US3472679A - Coating surfaces - Google Patents
Coating surfaces Download PDFInfo
- Publication number
- US3472679A US3472679A US779339A US3472679DA US3472679A US 3472679 A US3472679 A US 3472679A US 779339 A US779339 A US 779339A US 3472679D A US3472679D A US 3472679DA US 3472679 A US3472679 A US 3472679A
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- US
- United States
- Prior art keywords
- coating material
- carrier gas
- plasma
- coating
- selenium
- 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.)
- Expired - Lifetime
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- 238000000576 coating method Methods 0.000 title description 80
- 239000011248 coating agent Substances 0.000 title description 74
- 239000000463 material Substances 0.000 description 77
- 239000012159 carrier gas Substances 0.000 description 51
- 210000002381 plasma Anatomy 0.000 description 51
- 238000000034 method Methods 0.000 description 35
- 239000010408 film Substances 0.000 description 30
- 239000000758 substrate Substances 0.000 description 22
- 229910052711 selenium Inorganic materials 0.000 description 21
- 239000011669 selenium Substances 0.000 description 21
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000003384 imaging method Methods 0.000 description 9
- 229910052785 arsenic Inorganic materials 0.000 description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 7
- 229910052714 tellurium Inorganic materials 0.000 description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 6
- 229910052716 thallium Inorganic materials 0.000 description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32422—Arrangement for selecting ions or species in the plasma
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
- G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
- G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
- G03G5/08207—Selenium-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
Definitions
- a process for coating a film on a surface which comprises; establishing a carrier gas stream flowing from a source of coating material toward a surface to be coated With said material; said carrier gas stream being made up substantially of a carrier gas and a coating material, exciting said carrier gas into plasma state in the vicinity of said coating material, and diminishing said plasma at a point intermediate said source and said surface to be coated, whereby said carrier stream in a vapor state contacts said surface, and a film of said coating material is formed thereon, with said coating material being selected from the group comprising selenium, arsenic, tellurium, antimony, bismuth, thallium, sulfur, and mixtures thereof.
- This invention relates to improved vapor coating techniques plasma transport for producing highly uniform films on support substrates.
- a coating material is vaporized in a controlled atmosphere and allowed to condense on a substrate placed in the vapor stream.
- the coating material must remain in the vapor state until it reaches the substrate to be coated, various practical limitations are involved. For example, the distance the vapor can travel before condensation occurs is limited, and direction of the vapor stream is diflicult. Moreover, special precautions are frequently necessary to insure the chemical uniformity of the coatings.
- a plasma carrier can be used to transport a suitable film forming material and that this process can be used to produce films of excellent adherency and extremely high chemical uniformity, including photoconductive films suitable for use in xerography and in migration imaging systems. Adherency and uniformity are especially advantageous in these two instancesbecause of the strict physical and electrical parameters that are imposed in high quality imaging and recording.
- the present invention it is preferable to practice the present invention with a plasma that will react with the coating material and transport it in a metastable form to, or near, the substrate to be coated.
- a plasma that will react with the coating material and transport it in a metastable form to, or near, the substrate to be coated.
- a method and apparatus for coating a film on a surface which comprises establishing a carrier stream flowing from a source of coating material toward the surface to be coated, in which the carrier stream is made up of a carrier gas and a coating material.
- an external inductively coupled excitation source is used to generate a carrier gas to the plasma state which reacts with a coating material, such as selenium, or other suitable material placed in a chamber.
- the carrier gas in the plasma state carries the coating material toward a surface to be coated with the plasma being diminished by means of a grounded electrode at some point intermediate the coating material source and the surface to be coated.
- the vapor stream then contacts the surface to be coated resulting in a uniform film or coating of the coated material formed on the surface or substrate.
- This novel method is particularly adapted to forming photoconductive coatings having xerographic utility in which the material to be coated comprises selenium, arsenic, tellurium, antimony, bismuth, thallium, sulphur, and mixtures thereof.
- the material to be coated comprises selenium, arsenic, tellurium, antimony, bismuth, thallium, sulphur, and mixtures thereof.
- these photoconductive materials may optionally contain small amounts of certain additives which modify or enhance their electrical or physical properties.
- materials such as halogens, which include iodide, chlorine, fluorine, and bromine, may be added either as or in the carrier gas or be inherently contained in the coating materials themselves in order to impart added sensitivity or spectral response.
- the reactive carrier gas for the above grouping of materials preferably includes hydrogen and ammonia. It should be understood, however, that other carrier gases may be used. These include gases containing halogens, hydrides of phosphorus, arsenic, selenium, and antimony, and halides of phosphorus, arsenic, selenium antimony, sulphur, and bismuth.
- gases containing halogens, hydrides of phosphorus, arsenic, selenium, and antimony, and halides of phosphorus, arsenic, selenium antimony, sulphur, and bismuth gases containing halogens, hydrides of phosphorus, arsenic, selenium, and antimony, and halides of phosphorus, arsenic, selenium antimony, sulphur, and bismuth.
- the Group IV, V, VI elements present in these gases will also be deposited out during the coating step and will be included in small amounts in the resultant film.
- hydrogen is introduced at one end of a reaction chamber maintained at reduced pressure by means of a vacuum pump connected to an outlet tube at the opposite end of the "chamber.
- An external inductively coupled excitation source is used to generate a plasma which reacts with a source of selenium placed in the chamber.
- the plasma is terminated or effectively diminished at a predetermined point by means of a grounded electrode, for example, strapped to the outside of the reaction chamber.
- the coating material is found to deposit on an aluminum substrate positioned in the vapor stream beyond the plasma zone.
- FIG. 1 illustrates the reaction tube and apparatus for a continuous flow system according to the present invention
- FIG. 2 illustrates a continuous flow system wherein the coating material is injected in vapor form
- FIG. 3 is another embodiment of coating apparatus.
- FIG. 1 schematically illustrates a continuous flow system for producing coatings in accordance with the present invention.
- Reaction chamber 5 preferably of glass or quartz, includes a vessel 6 having inlet port 7, and end-plate 8 having outlet port 9.
- the inlet port is connected to carrier gas supply tank 11; the outlet port is connected to pump 12.
- the apparatus is provided with inlet and outlet valves, represented at 13 and 14, to control the gas flow.
- An excitation source is provided to produce a plasma zone within the chamber.
- this comprises a water-cooled copper coil 15, surrounding part of the chamber and connected to electrical power generator 16.
- Grounded electrode 17 is provided to terminate the plasma at a predetermined point.
- a vapor stream flowing in the general direction indicated by the arrow is established by means of the illustrated apparatus to transport coating material at source 18 to substrate 19 (of a metal such as stainless steel, aluminum, brass, glass, plastic, or the like) located downstream beyond the point where the plasma is terminated.
- substrate 19 of a metal such as stainless steel, aluminum, brass, glass, plastic, or the like
- carrier gas is continuously fed into the reaction chamber, excited to the plasma state, and then returned to the ground state at a predetermined point downstream.
- the carrier gas and coating material are used in proper combination so that the plasma reacts with the coating material placed in the reaction chamber and is capable of transporting it towards the member to be coated. It is desirable, however, that the coating material be transported in a sufficiently unstable form so that it will deposit on surfaces (including those of the substrate to be coated) with which it comes in contact beyond the plasma zone. That is, the coating material should be transportable in the plasma phase of the carrier gas but should be sufiiciently unstable in the vapor phase to return to solid form on the substrate to be coated.
- pump 12 is operated to pass hydrogen from the supply tank 11 at a rate of about 1 cc./rnin. (measured at room temperature and atmospheric pressure) through reaction chamber under a reduced pressure in the range of 20-100 microns of mercury.
- a 100 watt electrical power generator 16 such as a Viking Challenger, Model 240-182 (E. F. Johnson Co., Waseca, Minn.), is operated to supply a 30 megacycle alternating current to coil 15. It is noted that the light intensity emitted by the plasma appears to be highest at the region close to the coil and gradually diminishes in intensity downstream.
- source 18 comprises substantially pure selenium (99.999% pure obtained from the American Smelting and Refining Co.) in the form of pellets to Mt inch in diameter are placed in the plasma zone of the chamber.
- Deposition of selenium on substrates 19, in the form of a highly uniform film, takes place only on the surfaces beyond the plasma zone; selenium does not coat out within the plasma region itself.
- the thickness of the selenium film builds up at the rate of about 1 micron per hour. It should be understood, however, that the rate of evaporation for any of the aforementioned coating materials may be increased or decreased by simply varying the process parameters by techniques well known to the art.
- the operating pressure of the above-described process may be selected within the range of from about 10 microns to several millimeters of mercury, depending upon the power supplied to the coil.
- Other suitable plasma such as ammonia, may also be used.
- the applied alternating current is desirably within radio frequency range.
- the imaging member, or plate, use in migration imaging as more fully described in patent application Ser. No. 460,377, filed June 1, 1965, comprises a discontinuous easily fracturable photoconductive layer overlying a softenable layer coated on a stable mechanical support.
- the above-described process may be used to form a thin selenium film on a substrate 19 comprising a 2 micron layer of Staybelite Ester 10 (Hercules Powder Company) on a Mylar polyester film (E. I. du Pont de Nemours Co., Inc.) having a thin transparent aluminum coating.
- the deposited selenium film is preferably about 0.2 micron in thickness.
- the plate is then electrostatically charged in darkness to a positive potential of about 60 volts by means of a corona discharge device in accordance with well-known xerographic techniques. Charging is followed by an optical image exposure of 1.5l 10 photons/cm. by means of a 4,000 Angstrom unit light source. The plate is immersed in a bath of liquid cyclohexane for about 2 seconds and removed. A faithful replica of the optical image is thereby produced.
- the present invention is not restricted to a reaction of the plasma with coating material in solid form only.
- the coating material may be injected into the plasma in vapor form.
- the apparatus of FIG. 2 is the same as that of FIG. 1, except that the reaction chamber, designated 5', is provided with one or more sidearms represented at 21, adapted to hold a coating material. Each sidearm is provided with a heating means, such as an electric heating element shown at 20.
- pump 12 is connected to outlet port 9 and tank 11' is connected to inlet port 7'.
- the apparatus includes valves 13' and 14' and a plasma generating means including coil 15 connected to electrical power generator 16'. Electrically grounded electrode 17' surrounds vessel 6 downstream from the plasma zone.
- End-plate 6' permits access to the interior of vessel 6' for positioning substrates 19' and the coating material source.
- the rate of flow of the carrier gas and coating material in the vapor form should preferably be in a molar ratio of 1 or more in favor of the carrier gas. For example, for every mole of hydrogen, less than 1 atom equivalent of selenium should be used. Ratios of less than 1 can be used, but the above ratio is preferred.
- FIG. 3 schematically illustrates another embodiment of the present invention.
- Bell-jar 22 rests on support base 23 which is provided with inlet port 24 and outlet port 25 for connection to the carrier gas supply and an exhaust pump or other evacuation means, respectively, not shown in this figure.
- the apparatus also includes one or more pedestals represented at 26, each of which is provided with a heater represented at 27.
- Coil 28 surrounding insulating chimney 29, of glass, is adapted for example, for connection to a radio frequency power source similar to those described above in FIGS. 1 and 2.
- Substrate 31, supported by any conventional means, is positioned above the chimney in the vapor stream produced when coating material 32 is heated.
- substrate 31 is schematically shown as suspended over the chimney by means of glass hangers 33 attached to chamber 22 by means of suction fittings 34.
- FIG. 3 Operation of the apparatus illustrated in FIG. 3 is essentially the same as described in connection with FIG. 2.
- An appropriate carrier gas is introduced into the bell-jar through the inlet port 24, a reduced pressure is created by the evacuation means attached to port 25.
- a radio frequency current applied to the coil excites the carrier gas in the chimney to the plasma state.
- the heated coating material which is evaporated upwards is injected into the plasma zone and transported in the direction of the substrate on which it forms as a highly uniform adherent film.
- carrier gas and coating material should be used.
- gases such as argon are ineffective in the described process for transporting selenium, arsenic, tellurium, antimony, bismuth, thallium, sulphur, and mixtures thereof.
- halogen plasmas such as, for example, chlorine plasma and iodine plasma can be used effectively to produce uniform coatings of the above coating materials.
- Group IV, V, VI, VIII elements are present in the carrier gas, these elements will also be deposited out in the coating or film. Therefore, the combination of carrier gas and coating material should be selected so as to yield a coating having the desired composition and properties.
- a process for coating a film on a surface which comprises; establishing a carrier gas stream flowing from a source of coating material toward a surface to be coated with said material; said carrier gas stream being made up substantially of a carrier gas and a coating material, exciting said carrier gas into plasma state in the vicinity of said coating material, and diminishing said plasma at a point intermediate said source and said surface to be coated, whereby said carrier gas stream in a vapor state contacts said surface, and a film of said coating material is formed thereon, with said coating material being selected from the group comprising selenium, arsenic, tellurium, antimony, bismuth, thallium, sulphur, and mixtures thereof.
- the carrier gas comprises a material selected from the group comprising hydrogen, ammonia, chlorine, and iodine.
- the process for forming a film on a surface which comprises; establishing a carrier gas stream in the reaction chamber containing a source of coating material, generating a high frequency electrical field to excite a carrier gas to the plasma state in the vicinity of said coating material whereby said material coacts with and is transported in said carrier gas stream, with said coating material comprising a material selected from the group comprising selenium, arsenic, tellurium, antimony, bismuth, thallium, sulfur, and mixtures thereof, and causing said carrier to contact said surface outside the plasma zone produced above, whereby a film of said coating material is formed on said surface.
- the carrier gas comprises a material selected from the group comprising hydrogen, ammonia, chlorine and iodine.
- a process for coating a surface which comprises producing a carrier gas stream flowing through a first zone and a second zone, sequentially, exciting a carrier gas in a first zone to the plasma state, vaporizing a coating material selected from the group comprising selenium, arsenic, tellurium, antimony, bismuth, thallium, sulfur, and mixtures thereof, and injecting the vapor of said material into the carrier gas in said first zone, and terminating the plasma in said second zone whereby said coating material deposits on said surface.
- the carrier gas comprises a material selected from the group comprising hydrogen, ammonia, chlorine and iodine.
- Coating apparatus comprising:
- reaction chamber in which members to be coated can be placed, said chamber including an inlet port,
- the means including a supply tank for said carrier gas connected to the inlet port,
- valve means connected to the inlet and outlet ports to control the flow of carrier gas
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US48235465A | 1965-08-25 | 1965-08-25 | |
US77933968A | 1968-11-27 | 1968-11-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3472679A true US3472679A (en) | 1969-10-14 |
Family
ID=27047253
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US779339A Expired - Lifetime US3472679A (en) | 1965-08-25 | 1968-11-27 | Coating surfaces |
Country Status (4)
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3776181A (en) * | 1970-02-02 | 1973-12-04 | Ransburg Electro Coating Corp | Deposition apparatus for an organometallic material |
US3874917A (en) * | 1966-05-16 | 1975-04-01 | Xerox Corp | Method of forming vitreous semiconductors by vapor depositing bismuth and selenium |
US3886896A (en) * | 1973-07-13 | 1975-06-03 | Tellecommunications Cit Alcate | Device for plasma depositing of thin layers onto substrates |
US3906892A (en) * | 1971-04-27 | 1975-09-23 | Cit Alcatel | Plasma deposition of thin layers of substrated or the like |
FR2290504A1 (fr) * | 1974-11-05 | 1976-06-04 | Eastman Kodak Co | Procede pour deposer une couche de matiere dielectrique photosensible sur un support |
US4013463A (en) * | 1975-08-15 | 1977-03-22 | Leder Lewis B | Photoreceptor fabrication utilizing AC ion plating |
US4091257A (en) * | 1975-02-24 | 1978-05-23 | General Electric Company | Deep diode devices and method and apparatus |
US4099969A (en) * | 1974-10-10 | 1978-07-11 | Xerox Corporation | Coating method to improve adhesion of photoconductors |
US4148275A (en) * | 1976-02-25 | 1979-04-10 | United Technologies Corporation | Apparatus for gas phase deposition of coatings |
US4223048A (en) * | 1978-08-07 | 1980-09-16 | Pacific Western Systems | Plasma enhanced chemical vapor processing of semiconductive wafers |
US4492716A (en) * | 1979-08-16 | 1985-01-08 | Shunpei Yamazaki | Method of making non-crystalline semiconductor layer |
US4500565A (en) * | 1983-09-28 | 1985-02-19 | Ushio Denki Kabushiki Kaisha | Deposition process |
WO1985000999A1 (fr) * | 1983-08-25 | 1985-03-14 | Vsesojuzny Nauchno-Issledovatelsky Instrumentalny | Outil de coupe et son procede de fabrication |
US4505949A (en) * | 1984-04-25 | 1985-03-19 | Texas Instruments Incorporated | Thin film deposition using plasma-generated source gas |
US4509451A (en) * | 1983-03-29 | 1985-04-09 | Colromm, Inc. | Electron beam induced chemical vapor deposition |
EP0218916A1 (en) * | 1985-09-10 | 1987-04-22 | Yifei Zhang | A process to form a sulphide case at the surface of a metal part |
US5707692A (en) * | 1990-10-23 | 1998-01-13 | Canon Kabushiki Kaisha | Apparatus and method for processing a base substance using plasma and a magnetic field |
US6448148B2 (en) * | 2000-03-17 | 2002-09-10 | Tokyo Institute Of Technology | Method for forming a thin film |
US6539890B1 (en) * | 1998-05-28 | 2003-04-01 | Nano Scale Surface Systems, Inc. | Multiple source deposition plasma apparatus |
US20110177260A1 (en) * | 2008-07-01 | 2011-07-21 | Yuuji Honda | Plasma cvd device, method for depositing thin film, and method for producing magnetic recording medium |
CN103874316A (zh) * | 2014-03-24 | 2014-06-18 | 青岛科技大学 | 一种实验室用感应等离子处理设备的设计 |
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US3290567A (en) * | 1960-09-23 | 1966-12-06 | Technical Ind Inc | Controlled deposition and growth of polycrystalline films in a vacuum |
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US3310424A (en) * | 1963-05-14 | 1967-03-21 | Litton Systems Inc | Method for providing an insulating film on a substrate |
US3329601A (en) * | 1964-09-15 | 1967-07-04 | Donald M Mattox | Apparatus for coating a cathodically biased substrate from plasma of ionized coatingmaterial |
US3355371A (en) * | 1964-06-29 | 1967-11-28 | Gen Motors Corp | Method of anodizing a metal in a plasma including connecting said metal in a separate electrical circuit |
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- 1966-08-12 GB GB36095/66A patent/GB1160895A/en not_active Expired
- 1966-08-22 NL NL6611792A patent/NL6611792A/xx unknown
- 1966-08-23 DE DE1621325A patent/DE1621325B2/de active Pending
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US2501563A (en) * | 1946-02-20 | 1950-03-21 | Libbey Owens Ford Glass Co | Method of forming strongly adherent metallic compound films by glow discharge |
US3024761A (en) * | 1958-07-01 | 1962-03-13 | Ibm | Vacuum evaporation apparatus |
US3108900A (en) * | 1959-04-13 | 1963-10-29 | Cornelius A Papp | Apparatus and process for producing coatings on metals |
US3290567A (en) * | 1960-09-23 | 1966-12-06 | Technical Ind Inc | Controlled deposition and growth of polycrystalline films in a vacuum |
US3310424A (en) * | 1963-05-14 | 1967-03-21 | Litton Systems Inc | Method for providing an insulating film on a substrate |
US3297465A (en) * | 1963-12-31 | 1967-01-10 | Ibm | Method for producing organic plasma and for depositing polymer films |
US3296115A (en) * | 1964-03-02 | 1967-01-03 | Schjeldahl Co G T | Sputtering of metals wherein gas flow is confined to increase the purity of deposition |
US3355371A (en) * | 1964-06-29 | 1967-11-28 | Gen Motors Corp | Method of anodizing a metal in a plasma including connecting said metal in a separate electrical circuit |
US3329601A (en) * | 1964-09-15 | 1967-07-04 | Donald M Mattox | Apparatus for coating a cathodically biased substrate from plasma of ionized coatingmaterial |
US3275412A (en) * | 1965-02-04 | 1966-09-27 | American Cyanamid Co | Production of oxides by plasma process |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3874917A (en) * | 1966-05-16 | 1975-04-01 | Xerox Corp | Method of forming vitreous semiconductors by vapor depositing bismuth and selenium |
US3776181A (en) * | 1970-02-02 | 1973-12-04 | Ransburg Electro Coating Corp | Deposition apparatus for an organometallic material |
US3906892A (en) * | 1971-04-27 | 1975-09-23 | Cit Alcatel | Plasma deposition of thin layers of substrated or the like |
US3886896A (en) * | 1973-07-13 | 1975-06-03 | Tellecommunications Cit Alcate | Device for plasma depositing of thin layers onto substrates |
US4099969A (en) * | 1974-10-10 | 1978-07-11 | Xerox Corporation | Coating method to improve adhesion of photoconductors |
FR2290504A1 (fr) * | 1974-11-05 | 1976-06-04 | Eastman Kodak Co | Procede pour deposer une couche de matiere dielectrique photosensible sur un support |
US4091257A (en) * | 1975-02-24 | 1978-05-23 | General Electric Company | Deep diode devices and method and apparatus |
US4013463A (en) * | 1975-08-15 | 1977-03-22 | Leder Lewis B | Photoreceptor fabrication utilizing AC ion plating |
US4148275A (en) * | 1976-02-25 | 1979-04-10 | United Technologies Corporation | Apparatus for gas phase deposition of coatings |
US4223048A (en) * | 1978-08-07 | 1980-09-16 | Pacific Western Systems | Plasma enhanced chemical vapor processing of semiconductive wafers |
US4492716A (en) * | 1979-08-16 | 1985-01-08 | Shunpei Yamazaki | Method of making non-crystalline semiconductor layer |
US4543267A (en) * | 1979-08-16 | 1985-09-24 | Shunpei Yamazaki | Method of making a non-single-crystalline semi-conductor layer on a substrate |
US4505950A (en) * | 1979-08-16 | 1985-03-19 | Shunpei Yamazaki | Method of manufacturing a multiple-layer, non-single-crystalline semiconductor on a substrate |
US4509451A (en) * | 1983-03-29 | 1985-04-09 | Colromm, Inc. | Electron beam induced chemical vapor deposition |
WO1985000999A1 (fr) * | 1983-08-25 | 1985-03-14 | Vsesojuzny Nauchno-Issledovatelsky Instrumentalny | Outil de coupe et son procede de fabrication |
GB2156387A (en) * | 1983-08-25 | 1985-10-09 | Vni Instrument Inst | Cutting tool and method of manufacture thereof |
US4500565A (en) * | 1983-09-28 | 1985-02-19 | Ushio Denki Kabushiki Kaisha | Deposition process |
US4505949A (en) * | 1984-04-25 | 1985-03-19 | Texas Instruments Incorporated | Thin film deposition using plasma-generated source gas |
EP0218916A1 (en) * | 1985-09-10 | 1987-04-22 | Yifei Zhang | A process to form a sulphide case at the surface of a metal part |
US5707692A (en) * | 1990-10-23 | 1998-01-13 | Canon Kabushiki Kaisha | Apparatus and method for processing a base substance using plasma and a magnetic field |
US6539890B1 (en) * | 1998-05-28 | 2003-04-01 | Nano Scale Surface Systems, Inc. | Multiple source deposition plasma apparatus |
US6448148B2 (en) * | 2000-03-17 | 2002-09-10 | Tokyo Institute Of Technology | Method for forming a thin film |
US20110177260A1 (en) * | 2008-07-01 | 2011-07-21 | Yuuji Honda | Plasma cvd device, method for depositing thin film, and method for producing magnetic recording medium |
CN103874316A (zh) * | 2014-03-24 | 2014-06-18 | 青岛科技大学 | 一种实验室用感应等离子处理设备的设计 |
CN103874316B (zh) * | 2014-03-24 | 2016-05-11 | 青岛科技大学 | 一种实验室用感应等离子处理设备的设计 |
Also Published As
Publication number | Publication date |
---|---|
DE1621325B2 (de) | 1975-08-07 |
NL6611792A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1967-02-27 |
GB1160895A (en) | 1969-08-06 |
DE1621325A1 (de) | 1971-05-13 |
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