WO2014170503A1 - Cellule d'effusion de craqueur à vanne pulsée - Google Patents

Cellule d'effusion de craqueur à vanne pulsée Download PDF

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Publication number
WO2014170503A1
WO2014170503A1 PCT/EP2014/058142 EP2014058142W WO2014170503A1 WO 2014170503 A1 WO2014170503 A1 WO 2014170503A1 EP 2014058142 W EP2014058142 W EP 2014058142W WO 2014170503 A1 WO2014170503 A1 WO 2014170503A1
Authority
WO
WIPO (PCT)
Prior art keywords
valve
cracker
effusion cell
pulsed
pulsed valve
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2014/058142
Other languages
English (en)
Inventor
Fernando Briones
Iván FERNÁNDEZ
Ambiörn WENNBERG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NANO4ENERGY SLNE
Original Assignee
NANO4ENERGY SLNE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NANO4ENERGY SLNE filed Critical NANO4ENERGY SLNE
Publication of WO2014170503A1 publication Critical patent/WO2014170503A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • C23C14/243—Crucibles for source material

Definitions

  • This invention relates to a pulsed valve cracker effusion cell, and in particular, but without limitation, to a pulsed valve cracker effusion cell for the injection of vapours generated by solid or liquid sublimation into a process system, mainly a vacuum system.
  • This invention also relates to the regulation of the vapour flow by means of an intermittent valve.
  • the invention has been designed for various types of injection of gases from solid or liquid sources, e.g. sulphur, tellurium, selenium etc. as an elemental atomized vapour.
  • the injection can be linear, uniform, point source or circular etc.
  • Cracker valves are used in extensively in vacuum deposition systems to introduce gasses, in particular, reactive gasses, into the process chamber.
  • the gasses so introduced typically condense on substrates to form deposited layers, or act as reagents or catalysts that interact with the substrate or with other layers thereon.
  • a cracker valve typically comprises an evaporation chamber containing a quantity of material to be evaporated, and a control valve to control the egress of the vapour into a delivery system, which is typically a perforated tube extending into the process chamber.
  • a cracking heater element is interposed between the evaporation chamber and the delivery system to crack the vapour into a desired reagent for the process.
  • Needle valves have proven to be a good choice in most circumstances because a finely- tapered needle valve affords relatively accurate control of the flux of gas, as well as being reliable. For these reasons, existing cracker valves use needle valves to control the flow of gas into the process chamber.
  • the needle valve is controlled by a screw thread to convert rotation into axial displacement of the needle relative to the aperture
  • the screw thread provides sufficient mechanical advantage that even gentle manipulation of the needle valve upon collision of the needle with the aperture (i.e. when in the fully-closed position), can lead to plastic deformation of the needle.
  • a needle valve needs to be re-calibrated every time it is first used, to counteract the plastic deformation of the needle that occurred the previous time it was fully-closed. Having to re-calibrate the needle valve is time-consuming and inconvenient.
  • a first aspect of the invention provides a pulsed valve cracker effusion cell.
  • a second aspect of the invention provides an effusion cell comprising an evaporation chamber, a delivery system and a conduit in fluid communication with the evaporation chamber and the delivery system, a high temperature heating element located in the conduit and a flow controller for controlling the flux of a gas into the delivery system, characterised in that the flow controller comprises an on/off valve and a controller for controlling the on/off state of the valve.
  • a third aspect of the invention provides a method of controlling the flux of gas from an effusion cell cracker by pulsing an on/off valve for controlling the flux of a gas into a delivery system of the effusion cell.
  • an on/off valve typically has a faster switching speed (from the fully-on to the fully-off position), thereby enabling the flow controller to react more quickly to changes in controller inputs.
  • an on/off valve generally comprises a planar closing surface, as opposed to the tapered needle arrangement of a needle valve, plastic deformation of the contacting parts of the on/off valve is avoided upon closing thereof. This may reduce, or avoid, the need for re-calibration each time the flow controller is first used.
  • the flux of gas into the system is variable.
  • a plasma process may produce mainly cracking, but also a black carbonaceous coating, which is a result of the dynamics of the reaction, whereby relatively low concentrations are able to react fully and thus produce the carbonaceous coating.
  • the overall amount of evaporate is moderated (i.e. the total amount of evaporate per unit time), but because it is delivered in short, relatively high- concentration bursts, the dynamics of the reaction are not able to keep up, thus reducing the amount of black carbonaceous coating in the process.
  • the dynamics of a range of chemical reactions in the process can be better controlled by pulsing.
  • water could be introduced into the system, and under needle valve control, the water might be cracked into H and O, whereas, by pulsing the on/off valve, it may be possible to avoid cracking the water to deliver H 2 0 into the process, which reacts differently to H and O.
  • the effusion cell comprises an evaporation vessel closed by means of a hermetic valve, which regulates its flow by the sublimation of a solid or liquid source material.
  • the sublimated source material is essentially allowed to "leak" from the evaporation vessel. This makes it difficult to determine, with precision, the flux of gas from the evaporation vessel because the internal pressure is a variable quantity.
  • by closing the valve it is possible to obtain a known pressure of sublimated source material, and then by opening it for a known period of time, a known volume of sublimated source material can be released.
  • the invention enables the delivery of sublimated source material to be controlled volumetrically, and with greater precision, than existing systems that rely on estimating the flux of sublimated source material based on the internal pressure of the evaporation vessel (a dynamic value) and the valve setting (which is prone to inaccuracy).
  • the effusion cell comprises three, individually thermostatically controlled parts, namely: a hot thermostatically controlled evaporation zone; a thermostatically controlled gas conduction zone; and a high temperature distribution cracker.
  • a hot thermostatically controlled evaporation zone namely: a hot thermostatically controlled evaporation zone; a thermostatically controlled gas conduction zone; and a high temperature distribution cracker.
  • a hot thermostatically controlled evaporation zone namely: a hot thermostatically controlled evaporation zone; a thermostatically controlled gas conduction zone; and a high temperature distribution cracker.
  • All the components of the effusion cell are suitably manufactured from quartz to avoid chemical corrosion. This is particularly beneficial when handling selenium, arsenic etc.
  • the hot thermostatically controlled evaporation zone is used for the generation of vapour from solid or liquid source, where: the solid or liquid evaporates (source materials) are thermally heated in the thermo stated evaporation zone to a sublimation temperature sufficient to produce a vapour stream.
  • the hot thermo stated evaporation zone is hermetically closed with a heated quartz valve to minimize material waste.
  • thermocouple-based PID temperature control is used to obtain ⁇ 0.1°C temperature accuracy of the reservoir zone.
  • the hot thermo stated evaporation zone is constructed of quartz to avoid chemical corrosion.
  • the invention is additionally comprises an on/off flux control valve to control the flow of the said vapour (sublimated source material) stream into the vacuum chamber.
  • the on/off valve suitably comprises a hermetic valve allowing complete flux shut-off.
  • the on/off valve is suitably a fast actuation pulsed flux control valve, and is suitably manufactured from quartz for corrosion resistance.
  • a high Curie temperature magnet is suitably operatively connected to the valve, which interacts with an externally actuated electromagnetic pulse generator, which actuates the valve.
  • the electromagnetic pulse generator suitably comprises an electric coil, such that the coil and magnet together operate as a solenoid for controlling the opening and closing of the on/off valve.
  • the frequency of operation of the on/off valve can be at any desired frequency, on time and off time, although the on/off valve can suitably be operated in a continuously on, or continuously off state, or with an opening/closing rate of substantially 20Hz.
  • the on/off flux control valve is temperature-controlled, and is suitably maintained above the temperature of the hot thermo stated evaporation zone to avoid material condensation on the valve.
  • the invention also provides a method of controlling the said actuating valve by changing the opening time of each pulse.
  • the effusion cell suitably comprises a high temperature thermo stated gas conduction zone to channel the vapour stream.
  • the gas conduction zone is maintained at a temperature above the temperature of the evaporation zone to avoid material condensation.
  • the gas conduction zone is constructed of quartz to avoid chemical corrosion.
  • the effusion cell suitably comprises a high temperature thermo stated linear distribution cracker to achieve a uniform distribution of vapour stream in the vacuum chamber.
  • the linear distribution cracker comprises an array of nozzles, which suitably form an even and/or uniform gas distribution.
  • the linear distribution cracker is constructed of quartz to avoid chemical corrosion.
  • the linear distribution cracker is electrically heated up to 850 5 C by means of a resistance of refractory material, e.g. tantalum to achieve thermal dissociation of the vapour stream molecules.
  • the linear distribution cracker of the invention delivers a uniform vapour distribution along the cracker length.
  • the pulsed valve cracker effusion cell of the invention enables users to introduce an essentially atomized vapour from a solid or liquid source with a great degree of controllability, offering the possibility to achieve long deposition campaigns with controlled parameters.
  • FIG. 1 is a schematic view of an effusion cell vessel in accordance with the invention.
  • Figure 2 is a schematic view of the effusion cell of Figure 1;
  • Figure 3 is a plot of the experimental results achieved with the invention.
  • FIG. 1 shows a schematic view of the effusion cell vessel.
  • Solid or liquid source material is loaded in the thermo stated evaporation zone 1 which is heated and the temperature is controlled by using the power/thermocouple feedthroughs 2.
  • the flux control valve opens the access of the vapour into a high temperature thermo stated gas conduction zone 3 to channel the vapour stream. This zone is heated and the temperature is controlled by using the power/thermocouple feedthroughs 4.
  • the valve is remotely actuated by an external solenoid 5, fed with a pulsed or continuous electrical current.
  • a high temperature cracker zone 6 is used to crack the vapour stream prior to its release in to the process system, mainly a vacuum system. This zone is heated and the temperature is controlled by using the power/thermocouple feedthroughs 7.
  • FIG. 2 shows a schematic view of the effusion cell.
  • the effusion cell provides a cooled external stainless steel vessel 9, which is connected to the process system by a vacuum flange 10.
  • the effusion cell also comprises a thermo stated evaporation zone 11, a high temperature thermo stated gas conduction zone 12 and a high temperature cracking zone 13. These three zones are assembled with polished conical or spherical fittings 14a and 14b.
  • the thermo stated evaporation zone is heated by an energy source and temperature controlled 15.
  • the solid or liquid source material 16 is loaded in this zone and sublimated.
  • the effusion cell further comprises a fast actuating valve 17, which is heated by an energy source to avoid material re-condensation.
  • the vapour flow is regulated by an intermittent opening of the valve.
  • a high Curie temperature magnet 18 is attached to the valve for external remote actuation by an external solenoid 19, fed with a pulsed electrical current.
  • the high temperature thermo stated gas conduction zone and the valve are heated by an energy source and temperature controlled 20.
  • the vapour stream passes through the valve and the high temperature thermo stated gas conduction zone prior to the injection to the high temperature cracking zone 13.
  • the high temperature thermo stated gas is heated by an energy source and temperature controlled 21.
  • the cracked vapour stream is then delivered to the process system through a series of holes, mainly into a vacuum system.
  • Figure 3 shows a plot of the experimental results achieved with the invention.
  • the evaporation rate of the invention for different aperture times is represented as a function of the valve opening repetition frequency.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

La présente invention se rapporte à une cellule d'effusion de craqueur à vanne pulsée, ladite cellule comprenant une chambre d'évaporation (11), un système de distribution (13) et un conduit (20) en communication fluidique avec la chambre d'évaporation (11) et le système de distribution (13), un élément de chauffage haute température situé dans le conduit et un dispositif de régulation d'écoulement (17) destiné à réguler l'écoulement d'un gaz dans le système de distribution (13), caractérisée par le dispositif de régulation d'écoulement (17) qui comprend une vanne d'ouverture/de fermeture et un dispositif de commande destiné à commander l'état d'ouverture/de fermeture de la vanne. L'invention se rapporte à une cellule d'effusion de craqueur à vanne pulsée pour permettre l'injection de vapeurs produites par une sublimation d'un solide ou d'un liquide dans un système de traitement, surtout dans un système de dépression. La présente invention se rapporte également à la régulation du flux de vapeur au moyen d'une vanne intermittente (17). L'invention a été conçue pour permettre une injection linéaire et uniforme de gaz provenant de sources solides ou liquides, par exemple du soufre, du tellure, du sélénium, etc. sous forme de vapeur atomisée élémentaire.
PCT/EP2014/058142 2013-04-19 2014-04-22 Cellule d'effusion de craqueur à vanne pulsée Ceased WO2014170503A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1307073.5A GB201307073D0 (en) 2013-04-19 2013-04-19 Pulsed valve cracker effusion cell
GB1307073.5 2013-04-19

Publications (1)

Publication Number Publication Date
WO2014170503A1 true WO2014170503A1 (fr) 2014-10-23

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PCT/EP2014/058142 Ceased WO2014170503A1 (fr) 2013-04-19 2014-04-22 Cellule d'effusion de craqueur à vanne pulsée

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GB (1) GB201307073D0 (fr)
WO (1) WO2014170503A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110199050A (zh) * 2017-01-31 2019-09-03 应用材料公司 材料沉积布置、真空沉积系统和其方法
FR3123660A1 (fr) * 2021-06-07 2022-12-09 Air Liquide Electronics Systems Dispositif et procédé de distribution d’une phase gazeuse d’un précurseur solide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4583710A (en) * 1982-05-10 1986-04-22 Cornell Research Foundation, Inc. Electromagnetic valve for pulsed molecular beam
US5080870A (en) * 1988-09-08 1992-01-14 Board Of Regents, The University Of Texas System Sublimating and cracking apparatus
ES2067381A1 (es) 1993-01-14 1995-03-16 Consejo Superior Investigacion Celula de efusion de fosforo para epitaxia de haces moleculares.
US5681535A (en) * 1994-07-16 1997-10-28 Oxford Applied Research Limited Cracking of feedstocks
EP2186920A1 (fr) * 2008-10-22 2010-05-19 Applied Materials, Inc. Dispositif et méthode de régulation de vapeur ou de gaz

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4583710A (en) * 1982-05-10 1986-04-22 Cornell Research Foundation, Inc. Electromagnetic valve for pulsed molecular beam
US5080870A (en) * 1988-09-08 1992-01-14 Board Of Regents, The University Of Texas System Sublimating and cracking apparatus
ES2067381A1 (es) 1993-01-14 1995-03-16 Consejo Superior Investigacion Celula de efusion de fosforo para epitaxia de haces moleculares.
US5431735A (en) 1993-01-14 1995-07-11 Riber S.A. Phosphorus effusion cell for molecular beam epitaxy
US5681535A (en) * 1994-07-16 1997-10-28 Oxford Applied Research Limited Cracking of feedstocks
EP2186920A1 (fr) * 2008-10-22 2010-05-19 Applied Materials, Inc. Dispositif et méthode de régulation de vapeur ou de gaz

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110199050A (zh) * 2017-01-31 2019-09-03 应用材料公司 材料沉积布置、真空沉积系统和其方法
FR3123660A1 (fr) * 2021-06-07 2022-12-09 Air Liquide Electronics Systems Dispositif et procédé de distribution d’une phase gazeuse d’un précurseur solide
WO2022258247A1 (fr) * 2021-06-07 2022-12-15 Air Liquide Electronics Systems Dispositif et procédé de distribution d'une phase gazeuse d'un précurseur solide

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GB201307073D0 (en) 2013-05-29

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