into material treating chamber, and acting the material surface with microwave plasma and laser simultaneously so as to make the material surface change in component or structure and to improve the performance of material surface. The present invention has wide application range, convenient parameter regulation and capacity of local treatment.
Description
Technical field
The present invention is a kind of novel method of material surface being implemented the modification processing, this method organically combines two kinds of technology of plasma surface treatment and Laser Surface Treatment, and microwave plasma and laser combination treatment are carried out to reach the particular processing effect in material (or parts) surface.This method be particularly suitable for the surface treatment of material regional area and parts part and during to high temperature the material (or parts) of easy deformation or thermal damage carry out surface treatment.
Background technology
The world today is growing to the demand of advanced material with excellent properties, current technology has proposed special requirement to surface property such as the friction of some component, wearing and tearing, burn into high temperature etc., and the microminiaturization of device is more outstanding to the parts surface performance demands.Existing common material often can not satisfy above-mentioned requirements, and expense is expensive or do not meet whole requirement again to use exotic materials.Thereby utilizing methods such as physics, chemistry, machinery to make common material have special surface property and prepare satisfactory parts, is important channel and direction current and from now on.Except material (or parts) surface coverage protective layer; directly certain modification being carried out on material (or parts) surface by specific process for treating surface and handled to change the chemical ingredients and the weave construction of material surface, is to change or improve the material surface performance to make it be fit to specific application scenario, satisfy special service requirements or prolong the parts effective means in work-ing life.
At present, year beam process for treating surface that process for treating surface commonly used has traditional thermal treatment, thermo-chemical treatment technology and develops rapidly in nearly decades comprises Ion Beam Treatment, electron beam treatment, laser treatment and Cement Composite Treated by Plasma etc.Wherein plasma surface treatment forms the plasma body that activatory contains elements such as nitrogen, carbon or boron by the discharge to operation source gas, it is directly acted on be in pyritous material (or parts) surface, thus the top layer of adding elements such as nitrogen, carbon or boron to material (or parts).This treatment technology is the activity and the energy of activation of source gas, raising interpolation element effectively, is to the heat treated development of traditional chemical, has developed into sophisticated process for treating surface.But, can reduce treatment temp and shorten the treatment time although compare with traditional thermo-chemical treatment, the required temperature also higher (common more than 400 ℃) of plasma surface treatment, treatment time also long (a few hours were to tens of hours), particularly the regional area of material (or parts) is carried out surface treatment and often seem powerless.Laser Surface Treatment starts from the seventies in 20th century, kinds of processes such as laser transformation, laser melting, laser surface alloying have now been developed into, compare with conventional art that the heat affected zone is little, the thermal deformation that can avoid matrix and thermal damage etc., and have characteristics quick, non-equilibrium thermodynamics, thereby reach with the unapproachable effect of conventional art, can also carry out surface treatment to the specific region of material (or parts) selectively.
These two kinds of treatment processs of plasma surface treatment and Laser Surface Treatment respectively are complementary, in conjunction with the associated treatment material surface, are preferable processing scheme with both, but such report is not arranged at present as yet.
Summary of the invention
The objective of the invention is to obtain a kind of can binding plasma under the normal temperature condition and laser surface treating technology to material (or parts) thus the surface carry out modification and handle the novel method that reaches the particular processing effect.
The present invention combines plasma surface treatment and two kinds of technology of Laser Surface Treatment with certain form, effect to material (or parts) surface the time realizes material (or parts) surface microwave plasma and laser combination treatment by microwave plasma and laser beam.
The present invention adopts this at present effective gas discharge technology discharge of electron cyclotron resonace (ECR) microwave discharge to activate operation source gas and produces high-density, high ionization degree, high chemically active plasma body, the plasma body line that contains interpolation elements such as activatory nitrogen, carbon or boron of Xing Chenging acts on material (or parts) surface thus, and the energy that adds element then can be added in bias voltage change on the material (or parts) by adjustment., improve and add the rate of diffusion of element to the local heating on material (or parts) top layer or fusing or with the transient melting and the rapid solidification of pulse laser beam with continuous laser beam on the top layer to material (or parts) top layer.Under the combined action of plasma body and laser beam, undergo phase transition the infiltration with extraneous element simultaneously on the top layer of material (or parts), cause the variation of chemical ingredients and weave construction, realize the change or the improvement of surface property.
Basic technical scheme of the present invention is: 1) under the ECR condition specific working gas is carried out microwave discharge and produce high-density, high ionization degree, the high chemically active ECR microwave discharge plasma (being called for short the ECR microwave plasma) that contains activation interpolation element; 2) this plasma body being introduced the formation of material processing chamber has the plasma body line of certain energy and acts on processed material (or parts) surface; 3) laser beam of certain intensity is introduced the material processing chamber and act on material surface simultaneously; 4) implement plasma body and laser combination treatment at material (or parts) surface plasma and laser beam acting in conjunction zone.
The treatment process of foregoing invention can realize on as lower device: complete assembly is made up of microwave part [comprising microwave source (1) and microwave transmission coupled system (2)], discharge portion [comprising solenoid and supporting coil power (3) and ECR microwave discharge chamber (5)], gas distributing system (4), material processing chamber (6) and vacuum unit (7), other joins laser apparatus (9) and some optical elements (10), as shown in Figure 1.The microwave that microwave source produces is by microwave transmission coupled system input ECR microwave discharge chamber (abbreviation discharge cavity); Discharge cavity is the place that produces microwave plasma (13), and gas distributing system provides working gas to it, and discharge cavity is around with solenoid, and the discharge cavity lower end directly is communicated with material processing chamber (abbreviation treatment chamber); Treatment chamber is the place that material surface is handled, (one of them flange as optical window only draws among Fig. 1 to have eight identical flange-interfaces (8), eight flanges all draw by practice sites among Fig. 2), be used separately as optical window or be used for installing specimen holder (11); The vacuum unit is connected with treatment chamber, is used for treatment chamber and discharge cavity are vacuumized; Specimen holder is installed on one of them flange-interface, is used for placing processed material (or parts) (12), and can be by its rotation of magnetic force coupled transmission mechanism control outside treatment chamber; Laser apparatus is positioned at the treatment chamber outside, and the laser beam of output (15) passes through optical element after optical window is introduced treatment chamber; Can also on processed material (or parts), add the energy that certain bias voltage (13) is used for changing the plasma body line that acts on material (or parts).
By the vacuum unit discharge cavity and treatment chamber are evacuated to base vacuum (10
-5～1 * 10
-4Pa), charge into certain kind, certain air pressure (9 * 10 by gas distributing system to discharge cavity
-3～1 * 10
-1Pa) contain the working gas that adds element; The energising solenoid provides and satisfies the required stationary magnetic field of ECR working order; Is the microwave of 2.45GHz by microwave source to the discharge cavity incoming frequency by the microwave transmission coupled system, under the ECR state working gas in the discharge cavity is carried out microwave discharge and produce microwave plasma and activation interpolation element wherein, the variation range of microwave power is 100～1000W; Plasma body is introduced treatment chamber, and formed low-power plasma body line with active interpolation element directly acts on material (or parts) surface; The energy of plasma body line determines by bias voltage, bias voltage can be-10～-the 1000V range; Laser apparatus can be selected continuous wave laser or pulsed laser for use according to concrete processing requirements, and wavelength and pulse width are by selected laser apparatus decision, the power density 10～10 of continuous laser
5W/cm
2, the power density 1 * 10 of pulse laser
7～4 * 10
8W/cm
220 seconds to 10 minutes treatment time.
The present invention organically combines plasma surface treatment and these two kinds of technology of Laser Surface Treatment, and adopt effective ECR microwave discharge technology, its essence is laser-enhanced or the thermal treatment of auxiliary plasma body gas chemistry, and have the feature of Ion Beam Treatment concurrently: ECR microwave discharge produces high chemically active microwave plasma, provide activatory gas phase nitrogen to processed material (or parts) surface, carbon or boron etc. add element, and charged particle makes the ion beam current (comprise and add element ion) that acts on the surface have certain energy in the bias voltage accelerate plasma that applies, nitrogen in the presence of laser beam, element such as carbon or boron adds the top layer that penetrates into material (or parts) fast, and the phase transformation that occurs in material surface of following laser to cause, thereby change the chemical ingredients and the weave construction of skin-material, reach the purpose that changes or improve material (or parts) surface property.Because the enhancing or the booster action of laser need not the whole heating of processed material (or parts), thereby can avoid thermal deformation and other various possible thermal damages of matrix.Can realize laser auxiliary plasma surface treatment based on Cement Composite Treated by Plasma also can realizing plasma body auxiliary laser surface treatment according to specific requirement based on laser treatment.Use the scanning of focussed laser beam and control laser beam, can also realize the microcell of surperficial specific region is handled at material surface.
The present invention can be added in bias voltage on the substrate by change come the energy of control action kou in the plasma body line on treated material (or parts) surface, bias voltage-10～-1000V between.
Operation source gas has multiple choices, can use oxygen (O
2) or nitrogen (N
2) wait elementary gas to carry out processing such as surface oxidation or nitrogenize, also can use ammonia (NH
3), methane (CH
4) or boron trichloride (BCl
3) wait chemical compound gas to carry out processing such as surfaces nitrided, carburizing or boronising, two or more source gas mixing can also be carried out multielement as working gas and ooze processing altogether, perhaps above-mentioned source gas is mixed in other carrier gas and carry out corresponding surface treatment as working gas; Adding element and be generally gaseous sources, can directly use above-described operation source gas, serve as to add element with some element in the gas, or the steam of some liquid is added in the carrier gas, serves as to add element with some element in the liquid vapour.
The present invention also can be with solid as adding element source, a certain amount of solid source become gaseous substance be added in the carrier gas as working gas by physics (as sputter etc.) method.
The present invention is 10～10 if use continuous wave laser, power density
5W/cm
2If use pulsed laser, power density is 1 * 10
7～4 * 10
8W/cm
2
The present invention combines plasma surface treatment and these two kinds of technology of Laser Surface Treatment, combine the characteristics of these two kinds of technology: when laser beam acts on material (or parts) surface, provide activatory to add element by plasma body to the zone of action of laser beam, implement plasma body and laser combination treatment, thereby realize normal temperature, fast, the surface treatment little to the matrix heat affecting, thing phase and structure that acquisition is difficult to obtain with other method, reach special surface treatment effect, and can realize surperficial microcell processing as required.
Description of drawings Fig. 1 is a structural representation of realizing plasma body of the present invention and laser associating material handling device.Fig. 2 is the synoptic diagram of embodiments of the invention implementation procedure.
Among the above-mentioned figure, the 1st, microwave source, the 2nd, microwave transmission coupled system, the 3rd, solenoid and supporting coil power, the 4th, gas distributing system, the 5th, ECR microwave discharge chamber, the 6th, material processing chamber, the 7th, vacuum unit, the 8th, the flange-interface on the material processing chamber, the 9th, laser apparatus, 10 optical elements, the 11st, specimen holder, the 12nd, treated material (or parts), the 13rd, bias voltage, the 14th, ECR microwave plasma, the 15th, laser beam.The material processing chamber has eight identical flange-interfaces and is used separately as optical window or is used for installing specimen holder, one of them flange that only draws among Fig. 1 as optical window, and eight flanges all draw by practice sites among Fig. 2; Treated material in the treatment chamber (or parts) rotates can be by the magnetic force coupled transmission mechanism by the outer electric machine control (not drawing in the drawings) of treatment chamber.
Embodiment
Can obtain satisfied surface treatment result to the concrete processing of multiple requirements such as the enforcement oxidation of material (or parts) surface, nitrogenize (nitriding), carburizing, boronising with the inventive method.Embodiment one. the monocrystalline silicon surface oxide treatment
Press Fig. 2 configuration, pending monocrystalline silicon piece is removed surface impurity and natural oxidizing layer through the standard program matting and is placed on the specimen holder in the treatment chamber, connects-the 10V bias voltage, does the per minute rotation in 5 weeks by the electric machine control that treatment chamber is outer; With the vacuum unit treatment chamber and discharge cavity are evacuated to base vacuum (～10
-5Pa), charging into air pressure by gas distributing system to discharge cavity is 9 * 10
-3The high purity oxygen gas of Pa is as working gas and make gas be in stable flow state; In discharge cavity, produce the stabilizing magnetic field that satisfies the ECR state to the magneticfield coil energising, providing frequency by the microwave transmission coupled system to discharge cavity by microwave source is the microwave of 2.45GHz, under the microwave power of 100W oxygen is carried out ECR microwave discharge and obtains the ECR oxygen plasma; Oxygen plasma is introduced the treatment chamber that is communicated with discharge cavity and is acted on the monocrystalline silicon surface that is fixed on the specimen holder; Continuous CO 2 (CO
2) the laser beam scioptics of wavelength 10.6 μ m of laser apparatus output focus on monocrystalline silicon surface after optical window is introduced treatment chamber, act on the LASER SPECKLE radius 0.5mm of silicon face, from the center of rotation 20mm of silicon chip, power density～10W/cm
2In plasma body and coefficient while of laser beam, processed monocrystalline silicon piece is done uniform slow rotation makes laser beam scan at silicon chip surface.After silicon chip rotated for 5 weeks (about 1 minute), can realize oxide treatment, obtain radius and be about the even zone of oxidation of ring-type that 20mm, width are about 1mm that main component is silicon-dioxide (SiO in the coefficient zone of silicon chip surface plasma body and laser beam
2).The surfaces nitrided processing of embodiment two metal titaniums
Pending metal titanium is placed on the specimen holder in the treatment chamber through surface finish, cleaning, connects-the 500V bias voltage; By gas distributing system to being evacuated to base vacuum (～10
-4Pa) discharge cavity charges into high pure nitrogen, is 1 * 10 to air pressure
-1The flowing nitrogen of Pa carries out ECR microwave discharge and produces ECR nitrogen plasma, microwave power 500W; Nitrogen plasma is introduced treatment chamber and is acted on the titanium surface; Wavelength 532nm, the pulsewidth 5ns of accent Q:Nd:YAG laser-doubled output, the pulse laser beam scioptics of repetition rate 10Hz act on the laser power density 1 * 10 on titanium surface after optical window is introduced treatment chamber irradiation titanium surface
7W/cm
2Continuous action (lasting 20 seconds) through 200 laser pulses, obtain containing δ-TiN at titanium surface plasma and the coefficient zone of laser beam, thickness is the surface nitride layer of micron dimension, realize the nitrogenize of titanium surface plasma auxiliary laser, and plasma body does not cause the considerable change on titanium surface to the independent effect of the short period of time of titanium beyond in the lasing zone.Embodiment three. tungsten surface microcell carburizing treatment
The solubleness of carbon in tungsten is almost nil under the normal temperature, and ordinary method is difficult to tungsten is carried out carburizing treatment, even plasma carbonizing also need carry out under high temperature (being higher than 900 ℃) condition.In plasma carbonizing, use laser beam irradiation, then under matrix the temperature remains within the normal range condition, can carry out laser beam and strengthen plasma carbonizing and handle.Employing Fig. 2 configuration is 4 * 10 to the air pressure of steady flow in the discharge cavity
-2Methane (the CH of Pa
4) gas carries out ECR microwave discharge, produces carbonaceous microwave plasma, microwave power 800W; The plasma body line of drawing from discharge cavity directly acts on and is placed on tungsten surface processed on the specimen holder; Simultaneously, be that the diaphragm of 5mm is chosen uniform part laser focusing irradiation tungsten surface, cross section with diameter from the laser beam of the wavelength 532nm, the pulsewidth 5ns that transfer the output of Q:Nd:YAG laser-doubled, repetition rate 10Hz, the radius that acts on the LASER SPECKLE on tungsten surface is that 0.2mm, power density are 4 * 10
8W/cm
2Processed tungsten connects-the 1000V bias voltage.Combined action (time-consuming 20 seconds) through nearly 200 laser pulses and plasma body, obtain the thick cementation zone that reaches micron dimension at tungsten surface plasma and the coefficient zone of laser beam (the about 0.2mm of radius) based on wolfram varbide, and the tungsten surface observation outside the laser beam zone of action is less than obvious variation, thereby realizes the microcell carburizing treatment on tungsten surface.Embodiment four. and the steel surface boronising is handled
Steel are handled through boronising can form stone top layer to improve wear-resistant and corrosion resistance.Processed plain carbon stool sample places on the specimen holder of treatment chamber, connects-the 800V bias voltage; Charge into boron trichloride (BCl by gas distributing system to the discharge cavity that is evacuated to base vacuum
3) as working gas; Air pressure is 6 * 10 in discharge cavity
-4Pa, be in the BCl of steady flow condition
3The microwave power of gas input 1000W carries out the plasma body that ECR microwave discharge produces boracic, and the plasma body line of drawing from discharge cavity directly acts on the steel sample surface, and boron wherein is the interpolation element; Continuous CO 2 (CO
2) after optical window introducing material processing chamber irradiation steel surface, the laser power density that acts on the steel surface is 1 * 10 by certain optical element for the laser beam of wavelength 10.6 μ m of laser apparatus output
5W/cm
2It is 2mm/s in the sweep velocity of sample surfaces that rotation by treated sample makes laser beam.Through 10 times multiple scanning, last 10 minutes, obtain at plasma body and the coefficient zone of laser beam～the surface boronizing layer of 10 μ m, realized that the boronising of steel surface is handled.
Claims (5)
1. the method for microwave plasma and laser combination treatment material surface under the normal temperature is characterized in that electron cyclotron resonace microwave plasma and laser beam are introduced the material processing chamber simultaneously, and acting in conjunction is carried out combination treatment in material surface to material surface;
Concrete steps are: treated material is fixed in the material processing chamber on the specimen holder, material processing chamber and microwave discharge chamber are evacuated to vacuum, charge into working gas by gas distributing system to the microwave discharge chamber, under the electron cyclotron resonace condition, working gas is carried out microwave discharge and produce microwave plasma; Plasma body is introduced the material processing chamber, simultaneously laser beam is also introduced the material processing chamber, plasma body and laser beam acting in conjunction are in the surface of treated material, be added with bias voltage on the pending material, implement microwave plasma and laser combination treatment at plasma body and laser beam acting in conjunction zone;
Actual conditions is: the base vacuum 10 in material processing chamber and microwave discharge chamber
-5～1 * 10
-4Pa, operating air pressure 9 * 10
-3～1 * 10
-1Pa; The frequency of microwave is 2.45GHz, and power is 100～1000W; Laser apparatus, power density is 10～4 * 10
8W/cm
2Substrate bias voltage-10～-1000V; 20 seconds to 10 minutes treatment time.
2. the method for microwave plasma according to claim 1 and laser combination treatment is characterized in that working gas can be elementary gas, chemical compound gas or mixed gas.
3. the method for microwave plasma according to claim 1 and laser combination treatment, it is characterized in that adding the normally gaseous sources of element, can be the steam of working gas itself or liquid, if the latter, then the steam with liquid be added in the carrier gas as working gas.
4. the method for microwave plasma according to claim 1 and laser combination treatment, the source that it is characterized in that adding element also can be a solid, by sputtering method a certain amount of solid source is become gaseous substance and is added in the carrier gas as working gas.
5. the method for microwave plasma according to claim 1 and laser combination treatment is characterized in that if use continuous wave laser, power density be 10～10
5W/cm
2, be 1 * 10 if use pulsed laser, power density
7～4 * 10
8W/cm
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031418023A CN1473952A (en) | 2003-07-24 | 2003-07-24 | Method for treating material surface under nornal temperature with microvave plasma and laser |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031418023A CN1473952A (en) | 2003-07-24 | 2003-07-24 | Method for treating material surface under nornal temperature with microvave plasma and laser |
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|---|---|
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404723C (en) * | 2006-03-31 | 2008-07-23 | 清华大学 | Surface modification device based on laser induced in-situ chemical reaction |
| CN101851741B (en) * | 2009-04-03 | 2012-06-27 | 复旦大学 | Method for preparing metal oxide thin film without transition layer on silicon substrate |
| CN108251892A (en) * | 2018-02-26 | 2018-07-06 | 湖北碳六科技有限公司 | Device and method for preparing single crystal diamond by laser-enhanced plasma CVD |
| WO2022032931A1 (en) * | 2020-08-12 | 2022-02-17 | 天津大学 | Extreme ultraviolet light and plasma combined atomic-scale processing method |
| CN114921753A (en) * | 2022-04-27 | 2022-08-19 | 深圳大学 | Carbon film deposition method based on mixed irradiation and carbon film |
-
2003
- 2003-07-24 CN CNA031418023A patent/CN1473952A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404723C (en) * | 2006-03-31 | 2008-07-23 | 清华大学 | Surface modification device based on laser induced in-situ chemical reaction |
| CN101851741B (en) * | 2009-04-03 | 2012-06-27 | 复旦大学 | Method for preparing metal oxide thin film without transition layer on silicon substrate |
| CN108251892A (en) * | 2018-02-26 | 2018-07-06 | 湖北碳六科技有限公司 | Device and method for preparing single crystal diamond by laser-enhanced plasma CVD |
| WO2022032931A1 (en) * | 2020-08-12 | 2022-02-17 | 天津大学 | Extreme ultraviolet light and plasma combined atomic-scale processing method |
| US11600465B2 (en) | 2020-08-12 | 2023-03-07 | Tianjin University | Atomic-scale processing method by combining extreme ultraviolet light and plasma |
| CN114921753A (en) * | 2022-04-27 | 2022-08-19 | 深圳大学 | Carbon film deposition method based on mixed irradiation and carbon film |
| CN114921753B (en) * | 2022-04-27 | 2023-11-10 | 深圳大学 | Carbon film deposition method based on mixed irradiation and carbon film |
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