US3756847A - Method for controlling the composition of a deposited film - Google Patents

Method for controlling the composition of a deposited film Download PDF

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Publication number
US3756847A
US3756847A US00195784A US3756847DA US3756847A US 3756847 A US3756847 A US 3756847A US 00195784 A US00195784 A US 00195784A US 3756847D A US3756847D A US 3756847DA US 3756847 A US3756847 A US 3756847A
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Prior art keywords
substrate
compound
film
composition
potential
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Expired - Lifetime
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US00195784A
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English (en)
Inventor
Iii F Tams
D Leobowitz
D Hoffman
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RCA Corp
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RCA Corp
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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
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/548—Controlling the composition

Definitions

  • This invention relates to a method for depositing a film of a compound on a substrate and more particularly to a method for controlling the composition of a compound film during deposition on a substrate to affect the electrical and physical properties of the final compound film.
  • Apparatus and methods utilizing electron beams for evaporating a material for deposition on a substrate are well known in the art.
  • the high temperature generated at the focal point of an electron beam permits rapid heating and evaporation of many materials including refractory materials and insulators, e.g. aluminum oxide, cerium oxide, and silicon dioxide. Evaporation of these materials permits their utilization upon deposition as thin films for optical filters (e.g., cerium oxide), insulating layers for thin film capacitors (e.g., silicon dioxide) or as passivating and radiation resistant films (e.g., aluminum oxide on metal oxide semiconductors). Success of such utilization, however, is often highly dependent on the quality of film deposited.
  • FIG. 1 is a schemaic section view of an apparatus that may be used for carrying out the method of the present invention
  • FIG. 2 is a bottom plan view of a portion of the apparatus of FIG. 1 taken along the line 22 of FIG. 1;
  • FIG. 3 is a graph of ultraviolet absorption spectra of two films deposited by the method of the invention.
  • FIG. 1 An eighteen inch stainless-steel cylindrical vacuum chamber 10', closed at one end by an aluminum lid 12, is positioned on a stainlesssteel base collar 14. Internal evacuation of chamber 10 is accomplished by withdrawing the contained air or gasses from the chamber through a six inch pipe 16, located in the collar 14, that is in communication with the interior of the chamber and connected to a suitable vacuum pump (not shown).
  • a substrate 18 is attached to a disk-shaped substrate holder 20 that is positioned in the upper portion of chamber 10. The relative position of the substrate on the substrate holder is shown in greater detail in FIG. 2.
  • the substrate holder 20 is suspended from a vertical shaft 22 which has an insulator portion 24 to provide both thermal and electrical isolation of the substrate holder 20.
  • the shaft 22 extends through the lid 12 and is directly connected to the armature of an electrical rotor 26 that is mounted on the top of the lid 12. Rotation of the substrate 18 by the rotor 26 permits greater uniformity of deposition when the substrate area is large.
  • This heater is designed to provide uniform heat over a flat surface.
  • the heater 28 is mounted to a heat shield 30 by ceramic insulators 32 and in turn the heat shield 30 is mounted to the lid 12 by other ceramic insulators 34.
  • An electron beam gun 36 is mounted on collar 14 with its electron beam 38 directed horizontally toward the center of chamber 10.
  • Gun 36 is preferably one specifically designed for vaporization of materials in a vacuum sys tem, such as that manufactured by Denton Vacuum, Inc. and designated model number DEG-801.
  • the electron beam 38 passes through an aperture 40 in a gun shield 42 and is deflected downwardly toward a water cooled copper hearth 44 by deflection plates 46 that are integral parts of the electron beam gun.
  • a compound 48 to be evaporated is placed in hearth 44 for vaporization by the electron beam 38. It is desirable to shield the substrate from the evaporated material prior to establishment of a constant evaporation rate and following deposition of the compound on the substrate. Therefore, a shutter 50, such as a Japanese fan shutter, is provided between the hearth 44 and the substrate 18.
  • Temperature of the substrate holder 20 may be monitored by a stainless-steel sheathed chromel-alumel thermocouple 52 in contact with the holder 20. Since it is desirable to control deposition thickness, a quartz crystal oscillator 54 also may be placed adjacent the substrate holder. Oscillator 54 should be heat bafiled and thermally insulated from the heater 28. As deposition on the substrate takes place, simultaneous deposition on the quartz crystal oscillator 54 also occurs thereby varying the output frequency of the oscillator. Therefore, by predetermining the correlation between deposit thickness and oscillator output frequency, the frequency can be monitored and deposit thickness continuously determined. Suitable gases to aid in controlling the composition of the deposited film may also be provided to an area surrounding the substrate through a tube 56 which enters the vacuum chamber through the collar 14 and projects upwardly to a point adjacent the substrate 18.
  • the particular method selected is determined by the respective positions of two switches 58 and 60.
  • One method is set-up by connecting the substrate 18 to the negative terminal of a variable direct current voltage supply 62 and the positive terminal of the voltage supply to ground G. This configuration is accomplished by moving switch 58 to contact A and switch 60 to contact C. In this configuration, the potential difference between the substrate 18 and the electron gun 36 can be varied by adjusting the voltage level of voltage supply 62.
  • switch 60 is moved to open contact D and switch 58 to contact B thereby connecting the substrate 18 directly to ground G.
  • a third configuration is set-up by moving switch 58 to contact A and switch 60 to contact E.
  • the substrate 18 is isolated from ground and is connected to the negative terminal of voltage supply 62 and the positive terminal of supply 62 is connected to a grid 64 located between the hearth 44 and the substrate 18.
  • Grid 64 is a highly transparent wire mesh that also may be heated to prevent excessive adherence of the vaporated material.
  • One method of electrostatic potential control utilizing this configuration is accomplished by adjusting the voltage of supply 62.
  • Another method of control is also possible by moving grid 64 vertically to various positions with respect to the substrate.
  • a DC. voltage potential of 22 volts was established between the substrate 18 and the grid 64 by the appropriate adjustment of voltage supply 62.
  • the shutter 50 was then opened and the substrate 18 was coated to a predetermined thickness.
  • the crystal oscillator frequency output indicated that the desired thickness had been achieved, the shutter 50 was closed and the oxygen turned off.
  • the apparatus was then allowed to cool to room temperature and the chamber was opened by back filling with nitrogen to break the seal. Later the preceeding experiment was repeated under the same conditions, only this time, utilizing a substrate-to-grid voltage potential of 8 volts.
  • results of this experiment indicate that the optical density of the resultant aluminum oxide film can be varied from a dark brown coloration, when a relatively high resultant negative potential is applied to the substrate, to an essentially clear film at relatively low resultant potentials. Therefore, the variations in film shading may be correlated with resultant potential and the results used to predetermine the proper setting of voltage or grid position to meet any particular shading requirement.
  • FIG. 3 shows the optical density results for the foregoing experiment.
  • Curve A was obtained at the resultant negative potential of -22 volts and Curve B at the re sultant negative potential of -8 volts.
  • the film of Curve A appeared to be dark brown whereas the film of Curve B had a light brownish shading. Further experimentation confirmed these results and also established that an essentially clear film could be obtained at a 2.5 volts resultant potential.
  • the color variations noted in the aluminum oxide films prepared at various electrostatic potentials are the result of composition variations induced by the electrostatic charges.
  • One possible mechanism for this result is that dissociated positive aluminum ions and negative oxygen ions are produced during electron beam bombardment. Divergent electrons from the beam negatively charge the substrate which thereby repels the oxygen ions. Proper recombination of the oxygen ions with the aluminum can only occur if the energy of the impacting ions exceeds the repelling potential of the substrate. Therefore, by adjusting substrate potential it is possible to repel or attract various portions of the available oxygen ions.
  • ferroelectric materials i.e., niobates (lithium and potassium) and titanates (barium and lead).
  • ferroelectric properties of these materials are dependent upon the composition obtained at the substrate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
US00195784A 1971-11-04 1971-11-04 Method for controlling the composition of a deposited film Expired - Lifetime US3756847A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US19578471A 1971-11-04 1971-11-04

Publications (1)

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US3756847A true US3756847A (en) 1973-09-04

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US00195784A Expired - Lifetime US3756847A (en) 1971-11-04 1971-11-04 Method for controlling the composition of a deposited film

Country Status (12)

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US (1) US3756847A (enrdf_load_stackoverflow)
JP (1) JPS5216467B2 (enrdf_load_stackoverflow)
AU (1) AU464727B2 (enrdf_load_stackoverflow)
BE (1) BE790940A (enrdf_load_stackoverflow)
CA (1) CA975628A (enrdf_load_stackoverflow)
CH (1) CH590935A5 (enrdf_load_stackoverflow)
DE (1) DE2252484A1 (enrdf_load_stackoverflow)
FR (1) FR2156413B1 (enrdf_load_stackoverflow)
GB (1) GB1392865A (enrdf_load_stackoverflow)
IT (1) IT975345B (enrdf_load_stackoverflow)
NL (1) NL7214898A (enrdf_load_stackoverflow)
SE (1) SE379059B (enrdf_load_stackoverflow)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847659A (en) * 1971-11-13 1974-11-12 Teijin Ltd Process for producing plastic articles having transparent electroconductive coatings
US3889019A (en) * 1969-03-13 1975-06-10 United Aircraft Corp Vapor randomization in vacuum deposition of coatings
US4021277A (en) * 1972-12-07 1977-05-03 Sprague Electric Company Method of forming thin film resistor
US4416912A (en) * 1979-10-13 1983-11-22 The Gillette Company Formation of coatings on cutting edges
US4472453A (en) * 1983-07-01 1984-09-18 Rca Corporation Process for radiation free electron beam deposition
US4617192A (en) * 1982-12-21 1986-10-14 At&T Bell Laboratories Process for making optical INP devices
US5514229A (en) * 1993-11-24 1996-05-07 Ramot-University Authority For Applied Research And Industrial Development Ltd., Tel Aviv University Method of producing transparent and other electrically conductive materials
US6503379B1 (en) 2000-05-22 2003-01-07 Basic Research, Inc. Mobile plating system and method
US6521104B1 (en) * 2000-05-22 2003-02-18 Basic Resources, Inc. Configurable vacuum system and method
US20030180450A1 (en) * 2002-03-22 2003-09-25 Kidd Jerry D. System and method for preventing breaker failure
US20050126497A1 (en) * 2003-09-30 2005-06-16 Kidd Jerry D. Platform assembly and method
US7250196B1 (en) 1999-10-26 2007-07-31 Basic Resources, Inc. System and method for plasma plating
US20080057195A1 (en) * 2006-08-31 2008-03-06 United Technologies Corporation Non-line of sight coating technique

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5181791A (ja) * 1975-01-13 1976-07-17 Osaka Koon Denki Kk Ionkapureeteinguhoho
JPS60251273A (ja) * 1984-05-28 1985-12-11 Mitsubishi Heavy Ind Ltd 真空蒸発装置の蒸発量制御方法
US4842710A (en) * 1987-03-23 1989-06-27 Siemens Aktiengesellschaft Method of making mixed nitride films with at least two metals

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3889019A (en) * 1969-03-13 1975-06-10 United Aircraft Corp Vapor randomization in vacuum deposition of coatings
US3847659A (en) * 1971-11-13 1974-11-12 Teijin Ltd Process for producing plastic articles having transparent electroconductive coatings
US4021277A (en) * 1972-12-07 1977-05-03 Sprague Electric Company Method of forming thin film resistor
US4416912A (en) * 1979-10-13 1983-11-22 The Gillette Company Formation of coatings on cutting edges
US4617192A (en) * 1982-12-21 1986-10-14 At&T Bell Laboratories Process for making optical INP devices
US4472453A (en) * 1983-07-01 1984-09-18 Rca Corporation Process for radiation free electron beam deposition
US5514229A (en) * 1993-11-24 1996-05-07 Ramot-University Authority For Applied Research And Industrial Development Ltd., Tel Aviv University Method of producing transparent and other electrically conductive materials
US7250196B1 (en) 1999-10-26 2007-07-31 Basic Resources, Inc. System and method for plasma plating
US6521104B1 (en) * 2000-05-22 2003-02-18 Basic Resources, Inc. Configurable vacuum system and method
US20030136670A1 (en) * 2000-05-22 2003-07-24 Kidd Jerry D. Mobile plating system and method
US20030159926A1 (en) * 2000-05-22 2003-08-28 Kidd Jerry D. Configurable vacuum system and method
US6858119B2 (en) 2000-05-22 2005-02-22 Basic Resources, Inc. Mobile plating system and method
US6905582B2 (en) 2000-05-22 2005-06-14 Basic Resources, Inc. Configurable vacuum system and method
US7189437B2 (en) 2000-05-22 2007-03-13 Basic Resources, Inc. Mobile plating system and method
US6503379B1 (en) 2000-05-22 2003-01-07 Basic Research, Inc. Mobile plating system and method
US20030180450A1 (en) * 2002-03-22 2003-09-25 Kidd Jerry D. System and method for preventing breaker failure
US20050126497A1 (en) * 2003-09-30 2005-06-16 Kidd Jerry D. Platform assembly and method
US20080057195A1 (en) * 2006-08-31 2008-03-06 United Technologies Corporation Non-line of sight coating technique

Also Published As

Publication number Publication date
FR2156413A1 (enrdf_load_stackoverflow) 1973-05-25
AU464727B2 (en) 1975-09-04
DE2252484A1 (de) 1973-05-10
BE790940A (fr) 1973-03-01
JPS4855670A (enrdf_load_stackoverflow) 1973-08-04
JPS5216467B2 (enrdf_load_stackoverflow) 1977-05-10
CH590935A5 (enrdf_load_stackoverflow) 1977-08-31
SE379059B (enrdf_load_stackoverflow) 1975-09-22
IT975345B (it) 1974-07-20
FR2156413B1 (enrdf_load_stackoverflow) 1976-05-21
GB1392865A (en) 1975-05-07
CA975628A (en) 1975-10-07
NL7214898A (enrdf_load_stackoverflow) 1973-05-08
AU4778272A (en) 1974-04-26

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