WO1994012680A1 - Dopage de carbone amorphe fortement tetraedrique et semblable au diamant - Google Patents

Dopage de carbone amorphe fortement tetraedrique et semblable au diamant Download PDF

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Publication number
WO1994012680A1
WO1994012680A1 PCT/GB1993/002424 GB9302424W WO9412680A1 WO 1994012680 A1 WO1994012680 A1 WO 1994012680A1 GB 9302424 W GB9302424 W GB 9302424W WO 9412680 A1 WO9412680 A1 WO 9412680A1
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dopant
carbon
chamber
source
ions
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PCT/GB1993/002424
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Gehan Anil Joseph Amaratunga
David Robert Mckenzie
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Gehan Anil Joseph Amaratunga
David Robert Mckenzie
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Application filed by Gehan Anil Joseph Amaratunga, David Robert Mckenzie filed Critical Gehan Anil Joseph Amaratunga
Priority to AU55321/94A priority Critical patent/AU5532194A/en
Priority to HU9501537A priority patent/HU225918B1/hu
Publication of WO1994012680A1 publication Critical patent/WO1994012680A1/fr

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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
    • C23C14/221—Ion beam deposition
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • 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
    • C23C14/48—Ion implantation

Definitions

  • the present invention relates to doping of highly tetrahedral diamond-like amorphous carbon.
  • a filtered cathodic arc is an efficient source of hydrogen free carbon plasma which can be used to deposit extremely hard and resistive thin films on a variety of substrates. These films have been denoted tetrahedral amorphous carbon (ta-C) or "amorphous diamond" due to the high proportion (generally greater than 50% and less than 90%, and more particularly greater than 65% and less than 85%, ⁇ 10%) of tetrahedral (sp ) bonds which give a structure analogous to amorphous silicon and properties similar to those of diamond, see, for example, McKenzie, D.R., Muller, D.A. & Pailthorpe, B.A. Phys . Rev. Lett .
  • ta-C tetrahedral amorphous carbon
  • amorphous diamond due to the high proportion (generally greater than 50% and less than 90%, and more particularly greater than 65% and less than 85%, ⁇ 10%) of tetrahedral (sp
  • Hydrogenated amorphous silicon (a-Si:H) has become an important semiconductor because of its high sensitivity to light and the ability to deposit it at low temperatures and over large areas. Solar cells and large transistor arrays for switching display elements in portable computers and television sets are examples of where it is widely used.
  • Another group IV material such as carbon to form a-C:H would at first sight seem to be a viable alternative.
  • a-C:H contains a high proportion of non-tetrahedral (sp ) bonding which prevents the formation of a semiconductor band gap.
  • the equivalent tetrahedral form of amorphous carbon (ta-C) is produced by cathodic arc deposition in the absence of hydrogen.
  • a method of forming doped highly tetrahedral diamond-like amorphous carbon comprising the steps of: ionising a cathode made of carbon in an evacuated chamber with a dopant present in the chamber; is characterised by: ionising the dopant; and, collecting the carbon ions and dopant ions on a substrate.
  • the present invention allows a ta-C film to be produced which has been doped in a controlled way to control its electronic, optical, magnetic and/or tribological properties.
  • the film generally has a high proportion (generally greater than 50% and less than 90%, and more particularly greater than 65% and less than 85%, ⁇ 10%) of tetrahedral (sp z ) bonds.
  • the dopant may be incorporated into the cathode or provided as a secondary source in the chamber.
  • the dopant may be introduced as a gas into the chamber; the gas is preferably ionised prior to its introduction into the chamber.
  • the dopant may be such as to produce n-type or p-type doped highly tetrahedral diamond-like amorphous carbon.
  • the dopant may be phosphorous.
  • the cathode may consist of up to substantially 5% by mass of phosphorous and preferably up to substantially 1% by mass of phosphorous to 99% carbon.
  • the dopant may be boron.
  • the boron may be introduced into the chamber as boron ions by ionising a compound including boron, such as B 2 H 6 . Boron powder may alternatively be incorporated in a carbon cathode.
  • the dopant may alternatively be aluminium or an aluminium- containing compound.
  • the dopant may be aluminium or an aluminium-containing compound, or iron or an iron-containing compound (eg Fe 2 0 3 ) , or at least one of Au and Ag, or nitrogen, or MoS 2 .
  • apparatus for producing doped highly tetrahedral diamond-like amorphous carbon comprising: a vacuum chamber; a source of carbon; means for ionising the carbon; a substrate; means for directing the carbon ions into the chamber to the substrate; and, a source of dopant; characterised by: means for ionising the dopant.
  • the carbon source may be a solid.
  • the dopant source may be incorporated into the solid carbon source.
  • the dopant may be incorporated into a separate, secondary source within the vacuum chamber.
  • the dopant ions may be generated from a gaseous source of the dopant outside of the chamber.
  • the ions are introduced into the chamber as the carbon ions are produced from the carbon source.
  • the dopant may be such as to produce n-type or p-type doped highly tetrahedral diamond-like amorphous carbon.
  • Fig. 1 is a composite diagram of alternative examples of apparatus for use in the present invention
  • Fig. 2 is a current-voltage curve for a phosphorous- containing ta-C film deposited on an insulating quartz substrate;
  • Fig. 3 shows Arrhenius plots for a phosphorous- containing ta-C film
  • Fig. 4 shows current-voltage curves of heterojunctions between ta-C and 1.5 ⁇ cm n-type silicon for (i) undoped ta-C and (ii) phosphorous-containing ta-C;
  • Fig. 5 shows the band levels for a rectifying junction between n-type silicon and phosphorous-containing ta-C
  • Fig. 6 is a graph of nitrogen content in a nitrogen- doped film
  • Fig. 7(a) to (d) are graphs of activation energy, electrical resistivity, Tauc optical gap, and compressive stress for varying N 2 partial pressure respectively;
  • Fig. 8 is a graph showing the C K-edge spectra for a range of films having different level of nitrogen doping.
  • Fig. 9 is a graph showing a comparison between C K-edge and N K-edge spectra for a 10% N doped ta-C film.
  • a cathode 1 is used as a source of at least carbon ions which are directed into a vacuum chamber 2 through a curved magnetic plasma guide 3 as suggested by Veerasamy,
  • the ions are directed towards a substrate 4 within the vacuum chamber 2.
  • the cathode was fabricated from a mixture of 1% by mass of 99.999% pure red phosphorous powder in 99.999% pure graphite powder.
  • the powders were ultrasonically mixed and compressed into a 50mm diameter disc under 20-30MPa pressure.
  • a cathodic arc was struck with the phosphorous- containing carbon disc as the cathode 1 and using a high voltage source 5 to an electrode 6 in close proximity to the cathode 2.
  • the vacuum base pressure in the chamber 2 was 10 " Pa and care was taken to eliminate water vapour and oxygen from the system.
  • the arc voltage of 32-35V at a current of 60A was significantly larger than the 19-24V observed for a pure graphite cathode.
  • the plasma passes through a 90° curved solenoid as the plasma guide 3 with an axial magnetic field of 30mT.
  • the substrate 4 is held at a negative voltage of approximately -30V.
  • Films of 30-35nm thickness were deposited at a rate of l-2nms ' onto (100) silicon and quartz as the substrate.
  • the species P + , P and P 2 were observed by a mass spectrometer in the deposition chamber 2.
  • the advantage of introducing the phosphorous at the cathode 1 is that it enables phosphorous-containing carbon films to be grown from ionic species.
  • the phosphorous and carbon ions are emitted from the cathode 1 with 20-50eV kinetic energy and are further accelerated by the bias voltage of the substrate 4. Under these conditions a significant fraction of the phosphorous ions will be implanted a few monolayers beneath the surface of the growing film.
  • a typical current-voltage curve measured across a phosphorous containing film deposited on an insulating quartz substrate is shown in Figure 2. Electrical contact to the film was made through 25nm thick gold coatings which were thermally evaporated under a vacuum of 10 ' Pa. A shadow mask was used to restrict the gold contacts to a 5mm wide strip containing the 0.5mm gaps across which the measurements were made. Leakage current through the quartz substrate was less than 10 " A. The linearity of this curve clearly demonstrates that there is an ohmic contact between the phosphorous-containing carbon film and the gold contact. The resistivity of the film was calculated to be 5 ⁇ .cm at room temperature.
  • Undoped ta-C also shows non-linear space charge limited current flow characteristics below
  • the conductivity of the phosphorous containing film of Figure 2 was measured as a function of temperature between 13OK and 33OK.
  • the Arrhenius plot (a) in Figure 3 shows conductivity in the dark and shows that the dark conduction in the phosphorous containing film is thermally activated with an activation energy of 0.13eV in the temperature range 20OK to 33OK.
  • the conductivity had an additional component which gives the logarithm of conductivity a T -1/4 dependency which is typical of hopping conduction in amorphous materials.
  • Curve (b) in Figure 3 shows the Arrhenius plot which is obtained when the sample is exposed to AM-1 light.
  • the photoconductive component of the conductivity is larger than the thermally activated conduction component only for temperatures below 200K, which is typical of a doped semiconductor.
  • Preliminary Hall effect measurements on the same sample gave a Hall voltage consistent with conduction by electrons.
  • the carrier density at room temperature estimated from the Hall voltage is of order 10 cm " .
  • the carrier density when combined with the conductivity gives an electron mobility in the extended states of around 10cm V " s " . Together with the dramatic change in conductivity, the low activation energy suggests that phosphorous has been incorporated into the film and is electronically active.
  • the sample was not thermally annealed.
  • Heterojunction diodes which are formed by depositing ta-C on silicon can give useful information about the band structure and defects in the material, as mentioned in Amaratunga, G.A.J., Segal, D.E. & McKenzie, D.R. Appl .Phys . Lett .59, 69 (1991) .
  • the current-voltage curve of an n-type silicon to undoped ta-C heterojunction diode is shown as curve (i) in Figure 4. At positive voltages, the junction is forward biased and there is majority carrier (electron) injection from the silicon into the ta-C. In contrast, curve (ii) in Figure 4 shows that, when the film contains phosphorous, the polarity of the device is reversed.
  • the Fermi level in the ta-C was estimated on the basis of a 10 c carrier density and a density of states of I0 18 cm *3 at the conduction band edge calculated from space charge limited current data.
  • Contact to the film was made through 1mm diameter vacuum evaporated gold contacts to form Au/carbon film/Si sandwich structures.
  • the silicon substrates were pressure contacted onto a large metal base which was held at earth potential.
  • the bias voltage was applied to the gold contact and the current-voltage characteristic measured using a Hewlett Packard 4140B pA meter/DC voltage source.
  • a free-standing film was analysed by transmission electron microscopy and parallel electron energy loss spectroscopy (PEELS) .
  • the diffraction pattern showed diffuse rings characteristic of an amorphous material.
  • the plasmon energy which is related to the valence electron density, was found to be 30.9eV.
  • a plasmon energy of 30.5eV corresponds to about or more than 90% tetrahedral bonding in the film.
  • Energy dispersive spectroscopy (EDS) in a scanning electro microscope operated at 2KeV confirmed the pressure of phosphorous in a ta-C film on the quartz substrate. No other impurities were detected.
  • MoS 2 Another dopant which may be incorporated into the solid cathode is MoS 2 , which may be incorporated as a powder. This would give a ta-C film mixed with MoS 2 to enhance the lubrication and wear properties of the films.
  • Further dopants which may be incorporated into the solid cathode include metals such as Ag and Au, which would allow a mixed ta-C metal film, the optical transmission properties of which can be controlled. These films would have application in optical coatings (e.g. for sunglasses, windows) where the ta-C matrix provides a hard mechanical coating and the metal particles allow for optical absorption.
  • Au and Ag are known to have surface plasmon modes which can emit light. By confining Ag, Au or a similar material in small particle form, it would be possible to enhance the photoemission properties of the ta-C/Au(Ag) films. This may have application in electroluminescent cells.
  • Fe or Fe-containing compounds can also be used as a dopant in order to control the magnetic properties of the ta-C film. This may provide a mechanically hard magnetic film, which may have use for fabricating magnetic disks and tapes.
  • the dopant is a gas
  • this can be introduced into the system as a gas in the vacuum chamber in which deposition takes place.
  • Apparatus suitable for this method is shown in Figure 1.
  • the cathode 1 is substantially pure carbon.
  • a Kaufmann ion source 7 is connected to the vacuum chamber 2 to form dopant ions from gaseous sources supplied to the Kaufmann source 7, and the Kaufmann ion source 7 directs those ions into the vacuum chamber 2.
  • the dopant ions from the Kaufmann source 7 are similarly accelerated towards the substrate 4 and a doped film of ta-C builds up on the surface of the substrate.
  • B 2 H 6 can be used as the gaseous source to introduce boron ions in this way.
  • Other suitable gaseous dopant sources include PH 3 , AsH 3 , N 2 .
  • a gaseous dopant may be introduced into the apparatus via a leak valve (not shown) in the bend region 10 of the curved magnetic plasma guide 3, used to remove macroparticles and neutrals from the plasma stream.
  • N 2 99.9995% pure
  • the pressure during deposition varied between 10 to 10 " bar (10 " to 10 " Pa) and hence only the initial N 2 partial pressure and flow rate prior to arcing was used as the controllable parameter.
  • the arc current and voltage used were 60A and 20V respectively.
  • the N 2 background partial pressures were varied from below 10 " bar to 10 "2 mbar (l ⁇ "5 to 1 Pa) . Dissociation and ionisation of the background gas (N 2 in this case) is effected by the highly energetic ions and electrons from the plasma stream. Evidence for the presence of N ions in the plasma was obtained from optical spectroscopic analysis which showed the most likely N 2 P ⁇ 4 S transition at 346.6 nm. Highly reactive N + gas ions were thus incorporated into the growing films. The substrates were left at floating potential and their temperature never exceeded 80°C during deposition.
  • Films with thicknesses ranging from 50 to 100 nm and doped with nitrogen in this manner were grown on quartz and silicon (100) substrates. Using a photo-resist patterning and lift-off technique, each substrate was partly coated from the plasma stream so as to allow step measurements of film thickness using a DekTak profilometer. Film thickness on silicon substrates was also estimated by ellipso etry.
  • XPS X-ray Photoelectron Spectroscopy
  • the X-ray source was operated at 250 W (15kV) using a Mg anode.
  • the source was positioned at an angle of 54° with respect to the import lens axis of the analysing system kept at a distance of 6 mm from the sample.
  • the sample positioned was at an angle of 45° with respect to the lens axis and the area analysed at a time was 0.8-1.2 mm 2.
  • the data evaluation was carried out on the basis of empirical sensitivity factors taken to be 0.477 for N in the present system.
  • the detection limit of this technique is 0.2 at% N, which is sensitive enough for the detection of low levels of N( ⁇ 1%) .
  • Analysis of ta-C samples with no intentional leakage of N 2 gas yields concentrations of 99.9% C with traces of O and Ar.
  • the traces of Ar are attributed to the sputter-cleaning of the ⁇ sample surface by Ar bombardment prior to the XPS measurements.
  • the lowest observable N concentration was 0.25% and the highest concentration of N was found to be about 1% ( Figure 6) .
  • the N content was below the level of detection in the ta-C film with no intentional introduction of N.
  • the resistivities of the films were found to vary as a function of N 2 partial pressure and hence N content. Films doped with nitrogen as described above and deposited on quartz were used for both optical and electrical measurements. The variation of film resistivity with N 2 partial pressure is shown in Figure 7(b).
  • thermopower measurements are essential to determine whether doping has been achieved and, if it has, whether the carriers are electrons or holes. From our results, there is a clear change in the sign of the thermopower from positive to negative in the case of undoped films compared to films containing 2% N. In the latter films, the offer of magnitude of thermopower values (in the mV/K range) suggests a conduction mechanism involving electrons thermally activated into the conduction band, corresponding to regular n-type doping. In the case of undoped films, the thermopower is positive and of the order of 0.1 mV/K indicating that conduction takes place via valence band extended states.
  • thermopower i.s in the ⁇ V/K regime which suggests a conduction mechanism around the Fermi level and correlates with the variable range hopping type mechanism suggested by the T 1/4 dependence discussed above.
  • the optical bandgap E g was determined for nitrogen- doped films grown under similar conditions on quartz substrates. The corresponding absorbtion coefficients of the thin films in the range of 30-50 nm were measured in the wavelength range 190-750 nm. E g was determined using a Tauc plot, the usual procedure for amorphous materials. The variation of E g with N content is shown in Figure 7(c) . Thus, within the limits of experimental error, the optical bandgap decreases slightly to 1.8 eV with up to 1.5% N. With 10% incorporation, the optical bandgap reduces to 1.5 eV. Using the reflectance and transmission of the ta-C thin films, the real and the imaginary parts of the refractive index have also been extracted.
  • the convergence angle of the electron probe was 5 mrad and the spectrometer collector subtends a semi- angle of 7 mrad. With a total beam current of the order of 10 " A and a defocused probe, no sign of radiation-induced change in the energy-loss spectra was observed. Thus, we are confident that the results obtained are intrinsic to the samples under investigation.
  • Four samples were examined, the first (a) undoped, the rest containing (b) 0.45%, (c) 1% and (d) 10% N respectively. The first three samples cover the entire range of N concentrations where controlled doping has been achieved.
  • the area under the ls ⁇ 2p( ⁇ *) peak is constant, indicating that the effect of the N doping on the film at this level is minimal and local as far as the sp 2 /sp 3 fraction is concerned.
  • the broadening of the peak at 292 eV with N doping up to 1% N could therefore be attributed to an increased range of disorder in the ⁇ - bonded structure, instead of a growth of the fraction of sp 2 bonds.
  • the C K-edge spectrum in the case of the sample containing 10% N shows a very different fine structure from the others.
  • the pre-edge peak is not only increased in intensity, but its position is also shifted to a lower energy by 0.5 eV and becomes broadened.
  • N K-edge shows a structure similar to that of the C K-edge ( Figure 9) , indicating that the N atoms do not appear exclusively as either sp 2 or sp3 bonded si•tes, but rather on average sample the same local environment as that of the C atoms. Small differences do appear however in the fine structure of the C and N K-edge, but this probably reflects atomic differences between N and C.
  • the net role of N is consistent with the fact that the increase in the fraction of sp 2-bonded C i.s much higher than the i.ncrease in N concentration.
  • the compressive stress in these films has been identified to be an important parameter which is strongly correlated with the sp bonding in the material and the stress with differing N 2 partial pressures and hence flow rate has therefore been determined. Measurements have been made for three independent runs over the same range of N 2 partial pressures.
  • the stress in the films has been calculated using a method in which the curvature of the silicon ⁇ 100 ⁇ substrate is measured prior to and after deposition using a Dektak 3030 stylus profilometer. The subsequent use of Stoney's equation allows calculation of the film stress. The stress is maintained and interestingly rises initially with increasing gas flow rate, and then at higher flow rate starts to decrease (Figure 7(d)). We conclude that the sp fraction in the films is preserved with low N incorporation.
  • the cathode 1 may be a substantially pure carbon source and the solid dopant may be present in a secondary target 8.
  • An RF supply 9 generates an RF field which is followed by the lighter mass electrons travelling with the plasma beam, causing the secondary source 8 to develop a DC bias relative to the vacuum arc plasma beam. Ions from the main beam are thereby attracted to the secondary source 8, sputtering that source 8 to produce dopant ions in the vicinity of the substrate 4. The dopant ions and carbon ions then deposit on the substrate, itself held at a DC bias voltage, to form doped ta-C. Almost any solid dopant can be introduced in this manner, including Fe, Au, Ag and MoS 2 mentioned above, either instead of or in addition to incorporation of the dopant into the cathode 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

Procédé de formation de carbone amorphe dopé, fortement tétraédrique et semblable au diamant, selon lequel on ionise une cathode (1) en carbone dans une chambre sous vide (2) en présence d'un dopant. On ionise un dopant et on rassemble les ions de carbone et de dopant sur un substrat (4). Les dopants appropriés sont notamment B, P, Fe, Al, Au, Ag, N et MoS2.
PCT/GB1993/002424 1992-11-25 1993-11-25 Dopage de carbone amorphe fortement tetraedrique et semblable au diamant WO1994012680A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU55321/94A AU5532194A (en) 1992-11-25 1993-11-25 Doping of highly tetrahedral diamond-like amorphous carbon
HU9501537A HU225918B1 (en) 1992-11-26 1993-11-25 Combination of atovaquone with proguanil for the treatment of protozoal infections and p. carinii

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB929224697A GB9224697D0 (en) 1992-11-25 1992-11-25 Doping of highly tetrahedral diamond-like amorphous carbon
GB9224697.4 1992-11-25

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996010102A1 (fr) * 1994-09-27 1996-04-04 Widia Gmbh Corps composite, son utilisation et son procede de fabrication
GB2289061B (en) * 1992-12-21 1996-06-19 Ion Coat Ltd Atomic beam coating of polymers
WO1998054376A1 (fr) * 1997-05-30 1998-12-03 Patinor As Procede de fabrication sous vide d'un revetement a base de carbone semblable au diamant
EP0914497A1 (fr) * 1996-06-17 1999-05-12 Benjamin F. Dorfman Materiau similaire au graphite dur lie par une structure similaire au diamant
WO1999060183A1 (fr) * 1998-05-18 1999-11-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Revetement anti-adhesif et son procede de production
US6100628A (en) * 1996-09-30 2000-08-08 Motorola, Inc. Electron emissive film and method
WO2000066506A1 (fr) * 1999-05-03 2000-11-09 Guardian Industries Corporation Verre revetu de carbone amorphe fortement tetraedrique
WO2001029544A1 (fr) * 1999-10-15 2001-04-26 Philips Electron Optics Procede de determination de la concentration de porteurs de charge contenus dans des materiaux, et dans les semi-conducteurs en particulier
US6273488B1 (en) 1999-05-03 2001-08-14 Guardian Industries Corporation System and method for removing liquid from rear window of a vehicle
WO2001090016A1 (fr) * 2000-05-24 2001-11-29 Guardian Industries Corporation Revetement hydrophile comprenant du carbone diamant amorphe (cda) sur substrat
WO2002036513A2 (fr) * 2000-10-30 2002-05-10 Guardian Industries Corp. Systeme de revetement a faible emissivite avec depot cda
US6395333B2 (en) * 1999-05-03 2002-05-28 Guardian Industries Corp. Method of making hydrophobic coated article
WO2002038515A3 (fr) * 2000-10-30 2002-07-04 Guardian Industries Systeme de revetement de gestion solaire comprenant un depot cda de protection
US6713179B2 (en) 2000-05-24 2004-03-30 Guardian Industries Corp. Hydrophilic DLC on substrate with UV exposure
GB2417490A (en) * 2004-08-27 2006-03-01 Nanofilm Technologies Int Tetrahedral amorphous carbon coating with pre-determined resistivity
EP1837418A1 (fr) * 2006-03-20 2007-09-26 Hitachi, Ltd. Revêtement en carbone à dureté élevée
DE102009002320A1 (de) * 2009-04-09 2010-10-14 Hochschule für angewandte Wissenschaft und Kunst Fachhochschule Hildesheim/Holzminden/Göttingen Reduzierung des elektrischen Kontaktwiderstands einer Oberfläche eines metallischen Körpers
US10370613B2 (en) 2014-10-24 2019-08-06 Parag Gupta Grey cast iron-doped diamond-like carbon coatings and methods for depositing same
CN114990476A (zh) * 2022-05-17 2022-09-02 华南理工大学 一种氮掺杂四面体非晶碳薄膜及其制备方法和应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5966045A (ja) * 1982-10-08 1984-04-14 Hitachi Ltd 表面改質装置
JPS5993869A (ja) * 1982-11-19 1984-05-30 Sumitomo Electric Ind Ltd ダイヤモンドを含有する硬質層被覆構造物
JPS60218464A (ja) * 1984-04-13 1985-11-01 Nippon Telegr & Teleph Corp <Ntt> 薄膜の製造装置
JPS62177168A (ja) * 1986-01-31 1987-08-04 Meidensha Electric Mfg Co Ltd 炭素薄膜の製造方法
JPS6353916A (ja) * 1986-08-22 1988-03-08 Meidensha Electric Mfg Co Ltd 半導体化炭素薄膜の形成方法
JPS63186417A (ja) * 1987-01-29 1988-08-02 Meidensha Electric Mfg Co Ltd 半導体化炭素薄膜の形成方法
JPS63203762A (ja) * 1987-02-19 1988-08-23 Meidensha Electric Mfg Co Ltd 半導体化炭素薄膜の形成方法
WO1988010321A1 (fr) * 1987-06-25 1988-12-29 University Of Houston-University Park Procede de deposition de pellicules en diamant
WO1989010427A1 (fr) * 1988-04-18 1989-11-02 Board Of Regents, The University Of Texas System Procede et appareil de production d'une couche de materiau a partir d'une source d'ions laser
JPH03149186A (ja) * 1989-11-04 1991-06-25 Toshiba Corp メタルボンド工具

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5966045A (ja) * 1982-10-08 1984-04-14 Hitachi Ltd 表面改質装置
JPS5993869A (ja) * 1982-11-19 1984-05-30 Sumitomo Electric Ind Ltd ダイヤモンドを含有する硬質層被覆構造物
JPS60218464A (ja) * 1984-04-13 1985-11-01 Nippon Telegr & Teleph Corp <Ntt> 薄膜の製造装置
JPS62177168A (ja) * 1986-01-31 1987-08-04 Meidensha Electric Mfg Co Ltd 炭素薄膜の製造方法
JPS6353916A (ja) * 1986-08-22 1988-03-08 Meidensha Electric Mfg Co Ltd 半導体化炭素薄膜の形成方法
JPS63186417A (ja) * 1987-01-29 1988-08-02 Meidensha Electric Mfg Co Ltd 半導体化炭素薄膜の形成方法
JPS63203762A (ja) * 1987-02-19 1988-08-23 Meidensha Electric Mfg Co Ltd 半導体化炭素薄膜の形成方法
WO1988010321A1 (fr) * 1987-06-25 1988-12-29 University Of Houston-University Park Procede de deposition de pellicules en diamant
WO1989010427A1 (fr) * 1988-04-18 1989-11-02 Board Of Regents, The University Of Texas System Procede et appareil de production d'une couche de materiau a partir d'une source d'ions laser
JPH03149186A (ja) * 1989-11-04 1991-06-25 Toshiba Corp メタルボンド工具

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
C-P KLAGES ET AL.: "PROPERTIES AND MICROSTRUCTURES OF METAL CONTAINING A-C:H FILMS", EXTENDED ABSTRACTS, vol. 89/1, 1989, N.J,U.S, pages 133, XP000133691 *
D.R. MCKENZIE ET AL.: "COMPRESSIVE-STRESS-INDUCED FORMATION OF THIN-FILM TETRAHEDRAL AMORPHOUS CARBON", PHYSICAL REVIEW LETTERS, vol. 67, no. 6, 5 August 1991 (1991-08-05), USA, pages 773 - 776 *
G.A.J. AMARATUNGA: "AMORPHOUS DIAMOND-SI SEMICONDUCTOR HETEROJUNCTIONS", APPLIED PHYSICS LETTERS, vol. 59, no. 1, 1 July 1991 (1991-07-01), US, pages 69 - 71, XP000234400, DOI: doi:10.1063/1.105525 *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 205 (C - 243) 19 September 1984 (1984-09-19) *
PATENT ABSTRACTS OF JAPAN vol. 015, no. 374 (M - 1160) 20 September 1991 (1991-09-20) *
PATENT ABSTRACTS OF JAPAN vol. 10, no. 85 (C - 336)<2142> 4 April 1986 (1986-04-04) *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 273 (E - 639) 29 July 1988 (1988-07-29) *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 28 (C - 471)<2875> 27 January 1988 (1988-01-27) *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 465 (E - 690) 7 December 1988 (1988-12-07) *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 491 (C - 554)<3338> 21 December 1988 (1988-12-21) *
PATENT ABSTRACTS OF JAPAN vol. 8, no. 173 (E - 259) 9 August 1984 (1984-08-09) *

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EP0914497A1 (fr) * 1996-06-17 1999-05-12 Benjamin F. Dorfman Materiau similaire au graphite dur lie par une structure similaire au diamant
EP0914497A4 (fr) * 1996-06-17 2002-09-04 Benjamin F Dorfman Materiau similaire au graphite dur lie par une structure similaire au diamant
US6100628A (en) * 1996-09-30 2000-08-08 Motorola, Inc. Electron emissive film and method
WO1998054376A1 (fr) * 1997-05-30 1998-12-03 Patinor As Procede de fabrication sous vide d'un revetement a base de carbone semblable au diamant
US6261424B1 (en) 1997-05-30 2001-07-17 Patinor As Method of forming diamond-like carbon coating in vacuum
WO1999060183A1 (fr) * 1998-05-18 1999-11-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Revetement anti-adhesif et son procede de production
US6478843B1 (en) 1998-05-18 2002-11-12 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V Anti-adherent coating and method for the production thereof
WO2000066506A1 (fr) * 1999-05-03 2000-11-09 Guardian Industries Corporation Verre revetu de carbone amorphe fortement tetraedrique
US6273488B1 (en) 1999-05-03 2001-08-14 Guardian Industries Corporation System and method for removing liquid from rear window of a vehicle
US6713178B2 (en) * 1999-05-03 2004-03-30 Vijayen S. Veerasamy Highly tetrahedral amorphous carbon coating on glass
US6340192B2 (en) 1999-05-03 2002-01-22 Guardian Industries Corporation System and method for removing liquid from rear window of vehicle
EP1338576A1 (fr) * 1999-05-03 2003-08-27 Guardian Industries Corp. Verre revêtu de carbone amorphe fortement tetraedrique
US6395333B2 (en) * 1999-05-03 2002-05-28 Guardian Industries Corp. Method of making hydrophobic coated article
US6592992B2 (en) 1999-05-03 2003-07-15 Guardian Industries Corp. Hydrophilic coating including DLC
WO2001029544A1 (fr) * 1999-10-15 2001-04-26 Philips Electron Optics Procede de determination de la concentration de porteurs de charge contenus dans des materiaux, et dans les semi-conducteurs en particulier
US6690009B1 (en) 1999-10-15 2004-02-10 Koninklijke Philips Electronics N.V. Method of determining the charge carrier concentration in materials, notably semiconductors
US6793979B2 (en) 2000-05-24 2004-09-21 Guardian Industries Corp. Hydrophilic DLC on substrate with UV exposure
WO2001090016A1 (fr) * 2000-05-24 2001-11-29 Guardian Industries Corporation Revetement hydrophile comprenant du carbone diamant amorphe (cda) sur substrat
US6713179B2 (en) 2000-05-24 2004-03-30 Guardian Industries Corp. Hydrophilic DLC on substrate with UV exposure
US7033649B2 (en) 2000-05-24 2006-04-25 Guardian Industries Corp. Hydrophilic DLC on substrate with UV exposure
WO2002036513A2 (fr) * 2000-10-30 2002-05-10 Guardian Industries Corp. Systeme de revetement a faible emissivite avec depot cda
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WO2002038515A3 (fr) * 2000-10-30 2002-07-04 Guardian Industries Systeme de revetement de gestion solaire comprenant un depot cda de protection
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