US3803057A - Resistive materials and method of making such materials - Google Patents

Resistive materials and method of making such materials Download PDF

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Publication number
US3803057A
US3803057A US00227070A US22707072A US3803057A US 3803057 A US3803057 A US 3803057A US 00227070 A US00227070 A US 00227070A US 22707072 A US22707072 A US 22707072A US 3803057 A US3803057 A US 3803057A
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United States
Prior art keywords
resistive
tin
zrn
films
aln
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Expired - Lifetime
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US00227070A
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English (en)
Inventor
K Wasa
F Hosomi
S Hayakawa
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Publication date
Priority claimed from JP46013829A external-priority patent/JPS5110677B1/ja
Priority claimed from JP46015273A external-priority patent/JPS5110678B1/ja
Priority claimed from JP46015274A external-priority patent/JPS5110679B1/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to US05/433,892 priority Critical patent/US4016061A/en
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Publication of US3803057A publication Critical patent/US3803057A/en
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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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/075—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques
    • H01C17/12—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques by sputtering
    • 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
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering

Definitions

  • ABSTRACT A resistive film composition consisting essentially of AlN and solid solution of TiN and ZrN and a method of making the same by means of a cathodic sputtering.
  • the present invention relates to a novel resistive material for manufacturing thin film resistors and to a method of making such a material. More particularly, it relates to a resistive film composition consisting essentially of AIN and solid solution of TiN and ZrN and to a method of making this material by cathodic sputtering.
  • the present invention provides a novel resistive material consisting essentially of AIN and a solid solution of TiN and ZrN for the manufacturing of the precise thin film resistors having a wide range of resistivities and good electrical stability.
  • this novel material according to the present invention is indispensable to the manufacturing of precise thin film resistors having a wide range of resistivities.
  • a resistor composition which is especially good for thin film resistors and having a composition consisting essentially of AIN and a solid solution of TiN and ZrN, the composition having a cermet type of structure.
  • the material is made by electron beam deposition, ion beam deposition or cathodic sputtering on a suitable substrate.
  • FIGS. 1-5 are diagrams showing the resistive properties of the thin resistive films consisting essentially of AIN and a solid solution of TiN and ZrN for various concentrations of AlN, TiN and ZrN in accordance with the present invention.
  • FIGS. 6 and 7 are diagrammatic view of the cathodic sputtering apparatus which is used in the method of making precise thin film resistors having a wide range of resistivities in accordance with the present inven tion.
  • the resistive materials for the manufacturing of precise thin film resistors having a wide range of resistivities according to the present invention consist essentially of AIN and a solid solution of TiN and ZrN.
  • the structure of said resistive materials is similar to the cermets, wherein the metallic conductor is said solid solution of TiN and ZrN and the dielectric is said AIN.
  • Thin resistive films of said resistive materials according to the present invention can be made by suitable methods of depositing thin films, such as an electron beam deposition method, an ion beam deposition method or a cathodic sputtering method.
  • said thin resistive films can be made on substrates of suitable material, such as alumina, glass or any other material having a low electrical conductivity by ion beam deposition from a composite target electrode consisting essentially of AIN, TiN and ZrN, and can also be made on said substrates by cathodic sputtering from a composite cathode consisting essentially of Al, Ti and Zr in a nitriding atmosphere.
  • the partial pressure of residual gases including 0, 0 OH, H 0 and hydrocarbons, be kept below 1X10 Torr during deposition of said thin resistive films, and that said substrates be kept at an elevated temperature, such as to 300C during deposition of said thin resistive films. It is also preferable that said substrates be annealed after deposition of said thin resistive films in air for 5 to 10 hours at an elevated temperature, such as 250 to 300C. Keeping the residual gases at a low partial pressure inhibits the incorporation of oxides, such as Al O TiO, Ti0 or ZrO in said thin resistive films. Elevating said substrate temperature during deposition of said thin resistive films and during annealing of said substrate after deposition of said thin resistive films results in an increase in the stability of the resistive properties, of said thin resistive films according to the present invention.
  • FIGS. 1 and 2 show the resistive properties of said thin resistive films consisting essentially of AIN and a solid solution of TiN and ZrN for various concentrations of AlN, TiN and ZrN when the thin resistive films are made by said cathodic sputtering.
  • the resistivity is denoted for films having thicknesses of 800 to 3,000 A. on glass substrates.
  • the temperature coefficient of resistivity is determined from the average values between 20 to 80C.
  • concentrations of AIN, TiN and ZrN described are estimated by assuming that the amount of each component deposited will be proportional to a fraction of the area of the surface of said composite cathode which is of the metal of the component, and will also be proportional to the relative sputtering rate. These estimations are supported by electron micrographic analysis and the mass-spectropic analysis.
  • the resistivity and the temperature coefficient of resistivity are 250 pflcm and ppm/C, respectively, for the TiN thin films.
  • the resistivity of the resultant films consisting of the Ti-A- l-N system increases and the temperature coefficient decreases with increasing AlN concentration.
  • the films At about 50 mole percent of AlN in the Ti-AlN system, the films have a zero temperature coefficient and a resistivity of 600 uflcm.
  • the resistivity increases significantly.
  • the temperature coefficient tends to a large negative value. For instance, at 70 mole percent of AlN, the resistivity is about 3,000 cm with a temperature coefficient of 1 ,000 ppm/C.
  • FIG. 3 is a diagram showing the resistive properties of the Ti-A- l-N system and the TiZrAl-N system, the amounts of material in the film resistor being proportional to the amounts of metal in the composite cathode used to form the film which is exposed on the surface of the electrode.
  • the TiAl-N system has a resistivity of only 1,000 item for a material with a temperature coefficient of 200 ppm/C, while the TiZrAl--N system can provide a resisitivity as high as 8,000 ptQcm for a material with the same temperature coefficient.
  • a resistive film material consisting essentially of AlN and a solid solution of TiN and ZrN, wherein the concentration of AlN ranges from to 50 mole percent, the concentration of TiN ranges from 10 to 80 mole percent, the concentration of ZrN ranges from 10 to 90 mole percent, and the mole ratios of AlN to TiN, [AlN]/[TiN], are less than 1.2.
  • resistive films having a wide range of resistivities, such as from 350 to 10,000 uflcm, with temperature coefficients of 200 to +150 ppm/C.
  • a'resistive film material consisting essentially of AlN and a solid solution of TiN and ZrN, wherein the concentration of AlN ranges from 10 to 40 mole percent, the concentration of TiN ranges from 40 to 70 mole percent and the concentration of ZrN ranges from to 50mole percent, can provide resistive films with a very small temperature coefficient such as +125 to 125 ppm/.C with resistivities in a range of 350to 1,000 pflcm.
  • Table 1 summarizes the typical resistive properties of the resistive films according to the present invention.
  • the resistive films according to the present invention can be prepared by cathodic sputtering from a composite cathode consisting essentially of Ti, Zr and Al in a nitriding atmosphere as described hereinbefore. This causes the composite cathode materials to be nitrided so as to form mixed nitride films consisting essentially of MN and a solid solution of TiN and ZrN on a substrate.
  • FIGS. 4 and 5 show the variation in the resistive properties of said mixed nitride films with the composition of the composite cathode.
  • the composition denotes the area fraction of each component on the surface of said composite cathode.
  • the resistive films having a wide range of resistivities such as 350 to 10,000 uflcm, with temperature coefficients from 200 to :t150 ppm/C, and the composition of which consists essentially of 10 to 50 mole percent of AlN, 10 to mole percent of TiN, 10 to 90 mole percent of ZrN, and having mole ratios of AlN to TiN of less than 1.2
  • a composite cathode consisting essentially of Al, Ti and Zr and having a structure such that the surface area thereof is 5 to 40% Al, 15 to Ti, and 10 to Zr, and the ratio of the areas of Alto Ti being less than 0.7.
  • the resistive films having a very small temperature coefficient such as +125 to l25 ppm/C, and resistivitiesin the range of 50 to 1,000 uflcm, and having a composition which consists essentially of 10 to 40 mole percent of AlN, 40 to 70 mole percent of TiN and 20 to 5.0 mole percent of ZrN, can be made from a composite cathode consisting essentially of A1, Tiand Zr and having a composition such that the surface area is to 26% Al, 45 to 75% Ti, and 20 to 50% Zr.
  • the cathodic sputtering step be conducted at alow residual gas pressure by using a low pressure sputtering apparatus such as a magnetron type sputtering apparatus described in U.S. Pat. No. 3,528,902.
  • a magnetron type sputtering apparatus comprised of a pair of concentric cylindrical electrodes 2 and 3 mounted within a cylindrical envelope 4 having an inlet 5 and an outlet 6. Said electrodes 2 'and 3 are connected across a voltage supply source 7. Either of said cylindrical electrodes 2 and 3 can be the cathode, but it is preferred that said inner electrode 2 be the cathode. Substrates 8 to be coated are secured to the anode.
  • the cylindrical envelope 4 contains an ionizable medium and can be made of anygas-tight, nonmagnetic material.
  • Said cylindrical envelope 4 containing said pair of electrodes is positioned in a magnetic field parallel to the sides of said cylindrical electrodes 2 and 3 so that said field is transverse to the discharge from said electrodes.
  • Said field can be supplied by any available magnetic field creating means 9, such as an electro-magnet externally attached across the flat end surfaces of said cylindrical envelope 4.
  • the ionizable medium can be nitrogen gas or a mixture of nitrogen and argon gas at a pressure of 10" to 10 Torr.
  • the cathode is a composite cathode of Al, Ti and Zr, as described hereinbefore. Said composite cathode can be prepared by using any available and suitable method. A preferred method is to press a mixture of Al, Ti and Zr metal in powder form, the powder having a particle size of to 300 mesh, at a pressure of 30,000 to 100,000 psi.
  • Use of said magnetron type sputtering apparatus makes it possible to provide resistive films consisting essentially of AlN and a solid solution of TiN and ZrN, the resistive properties of which are as described in connection with FIGS. 1 and 2.
  • a low pressure sputtering apparatus such as r-f sputtering apparatus makes it possible to make thin resistive films consisting essentially of MN and a solid solution of TiN and ZrN by using a composite cathode under low residual gas pressure.
  • a composite cathode consisting essentially of to 50 mole percent of MN, 10 to 80 mole percent of TiN, 10 to 90 mole percent of ZrN, and having the mole ratio of AlN to TiN less than 1.2 can be used to make resistive films having a wide range of resistivities, such as from 350 to 10,000 #Qcrn, and having a temperature coefficient of 200 to +150 ppm/C, by using the cathode in an r-f sputtering process.
  • a composite cathode consisting essentially of 10 to 40 mole percent of AIN, 40 to '70 mole percent of TiN and 20 to 50 mole percent of ZrN can be used to make resistive films with a very small temperature coefficient, such as from +125 to l25 ppm/C, and having resistivities in a range of 350 to 1,000 uQcm, by using said cathode in an r-f sputtering process.
  • Such a composite cathode consisting essentially of TiN, ZrN and AIN can also be used to make resistive films according to the present invention by using the cathode in any other available method of cathodic disintegration, such as an ion beam deposition process as described hereinbefore.
  • the electrical stability of the resistance of the resistive films according to the present invention is found to be better than 0.1 percent after 1,000 hours in a test at C with no load, which is the same order of stability as that for TiN films.
  • the noise level depends somewhat on the film composition.
  • the typical values observed are -20 to -30 db with 2 to 3 mW/mm
  • the resistive films according to the present invention can be anodized in an electrolyte consisting of ammonium borate and ethylene glycol with a 4 to 16 A./Volt oxidation rate.
  • the present resistive films like TiN films, can be protected from aging, and at the same time can be trimmed accurately.
  • a resistive film consisting essentially of AlN, TiN and ZrN, wherein the concentration of said AIN is from 10 to 50 mole percent, the concentration of said TiN is from 10 to 80 mole percent, the concentration of said ZrN is from 10 to mole percent, and the mole ratio of said AlN to said TiN is less than 1.2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Adjustable Resistors (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
  • Physical Vapour Deposition (AREA)
US00227070A 1971-03-11 1972-02-17 Resistive materials and method of making such materials Expired - Lifetime US3803057A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/433,892 US4016061A (en) 1971-03-11 1974-01-16 Method of making resistive films

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP46013829A JPS5110677B1 (enrdf_load_stackoverflow) 1971-03-11 1971-03-11
JP46015273A JPS5110678B1 (enrdf_load_stackoverflow) 1971-03-17 1971-03-17
JP46015274A JPS5110679B1 (enrdf_load_stackoverflow) 1971-03-17 1971-03-17

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Application Number Title Priority Date Filing Date
US05/433,892 Division US4016061A (en) 1971-03-11 1974-01-16 Method of making resistive films

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US (1) US3803057A (enrdf_load_stackoverflow)
CA (1) CA985036A (enrdf_load_stackoverflow)
FR (1) FR2128858B1 (enrdf_load_stackoverflow)
GB (1) GB1379478A (enrdf_load_stackoverflow)
IT (1) IT957547B (enrdf_load_stackoverflow)
NL (1) NL7203234A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030522A (en) * 1988-06-24 1991-07-09 Asulab S.A. Black-colored coating deposited on a substrate
US5367285A (en) * 1993-02-26 1994-11-22 Lake Shore Cryotronics, Inc. Metal oxy-nitride resistance films and methods of making the same
US6255007B1 (en) * 1997-12-18 2001-07-03 Hartec Gesellschaft Fur Haststoffe Und Dunnschichttechnik Mbh & Co. Kg Laminate system, a process for the production thereof and use thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030522A (en) * 1988-06-24 1991-07-09 Asulab S.A. Black-colored coating deposited on a substrate
US5367285A (en) * 1993-02-26 1994-11-22 Lake Shore Cryotronics, Inc. Metal oxy-nitride resistance films and methods of making the same
US6255007B1 (en) * 1997-12-18 2001-07-03 Hartec Gesellschaft Fur Haststoffe Und Dunnschichttechnik Mbh & Co. Kg Laminate system, a process for the production thereof and use thereof

Also Published As

Publication number Publication date
DE2211993A1 (de) 1972-11-02
FR2128858A1 (enrdf_load_stackoverflow) 1972-10-20
DE2211993B2 (de) 1977-06-16
IT957547B (it) 1973-10-20
CA985036A (en) 1976-03-09
FR2128858B1 (enrdf_load_stackoverflow) 1974-06-28
GB1379478A (en) 1975-01-02
NL7203234A (enrdf_load_stackoverflow) 1972-09-13

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