US3916075A - Chemically highly resistant material - Google Patents

Chemically highly resistant material Download PDF

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Publication number
US3916075A
US3916075A US379459A US37945973A US3916075A US 3916075 A US3916075 A US 3916075A US 379459 A US379459 A US 379459A US 37945973 A US37945973 A US 37945973A US 3916075 A US3916075 A US 3916075A
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United States
Prior art keywords
titanium
films
boron nitride
weight
film
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Expired - Lifetime
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US379459A
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English (en)
Inventor
Heinz Dimigen
Hubertus Hubsch
Holger Luthje
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US Philips Corp
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US Philips Corp
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Priority claimed from DE19722236074 external-priority patent/DE2236074C3/de
Application filed by US Philips Corp filed Critical US Philips 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • 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
    • C23C14/0641—Nitrides
    • C23C14/0647—Boron nitride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture

Definitions

  • the thin films con- 26 stitute, for example, insulators or resistors.
  • the BN/Ti films have eminent sliding properties and may be used, 1 References Clted for example, as a solid lubricant and for potentiom- UNlTED STATES PATENTS eters.
  • the invention relates to chemically high resistant material which is provided in the form of thin films on substrates.
  • thin films are understood to mean films having a thickness of from 100 A to 10 ,um particularly having a thickness of from 1 to 2 pm.
  • chemically highly resistant will be come apparent hereinafter.
  • materials such as, for example, glass, metal, synthetic material, quartz and silicon discs are suitable as a substrate.
  • insulators which consist of, for example, SiO SiO or A1 or capacitors which comprise, for example, thin films of tantalum oxide or titanium dioxide must not only have the required electrical properties (low dielectric constant, small loss factor, high breakdown strength) but also a high chemical resistance and a satisfactory selective etching behaviour in order that a satisfactory structuring of all film materials present in the relevant construction is possible.
  • optical elements thin films having a defined refractive index are increasingly being used.
  • the field of use ranges from miniaturized optical elements in the integrated technique (for example, electro optical converters) to coating of optical elements (for example, lenses).
  • miniaturized optical elements in the integrated technique for example, electro optical converters
  • coating of optical elements for example, lenses.
  • materials having a high chemical resistance for example, a resistance to hydrofluoric acid.
  • chemically highly resistant is not only understood to mean a high resistance to environmental influences, for example, tapwater and industrial air but also a selective etching behaviour relative to the chemicals used in the above-mentioned technologies, for example, hydrofluoric acid.
  • boron nitride is a very suitable material particularly when it can be manufactured as a thin film tightly adhering to the surface of the article, which film is uniform, evenly compact and resilient.
  • boron nitride films may be advantageously used as dielectrics namely as insulators for leads, as fuses or as dielectrics in capacitors (German Auslegeschrift l ,52 l ,5 28
  • the invention is characterized in that the material constituting the thin film is boron nitride which comprises 0.5 to by weight of at least one element from the IVth sub-groupof the Periodic Table of Elements.
  • the elements from the IVth sub-group of the Periodic Table are titanium, zirconium and hafnium. As is known, these materials are very similar as regards their behaviour so that they may replace each other entirely or partly within the scope of the invention. Consequently if for the sake of simplicity the invention is described in detail with reference to titanium only, this should not be considered as a limitation of the invention because corresponding examples can be given with zirconium and hafnium.
  • Vapour deposition processes in which the material to be provided as a thin film is heated in a suitable ambience (for example, in vacuo or in a shielding gas) to such an extent that it evaporates and is deposited as a film on the substrates.
  • a suitable ambience for example, in vacuo or in a shielding gas
  • Plasma spray processes in which the material to be provided as a thin film is brought into a plasma are as a fine-grained powder. In that case the powder particles melt and are deposited as a film on adjacently provided substrates.
  • Cathode sputtering also referred to as RF ionic sputtering in which the material to be provided as a thin film is brought as a target in a gas discharge in such a manner that the material is sputtered by ion bombardment.
  • the removed (sputtered) particles are deposited as a thin film on the substrate which is provided adjacent in the counter electrode (substrate holder). Due to the choice of the filler gas in which the ionsare carriers for the occurring independent gas discharge, the composition of the film provided by sputtering may be influenced.
  • the invention therefore also relates to a method of providing thin films of a chemically highly resistant material on substrates and is characterized in that at least one target of boron nitride and of an element from the IVth sub-group of the Periodic Table is subjected in the presence of a gas to a cathode sputtering treatment.
  • one target which comprises the desired quantities of the elements from the IVth sub-group of the Periodic Table it is alternatively possible to use, for example, two targets one of which consists of boron nitride and the other consists of, for example, titanium.
  • a further possibility is to subject a boron nitride disc coated with discs of at least one element from the IVth sub-group of the Periodic Table in the presence of a gas to a cathode sputtering treatment.
  • the properties of the films obtained are dependent on the extent of coating of the boron nitride disc with the smaller discs of, for example, titanium. This provides the possibility of varying these properties. A further possibility of varying these properties is the choice of the gases (nitrogen or argon).
  • the graph of FIG. 1 shows the dependence of the etching rates A (in pm per minute) (removal of the film per unit of time) on the titanium content Ti (in by weight) of the film to be preferably used as an insulating material; line 1 for so called Permalloy etchant (see below) and line 2 for so-called titanium etchant (see also below).
  • FIG. 2 shows in a graph the dependence of the specific resistance p (in Ohm.cm) of the titanium content (Ti in by weight) of the films to be preferably used as a resistive material.
  • Line 1 for films provided in using nitrogen and line 2 for films provided in using argon as a shielding gas).
  • FIGS. 3a and 3b show in graphs the etching behaviour of film to be preferably used as a resistive material.
  • Line 1 is for so-called Permalloy etchant and line 2 for the use of so-called titanium etchant, in each figure respectively.
  • the diagram of FIG. 4 shows the relationship between the refractive index n and the titanium content (Ti, in by weight) of films to be preferably used as an optical material.
  • the graph of FIG. 5 shows the dependence of the temperature coefficient a (l/C) of the titanium content Ti (in by weight) of films to be preferably used as a resistive material.
  • Thin films of boron nitride and titanium with titanium contents of between 1 and 6% provided in nitrogen by sputtering constitute insulating materials having a high chemical resistance. Such an insulator has the specific resistance
  • the dielectric properties correspond to those of the known SiO insulators.
  • boron nitride-titanium insulators are equivalent to the known insulators.
  • boron nitride-titanium insulators are, however, very resistant to hydrofluoric acid.
  • a Permalloy etchant has, for example, the following composition:
  • the graph in FIG. 1 shows the etching rates A (in ,um/min.) of boron nitride-titanium insulators comprising 1 to 6% of titanium for the said Permalloy etchant (line 1) and for a so-called titanium etchant (line 2) comprising hydrofluoric acid and having the following composition:
  • Boron nitride-titanium films comprising 1 to 6% of titanium may be manufactured, for example, by cathode sputtering of a target of boron nitride-titanium material having a titanium content of between 1.5% to 8.5% in a nitrogen atmosphere.
  • a resistive material is obtained in which an (experimentally determined) correlation is present between titanium content and specific resistance (FIG. 2).
  • a defined specific resistance can be obtained with this material comprising from 5% to 95% of titanium which has as compared with the known resistive materials a better thermal conductivlty.
  • FIG. 3a N discharge
  • FIG. 3b Ar discharge
  • a negligibly small etching rate and in FIG. 3b an etching rate (removal of the film per unit of time) which is sufficient for film structures is obtained in the given etching solution.
  • Films which are provided by sputtering both in nitrogen and in argon are resistant to hydrofluoric acid.
  • the titanium content of the target in case of an N discharge must be between 8.5% and 97% and in case of an Ar discharge must be between 2% and 90% for the envisaged range of compositions of the film (5% to 95% of Ti).
  • the films thus manufactured exhibit a satisfactory thermal conductivity and an eminent sliding capacity.
  • the sliding property is of importance.
  • the temperature coefficient a of BN/Ti sputtered in Ar in the range having a titanium content of the film of from 40% to 100% is not larger than 3. l0 l/C and in addition has a zero crossing at approximately of titanium (FIG. 5).
  • Thin films of a boron nitride-titanium material whose titanium content is between 0.5% and IS% constitute a resistive optic material having a variable refractive index.
  • This material whosc etching behaviour is shown in FIG. 1 can only be etched in the given solutions. As compared with other acids (including hydrofluoric acid) it is found to be resistant.
  • the refractive index is shown in FIG. 4 as a function of the titanium content.
  • Films having the optical property as shown in FIG. 4 are provided by sputtering in a nitrogen discharge while a boron nitride-titanium material is used as a target whose titanium content may vary between 0.7% and 21% so as to obtain the desired refractive index.
  • a boron nitride-titanium material is used as a target whose titanium content may vary between 0.7% and 21% so as to obtain the desired refractive index.
  • nitrogen as a gas it is probable that the components of this material according to the invention are boron nitride and titanium nitride.
  • M05 boron nitride is among the known solid lubricants. Whereas pure BN films are sensitive to chemical reagents the etching behaviour is modified to a considerable extent already in low doped materials as is apparent from the above-mentioned examples.
  • This property causes the material according to the invention to be suitable as a lubricant even under circumstances promoting corrosion.
  • a boron nitride disc evenly coated with titanium discs (diameter 2 mm) on its surface was used as a target.
  • the substrates consisted of silicon wafers either coated or not coated with an SiO film and having a thickness of one-fourth mm and a diameter of 33 mm, and glass sheets of the same dimensions. They were present in a substrate holder at a distance of 30 mm from the target so that one of their surfaces faced the target.
  • the gas discharge was effected at a pressure of l.5.l0 Torr.
  • a transmitter having an operating frequency of 27.12 MHz and a maximum power of 2.5 kW was used as a high-frequency source.
  • the energy density of the ions on the target was approximately 3 W sq.cm.
  • the substrates were not separately heated, but reached a temperature of approximately 300C during sputtering.
  • the time to provide a l ,um thick film varied with the titanium content of the target and was one hour at an average, that is to say, a film of approximately 170 A thick was provided per minute.
  • a chemically resistant material which is provided in the form of a thin film on substrates, said material being a mixture consisting essentially of from 0.5 to by weight of at least one element from the group consisting of titanium, zirconium, and hafnium and the balance boron nitride.

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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)
  • Non-Adjustable Resistors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Inorganic Insulating Materials (AREA)
  • Surface Treatment Of Glass (AREA)
US379459A 1972-07-22 1973-07-16 Chemically highly resistant material Expired - Lifetime US3916075A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19722236074 DE2236074C3 (de) 1972-07-22 Chemisch hochresistenter -Werkstoff und Verfahren zur Herstellung dünner Oberflächenschichten aus diesem Werkstoff

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JP (1) JPS5212396B2 (de)
FR (1) FR2193886B1 (de)
GB (1) GB1431935A (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226932A (en) * 1979-07-05 1980-10-07 Gte Automatic Electric Laboratories Incorporated Titanium nitride as one layer of a multi-layered coating intended to be etched
US4321100A (en) * 1981-03-25 1982-03-23 The United States Of America As Represented By The Secretary Of The Army Method of joining boron nitride to a refractory
US4645621A (en) * 1984-12-17 1987-02-24 E. I. Du Pont De Nemours And Company Resistor compositions
US4680243A (en) * 1985-08-02 1987-07-14 Micronix Corporation Method for producing a mask for use in X-ray photolithography and resulting structure
US5035940A (en) * 1988-09-19 1991-07-30 Rexham Corporation Aluminum-fluoropolymer laminate
US5075130A (en) * 1990-11-19 1991-12-24 The United States Of America As Represented By The Secretary Of The Army Surface modification of boron carbide to form pockets of solid lubricant
US5403458A (en) * 1993-08-05 1995-04-04 Guardian Industries Corp. Sputter-coating target and method of use
US20090129762A1 (en) * 2005-07-01 2009-05-21 Ulrich Goetz Initial Wetting Auxiliary Material for a Vaporiser Body

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51150057A (en) * 1975-06-18 1976-12-23 Matsushita Electric Ind Co Ltd Variable resistor
JPS54184197U (de) * 1978-06-16 1979-12-27
GB8508338D0 (en) * 1985-03-29 1985-05-09 British Aerospace Application of stop-off coating
JPH0387563U (de) * 1989-12-18 1991-09-05
LU87988A1 (de) * 1991-08-08 1993-03-15 Europ Communities Verfahren zur herstellung einer ti-b-n-beschichtung auf einem substrat mittels sputtern

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2156803A (en) * 1934-05-03 1939-05-02 Cooper Products Inc Lubricant
US2842837A (en) * 1956-04-17 1958-07-15 United States Steel Corp Method of working wire and a lubricant therefor
US3003885A (en) * 1960-02-01 1961-10-10 Union Carbide Corp Titanium diboride article
US3242006A (en) * 1961-10-03 1966-03-22 Bell Telephone Labor Inc Tantalum nitride film resistor
US3256103A (en) * 1963-05-20 1966-06-14 Refractory article
US3275915A (en) * 1966-09-27 Beta tantalum thin-film capacitors
US3437592A (en) * 1963-11-04 1969-04-08 Westinghouse Electric Corp Electrically conductive solid lubricant members and apparatus employing them
US3551247A (en) * 1968-01-29 1970-12-29 Norton Research Corp Laminated vacuum coated titanium structural material
US3575858A (en) * 1969-05-20 1971-04-20 Us Air Force Lubricating composition consisting of perarylated silanes and solid lubricant powders
US3730507A (en) * 1971-01-18 1973-05-01 Union Carbide Corp Boron nitride base evaporation vessel having a surface coating of titanium-silicon thereon
US3824113A (en) * 1972-05-08 1974-07-16 Sherwood Refractories Method of coating preformed ceramic cores
US3841848A (en) * 1970-01-30 1974-10-15 Suwa Seikosha Kk HARD WATCH CASE COMPRISING TiN, T, AND AT LEAST ONE OF Mn, Al AND V

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3275915A (en) * 1966-09-27 Beta tantalum thin-film capacitors
US2156803A (en) * 1934-05-03 1939-05-02 Cooper Products Inc Lubricant
US2842837A (en) * 1956-04-17 1958-07-15 United States Steel Corp Method of working wire and a lubricant therefor
US3003885A (en) * 1960-02-01 1961-10-10 Union Carbide Corp Titanium diboride article
US3242006A (en) * 1961-10-03 1966-03-22 Bell Telephone Labor Inc Tantalum nitride film resistor
US3256103A (en) * 1963-05-20 1966-06-14 Refractory article
US3437592A (en) * 1963-11-04 1969-04-08 Westinghouse Electric Corp Electrically conductive solid lubricant members and apparatus employing them
US3551247A (en) * 1968-01-29 1970-12-29 Norton Research Corp Laminated vacuum coated titanium structural material
US3575858A (en) * 1969-05-20 1971-04-20 Us Air Force Lubricating composition consisting of perarylated silanes and solid lubricant powders
US3841848A (en) * 1970-01-30 1974-10-15 Suwa Seikosha Kk HARD WATCH CASE COMPRISING TiN, T, AND AT LEAST ONE OF Mn, Al AND V
US3730507A (en) * 1971-01-18 1973-05-01 Union Carbide Corp Boron nitride base evaporation vessel having a surface coating of titanium-silicon thereon
US3824113A (en) * 1972-05-08 1974-07-16 Sherwood Refractories Method of coating preformed ceramic cores

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226932A (en) * 1979-07-05 1980-10-07 Gte Automatic Electric Laboratories Incorporated Titanium nitride as one layer of a multi-layered coating intended to be etched
US4321100A (en) * 1981-03-25 1982-03-23 The United States Of America As Represented By The Secretary Of The Army Method of joining boron nitride to a refractory
US4645621A (en) * 1984-12-17 1987-02-24 E. I. Du Pont De Nemours And Company Resistor compositions
US4680243A (en) * 1985-08-02 1987-07-14 Micronix Corporation Method for producing a mask for use in X-ray photolithography and resulting structure
US5035940A (en) * 1988-09-19 1991-07-30 Rexham Corporation Aluminum-fluoropolymer laminate
US5075130A (en) * 1990-11-19 1991-12-24 The United States Of America As Represented By The Secretary Of The Army Surface modification of boron carbide to form pockets of solid lubricant
US5403458A (en) * 1993-08-05 1995-04-04 Guardian Industries Corp. Sputter-coating target and method of use
US20090129762A1 (en) * 2005-07-01 2009-05-21 Ulrich Goetz Initial Wetting Auxiliary Material for a Vaporiser Body

Also Published As

Publication number Publication date
DE2236074B2 (de) 1976-06-16
GB1431935A (en) 1976-04-14
JPS4945352A (de) 1974-04-30
FR2193886B1 (de) 1977-05-13
JPS5212396B2 (de) 1977-04-06
FR2193886A1 (de) 1974-02-22
DE2236074A1 (de) 1974-02-07

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