US20030068531A1 - Film deposition method and film deposition system for depositing a halogen compound film, and magnesium fluoride film - Google Patents

Film deposition method and film deposition system for depositing a halogen compound film, and magnesium fluoride film Download PDF

Info

Publication number
US20030068531A1
US20030068531A1 US10/247,081 US24708102A US2003068531A1 US 20030068531 A1 US20030068531 A1 US 20030068531A1 US 24708102 A US24708102 A US 24708102A US 2003068531 A1 US2003068531 A1 US 2003068531A1
Authority
US
United States
Prior art keywords
film
bias
substrate
halogen compound
power supply
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.)
Abandoned
Application number
US10/247,081
Other languages
English (en)
Inventor
Takanobu Hori
Hiroshi Kajiyama
Akira Kato
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.)
Hitachi Ltd
Shinmaywa Industries Ltd
Original Assignee
Shinmaywa Industries Ltd
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 Shinmaywa Industries Ltd filed Critical Shinmaywa Industries Ltd
Assigned to SHINMAYWA INDUSTRIES, LTD., HITACHI, LTD. reassignment SHINMAYWA INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HORI, TAKANOBU, KAJIYAMA, HIROSHI, KATO, AKIRA
Publication of US20030068531A1 publication Critical patent/US20030068531A1/en
Assigned to HITACHI, LTD., SHINMAYWA INDUSTRIES, LTD. reassignment HITACHI, LTD. CORRECTIVE ASSIGNMENT TO CORRECT ASSIGNEE'S ADDRESS, PREVIOUSLY RECORDED ON REEL 013575, FRAME 0745. Assignors: HORI, TAKANOBU, KAJIYAMA, HIROSHI, KATO, AKIRA
Priority to US10/858,178 priority Critical patent/US7223449B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • 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
    • C23C14/0694—Halides
    • 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
    • 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
    • C23C14/54—Controlling or regulating the coating process
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only

Definitions

  • the present invention relates to film deposition method and film deposition system for depositing a halogen compound film.
  • Optical members such as optical lenses, displays and optical communication members are formed at their surfaces with antireflection coating for lessening a loss in the amount of light or the like due to reflection.
  • the substrate on which such antireflection coating is to be formed is glass
  • magnesium fluoride (MgF 2 ) is typically used as the surface layer of the antireflection coating. This is because: magnesium fluoride has a refractive index as low as 1.38 and hence is highly effective in antireflection; a film of magnesium fluoride can be deposited easily by vacuum evaporation; such a magnesium fluoride film has sufficient durability if deposited on a substrate heated to about 300° C.; and a like reason.
  • the substrate is formed of a plastic, however, the vacuum evaporation cannot be employed because it is impossible to heat the substrate to such an elevated temperature.
  • the film-forming method employing the sputtering must control the temperature of the target to allow the film material to pop out of the target with its molecular state kept as it is.
  • the present invention has been made to resolve the foregoing problem and intends to provide a film deposition method and a film deposition system for depositing a halogen compound film, which are capable of depositing such a film while suppressing adverse effect that occur due to deficiency of a halogen element if the halogen element is dissociated from a film material.
  • the present invention provides a film deposition method for depositing a halogen compound film, comprising the steps of: placing a substrate on an obverse side of a bias supply electrode disposed in a vacuum chamber; evaporating a film material comprising a halogen compound; supplying a radio frequency voltage to the bias supply electrode used as one of electrodes to generate plasma in the vacuum chamber; and applying to the bias supply electrode a bias voltage varying in the form of a wave having a negative mean value and a maximum value exceeding a self-bias caused by the radio frequency voltage, whereby the evaporated film material is ionized and deposited on the substrate to form the halogen compound film on the substrate.
  • This method according to the present invention makes it possible to ionize a halogen compound and deposit the ionized film material on a substrate to deposit a film. Even if ions of the halogen element are dissociated from ions of the halogen compound, it is possible to guide such dissociated ions of the halogen element to the substrate and allow such ions to be incorporated into the film to be formed on the substrate by application of the bias voltage varying in the form of a wave having a negative mean value and a maximum value exceeding a self-bias caused by the radio frequency voltage to the bias supply electrode.
  • a halogen element which is easy to dissociate in the form of negative ions, can be incorporated into an intended film being formed through ionization of a halogen compound and, hence, it is possible to prevent the resulting film from being deficient in the halogen element. Further, since the film formation is based on ion plating, it is possible to deposit a film rendered dense.
  • the maximum value of the bias voltage may be a positive voltage. With this feature it is possible to lessen the deficiency in the halogen element.
  • the bias voltage may be applied by a power supply.
  • the bias voltage applied may be based on a voltage generated in a matching circuit provided for matching an impedance on a power supply side associated with the radio frequency voltage to that on a vacuum chamber side.
  • an evaporation source is provided for evaporating the film material, while a coiled ionization electrode is disposed between the evaporation source and the substrate for supplying the radio frequency power, whereby the film material evaporated by the evaporation source can be ionized by being passed through the coiled ionization electrode. Since the deposition of a film according to this feature of the present invention is also based on ion plating, it is also possible to deposit the film rendered dense.
  • the film material comprising the halogen compound may be evaporated and ionized in a clustered fashion by cluster ion generating means. This feature allows clustered ions to impinge upon the substrate thereby depositing the film.
  • the application of the bias voltage assuming the aforementioned positive voltage to the bias supply electrode allows ions of the halogen element dissociated from the clustered ions of the halogen compound to be incorporated into the film being deposited on the substrate.
  • a substrate holder holding the substrate on its back surface in the vacuum chamber is formed of an electrically-conductive material and is used also as the bias supply electrode.
  • This arrangement makes it possible to apply the bias voltage to the substrate holder holding the substrate to be deposited with the film on its back surface and, hence, the bias voltage for causing ions to be incorporated into the film being deposited on the substrate can be applied easily and efficiently.
  • an electron beam evaporation source comprising a crucible holding a material same as the halogen compound to be evaporated, an electron gun for evaporating the halogen compound held in the crucible by heating with an electron beam, and a shutter spaced a predetermined distance from the crucible in a direction toward the substrate, and that the halogen compound in the crucible is evaporated by heating with the electron beam, while direct impingement of the halogen compound thus evaporated upon the substrate is obstructed with the shutter, whereby the evaporated halogen compound is guided sidewardly of the shutter and the crucible.
  • the amount of ions of the halogen element to be supplied to the substrate can be increased relative to the amount of the evaporated halogen compound and, hence, it is possible to avoid a relative decrease in the amount of the halogen contained in the film to be deposited on the substrate.
  • the electron beam evaporation source evaporates the halogen compound by means of the electron beam, the halogen compound can be decomposed more finely, which facilitates the dissociation of ions of the halogen element. This makes it possible to supply such ions of the halogen element to the substrate more easily.
  • the aforementioned halogen compound may be magnesium fluoride (MgF 2 ).
  • Magnesium fluoride can be formed into an optical thin film.
  • the present invention is capable of forming a magnesium fluoride film without impairing optical function such as transparency.
  • the aforementioned bias voltage may have a frequency ranging between 100 kHz and 2.45 GHz. With the bias voltage having such a frequency the halogen element can advantageously be incorporated into the film and prevented from being eliminated from the film.
  • an apparatus for depositing a halogen compound film comprising: a vacuum chamber; a bias supply electrode disposed in the vacuum chamber and having an obverse side for receiving a substrate thereon; an evaporation source for evaporating a film material of the halogen compound film to be deposited on the substrate; a radio frequency power supply for supplying a radio frequency voltage to the bias supply electrode used as one of electrodes to generate plasma in the vacuum chamber; and a bias power supply for applying to the bias supply electrode a bias voltage having a frequency ranging between 100 kHz and 2.45 GHz and varying in the form of a wave having a negative mean value and a positive maximum value.
  • This apparatus is capable of incorporating the halogen element into the film and preventing elimination of the halogen element from the film.
  • a magnesium fluoride film obtainable by a method comprising the steps of: placing a substrate on an obverse side of a bias supply electrode disposed in a vacuum chamber; evaporating magnesium fluoride; supplying a radio frequency voltage to the bias supply electrode used as one of electrodes to generate plasma in the vacuum chamber; and applying to the bias supply electrode a bias voltage having a frequency ranging between 100 kHz and 2.45 GHz and varying in the form of a wave having a negative mean value and a positive maximum value, thereby depositing the magnesium fluoride film on the substrate.
  • the magnesium fluoride film thus obtained is a dense and hard film having a lowered absorption in the visible light region.
  • the magnesium fluoride film according to the present invention has a crystal grain diameter not less than 3 nm and not more than 10 nm.
  • FIG. 1A is a schematic overview of the configuration of a vacuum deposition system capable of practicing the present invention
  • FIG. 1B is a diagram showing an example of a bias voltage according to the present invention.
  • FIG. 2 is a diagram showing another example of the bias voltage according to the present invention.
  • FIGS. 3A to 3 C are views showing other examples of the configuration of a bias power supply unit according to the present invention.
  • FIG. 4 is a schematic view showing the configuration of a vacuum deposition system capable of practicing the present invention.
  • FIG. 5 is a schematic view showing the configuration of a vacuum deposition system capable of practicing the present invention.
  • FIG. 6 is a schematic view showing the configuration of a vacuum deposition system capable of practicing the present invention.
  • FIG. 7 is a graph showing the influence of a radio frequency power upon the absorption coefficient of a magnesium fluoride thin film
  • FIG. 8 is a graph showing the influence of a substrate temperature upon the absorption coefficient of a magnesium fluoride thin film
  • FIG. 9A is a schematic view illustrating obstruction to impingement of fluorine ions upon a substrate surface
  • FIG. 9B is a schematic view illustrating elimination of fluorine ions from a substrate surface
  • FIG. 10A is a view illustrating an action of the present invention, specifically the action of incorporating dissociated fluorine ions;
  • FIG. 10B is a view illustrating an action of the present invention, specifically the action of preventing elimination of fluorine ions
  • FIG. 11 is a graph showing the dependence of the absorptivity of a magnesium fluoride thin film upon the pulse frequency of a bias voltage
  • FIG. 12 is a graph showing the absorptivity of a magnesium fluoride thin film deposited on a quartz substrate within the visible light region;
  • FIG. 13A is a perspective view schematically showing the overview of a wear-resistance tester for illustrating a wear-resistance test
  • FIG. 13B is a table showing wear-resistance evaluation criteria for illustrating the wear-resistance test
  • FIG. 14 is a table showing the crystal grain diameters of magnesium fluoride films
  • FIG. 15A is a view showing the structure of a multi layered film for illustrating an application of an embodiment according to a practicing the present invention to a multi layered film;
  • FIG. 15B is a graph showing the reflectivity of a multi-layered film formed on a substrate within the visible light region for illustrating an application of an embodiment according to a practicing the present invention to a multi layered film;
  • FIG. 16 is a schematic view showing an example of the configuration of a vacuum deposition system that is suitable for a bias voltage having a higher pulse frequency
  • FIG. 17 is a graph showing variations in the electric potential of the substrate holder shown in FIG. 1;
  • FIG. 18 is a graph showing variations in the electric potential of the substrate holder shown in FIG. 1.
  • FIG. 1A is a schematic overview of the configuration of a film deposition system 10 as one example of such an system capable of practicing the present invention.
  • the film deposition system 10 is configured to deposit films on the basis of ion plating as a film deposition method.
  • the film deposition system 10 includes a vacuum chamber 1 and a power supply unit 8 comprising a radio frequency (RF) power supply unit 11 and a bias power supply unit 12 .
  • RF radio frequency
  • a substrate holder 2 for holding a substrate 5 from its reverse side opposite from its obverse side on which a film is to be deposited.
  • the substrate holder 2 is formed of an electrically-conductive material so that an electric power can be supplied into the vacuum chamber 1 .
  • the substrate holder 2 is adapted to be capable of functioning as a bias supply electrode as well as of supplying a radio frequency power.
  • the substrate holder 2 can be driven for rotatably by means of a motor not shown and, hence, a film can be deposited on the substrate 5 rotated by the substrate holder 2 rotating.
  • an evaporation source 3 for holding a film material comprising a halogen compound and evaporating it within the space defined in the chamber 1 .
  • the evaporation source 3 it is possible to use any one of various evaporation sources that are capable of evaporating a film material in the space defined in the chamber 1 , including one adapted to evaporate the film material through resistive heating by a heating power supply, one adapted to evaporate the film material through heating with an electron gun, one adapted to evaporate the film material by sputtering, and one adapted to evaporate the film material by arc discharge.
  • the vacuum chamber 1 is provided with evacuation means such as a vacuum pump and gas supply means, which are not particularly shown, for having a desired vacuum atmosphere therein. That is, the atmosphere within the vacuum chamber 1 can be adjusted to a desired vacuum atmosphere meeting film-depositing conditions established.
  • evacuation means such as a vacuum pump and gas supply means, which are not particularly shown, for having a desired vacuum atmosphere therein. That is, the atmosphere within the vacuum chamber 1 can be adjusted to a desired vacuum atmosphere meeting film-depositing conditions established.
  • the vacuum chamber 1 is formed of an electrically-conductive material and has a chamber wall grounded.
  • the radio frequency power supply unit 11 supplies an electric power for generating plasma in the chamber 1 to ionize (excite) the film material evaporated from the evaporation source 3 .
  • the radio frequency power supply unit 11 has one output terminal connected to the substrate holder 2 through a high pass filter 15 and other output terminal grounded. The radio frequency power outputted from the radio frequency power supply unit 11 is applied to the substrate holder 2 .
  • the high pass filter 15 which is located between the radio frequency power supply unit 11 and the substrate holder 2 , permits the power outputted from the radio frequency power supply unit 11 to pass therethrough toward the substrate holder 2 side while blocking the inputting of the power outputted from the bias power supply unit 12 to the radio frequency power supply unit 11 .
  • desired power value and frequency of the power outputted from the radio frequency power supply unit 11 are determined to meet the kind of the material of a film to be deposited and film depositing conditions.
  • the matching box includes a well-known matching circuit comprising a capacitor and a coil. Adjustment of the matching box allows matching to be made between the impedance of the radio frequency power supply unit 11 side and that of the vacuum chamber 1 side.
  • the bias power supply unit 12 comprises a waveform generator 13 and a bias power supply 14 .
  • the waveform generator 13 is adapted to generate a waveform of a bias voltage to be outputted from the bias power supply unit 12 .
  • the waveform generator 13 is capable of generating various waveforms such as DC component steadily assuming a constant value, AC components of respective frequencies, square waves and triangular waves as basic components.
  • the waveform generator 13 is also capable of composing a basic waveform based on plural basic components.
  • the bias power supply 14 outputs a bias voltage amplified to a predetermined magnitude of power based on such a basic waveform generated by the waveform generator 13 .
  • the bias power supply 14 has one output terminal connected to the substrate holder 2 through a first low pass filter 16 and other output terminal grounded. The bias voltage outputted from the bias power supply 14 is applied to the substrate holder 2 .
  • the first low pass filter 16 which is located between the bias power supply 14 and the substrate holder 2 , permits the power outputted from the bias power supply 14 to pass therethrough toward the substrate holder 2 side while blocking the inputting of the power outputted from the high-frequency power unit 11 to the bias power supply unit 12 .
  • FIG. 1B shows an example of a bias voltage waveform.
  • the horizontal axis corresponds to time (sec.) while the vertical axis corresponds to the magnitude of a voltage value (V).
  • the upper side above the horizontal axis is a positive voltage zone, while the lower side below the horizontal axis is a negative voltage zone.
  • the bias voltage comprises positive bias portions assuming a constant positive voltage value (V P1 ) and negative bias portions assuming a constant negative voltage value ( ⁇ V B1 ).
  • a film can be deposited in the following manner.
  • the evaporation source 3 is loaded with a film material comprising a halogen compound, and the substrate 5 is set on the substrate holder 2 .
  • the substrate 5 is placed so that its obverse side to be deposited with the film faces opposite to the evaporation source 3 .
  • the power supply unit 8 is actuated to supply the radio frequency power into the chamber 1 through the substrate holder 2 and apply the bias voltage to the substrate holder 2 , while the halogen compound is evaporated by the evaporation source 3 .
  • Such a negative potential due to the self-bias and the negative bias caused by the bias voltage make it possible to accelerate the movement of positively-charged ions of the halogen compound toward the substrate 5 .
  • the negative bias of the bias voltage enables further acceleration of the movement of such halogen compound ions, thus rendering denser the structure of the film to be deposited on the substrate.
  • the present invention allows the halogen element once dissociated to be incorporated into the film being deposited on the substrate 5 .
  • the positive bias of the bias voltage allows negatively-charged ions of the halogen element to be incorporated into the film being deposited on the substrate 5 .
  • the film to be deposited on the substrate 5 can be prevented from becoming deficient in the halogen element and, hence, it is possible to avoid any degradation in the function of the film which would otherwise occur due to the deficiency of the halogen element.
  • the high pass filter 15 has a blocking capacitor (not shown) serially connected to the radio frequency power supply unit 11 .
  • This blocking capacitor permits the radio frequency component of a current to pass therethrough but blocks the DC component of the current. Accordingly, when the radio frequency power is supplied into the vacuum chamber 1 , electric charge introduced into the substrate holder 2 from plasma generated by the radio frequency power is built up in the blocking capacitor. Since electrons present in plasma travel toward the substrate holder 2 at a higher speed than do ions present in plasma, an offset voltage, which is determined by the capacity of the blocking capacitor and the amount of charge in the capacitor, is generated between the opposite ends of the blocking capacitor and is applied to the substrate holder 2 .
  • a voltage generated at an electrode (the substrate holder 2 in this case) in contact with plasma according to this mechanism is referred to as a “self-bias”.
  • a self-bias is substantially a constant voltage (substantially a DC voltage) and is generated so that the substrate holder 2 assumes a negative potential.
  • Maximum value V P1 of the bias voltage generated by the bias power supply unit 12 is set higher than the voltage value (negative) of a self-bias that would be generated if the bias power supply unit 12 is absent. By so doing it is possible to suppress an electrical repulsion caused by the self-bias against negatively-charged ions of the halogen element thereby to facilitate incorporation of such halogen element ions into the film being deposited on the substrate 5 . Assuming that the absolute value of the self-bias that would be generated if the bias power supply unit 12 is absent is V dc , the maximum value V P1 of the bias voltage preferably within the range of from +0.5V dc to ⁇ 0.5V dc .
  • the absolute value V dc of the self-bias is about 200 V to about 300 V under typical film-forming conditions.
  • the maximum value V P1 of the bias voltage need not necessarily assume a positive value as shown in FIG. 1B and hence may assume a negative value.
  • a maximum value V P1 more than the upper limit of the aforementioned range is not preferable because discharge within the vacuum chamber 1 becomes unstable.
  • the width ⁇ t of a positive-direction pulse of the bias voltage is preferably 10 ⁇ s or less. If it is more than 10 ⁇ s, discharge within the chamber 1 becomes unstable.
  • the frequency of positive-direction pulses of the bias voltage is preferably within the range of from 100 kHz to 4 ⁇ 13.56 MHz. As will be described later, when the frequency of positive-direction pulses is 100 kHz or more, the effect of superposition of positive-direction pulses becomes noticeable, while if it is more than 4 ⁇ 13.56 MHz, discharge within vacuum the chamber 1 of the film deposition system 10 employing the radio frequency power supply unit 12 as shown in FIG. 1A becomes unstable.
  • FIG. 2 shows another waveform example of the bias voltage.
  • the bias voltage shown in FIG. 2 has a gently curved waveform as a whole and comprises sinusoidal-wave negative bias portions assuming a negative voltage value ( ⁇ V B2 ) and sinusoidal-wave positive bias portions assuming a positive voltage value (V P2 ).
  • a positive voltage is outputted as the bias voltage for the duration T W2 of one period (T W2 +T 2 ), while a negative voltage is outputted for the other duration T 2 .
  • the bias voltage of the waveform shown in FIG. 2 can be obtained by adding a DC voltage assuming a constant negative voltage value to an AC voltage.
  • the positive bias portions of the bias voltage having the waveform shown in FIG. 2 have a mean voltage value of a magnitude set larger than at least the absolute value of a negative potential at the substrate 5 caused by the aforementioned self-bias.
  • the mean value of the magnitudes of positive bias portions be larger than the absolute voltage value of a negative potential caused by the aforementioned self-bias. If so, it is possible to provide a positive potential at the substrate 5 thereby to cause halogen element ions to be incorporated into the film being deposited on the substrate 5 more easily.
  • a bias power supply unit 22 shown in FIG. 3A comprises a DC power supply 24 capable of outputting a constant negative DC voltage for providing a negative bias, and a pulse power supply 23 capable of outputting a constant positive pulse voltage for providing a positive bias.
  • the power outputted from the DC power supply 24 and the power outputted from the pulse power supply 23 form a bias voltage, which in turn is outputted to the substrate holder 2 side through a first low pass filter 21 .
  • the first low pass filter 21 permits the bias voltage outputted from the DC power supply 24 and the pulse power supply 23 to pass therethrough toward the substrate holder 2 side while blocking the inputting of the power outputted from the radio frequency power unit 11 to the bias power supply unit 22 side.
  • the DC power supply 24 for providing a negative bias and the pulse power supply 23 for providing a positive bias are independent of each other and, hence, it is possible to adjust the negative bias and the positive bias separately with ease.
  • FIG. 3B shows yet another example of the bias power supply unit.
  • Bias power supply unit 26 shown in FIG. 3B comprises a DC power supply 27 capable of outputting a constant negative DC voltage for providing a negative bias, and an impulse train power supply 28 for providing a positive bias.
  • the DC power supply 27 outputs a power to the substrate holder 2 side through a second low pass filter 29
  • the impulse train power supply 28 outputs a power to the substrate holder 2 side through a band pass filter 30 .
  • the second low pass filter 29 which is located between the DC power supply 27 and the substrate holder 2 , permits the power outputted from the DC power supply 27 to pass therethrough toward the substrate holder 2 side while blocking the inputting of respective powers outputted from the radio frequency power unit 11 and from the impulse train power supply 28 to the DC power supply 27 side.
  • the band pass filter 30 which is located between the impulse train power supply 28 and the substrate holder 2 , permits the power outputted from the impulse train power supply 28 to pass therethrough toward the substrate holder 2 side while blocking the inputting of respective powers outputted from the radio frequency power unit 11 and from the DC power supply 27 to the impulse train power supply 28 side.
  • the DC power supply 27 for providing a negative bias and the impulse train power supply 28 for providing a positive bias are independent of each other, and similarly the filters 29 and 30 associated with respective powers outputted from these power supplys to the substrate holder 2 side are independent of each other. Hence, it is possible to adjust the bias voltage more easily.
  • FIG. 3C shows yet another example of the power supply unit.
  • the power supply unit comprises a linear amplifier 31 and a function generator 32 .
  • the function generator 32 generates a waveform composed of the radio frequency waveform of the radio frequency power, the waveform of negative bias portions of the bias voltage and the waveform of positive bias portions of the bias voltage and causes the linear amplifier 31 to amplify the waveform thus composed and output the waveform amplified as a desired output to the substrate holder 2 side.
  • the power supply unit configured as shown in FIG. 3C does not require the provision of a filter and hence dispenses with adjustment of such a filter. Further, it is possible to unify controls over radio frequency outputs and negative and positive bias outputs of the bias voltage thereby to adjust the power balance easily.
  • the outputs of the DC power supply 24 or 27 and pulse power supply 23 or impulse train power supply 28 are adjusted relative to each other so that the bias voltage composed of these negative and positive bias outputs can provide a negative bias of a predetermined voltage value and a positive bias of a predetermined voltage value.
  • the foregoing description has been directed to an example of the bias voltage that provides both a positive bias and a negative bias
  • the negative bias need not necessarily be outputted and it is possible to exert an electrical attractive force upon ions of the halogen compound thereby to accelerate the movement of such ions toward the substrate 5 without the need of outputting the negative bias.
  • the self-bias since the aforementioned self-bias caused by the supply of the radio frequency power to plasma assumes a negative potential, the self-bias is capable of exerting an attractive force upon ions of the halogen compound.
  • the film deposition system 10 may be configured so that it is controlled through a controller not shown.
  • This controller is capable of exercising controls over the film deposition system 10 so that: the aforementioned radio frequency power supply unit 11 operates to output a radio frequency power having a desired power value and a desired frequency; the aforementioned bias power supply unit 12 , 22 or 26 operates to output desired negative bias and positive bias; and the aforementioned function generator 32 and linear amplifier 31 perform desired actions.
  • the controller may be configured to actuate the evacuation means such as a vacuum pump and the gas supply means so as to provide a desired vacuum atmosphere in the chamber 1 .
  • the present invention can use various halogen compounds as film materials for films that can be deposited according to the present invention.
  • the present invention is applied to magnesium fluoride as a most preferred application of the present invention.
  • FIG. 7 is a graph showing the influence of a radio frequency power upon the absorption coefficient of a magnesium fluoride thin film.
  • the horizontal axis and the vertical axis represent a wavelength and an absorption coefficient, respectively.
  • the radio frequency power was varied stepwise to assume three levels of 50 W, 300 W and 500 W as a parameter.
  • the absorption coefficient of a magnesium fluoride thin film deposited on a substrate in the visible light region increases as the radio frequency power supplied to a vacuum chamber becomes higher.
  • FIG. 8 is a graph showing the influence of a substrate temperature upon the absorption coefficient of a magnesium fluoride thin film.
  • the horizontal axis and the vertical axis represent a wavelength and an absorption coefficient, respectively.
  • the substrate temperature was varied stepwise to assume seven levels of not heated, 50° C., 100° C., 150° C., 200° C., 250° C., 300° C. as a parameter.
  • the radio frequency power was set to 300 W.
  • the absorption coefficient of a magnesium fluoride thin film deposited on a substrate in the visible light region increases as the substrate temperature rises.
  • FIGS. 9A and 9B are schematic views illustrating obstruction to impingement of fluorine ions upon a substrate surface and elimination of fluorine ions from a substrate surface; that is, FIG. 9A illustrates the obstruction to impingement, while FIG. 9B illustrates the elimination.
  • the magnesium fluoride thin film deposited on the substrate 5 is in a fluorine-deficient condition and hence has an increased absorption coefficient in the visible light region.
  • the amount of fluorine ions 103 dissociated from the magnesium fluoride 101 is proportional to the radio frequency power. For this reason the absorption coefficient of the magnesium fluoride thin film increases as the radio frequency power becomes higher.
  • FIGS. 10A and 10B are views illustrating actions of the present invention; specifically, FIG. 10A illustrates the action of incorporating dissociated fluorine ions, while FIG. 10B illustrates the action of preventing elimination of fluorine.
  • the bias voltage has a duration for which a positive bias is provided, fluorine ions 103 dissociated from magnesium fluoride 101 by plasma are incorporated into the film being deposited on the surface of the substrate 5 as shown in FIG. 10A. Further, since the bias voltage has a duration in which a positive bias is provided periodically, fluorine ions 103 are prevented from being eliminated from magnesium fluoride 101 deposited on the substrate surface. As a result, the absorption coefficient of the magnesium fluoride film to be deposited on the substrate 5 is prevented from increasing in the visible light region.
  • FIG. 11 is a graph showing the dependence of the light absorptance of a magnesium fluoride thin film upon the pulse frequency of a bias voltage.
  • the horizontal axis and the vertical axis represent a wavelength and a light absorptance, respectively.
  • the pulse frequency of a bias voltage of the waveform shown in FIG. 1B was varied to assume two levels of 65 kHz and 100 kHz.
  • the thin film deposited using the bias voltage having a pulse frequency of 100 kHz exhibited a considerably lowered absorptance as compared with the absorptance of the thin film deposited using the bias voltage having a pulse frequency of 65 kHz.
  • the absorptance obtained with the pulse frequency of 100 kHz was satisfactory.
  • the absorptance obtained with the pulse frequency of 65 kHz made substantially no difference from that obtained without application of a positive bias.
  • FIG. 12 to be specifically described later shows the case where the pulse frequency of a bias voltage was 350 kHz and a quartz (silica) substrate was used.
  • the pulse frequency is more than 350 kHz is not shown, it is theoretically preferred that the bias voltage have short positive bias durations with a shortest-possible cycle. Accordingly, a higher pulse frequency is more preferable.
  • the pulse frequency be not higher than 2.45 GHz because too high a pulse frequency makes plasma discharge in the vacuum chamber unstable. If the pulse frequency is set to 2.45 GHz, it is desirable to use an ECR (electron cyclotron resonance) apparatus. A film deposition system employing such an ECR apparatus will be described later.
  • FIG. 12 is a graph showing the light absorptance of a magnesium fluoride thin film deposited on a quartz substrate within the visible light region.
  • the magnesium fluoride thin film exhibited a lower absorptance than in the case of FIG. 11 where the magnesium fluoride film was deposited on a glass substrate by virtue of a combined effect of the use of the quartz substrate and the setting of the pulse frequency of a bias voltage to 350 kHz.
  • the absorptance of quartz is also shown in FIG. 12.
  • FIGS. 13A and 13B are drawings for illustrating a wear-resistance test; specifically, FIG. 13A is a perspective view schematically showing the overview of a wear-resistance tester, while FIG. 13B is a table showing wear-resistance evaluation criteria.
  • wear-resistance tester 201 used in this test comprises a reciprocating movable base 202 for receiving a test sample (a substrate deposited with a thin film) 203 thereon, and a press element 205 having steel wool 204 on the underside thereof for pressing the test sample 203 at a predetermined load (700 g in this case).
  • Reference numeral 206 denotes an arm holding the press element 205 .
  • the steel wool 204 used here was of #0000.
  • the wear-resistance of each test sample was rated on the following four ranks A to D as shown in FIG. 13B: rank A indicating a film condition with no flaw, rank B indicating a film condition with slight flaw, rank C indicating a film condition with flaw and peeling, and rank D indicating a film condition almost peeled.
  • the wear-resistance of a thin film deposited under application of a positive bias was rated higher by about one rank than that of a thin film deposited without application of a positive bias.
  • the wear-resistance of a thin film deposited with the degree of vacuum optimized in the film-depositing process was rated higher by about one to about two ranks than that of a thin film deposited under usual conditions.
  • FIG. 14 is a table showing the crystal grain diameters of magnesium fluoride films.
  • the crystal grain diameter of a magnesium fluoride thin film deposited by evaporation at 300° C. is 12 to 20 nm.
  • a magnesium fluoride thin film deposited by evaporation at a normal temperature (that is, the substrate was not heated) was not crystallized and, hence, determination of the crystal grain diameter thereof is impossible.
  • the crystal grain diameter of a magnesium fluoride thin film deposited using the film deposition system according to the subject example is 3 to 10 nm. From this fact it is found that the magnesium fluoride thin film according to the subject example has a crystal grain diameter that cannot be achieved by the prior art.
  • the main reason therefor is that the magnesium fluoride thin film according to the subject example is deposited by ion plating at a relatively low temperature (about 100° C. or below).
  • Preferable gas species for use in the present invention are as follows.
  • the vacuum chamber 1 is charged with argon gas.
  • a fluorine-containing gas such as CF 4 or SF 6 is more advantageous because such a gas can replenish the film to be deposited on the substrate with fluorine.
  • FIGS. 15A and 15B are drawings for illustrating an application of the subject example to a multi layered film; specifically, FIG. 15A is a view showing the structure of a multi layered film, while FIG. 15B is a graph showing the reflectivity of a multi layered film formed on a substrate within the visible light region.
  • This multi layered film had a favorable reflectance as shown in FIG. 15B.
  • FIG. 4 is a schematic overview of the configuration of film deposition system 35 capable of practicing the invention in another mode.
  • the film deposition system 35 is configured to form films on the basis of ion plating as a film deposition method.
  • the film deposition system 35 includes a vacuum chamber 36 , a radio frequency power supply (RF) 37 and a bias power supply unit (DC) 38 .
  • RF radio frequency power supply
  • DC bias power supply unit
  • the bias power supply unit 38 is capable of outputting a DC voltage having a constant positive voltage value. Application of the bias voltage outputted from the bias power supply unit 38 to the substrate holder 39 allows negatively-charged ions of a halogen element to be incorporated into the film being deposited on the substrate 5 as will be described later.
  • an evaporation source 3 for holding a film material comprising a halogen compound and for evaporating it into the space defined in the chamber 36 .
  • the evaporation source 3 is of the same construction as that used in the film deposition system 10 described earlier.
  • an ionization electrode 40 in the form of a coil.
  • the coiled ionization electrode 40 is connected to the radio frequency power supply 37 and, hence, it is possible to supply a radio frequency power into the chamber 36 through the ionization electrode 40 .
  • the radio frequency power supply 37 supplies a radio frequency power for ionizing the film material evaporated from the evaporation source 3 and passing through the inside of the ionization electrode 40 to generate plasma.
  • the radio frequency power supply 37 has one output terminal connected to the ionization electrode 40 through a matching box 41 and other output terminal grounded.
  • the matching box 41 includes a well-known matching circuit comprising a capacitor and a coil. Adjustment of the matching box allows matching to be made between the impedance of the radio frequency power supply 37 side and that of the vacuum chamber 36 side.
  • the vacuum chamber 36 is provided with evacuation means such as a vacuum pump and gas supply means, which are not particularly shown, for providing a desired vacuum atmosphere therein so that the atmosphere within the vacuum chamber 36 can be adjusted to a desired vacuum atmosphere meeting film-depositing conditions established.
  • evacuation means such as a vacuum pump and gas supply means, which are not particularly shown, for providing a desired vacuum atmosphere therein so that the atmosphere within the vacuum chamber 36 can be adjusted to a desired vacuum atmosphere meeting film-depositing conditions established.
  • the radio frequency power supply 37 is actuated to supply a radio frequency power into the chamber 36 through the ionization electrode 40 , while the halogen compound is evaporated by the evaporation source 3 .
  • the bias power supply unit 38 is actuated to apply a positive DC voltage to the substrate holder 39 .
  • the evaporated halogen compound passing through the ionization electrode 40 can be ionized to generate plasma, and resulting ions of the halogen compound are allowed to impinge upon and deposit on the substrate 5 thereby depositing the film.
  • FIG. 5 is a schematic overview of the configuration of film deposition system 45 capable of practicing the invention in yet another mode.
  • the film deposition system 45 is configured to deposit films with use of a cluster ion beam.
  • the film deposition system 45 includes a vacuum chamber 46 and a bias power supply unit (DC) 48 .
  • a substrate holder 49 for holding a substrate 5 on its back surface opposite from its obverse side on which a film is to be deposited.
  • the substrate holder 49 is configured so that it is capable of functioning also as a power supply electrode for supplying a bias voltage into the vacuum chamber 46 .
  • the substrate holder 49 is formed of an electrically-conductive material so as to be applied with the bias voltage outputted from the bias power supply unit 48 .
  • the bias power supply unit 48 is capable of outputting a DC voltage having a constant positive voltage value. Application of the bias voltage outputted from the bias power supply unit 48 to the substrate holder 49 allows negatively-charged ions of a halogen element to be incorporated into the film being deposited on the substrate 5 as will be described later.
  • Cluster ion generating means is disposed in the chamber 46 so as to face opposite to the substrate 5 .
  • the cluster ion generating means comprises well-known means for generating a cluster of atoms or molecules and well-known means for ionizing the cluster.
  • the cluster ion generating means has a cluster evaporation source 50 located in a lower portion of the inside of the chamber 46 and a coiled ionization electrode 53 .
  • the cluster evaporation source 50 has a crucible for holding therein a film material comprising a halogen compound and a coiled bombard filament surrounding the outer periphery of the crucible for heating the film material in the crucible.
  • the film material upwardly evaporated from a nozzle provided at the upper end of the crucible becomes clustered and is shot toward the substrate 5 .
  • This cluster is formed by cooling due to adiabatic expansion in the process of shooting of the film material from the nozzle of the crucible into the vacuum atmosphere and comprises hundreds or thousands of atoms or molecules of the film material loosely bound with an intermolecular force or the like.
  • the cluster shot out of the cluster evaporation source 50 is ionized by a radio frequency power supplied thereto through the ionization electrode 53 during its passage through the inside of the ionization electrode 53 , thus generating clustered ions.
  • the vacuum chamber 46 is provided with evacuation means such as a vacuum pump and gas supply means, which are not particularly shown, for providing a desired vacuum atmosphere therein so that the atmosphere within the vacuum chamber 46 can be adjusted to a desired vacuum atmosphere meeting film-depositing conditions established.
  • evacuation means such as a vacuum pump and gas supply means, which are not particularly shown, for providing a desired vacuum atmosphere therein so that the atmosphere within the vacuum chamber 46 can be adjusted to a desired vacuum atmosphere meeting film-depositing conditions established.
  • a film can be deposited in the following manner.
  • the cluster evaporation source 50 is loaded with a film material comprising a halogen compound, and substrate 5 is set on the substrate holder 49 .
  • a cluster is shot upwardly from the cluster evaporation source 50 and then passed through the inside of the ionization electrode 53 to generate clustered ions, which in turn are caused to impinge upon and deposit on the substrate 5 to deposit the film.
  • the halogen element with weak chemical bond in the cluster of the ionized halogen compound is easily dissociated from the ionized halogen compound in the film depositing process performed by the film deposition system 45 , it is possible to incorporate the halogen element once dissociated into the film being deposited on the substrate 5 .
  • application of a DC voltage outputted from the bias power supply unit 48 to the substrate holder 49 causes negatively-charged ions of the halogen element to be incorporated into the film being deposited on the substrate 5 .
  • the bias voltage outputted from the bias power supply unit 38 of the film deposition system 35 or from the bias power supply unit 48 of the film deposition system 45 described above may comprise a positive bias assuming a positive voltage and a negative bias assuming a negative bias.
  • the bias voltage used in the film deposition system 35 or 45 may be the bias voltage comprising a positive bias assuming a positive voltage value in the form of pulses and a negative bias assuming a constant negative voltage value, which has been described as an example of the bias voltage for use in the film deposition system 10 .
  • FIG. 6 is a schematic overview of the configuration of film deposition system 60 capable of practicing the invention in still another mode.
  • the film deposition system 60 is configured to deposit films on the basis of ion plating.
  • the film deposition system 60 shown in FIG. 6 is of the same configuration as the film deposition system 10 shown in FIG. 1A except the provision of an electron beam evaporation source 55 in the vacuum chamber 1 .
  • Members other than the electron beam evaporation source 55 are the same as corresponding members used in the film deposition system 10 . That is, the film deposition system 60 includes vacuum chamber 1 , substrate 5 , evaporation source 3 , and substrate holder 2 serving also as a bias voltage supply electrode.
  • Reference numeral 8 denotes an electric power supply unit comprising radio frequency power supply unit 11 and bias power supply unit 12 .
  • the bias power supply unit 12 comprises waveform generator 13 and bias power supply 14 .
  • Reference numeral 15 denotes a high pass filter, while reference numeral 16 denotes a first low pass filter.
  • These members provided in the film deposition system 60 are each constructed similarly to the corresponding member of the film deposition system 10 to operate in the same manner as does the corresponding member.
  • the electron beam evaporation source 55 is a well-known electron beam evaporation source capable of evaporating a film material by heating with an electron beam.
  • the electron beam evaporation source 55 includes a crucible 56 for holding a halogen compound as the film material.
  • the crucible 56 is loaded with the same material as the halogen compound stored in the evaporation source 3 .
  • the halogen compound in the crucible 56 is heated with electron beam 59 emitted from an electron gun not shown and is evaporated from an opening defined at an upper end of the crucible 56 into a space extending above the crucible 56 .
  • the electron beam evaporation source 55 is provided with a shutter 57 spaced a predetermined distance above the upper end of the crucible 56 and disposed to cover the crucible 56 .
  • the shutter 57 can revolve about a support shaft 55 a relative to the crucible 56 to switch its position between a closing position covering the crucible 56 from above and an open position retreated away from the position above the crucible 56 .
  • the evaporation source 55 evaporates the halogen compound using an electron beam, the evaporation source 55 is capable of evaporating the halogen compound in a more finely decomposed state, thus allowing ions of the halogen element to be dissociated more easily. Therefore, it becomes possible to supply such halogen ions to the substrate 5 more easily.
  • FIG. 16 is a schematic view showing the configuration of a vacuum film deposition system that is suitable for a bias voltage having a higher pulse frequency.
  • the vacuum film deposition system of this configuration includes an ECR apparatus 613 instead of the combination of the radio frequency power supply unit and the high pass filter shown in FIG. 1A.
  • the ECR apparatus 613 has an ECR cavity 607 open at a wall portion of the vacuum chamber 1 and an ECR power supply 608 and is configured to generate high-density plasma by directing a microwave of 2.45 GHz generated by the ECR power supply 608 into the ECR cavity 607 to cause electron cyclotron resonance under application of a magnetic field by a magnet not shown.
  • Such plasma 611 is supplied into the vacuum chamber 1 .
  • Other features are the same as the corresponding ones of the film deposition system shown in FIG. 1A.
  • This vacuum film deposition system employs evaporation source 603 of the resistive heating type adapted to evaporate a thin film material (magnesium fluoride) 606 placed on a boat 603 a by resistive heating. Behind the substrate holder 2 is disposed a heater 605 for heating the substrate 5 from behind.
  • Reference numeral 604 denotes a film thickness sensor, while reference numeral 609 denotes a gas outlet. Further, reference numeral 610 denotes the film material in an evaporated state.
  • the vacuum film deposition system thus configured supplies plasma 611 into the vacuum chamber 1 by means of the ECR apparatus 613 and hence prevents electric discharge from becoming unstable even if the pulse frequency of the bias voltage is made relatively high. It is possible to raise the pulse frequency up to a maximum of 2.45 GHz, which is equal to the frequency of the microwave supplied from the ECR power supply 608 .
  • a vacuum film deposition system configured for use in this mode is similar to the vacuum film deposition system shown in FIG. 1A except that the bias power supply unit 12 and the low pass filter 16 are not provided and that the resistor and the capacitor used in a matching box not shown have respective predetermined values.
  • This matching box comprises a fixed capacitor, a fixed resistor, a variable capacitor and the like. The inventor of the present invention has found that the following phenomenon occurs when the fixed capacitor and the fixed resistor have respective predetermined values.
  • FIG. 18 is a graph showing variations in the electric potential of the substrate holder 2 shown in FIG. 1A.
  • the radio frequency power supply unit of the subject vacuum film deposition system When the radio frequency power supply unit of the subject vacuum film deposition system is actuated to supply a radio frequency power into the vacuum chamber 1 , the electric potential of the substrate 2 varies like an oscillating wave that oscillates with an amplitude V a from a substantially constant negative voltage V dc serving as a center.
  • the frequency of this oscillating wave is equal to or an integer multiple of the frequency (usually 13.56 MHz) of a radio frequency power outputted from the radio frequency power supply unit.
  • the negative voltage V dc is considered to be a voltage corresponding to a self-bias that is generated in a usual case.
  • the mechanism based on which such a phenomenon occurs has not been elucidated yet. Since the amplitude V a of the oscillating wave is slightly larger than the negative voltage V dc in this vacuum film deposition system, the electric potential of the substrate holder 2 varies with a frequency equal to the frequency of a radio frequency power and periodically assumes a positive potential for a duration ⁇ t.
  • the subject vacuum film deposition system is capable of depositing a halogen compound thin film with lessened deficiency of the halogen element like the vacuum film deposition system shown in FIG. 1A.
  • the positive potential duration ⁇ t is preferably 10 ⁇ s or less.
  • the frequency of the oscillating wave is preferably within the range of from 13.56 MHz to 4 ⁇ 13.56 MHz.
  • the present invention is capable of depositing a film through ionization of a halogen compound as a film deposition system while allowing ions of the halogen element dissociated from ions of the halogen compound to be incorporated into the film being deposited, thereby making it possible to prevent the film from becoming deficient in the halogen element.
  • the present invention is capable of depositing a film through ionization of a halogen compound while preventing the film from becoming deficient in the halogen element, whereby the film thus deposited can be rendered dense and firm without impairment of the desired function.
  • the present invention is capable of preventing an intended film from becoming deficient in a halogen element, which is not easy to supplement in the form of a reactive gas to be supplied into the vacuum chamber.
  • a film of an oxide for example, it is possible to prevent the film from becoming deficient in oxygen by supplying oxygen gas to the film being deposited in the vacuum chamber.
  • oxygen gas to the film being deposited in the vacuum chamber.
  • the present invention provides the effect of depositing a halogen film while preventing the film from becoming deficient in the halogen element thereby ensuring the halogen compound film without impairment of its desired function.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Surface Treatment Of Optical Elements (AREA)
US10/247,081 2001-09-20 2002-09-19 Film deposition method and film deposition system for depositing a halogen compound film, and magnesium fluoride film Abandoned US20030068531A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/858,178 US7223449B2 (en) 2001-09-20 2004-06-01 Film deposition method

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001-287114 2001-09-20
JP2001287114 2001-09-20
JP2002080873A JP2003166047A (ja) 2001-09-20 2002-03-22 ハロゲン化合物の成膜方法及び成膜装置、並びにフッ化マグネシウム膜
JP2002-080873 2002-03-22

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/858,178 Division US7223449B2 (en) 2001-09-20 2004-06-01 Film deposition method

Publications (1)

Publication Number Publication Date
US20030068531A1 true US20030068531A1 (en) 2003-04-10

Family

ID=26622600

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/247,081 Abandoned US20030068531A1 (en) 2001-09-20 2002-09-19 Film deposition method and film deposition system for depositing a halogen compound film, and magnesium fluoride film
US10/858,178 Expired - Fee Related US7223449B2 (en) 2001-09-20 2004-06-01 Film deposition method

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/858,178 Expired - Fee Related US7223449B2 (en) 2001-09-20 2004-06-01 Film deposition method

Country Status (5)

Country Link
US (2) US20030068531A1 (enExample)
JP (1) JP2003166047A (enExample)
KR (1) KR100498278B1 (enExample)
CN (1) CN1284879C (enExample)
TW (1) TWI276695B (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050081999A1 (en) * 2003-10-17 2005-04-21 Naoki Yasui Plasma processing apparatus having high frequency power source with sag compensation function and plasma processing method
US20070098916A1 (en) * 2005-11-01 2007-05-03 Stowell Michael W System and method for modulation of power and power related functions of PECVD discharge sources to achieve new film properties
US20110175185A1 (en) * 2010-01-21 2011-07-21 Roper Scientific, Inc. Solid state back-illuminated photon sensor

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3981281B2 (ja) * 2002-02-14 2007-09-26 松下電器産業株式会社 半導体集積回路の設計方法及びテスト方法
USH2212H1 (en) * 2003-09-26 2008-04-01 The United States Of America As Represented By The Secretary Of The Navy Method and apparatus for producing an ion-ion plasma continuous in time
KR100674532B1 (ko) * 2005-02-28 2007-01-29 한국과학기술연구원 고분자 위에 접착력이 강한 금속 박막을 형성하기 위한 방법 및 장치
JP4757689B2 (ja) * 2006-03-31 2011-08-24 株式会社昭和真空 成膜装置及び成膜方法
US8540851B2 (en) * 2009-02-19 2013-09-24 Fujifilm Corporation Physical vapor deposition with impedance matching network
JP5504720B2 (ja) * 2009-07-14 2014-05-28 凸版印刷株式会社 成膜装置
JP5843491B2 (ja) * 2010-06-24 2016-01-13 キヤノン株式会社 塗布液、光学部品の製造方法および撮影光学系
US8760054B2 (en) * 2011-01-21 2014-06-24 Axcelis Technologies Inc. Microwave plasma electron flood
US9957618B2 (en) * 2012-02-28 2018-05-01 Massachusetts Institute Of Technology Single-unit reactor design for combined oxidative, initiated, and plasma-enhanced chemical vapor deposition
JP7094154B2 (ja) * 2018-06-13 2022-07-01 東京エレクトロン株式会社 成膜装置および成膜方法
TWI700967B (zh) * 2019-07-09 2020-08-01 日商住友重機械工業股份有限公司 負離子生成裝置
CN113604788B (zh) * 2021-07-27 2022-10-21 北京北方华创微电子装备有限公司 基座偏压调节装置和方法、半导体工艺设备

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030058547A1 (en) * 2001-09-20 2003-03-27 Takanobu Hori Optical system

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63106623A (ja) * 1986-10-23 1988-05-11 Fujitsu Ltd 液晶表示素子
JPH04224136A (ja) * 1990-12-26 1992-08-13 Matsunami Glass Kogyo Kk プラズマ放電処理を施したガラス材
US5756222A (en) * 1994-08-15 1998-05-26 Applied Materials, Inc. Corrosion-resistant aluminum article for semiconductor processing equipment
JP3585276B2 (ja) * 1994-12-01 2004-11-04 オリンパス株式会社 光学薄膜の製造方法およびこの光学薄膜を有する基板
JP3808917B2 (ja) * 1995-07-20 2006-08-16 オリンパス株式会社 薄膜の製造方法及び薄膜
JPH09243802A (ja) 1996-03-14 1997-09-19 Olympus Optical Co Ltd 光学薄膜の成膜方法および成膜装置
JPH09324262A (ja) * 1996-06-06 1997-12-16 Nikon Corp フッ化物薄膜の製造方法及びフッ化物薄膜
AU5354698A (en) * 1996-11-01 1998-05-29 Lawrence Berkeley Laboratory Low-resistivity photon-transparent window attached to photo-sensitive silicon detector
JP3987169B2 (ja) * 1997-10-02 2007-10-03 オリンパス株式会社 光学薄膜の製造方法
TW477009B (en) * 1999-05-26 2002-02-21 Tadahiro Ohmi Plasma process device
JP2001140067A (ja) * 1999-11-17 2001-05-22 Canon Inc 光学薄膜の成膜方法および成膜装置
JP4334723B2 (ja) * 2000-03-21 2009-09-30 新明和工業株式会社 イオンプレーティング成膜装置、及びイオンプレーティング成膜方法。
JP3840058B2 (ja) * 2000-04-07 2006-11-01 キヤノン株式会社 マイクロレンズ、固体撮像装置及びそれらの製造方法
US6677549B2 (en) * 2000-07-24 2004-01-13 Canon Kabushiki Kaisha Plasma processing apparatus having permeable window covered with light shielding film
US6875700B2 (en) * 2000-08-29 2005-04-05 Board Of Regents, The University Of Texas System Ion-Ion plasma processing with bias modulation synchronized to time-modulated discharges

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030058547A1 (en) * 2001-09-20 2003-03-27 Takanobu Hori Optical system

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050081999A1 (en) * 2003-10-17 2005-04-21 Naoki Yasui Plasma processing apparatus having high frequency power source with sag compensation function and plasma processing method
US20070186856A1 (en) * 2003-10-17 2007-08-16 Naoki Yasui Plasma processing apparatus having high frequency power source with sag compensation function and plasma processing method
US7615132B2 (en) * 2003-10-17 2009-11-10 Hitachi High-Technologies Corporation Plasma processing apparatus having high frequency power source with sag compensation function and plasma processing method
US20070098916A1 (en) * 2005-11-01 2007-05-03 Stowell Michael W System and method for modulation of power and power related functions of PECVD discharge sources to achieve new film properties
US7842355B2 (en) * 2005-11-01 2010-11-30 Applied Materials, Inc. System and method for modulation of power and power related functions of PECVD discharge sources to achieve new film properties
US20110175185A1 (en) * 2010-01-21 2011-07-21 Roper Scientific, Inc. Solid state back-illuminated photon sensor
WO2011091159A1 (en) * 2010-01-21 2011-07-28 Roper Scientific, Inc. Solid state back- illuminated photon sensor and its method of fabrication
US8436423B2 (en) 2010-01-21 2013-05-07 Roper Scientific, Inc. Solid state back-illuminated photon sensor

Also Published As

Publication number Publication date
US20040226509A1 (en) 2004-11-18
KR20030025886A (ko) 2003-03-29
TWI276695B (en) 2007-03-21
KR100498278B1 (ko) 2005-07-01
US7223449B2 (en) 2007-05-29
CN1410588A (zh) 2003-04-16
JP2003166047A (ja) 2003-06-13
CN1284879C (zh) 2006-11-15

Similar Documents

Publication Publication Date Title
US7223449B2 (en) Film deposition method
US5171607A (en) Method of depositing diamond-like carbon film onto a substrate having a low melting temperature
US6579428B2 (en) Arc evaporator, method for driving arc evaporator, and ion plating apparatus
US7252745B2 (en) Filtered cathodic arc deposition method and apparatus
EP0739001B1 (en) Deposition of insulating thin film by plurality of ion beams
US20040089535A1 (en) Process and apparatus for pulsed dc magnetron reactive sputtering of thin film coatings on large substrates using smaller sputter cathodes
US20040075910A1 (en) Optical antireflection film and process for forming the same
US6723209B2 (en) System and method for performing thin film deposition or chemical treatment using an energetic flux of neutral reactive molecular fragments, atoms or radicals
US6679976B2 (en) System and method for performing sputter deposition with multiple targets using independent ion and electron sources and independent target biasing with DC pulse signals
JPH0247256A (ja) 反応形スパッタリングによる酸化物膜の形成
JP2014520966A (ja) 基板上に少粒子層を形成するための方法および装置
KR101990658B1 (ko) 반응성 스퍼터링 공정
CN100587107C (zh) 带有预电离的脉冲式磁控管溅射沉积
JP2003512526A (ja) 複数の電極のスパッタリングシステムにおいて基板にバイアスをかける方法および装置
US9562283B2 (en) Coating of optical substrates using closed field system
EP0440326A1 (en) Method of depositing diamond-like film onto a substrate having a low melting temperature
US20050233089A1 (en) Sputter method or device for the production of natural voltage optimized coatings
Felmetsger et al. Dual cathode DC–RF and MF–RF coupled S-Guns for reactive sputtering
EP0968318A1 (en) Pulsed mode deposition for low rate film deposition
JPS596376A (ja) スパツタ装置
US7314525B2 (en) Plasma CVD apparatus
Glocker AC Magnetron Sputtering
JP2001140061A (ja) デポジションアシスト蒸着装置及び薄膜形成方法
JP2004035935A (ja) 成膜装置および成膜方法
JP2003321773A (ja) Ｅｃｒスパッタリング装置

Legal Events

Date Code Title Description
AS Assignment

Owner name: HITACHI, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HORI, TAKANOBU;KAJIYAMA, HIROSHI;KATO, AKIRA;REEL/FRAME:013575/0745

Effective date: 20021107

Owner name: SHINMAYWA INDUSTRIES, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HORI, TAKANOBU;KAJIYAMA, HIROSHI;KATO, AKIRA;REEL/FRAME:013575/0745

Effective date: 20021107

AS Assignment

Owner name: SHINMAYWA INDUSTRIES, LTD., JAPAN

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT ASSIGNEE'S ADDRESS, PREVIOUSLY RECORDED ON REEL 013575, FRAME 0745;ASSIGNORS:HORI, TAKANOBU;KAJIYAMA, HIROSHI;KATO, AKIRA;REEL/FRAME:014924/0327

Effective date: 20021107

Owner name: HITACHI, LTD., JAPAN

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT ASSIGNEE'S ADDRESS, PREVIOUSLY RECORDED ON REEL 013575, FRAME 0745;ASSIGNORS:HORI, TAKANOBU;KAJIYAMA, HIROSHI;KATO, AKIRA;REEL/FRAME:014924/0327

Effective date: 20021107

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION