CN103003467B - Spotless arc directed vapor deposition (SA-DVD) and related method thereof - Google Patents

Spotless arc directed vapor deposition (SA-DVD) and related method thereof Download PDF

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Publication number
CN103003467B
CN103003467B CN201180022808.4A CN201180022808A CN103003467B CN 103003467 B CN103003467 B CN 103003467B CN 201180022808 A CN201180022808 A CN 201180022808A CN 103003467 B CN103003467 B CN 103003467B
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substrate
anode
equipment according
carrier gas
jet
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CN103003467A (en
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H.N.G.瓦德利
G.马托施
F-H.勒格纳
B.舍费尔
C.梅茨纳
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
University of Virginia Patent Foundation
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
University of Virginia Patent Foundation
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/228—Gas flow assisted PVD deposition
    • 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
    • H01J37/30—Electron-beam or ion-beam tubes for localised treatment of objects
    • H01J37/305—Electron-beam or ion-beam tubes for localised treatment of objects for casting, melting, evaporating or etching
    • H01J37/3053—Electron-beam or ion-beam tubes for localised treatment of objects for casting, melting, evaporating or etching for evaporating or etching
    • 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
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32055—Arc discharge
    • 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
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32321—Discharge generated by other radiation
    • H01J37/3233—Discharge generated by other radiation using charged particles
    • 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
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32357—Generation remote from the workpiece, e.g. down-stream
    • 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
    • H01J37/3244—Gas supply means
    • H01J37/32449—Gas control, e.g. control of the gas flow
    • 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
    • H01J37/32532—Electrodes
    • H01J37/32568—Relative arrangement or disposition of electrodes; moving means
    • 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
    • H01J37/32532—Electrodes
    • H01J37/32614—Consumable cathodes for arc discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/006—Details of gas supplies, e.g. in an ion source, to a beam line, to a specimen or to a workpiece
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/30—Electron or ion beam tubes for processing objects
    • H01J2237/31—Processing objects on a macro-scale
    • H01J2237/3132—Evaporating
    • H01J2237/3137—Plasma-assisted co-operation

Abstract

A plasma assisted directed vapor deposition process that utilizes a spotless arc directed vapor deposition (SA-DVD) method for the creation of the plasma in a directed vapor deposition apparatus. Vapor is created by electron or other high intensity directed energy beam evaporation from one or more source materials contained in a water cooled crucible. This vapor is entrained in a transonic helium or other gas jet and transported to a substrate for deposition. The electron or other directed energy beam used for evaporation is simultaneously exploited to ionize the vapor and the jet forming gas (helium, or other gases including combinations of inert and reactant gases). An anode positioned near the electron beam impingement position attracts scattered electrons formed during the directed energy beams interaction with a target surface and enables the formation of an intense plasma. This plasma is at first transported towards the substrate by the vapor entraining gas jet through an ion-drag mechanism. However, if the substrate is sufficiently charged (electrically biased), the plasma ions are electrostatically accelerated towards the substrate and this extra momentum aids in vapor transport and deposition on a component surface.

Description

Without the directed vapour deposition (SA-DVD) of dirty electric arc and methods involving thereof
Related application
This application claims the sequence number being entitled as " Spotless Arc Activated Directed Vapor Deposition Concept and Implementation Thereof " submitted on May 6th, 2010 is No. 61/331, the U.S. Provisional Application of 844 and the sequence number being entitled as " Spotless Arc Activated Directed Vapor Deposition Concept and Implementation Thereof " in submission on July 22nd, 2010 are No. 61/366, the right of priority of the U.S. Provisional Application of 711, by reference the disclosure of above-mentioned U.S. Provisional Application is integrally incorporated herein.
Technical field
Present invention relates in general to the field of the physical vapor deposition from point-like vapor source.More particularly, the present invention is in the sub-field of the directed vapour deposition of plasmaassisted.
Background technology
Directed vapour deposition (DVD) is a kind of physical vapor deposition (PVD) technique, and rough vacuum electron beam (EB) evaporation is carried secretly with the steam in flowing gas stream (gas-jet) and combined effectively be deposited on substrate by one or more evaporation agent by it.It is a kind of PVD technology that plasma body activates directed vapour deposition (PA-DVD), and electron beam and plasma are formed technical combinations to allow to produce the coating of controlled composition, structure and unrelieved stress by it.In the preceding embodiment of PA-DVD, produce plasma body by hollow cathode discharge.In the process, be injected in the region seeking plasma body activation by the low voltage electronics that the inert gas jets easily ionized is carried together.Injection can to occur with the gas-jet of entraining vapor with becoming any angle.The coaxial concept of the formation gas-jet of plasma body being alignd with the gas-jet of entraining vapor is preferred for many application.
But there is several shortcoming by the plasma body activation of hollow cathode discharge in DVD technique.The first, the working gas of the plasma source launched from hollow cathode forms high-speed jet, the axle of this high-speed jet usually and the direction that transports of steam angled.By the working gas jet of hollow cathode may by transport the slow movement of carrying secretly in jet at steam or light (i.e. low-momentum) steam particle be scattered from substrate, especially when with the jet transporting steam vertically orientation time.The second, which needs to use sizable plasma working gas flow velocity, and it has disadvantageous economic consequences: except gas consumption, and it also needs the more powerful carrier gas jet transporting steam, and therefore needs the air-bleed system of more heavy body.3rd, hollow-cathode plasma source and supply thereof and control unit are expensive for maintenance and require great effort.Such as, in existing apparatus, radiation heater coil is used for star t-up discharge.These well heaters stand frequent fault, and causing needs to change.4th, but well heater and have the slow stable vaporization (High Operating Temperature and ionic bombardments due to them) of hollow cathode itself to produce pollutent, and described pollutent is merged in deposited layer.These last four shortcomings due to hollow cathode discharge that it should be noted that DVD technique even newer hollow cathode discharge and steam are transported in the hollow cathode technology of aliging also effective.
Exist the plasma body activated equipment of the improvement for DVD technique and the needs of method, so as to eliminate the existing plasma body based on hollow cathode activate the shortcoming of scheme and exploitation at a high speed, the economic and new paragon of the deposition of cleaning.
Summary of the invention
An aspect of embodiments of the invention provides a kind of plasmaassisted directed gas-phase deposition, and it utilizes and in directed vapor deposition apparatus, produces plasma body without directed vapour deposition (SA-DVD) method of dirty electric arc.Steam is produced by the one or more source materials be comprised in water cooling crucible by electronics or the evaporation of other high-strength directional energy-beams.This steam to be entrained in transonic speed helium or other gas-jets and to be transported to substrate for deposition.The gas (helium, or other gases of combination comprising rare gas element and reactant gases) faintly ionizing described steam and form jet is used simultaneously in for the electronics that evaporates or other oriented energy bundles.Be arranged and be placed near electron beam impingement position and the anode being connected to power supply attracts the scattered electrons that formed during the interaction on oriented energy bundle and target surface, and making it possible to form the arc-over towards the surface combustion of the evaporation agent as negative electrode.Arc-over facilitates the high plasma body of density.First the gas-jet of the entraining vapor of mechanism is pulled by means of ion towards substrate to transport this plasma body.But if substrate is fully charged (being electrically biased), then plasma ion is accelerated by towards substrate electrostatic, and this extra momentum contributes to deposition on parts surface and steam transports.Because the gas not forming plasma body is injected in deposition, therefore this aspects of embodiments of the invention overcomes and manyly activates with the coaxial hollow cathode of use the problem be associated for the plasma body in DVD technique, and causes generation low cost plasma body assisted conception.Instead, carrier gas jet is used for the part of entraining vapor plumage (vapor plume) as this technique.
Therefore an aspect of embodiments of the invention overcomes and manyly activates with the coaxial hollow cathode of use the problem be associated for the plasma body in DVD technique.Such as, some in the aspect of some embodiments of the present invention can be relevant with following:
Described arc-over burns in the steam of evaporated material and in gas-jet, thus avoid additional plasma working gas and has to be released in sediment chamber.Arc plasma is localized and aligns with the shape of steam stream and propagation.Like this, there is not the Detrimental characteristics of directed steam plumage.
Higher plasma density, macroion production rate and high ionization degree (about 50% scope) are the features of the method.These are such aspects, these aspects are provided to reach large must be enough to mate high deposition rate (about 15 μm/min scope) and the rising stably running the average energy of the condensation particle of electric discharge, and no matter when meeting in DVD technique by charged particle carrier that gas-jet is dragged away.
This equipment and method reduce the complicacy of plasma source, avoid wearing parts and eliminate source of pollution, and it causes producing the concept being easy to safeguard and low cost plasma body activates.
The concept of embodiments of the invention also allows steam over a large area injected, and utilizes effective plasmaassisted to control coating structure and characteristic simultaneously.
In a kind of mode, this can such as by arranging chaining or array by one group of contiguous mutually crucible, anode alone or common anode be equipped with eachly and for generation of the device of gas-jet transporting steam, or by utilizing the steam plumage that the device for the direction controlling gas-jet scans at least one crucible to realize.
And if substrate is by pulsed bias, then the most of positive ions near substrate can be electrostatically attracted and impact substrate surface during the cycle when substrate is electronegative.Because vapor atomic to be contained in the streamline of process near substrate and the characteristic velocity (it controls by jet flow condition and substrate geometry) had along this streamlined motion, the time between the pulse of pulsed bias can be used for controlling ion deposition and where to occur in go substrate.This makes to achieve the novel capabilities controlling thickness, structure, composition and unrelieved stress according to the position on substrate.It will be general for the vapour deposition field by point-like vapor source.
An aspect of embodiments of the invention provides a kind of equipment at least one coating being applied at least one substrate.This equipment can comprise: sediment chamber; At least one evaporation agent source; At least one high energy beam of steam plumage is formed for clashing at least one evaporation agent source described; At least one anode, it is placed near evaporation agent source for forming arc-over between at least one anode described and at least one evaporation agent source described; With form at least one jet and be used for steam plumage towards limited at least one carrier gas transported of the transverse direction of substrate.
An aspect of embodiments of the invention provides a kind of method at least one coating being applied at least one substrate.The method can comprise: provide at least one substrate described; Sediment chamber is provided; At least one evaporation agent source is provided; At least one high energy beam is utilized to clash at least one evaporation agent source described to produce steam plumage; Arc-over is formed between at least one anode and at least one evaporation agent source described; And launch at least one carrier gas, form at least one jet for transverse direction limited transport of steam plumage towards substrate along the direction of at least substantially aliging with steam plumage.
These and other objects of embodiments of the invention disclosed herein become more obvious together with the advantage of each side and feature by by description below, accompanying drawing and claim.
Accompanying drawing explanation
When reading together with accompanying drawing, foregoing and other object of the present invention, feature and advantage and the present invention itself, be more fully understood the description by preferred embodiment below.
Fig. 1 is the longitudinal cross-section schematic diagram of the embodiment without directed vapour deposition (SA-DVD) equipment of dirty electric arc and assembly.
Fig. 2 is the partial schematic diagram (just having single evaporation agent source) of the amplification of the embodiment without directed vapour deposition (SA-DVD) equipment of dirty electric arc and assembly as shown in Figure 1.
The figure of the relation between Fig. 3 room of being to provide pressure (nitrogen pressure, mbar) and the dynamic stiffness (GPa) being deposited on the coating on substrate represents, illustrates thus and uses the advantage be associated without (High Voltage) DVD embodiment of dirty arc method.
Fig. 4 is to provide the jet ion current density (mA/cm when it relates to the use of the carrier gas (such as, Ar) be just ionized or the carrier gas (such as, He) be not ionized 2) figure of relation between contrast jet flow (slm) represents, this figure represents and confirms that ion pulls the existence of phenomenon when plasma body is crossed in transonic speed gas-jet.In shown special case research, Ar is utilized to be passed by He or Ar carrier gas jet as the horizontal hollow cathode discharge of the working gas of plasma source.
Fig. 5 is provided in the signal diagram of the impact of pulsed bias when it relates to coated substrate.
Fig. 6 is provided in the signal diagram of the streamline had on the atom of the steam plumage carried secretly and the carrier gas jet of ion.
Fig. 7 is provided for using suitable bias voltage and carrier gas/steam particles mixture with conformal deposited pattern or with the signal diagram of the technology of trench fill sedimentation model coating non-planar surfaces.
To be merged in present description and the accompanying drawing forming a part for present description illustrates several aspect of the present invention and embodiment, and to be used from description one herein and to explain principle of the present invention.Accompanying drawing is provided only for illustrating the object of select embodiment of the present invention and not being interpreted as limiting the present invention.
Embodiment
Turn to accompanying drawing now, an aspect of the embodiments of the invention schematically shown as Fig. 1-2 is method and apparatus 10, at least one coating is applied at least one substrate 20(such as, sample for utilizing the directed gas-phase deposition of plasmaassisted) on.This equipment can comprise sediment chamber 30(and have upstream 33 and catchment 35), at least one evaporation agent source 40(such as, ingot or other types), 50 are restrainted with at least one the high energy oriented energy (such as electronics) forming steam plumage 90 at least one of clashing in evaporation agent source 40, be placed at least one anode 80 near evaporation agent source 40, for forming arc-over (not shown) between anode 80 and evaporation agent source 40, and at least one carrier gas 70, it forms transverse direction towards substrate 20 limited transport of at least one jet 71 for limiting steam plumage 90 and/or plasma body 105, as substantially described with deshed line 72 in Fig. 1.At least some in element included in equipment 10 can comprise " nozzle " 15, and it can participate at least one coating to be applied at least one substrate 20.In a kind of mode, anode 80 is placed in the position raised on evaporation agent source 40.In a further mode of operation, anode 80 is placed on substrate 20.Substrate 20 can be biased about 0 to about +/-200 V time, or can as required or require to be increased or decreased.
In a kind of mode, can by multiple oriented energy device 52, any other oriented energy device such as, now or later recognized in electron beam gun, laser source or this area, produces high energy oriented energy bundle 50.When electron beam gun 52, it can be operated in low vacuum state or be operated with the background pressure (that is, high vacuum state) reduced.Such as, rough vacuum operational stage can be more than about 0.001 holder to 100 holders, but as required or can require it is other levels.Electron beam gun can be approximated to be 70kV/10kW type, but also not necessarily, because voltage and wattage as required or can require change.High energy beam 50 can comprise for change evaporation agent source 40 at least one in the device of bundle rum point.Such as, can comprise can by the solenoid coil 55 that coaxially and/or is partly placed to close to evaporation agent source 40 or deflector coil for this device.Solenoid coil 55 can make high energy beam 50 bend at least in part.Evaporation agent source can be solid or liquid.
In a kind of mode, solenoid coil 55 can be placed like this and be powered up so that by making electronics move along spiral path plasma body-formation efficiency that (which increase the distance of electron institute movement and the ion between the atom thereby increasing electronics and evaporation agent or form gas-jet forms the probability of collision) carrys out mechanically enhanced system.In a kind of mode, solenoid coil 55 can be provided for and improve plasma density at least in part, and promotes the axial potential gradient for accelerating positive ion towards substrate 20.
In a kind of mode, aperture 73 can be comprised for the device launching carrier gas jet 71, such as, in following at least one: pipeline, conduit, pipe, groove, flexible pipe, handle, duct, entrance, groove, path and passage.Setting and transporting by carrier gas jet 71 pairs of steam plumages 90 is realized by the physics between steam plumage 90 and the formation of carrier gas jet 71 and/or electrostatic interaction at least in part.In a kind of mode, the momentum of carrier gas assists steam plumage transporting towards substrate.And carrier gas jet 71 substantially protects anode 80 and does not contact with steam plumage 90, thereby reduces the accumulation of evaporation agent on anode 80.Such as, the protection provided by high atomic weight carrier gas decreases the undesirable accumulation of condensation evaporation agent on anode.Carrier gas jet 71 can be placed with at least substantially coaxial with evaporation agent source 40.In a kind of mode, undesirable deposition that the surface of protection anode avoids steam particle can be gone out " rinsing gas " entering catchment 35 and provides or improve by being flow through jig drill hole (not shown) from anode 80 inside.Described boring can be so disposed and make rinsing gas contribute to steam plumage 90 to formalize, such as, when radially inwardly flowing out from anode 80.
The direction of carrier gas jet 71 and/or intensity can be used for plasma body 105 or described steam plumage 90 or both setting and/or orientation by control.Described setting and/or orientation can be completed by the pressure and/or gas flow rate controlling carrier gas jet 71.In a kind of mode, carrier gas jet can be placed on around evaporation agent source 40 with loop configurations, and wherein evaporation agent source 40 is coaxially incorporated into the loop configurations inside of carrier gas jet 71 at least substantially.This loop configurations can be a variety of arrangement type.In a kind of mode, by controlling pressure in each carrier gas jet of described arrangement one by one individually and/or gas flow rate completes described setting and orientation.It is one or more that the example of carrier gas can comprise in following any combination: rare gas element (such as, He), reactive gas (N 2, H 2, or O 2) or form the gas (Ar, Xe, or Kr) of ion; And the suitable carrier gas of any other type.
In various embodiments discussed from the beginning to the end, the relative pressure of carrier gas jet 71 and/or gas flow rate can be individually controlled for any one in the other side directional scanning plasma body or described steam plumage or both.
In various embodiments, carrier gas jet can introduce reactant gases.In a kind of mode, reactant gases can form compound with gas phase with steam plumage atom or molecule transporting period in carrier gas jet simultaneously.In a further mode of operation, reactant gases can form compound by the chemical reaction on the deposition surface of substrate.Alternatively, reactant gases can simultaneously with two kinds of pattern formation compounds below: transporting period and steam plumage in carrier gas jet simultaneously with gas phase; And by the chemical reaction on the deposition surface of this at least one substrate.
In a kind of mode, high energy beam 50 faintly ionizes steam plumage 90, forms plasma body 105 thus.And the arc-over between anode 80 and evaporation agent source 40 ionizes steam particle with effectively occupying an leading position, improve the ionization of plasma body 105 thus to provide Dense Plasma region 100.Carrier gas jet ionizes with being occupied an leading position, and crosses Dense Plasma region simultaneously.In a kind of mode, the electric current of arc-over can be changed to adjust or to control the density of plasma body.In a kind of mode, the balance between steam particle ion and carrier gas ion can be controlled by the flow of change carrier gas and/or composition.The carrier gas jet be ionized has the momentum that can be controlled by electrostatic force.Alternatively, carrier gas can previously be ionized; Or previous ionization and in Dense Plasma region time the combination of ionization.The steam particle be ionized controlling the carrier gas jet that is ionized and/or entrained with provides at least one coating of substrate or the surface topography of each several part of (multiple) coating and the manipulation of interior phase, structure and stress.
In a kind of mode, anode 80 can be annular or ring-type, and is placed with at least substantially coaxial with at least one carrier gas jet.In a kind of mode, anode is segmented to form two or more anode segments, and described anode segment is electrically isolated from each other and is mechanically arranged so that each anode segment corresponds to one of evaporation agent source 40.When by independent controllable current source supply one by one, the ionization which is provided in the steam particle that different evaporation agent source 40 place produces can be controlled independently of one another.
In a kind of mode, the embodiment of equipment 10 can comprise at least one refrigerating unit 42 for cooling at least one evaporation agent source 40.Such as, refrigerating unit 42 can be crucible, water or fluid cooling crucible as required or require other devices.Crucible can be biased about 0 to about-10 V time, or as required or require to be biased.
In a kind of mode, the embodiment of equipment 10 can comprise bias voltage 57, and this bias voltage is applied to substrate 20, for towards described substrate 20 speeding-up ion.Therefore, in a kind of mode, provide electrostatic ionic to draw and acceleration region 58, as shown in Figure 2.Will be appreciated that, bias voltage 57 can be DC, AC, or positive, negative or that two symbols have pulsed voltage.Scope can be about 0 to about 10 3v or can as required or require and change.Show the exemplary embodiment of the scope with about 100 to about 200V.In addition, in a kind of mode, the impact that thermal source 59 can be provided for advantageously heated substrates 20 or ion may be used for this heating.Well heater or heating can be optional.
The frequency that an aspect of the embodiment of the inventive method and equipment 10 comprises the pulsed bias 57 controlling substrate to change the deposition position on substrate 20 to control thickness, structure, composition, unrelieved stress and/or other coating characteristics on substrate 20.And another aspect of the embodiment of this equipment comprises for clashing at least one in evaporation agent source 40 to form the oriented energy bundle 50 of steam plumage 90.Oriented energy adjoint when oriented energy bundle 50 can also be controlled to such as by making oriented energy bundle pulse to change evaporation.By this way, the finite length (slug (slug)) of the steam arriving substrate position with the speed determined by jet flow condition can be set up.Further again, an aspect of embodiment can comprise coordinates substrate biasing voltage 57 and the control both oriented energy bundle 50.As the result of this coordination, this will strengthen the ability of the thickness of the deposition region controlled on substrate, structure, composition, unrelieved stress, other coating characteristics and/or position further.Such as, control to comprise the stage of pulsation is modified to substrate biasing voltage and oriented energy bundle.
In a kind of mode, anode can be arranged to be set up magnetic field and makes the magnetic field line before anode be arranged essentially parallel to its surface and be radially oriented for direct magnetic flux, and the circumferential direction thus along the surface being arranged essentially parallel to anode 80 forms closed electronic drift track.Magnetic field facilitates the axial potential gradient for accelerating positive ion towards substrate 20.
The figure of the relation between Fig. 3 room of being to provide pressure (nitrogen pressure, mbar) and the dynamic stiffness (Gpa) being deposited on the coating on substrate represents, illustrates thus and uses the advantage be associated without the embodiment of dirty arc method.By expanding to the higher pressure scope of DVD technique by the operating pressure without dirty arc procedure from previously contemplated, obviously harder coating can be produced.
Turn to Fig. 4, Fig. 4 is to provide jet ion current density (mA/cm 2) figure of relation between contrast jet flow (slm) represents.It illustrates that the ion(ic)current arriving substrate when plasma body is crossed by gas-jet can increase, and the nucleidic mass of this effect and gas-jet and plasma particle is proportional.Which illustrate ion and pull technique, the collision wherein between gas-jet atom and ion preferably guides ion into substrate, causes the non-electrostatic device for handling plasma body.
Fig. 5 provides the signal of the impact of the pulse bias mode when it relates to coated substrate 20 to illustrate.Namely Fig. 5 A illustrates Coating Ions 24 and non-ased substrates 20(, does not wherein apply bias voltage) between interaction.Thickness is that the plasma sheath 22 of ds is formed and positive charge Coating Ions 24 in this sheath 22 attracted to substrate 20 by sheath electromotive force.Fig. 5 B illustrates that the thickness d s of the sheath 22 when applying (or increase) negative bias voltage increases.This thickness extension and the flux of the correspondingly increase of Coating Ions 24 attracted to substrate 20 from steam plumage.Some ions also collide with coating neutrals (that is, neutral coating atom 26), and by them towards substrate scattering, further increase the mark of the vapor atomic be deposited on substrate.Fig. 5 C illustrates when bias voltage is turned off, and the thickness d s of sheath 22 increases due to previously from sheath deionizing.This thickness extension and the flux of the correspondingly increase of Coating Ions 24 attracted to substrate 20.Some ions collide with coating neutrals (that is, neutral coating atom 26) in addition, and by them towards substrate scattering.Major part ion is deposited to substrate, leaves positive ion depleted region 28.Finally, plasma sheath collapses gets back to its initial (not being biased) value.
Fig. 6 provides the signal of the streamline 75 had on the atom of the steam plumage carried secretly and the carrier gas jet 71 of ion to illustrate.Carrier gas jet 71 provides positive ion to supplement positive ion depleted region as shown in Figure 5 C.Steam deposition and atomic or supplementing of ion are occurred by the motion of these particle ions of streamline at substrate ambient dynamic.The particle be deposited is moved along streamline with the speed controlled by jet flow condition and substrate geometry.If be large compared with the time that the time between bias pulse and the particle in streamline cross substrate, then the particle near substrate is fully supplemented between the pulses.Exemplary pulse speed can be about 10 4hz, it is 100 μ s between the pulses, but can as required or require to be conditioned.The gas-jet streamline being rich in Coating Ions can have the velocity of particle of about 1000m/s (particle every 1 μ s on substrate moves the distance of about 1mm); Or can as required or require and change.Therefore 1mm length on substrate be added between these pulses.By handling the cycle between the speed of the particle in streamline and pulse, even or high localized deposition and plasmaassisted effect can be produced by the impact of rare gas element or condensation atom and substrate.
Fig. 7 provides the signal diagram for such as using constant bias to apply the technology of non-planar surfaces.With reference to figure 7A, the heavy Coating Ions 24 of high energy and the coating 25(such as metallic coating previously deposited) collide, and coating atom 27 is splashed to the region (such as, groove) of the low coating atom flux of usual reception on substrate again.The accumulation coating 29 obtained due to the coating atom again sputtered is illustrated in Fig. 7 B and 7C.
The device of various embodiment of the present invention disclosed herein, system, composition, equipment and method can utilize all respects disclosed in reference below, application, publication and patent, and are incorporated to herein by described reference, application, publication and entirety by reference thus:
The people such as U.S. Patent No. 5,368,897, Kurihra, " Method for Arc Discharge Plasma Vapor Deposition of Diamond ", on November 29th, 1994.
The people " Apparatus and Method for Magnetron-Enhanced Plasma-Assisted Chemical Vapor Deposition " such as U.S. Patent No. 4,668,365, Foster, on May 26th, 1987.
The people " Pulsed Gas Plasma-Enhanced Chemical Vapor Deposition of Silicon " such as U.S. Patent No. 5,242,530, Batey, on September 7th, 1993.
The people " Process and Apparatus for Plasma-Activated Electron Beam Vaporization " such as U.S. Patent No. 5,614,273, Goedicke, on March 25th, 1997.
The people " Process for the Stabilization of Plasma Generation by Means of Electron Beam Vaporizer " such as U.S. Patent No. 5,780,803, Goedicke, on July 14th, 1988.
The people " Method and Device for Pre-Treatment of Substrates " such as U.S. Patent No. 6,083,356, Goedicke, on July 4th, 2000.
International patent application No. PCT/US2010/025259, on February 24th, 2010, is entitled as " Coaxial Hollow Cathode Plasma Assisted Directed Vapor Deposition and Related Method Thereof ";
International patent application No. PCT/US2008/073071, on August 13rd, 2008 submits to, is entitled as " Thin Film Battery Synthesis by Directed Vapor Deposition "; Haydn N.G. Wadley;
U.S. Patent application No. 12/733,160, on February 16th, 2010 submits to, is entitled as " Thin Film Battery Synthesis by Directed Vapor Deposition "; Haydn N.G. Wadley;
International patent application No. PCT/US2006/025978, filed June 30,2006, be entitled as " Reliant Thermal Barrier Coating System and Related Methods and Apparatus of Making the Same "; Haydn N.G. Wadley;
U.S. Patent application No. 11/917,585, on December 14th, 2007 submits to, is entitled as " Reliant Thermal Barrier Coating System and Related Methods and Apparatus of Making the Same "; Haydn N.G. Wadley;
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U.S. Patent application No. 10/333,004, on January 14th, 2003 submits to, is entitled as " Heat Exchange Foam "; Haydn N.G. Wadley, U.S. Patent No. 7,401, July 22 in 643,2008 issues;
U.S. Patent application No. 11/928; 161; on October 30th, 2007 submits to, is entitled as " Method and Apparatus for Heat Exchange Using Hollow Foams and Interconnected Networks and Method of Making the Same "; Haydn N.G. Wadley;
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U.S. Patent application No. 10/297,347, on November 21st, 2002 submits to, is entitled as " Process and Apparatus for Plasma Activated Deposition in a Vacuum "; Haydn N.G. Wadley; U.S. Patent No. 7,014, on May 21st, 889,2006 issues.
U.S. Patent application No. 09/634; 457; on August 7th, 2000 submits to, is entitled as " Apparatus and Method for Intra-Layer Modulation of the Material Deposition and Assist Beam and the Multilayer Structure Produced There from "; Haydn N.G. Wadley; U.S. Patent No. 6,478, on November 12nd, 931,2002 issues.
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International patent application No. PCT/US2001/025158, August 10 calendar year 2001 submits to, is entitled as " Multifunctional Battery And Method Of Making The Same "; Haydn N.G. Wadley;
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Unless expressly contrary provisions, for any specific mutual relationship not requirement of any specific description or the action illustrated or element, any particular order or this kind of action, any specific dimensions, speed, material, time length, profile, yardstick or frequency or this class component.And any action can be repeated, any action can be performed by multiple entity, and/or any element can be replicated.Further, any action or element can be excluded, and the order of action can change, and/or the mutual relationship of element can change.Will be appreciated that, each aspect of the present invention as required or can require to have sizes, profile, shape, composition and material.
In a word, although describe the present invention about specific embodiment, many amendments, modification, change, replacement and equivalent will be obvious to those skilled in the art.The invention is not restricted to the scope according to specific embodiment described herein.In fact, according to description above and accompanying drawing, in addition to those described herein, various amendment of the present invention will be also obvious to those skilled in the art.Therefore, the present invention is only limited being considered to by the spirit and scope of claim that is appended, that comprise all modifications and equivalent.
By the accompanying drawing reading detailed description recited above and certain exemplary embodiments, other embodiment is also had will easily to become obvious for those skilled in the art.Should be appreciated that multiple modification, amendment and additional embodiment are possible, and therefore all these modification, amendment and embodiment will be regarded as in the spirit and scope of the application.Such as, no matter any part of the application (such as, exercise question, field, background, summary, summary, accompanying drawing etc.) content how, unless expressly contrary provisions, the inclusion for this paper's or in any claim of any application requiring its right of priority, any specific description or the action illustrated or element, any particular order of this kind of action or any specific phase mutual relation not requirement of this class component.And any action can be repeated, any action can be performed by multiple entity, and/or any element can be replicated.Further, any action or element can be excluded, and the order of action can change, and/or the mutual relationship of element can change.Unless expressly contrary provisions, for any specific mutual relationship not requirement of any specific description or the action illustrated or element, any particular order or this kind of action, any specific dimensions, speed, material, yardstick or frequency or this class component.Therefore, description and accompanying drawing are regarded as being illustrative in essence, and are not regarded as restrictive.And when any number or scope are described herein, illustrate in addition unless clear and definite, this number or scope are approximate.When any scope is described herein, illustrate in addition unless clear and definite, this scope comprises all values wherein and all subranges wherein.Be merged in any material herein by reference (such as, the U.S./foreign patent, the U.S./foreign patent application, books, article etc.) in any information be incorporated into such degree by means of only quoting, namely this category information and described in this paper other statement with accompanying drawings between there is not conflict.If there is this conflict, comprise and will cause the invalid conflict of any claim herein or seek its right of priority, any this kind of conflicting information so in this kind of material be merged in by reference be incorporated to herein especially by reference.

Claims (22)

1., at least one coating being applied to the equipment at least one substrate, described equipment comprises:
Sediment chamber;
At least one evaporation agent source;
For clashing at least one evaporation agent source described thus at least one high energy beam of formation steam plumage;
At least one anode, it is placed near described evaporation agent source for forming arc-over between at least one anode described and at least one evaporation agent source described; And
Form at least one jet for described steam plumage towards limited at least one carrier gas transported of the transverse direction of substrate;
Wherein said anode is placed with at least substantially coaxial with at least one carrier gas jet described.
2. equipment according to claim 1, at least one carrier gas jet wherein said at least substantially protects at least one anode described and does not contact with described steam plumage, for reducing the accumulation of evaporation agent at least one anode described.
3. equipment according to claim 1, wherein when at least one carrier gas jet described is ionized, at least one carrier gas jet be ionized described has the momentum that can be controlled by electromagnetic force.
4. equipment according to claim 1, described steam plumage ionizes by wherein said high energy beam, thus forms plasma body.
5. equipment according to claim 4, wherein said arc-over adds the ionization of described plasma body to provide Dense Plasma region.
6. equipment according to claim 4, the direction of at least one carrier gas jet wherein said and/or intensity can be used for described plasma body or described steam plumage or both setting and/or orientation by control.
7. equipment according to claim 6, wherein completes described setting and/or orientation by the gas flow rate of pressure or control at least one the carrier gas jet described controlling at least one carrier gas jet described.
8. equipment according to claim 1, wherein said high energy electron gun comprises the device for changing the bundle rum point at least one evaporation agent source described further.
9. equipment according to claim 1, comprises further and is applied to described substrate for the bias voltage towards described substrate speeding-up ion.
10. equipment according to claim 9, wherein said bias voltage is DC, AC or pulsed voltage.
11. equipment according to claim 10, wherein said pulsed bias is controlled to the deposition position of change at least one substrate described to control thickness, structure, composition, unrelieved stress and/or other coating characteristics at least one substrate described.
12. equipment according to claim 1, wherein said carrier gas jet introduces reactant gases.
13. equipment according to claim 1, wherein said anode is segmented to form two or more anode segments.
14. equipment according to claim 1, wherein said anode comprises such device further, this device is for setting up magnetic field and making the magnetic field line before described anode be arranged essentially parallel to its surface and be radially oriented for direct magnetic flux, and the circumferential direction thus along the surface being arranged essentially parallel to described anode forms closed electronic drift track.
15. equipment according to claim 1, comprise by coaxially and at least in part close to the solenoid coil that described evaporation agent source is placed further.
16. equipment according to claim 1, wherein said anode is placed in the position raised on described evaporation agent source.
17. equipment according to claim 1, wherein said anode is placed on described substrate.
18. equipment according to claim 1, wherein said high energy beam is controlled to the deposition position of change at least one substrate described to control thickness, structure, composition, unrelieved stress and/or other coating characteristics at least one substrate described.
19. equipment according to claim 18, the wherein said control to described high energy beam provides the foundation of the finite length of the steam plumage arriving at least one substrate described, and the finite length of described steam plumage limits slug thus.
20. 1 kinds at least one coating being applied to the method at least one substrate, described method comprises:
At least one substrate described is provided;
Sediment chamber is provided;
At least one evaporation agent source is provided;
At least one evaporation agent source described is clashed into produce steam plumage with at least one high energy beam;
Arc-over is formed between at least one anode and at least one evaporation agent source described; And
Launch at least one carrier gas, form at least one jet for transverse direction limited transport of described steam plumage towards described substrate along the direction of at least substantially aliging with described steam plumage;
Wherein said anode is placed with at least substantially coaxial with at least one carrier gas jet described.
21. methods according to claim 20, described steam plumage ionizes by wherein said high energy beam, thus forms plasma body.
22. methods according to claim 21, comprise the electric current that changes described arc-over further with adjustment or the density controlling described plasma body.
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