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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/24—Deposition of silicon only
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
  • C23C16/503—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using DC or AC discharges
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
  • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/52—Controlling or regulating the coating process

Definitions

• the present invention basically aims to be reactive plasma-assisted, i.e. using a PECVD process to deposit materials on a deposition surface, on the one hand with the highest possible deposition rate on the deposition surface, and on the other hand at the lowest possible temperature of this surface.
• the deposition rate as the material thickness applied to a surface per unit of time if the surface mentioned is arranged in a place defined within the vacuum recipient, as will be explained below. This is because, in the present context in particular, the amount of material stored per unit of time on a surface unit depends on the location at which the surface is arranged in the recipient.
• a plasma jet is generated in an evacuated recipient and workpieces are arranged radially offset with respect to the region of the highest plasma density, along the jet axis, fresh reactive gas being let into the recipient and used material is sucked out of the recipient and surfaces to be treated are arranged with the same spacing with respect to the beam axis, for the deposition of material onto a deposition surface with a material generation rate of at least 400 nm / min and at a temperature of at most 550 ° C.
• significantly lower temperatures are possible.
• EP 0 724 026 by the same applicant as the present invention is namely a method for the reactive treatment of workpieces, in which a plasma jet is generated in an evacuated recipient and, with respect to the area of maximum plasma density radially offset along the beam axis, ke are arranged, whereby fresh reactive gas is let into the recipient and used one is sucked out of the recipient and in which workpiece surfaces to be treated further are distributed along a longitudinally extended rotating surface around the plasma jet, in such a way that the plasma density on the surfaces is at most 20% the maximum beam plasma density, viewed in planes perpendicular to the beam axis, is known, which is suitable for the deposition of difficult to produce, metastable layers, in particular diamond, cBN, ⁇ -Al 2 0 3 or C 3 N "layers .
• the diffusion area of high-current arc discharges ie the area with a plasma density ⁇ 20% of the beam center plasma density, is extremely well suited for the deposition of extremely hard layers, in particular for the deposition of layers under normal conditions difficult to produce, metastable phases such as the above.
• microcrystalline silicon in this case very particularly of ⁇ c-Si: H.
• the plasma beam is designed in a much preferred manner and as described in EP 0 724 026 as a low-voltage arc discharge, preferably as a high-current arc discharge.
• the deposition is used as a coating deposition or as a deposition of the material in powder or cluster form, i.e., in the latter case, to obtain the material powders or clusters mentioned.
• the deposition surface be arranged along rotating surfaces around the jet axis.
• the deposition surface be it formed by a collecting surface for deposited powder or cluster, be it formed by workpiece to be coated. Arrange surfaces in a ring around the axis of the plasma jet.
• the deposition thickness homogeneity is an essential criterion, it is further proposed to add the deposition surface around the beam axis and / or in each case about a rotation axis offset from the beam axis, preferably parallel thereto, during the deposition rotate.
• Homogenization of the deposition distribution is also achieved by a reactive gas flow in the recipient which is essentially parallel to the beam axis.
• the plasma density distribution is controlled by means of a magnetic field generated essentially parallel to the beam axis. If such a field is created, then preferably at most 250 Gauss, preferably 100 Gauss, particularly preferably 60 Gauss.
• the deposition surface can be placed floating or at a preferably adjustable electrical potential, in this case a DC, an AC or an AC + DC potential.
• the plasma jet is further generated by means of a low-voltage arc discharge with a hot cathode or with a cold cathode, preferably as a high-current arc discharge.
• a low-voltage arc discharge with a hot cathode or with a cold cathode, preferably as a high-current arc discharge.
• Far preferred and essential for the training especially of low voltage / high current arc discharge is to keep the total pressure in the recipient at least 1 mbar.
• the use according to the invention aims at the deposition of microcrystalline silicon, in particular from ⁇ C-Si: H, silane being preferably used as the reactive gas. It is also particularly important that, according to the invention, microcrystalline silicon can be deposited in nm to ⁇ m powder or cluster form. Furthermore, with the high deposition rate mentioned, as a layer or powder, further silicon compounds can be deposited, such as you, SiN, but also also metal compound layers, such as, in particular, hard material materials, such as, for example, TiN, TiAlN, SiAlON layers or layers with low Coefficient of friction, such as CrC, FeC, WCC layers etc. In the case of deposition as a coating, despite the high deposition rates, the coating quality is suitable for epitaxial layer formation.
• 1 schematically, a high-current arc and the related arrangement of deposition surfaces according to the invention
• 2 schematically, an installation used according to the invention for the preferred deposition according to the invention of microcrystalline silicon
• the plasma jet which is preferably in the form of a high-current arc 1, diverges rapidly after a diaphragm opening 2 in a cathode chamber 3 to a certain extent, in order to then maintain a largely constant formation right up to the anode, up to a few cm in front.
• the extent of the arc in front of the anode depends on the geometric shape of the anode. With the exception of a small area after the aperture 2 and above the anode 4, this results in a largely homogeneous, long area 1 of the high-current arc.
• bell-curve-like distributions of the plasma density result in diametrical sectional planes E, as entered, for example. In each level E, the plasma density distribution has a maximum position Max.
• the arc length is preferably between 50 and 120 cm, particularly preferably approximately 90 cm.
• the total pressure in the recipient is selected to be more than 1 mbar.
• the surfaces to be provided according to the invention for the deposition of materials are preferably arranged in a radius r from the beam axis A, at which point a plasma density of at most 20% still prevails.
• the width of the plasma jet and thus also the plasma density distribution is determined via points of the arc current and / or in particular special about an axial magnetic field H, as shown in Fig. 1, adjusted according to the respective needs.
• the field strength is preferably set to a maximum of 250 Gauss, but in particular to a maximum of 100 Gauss, very particularly preferably between 0 Gauss (without field) and 60 Gauss.
• the arrangement of the deposition surfaces in the area of low plasma density also has the advantage that it varies only slightly along straight lines parallel to the beam axis and in the homogeneous area 1.
• the distance r between the workpiece surfaces to be treated and the beam axis A is preferably selected
• larger separation surfaces to be used and in particular such surfaces on which a coating is to be produced, are preferably moved in an oscillating or circumferential manner to axes parallel to the beam axis, as represented by ⁇ M , and / or possibly around the beam axis A, as shown with ⁇ A , rotated.
• the reactive gas flow, as represented by G is preferably generated essentially parallel to the beam axis A.
• the plasma jet 1 is preferably generated as a high-current arc discharge, preferably in the form of a hot cathode, low voltage, high current arc discharge, but a cold cathode arc discharge can also be used.
• a cathode chamber 12 is flanged to the vacuum recipient 10 with an electron-emitting hot cathode 14, which is connected in a heating circuit for the heating current I H with a preferably adjustable heating current generator 16.
• the anode 20 is arranged opposite a beam outlet screen 18 provided on the cathode chamber 12.
• the preferably adjustable discharge generator 22 is connected between the hot cathode 14 or the heating circuit and anode.
• a workpiece carrier arrangement 24 defining a cylindrical surface is provided for deposition surfaces to be coated with the use according to the invention or as a collecting surface for the deposition of material powder or cluster.
• the radius r is, as can be seen from the above explanations, beam power-dependent.
• Workpieces to be coated are provided along the cylindrical workpiece carrier arrangement, while observing the plasma density conditions mentioned. This is particularly true for the high-rate deposition of microcrystalline silicon.
• other workpieces such as tools, for example drills, indexable inserts, milling cutters, etc. can also be arranged thereon in order to coat them with hard material layers, such as layers made of TiN, TiAlN, Si-Al-ON, SiC, SiN etc., or with Layers with a low coefficient of friction, such as layers made of CrC, FeC, WCC, for example metal-carbon layers.
• any substrate carriers provided are built as transparently as possible so that the main surface is formed by the workpieces or substrates themselves and not by their holders.
• reactive gas R for the preferred embodiment, namely the deposition of microcrystalline silicon, preferably silane, is admitted into the recipient 10 on the cathode side at 29, and the pump arrangement 26 is provided on the anode side.
• Workpieces or generally deposition surfaces are operated in a floating manner via a carrier arrangement or are connected to a reference potential, for example ground potential, or to a DC bias potential, an AC or a mixed AC + DC potential, for example to a pulsed DC potential .
• ⁇ c-Si H structures were deposited directly on the glass or silicon substrates used. Some of the layers were of epitaxial quality. It should be noted that none of the layers produced an amorphous intermediate layer directly on the substrate. This is unusual, because with conventional coating processes, an amorphous silicon intermediate layer, which then prevents the growth of epitaxial layers, is usually always created first. This shows that the method used according to the invention is also suitable for the deposition of epitaxial layers. Also striking is the extremely high growth rate, which is also achieved at low separation temperatures.
• Arc current 80 - 170 A.
• Axial magnetic field H 0 - 250 Gauss, preferably 0 - 100 Gauss, particularly advised 0 - 60 Gauss.
• Substrate temperatures are reached that are not higher than 450 ° C, usually between 250 and 500 ° C.
• the plasma density conditions preferably at most 20% of the maximum density at the beam axis, result in radial distances from the beam axis between 6 and 20 cm, preferably, as mentioned, from 9 to 13 cm.
• the above-mentioned layers are obtained as coatings or deposits in the form of powders or clusters in nm to ⁇ m size, particularly when depositing microcrystalline silicon.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Metallurgy (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Plasma & Fusion (AREA)
• Inorganic Chemistry (AREA)
• Chemical Vapour Deposition (AREA)
• Physical Vapour Deposition (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Cited By (4)

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• 1999
  • 1999-04-29 CH CH00794/99A patent/CH694699A5/de not_active IP Right Cessation
• 2000
  • 2000-04-11 US US10/031,258 patent/US6685994B1/en not_active Expired - Fee Related
  • 2000-04-11 HK HK02106186.9A patent/HK1044571B/zh not_active IP Right Cessation
  • 2000-04-11 DE DE50009169T patent/DE50009169D1/de not_active Expired - Lifetime
  • 2000-04-11 WO PCT/CH2000/000208 patent/WO2000066806A1/de not_active Ceased
  • 2000-04-11 JP JP2000615426A patent/JP2002543293A/ja active Pending
  • 2000-04-11 EP EP00914006A patent/EP1187945B1/de not_active Expired - Lifetime
  • 2000-04-20 TW TW089107450A patent/TW507020B/zh not_active IP Right Cessation

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