US3607699A - Technique for the deposition of gallium phosphide resistive films by cathodic sputtering - Google Patents

Technique for the deposition of gallium phosphide resistive films by cathodic sputtering Download PDF

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Publication number
US3607699A
US3607699A US848612A US3607699DA US3607699A US 3607699 A US3607699 A US 3607699A US 848612 A US848612 A US 848612A US 3607699D A US3607699D A US 3607699DA US 3607699 A US3607699 A US 3607699A
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United States
Prior art keywords
gallium phosphide
sputtering
technique
deposition
substrate
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Expired - Lifetime
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US848612A
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English (en)
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Jacob Sosniak
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AT&T Corp
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Bell Telephone Laboratories Inc
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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
    • C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/065—Gp III-V generic compounds-processing
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/119—Phosphides of gallium or indium
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/122—Polycrystalline
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/169—Vacuum deposition, e.g. including molecular beam epitaxy

Definitions

  • This invention relates to a technique for the deposition of thin films of gallium phosphide. More particularly, the present invention relates to a technique for cathodically sputtering films of gallium phosphide.
  • the inventive technique involves sputtering a polycrystalline gallium phosphide sample by cathodic sputtering techniques-upon a heated substrate member at a deposition rate within a specified range and subsequently annealing the deposited stoichiometric film.
  • Studies of the deposited films have revealed that they evidence resistivities within the range of to 10 ohm-centimeters, which may be increased to about 10 ohm-centimeters by annealing, so suggesting their use in diverse resistor applications.
  • the described technique is also considered suitable in the sputtering of bulk doped gallium phosphide for the preparation of resistor material having a resistivity of the order of 10,000 micro-ohm cm., such as is required in thin film circuitry.
  • FIG. 3 is a graphical representation on coordinates of sub- 6 strate heater temperature in degrees Centigrade against film deposition rate in angstroms per minute showing the conditions required to obtain polycrystalline gallium phosphide in accordance with the present invention.
  • FIG. 1 there is shown a typical apparatus suitable for depositing a gallium phosphide film by cathodic sputtering. Shown in the Figure is a vacuum chamber 11 in which are disposed cathode 12 and anode l3. Cathode 12 is composed of a polycrystalline sample of gallium phosphide. A source of electrical potential 14 is shown connected between cathode l2 and anode 13. Platform 15 is employed as a positioning support for substrate 16 upon which the sputtered film is to be deposited.
  • gallium phosphide is chosen as the cathode for use inn an apparatus similar to that shown in FIG. I.
  • Substrate materials suitable for use in the practice of the present invention are required to conform to the restrictions imposed by the various process steps. It is preferred that the substrate material be possessed of a smooth surface which is completely free from sharp changes in contour and able to withstand the temperatures to which it will be subjected during the course of the processing. All types of refractory materials such as glass, ceramics and high melting metals meet this requirement.
  • the gallium phosphide selected for use as the source material or cathode in the sputtering process may be a polycrystalline grown material evidencing a purity of the order of 99.99 percent, such material typically being obtained from commercial sources. It will be appreciated that the presence of certain dopants, such as zinc, may be desirable from the standpoint of device applications and when so desired may be present in an amount ranging up to 2 10 atoms per cm.
  • the substrate member is first vigorously cleaned.
  • Conventional cleansing agents are suitable for this purpose, the choice of a specific agent being dependent upon the composition of the substrate itself.
  • the substrate chosen for use in the practice of the invention is glass, boiling in organic solvents is a convenient method for cleaning the surface.
  • the cleansed substrate is next placed in a cathodic sputtering apparatus of the type shown in FIG. 1 containing a gallium phosphide cathode with a vacuum chamber evacuated to a pressure of 10 torr. After attaining the desired background pressure, a suitable inert sputtering gas is admitted to the chamber in an amount sufficient to result in a pressure ranging up to 30 microns.
  • the extent of the vacuum is dependent upon consideration of several factors as follows.
  • Increasing the inert gas pressure and thereby reducing the vacuum within the chamber increases the rate at which the gallium phosphide being sputtered is removed from the cathode and accordingly increases the rate of deposition.
  • the maximum pressure is usually dictated by power supply limitations, since increasing the pressure also increases the current fiow between cathode l3 and anode 12 of the apparatus shown in FIG. 1.
  • a practical upper limit in this respect is 30 microns for a sputtering voltage of 3000 volts, although it may be varied depending upon the size of the cathode, sputtering rate, etc.
  • the ultimate maximum pressure is that which the sputtering can be reasonably controlled within the prescribed tolerances. It follows from the above discussion that the minimum pressure is determined by the lowest deposition rate which can be economically tolerated.
  • the substrate member is heated to a temperature within the range of 25 to 650 C., by a conventional heater.
  • a conventional heater An extensive evaluation of the various factors involved in sputtering of gallium phosphide in accordance with the invention have revealed that there is a direct correlation between the substrate temperature, deposi- 5 tion rate and the type of films deposited, that is, amorphous or polycrystalline films.
  • the sputtering rate must be at least angstroms per minute, whereas sputtering in a system wherein the substrate member is maintained at a temperature of the order of 25 C. requires a sputtering rate of at least 380 angstroms per minute to yield polycrystalline gallium phosphide films.
  • the cathode member is made electrically negative with respect to the anode member.
  • the minimum voltage necessary to produce sputtering is approximately 1000 volts.
  • Increasing the potential difference between the cathode and the anode has the same effect as increasing the pressure, that of increasing both the rate of deposition and the current flow. Accordingly, the maximum voltage, 5000 volts, is dictated by 5 consideration of the factors which control the maximum pressure.
  • the balancing of the various factors of voltage pressure and the relative positions of the cathode, anode and substrate to obtain a high quality deposit is well known in the sputtering art.
  • the sputtering rate and the temperature to which the substrate member is heated during the course of the processing is considered critical.
  • the balancing of these factors must be such as to result in a sputtering rate ranging from approximately 80 angstroms per minute to 380 angstroms per minute over the noted temperature range of from 25 to 650 C., the lower rates corresponding with the higher temperature and vice versa.
  • H0. 2 there is shown a bar graph on coordinates of substrate heater temperature in degrees centigrade against deposition rate in angstroms per minute showing the relationship between these parameters and the type of gallium phosphide film produced. It will be noted by reference to the graph that at a temperature of C., amorphous films of gallium phosphide are produced at sputtering rates ranging up to approximately 260 angstroms per minute. In order to obtain the desired polycrystalline films at this temperature, it is seen that a sputtering rate of the order of 380 angstroms per minute is required.
  • a polycrystalline film of gallium phosphide may be deposited upon the substrate member.
  • Sputtering is conducted for a period of time calculated to produce the desired thickness.
  • the specific sputtering technique chosen for use in the practice of the present invention may be selected from among conventional DC sputtering radio frequency (RF) sputtering by or combined RF-DC sputtering.
  • RF radio frequency
  • the minimum thickness of the layer deposited upon the substrate is approximately 500 angstroms. There is no maximum limit on this thickness, although little advantage is gained by an increase above 80,000 angstroms.
  • the gallium phosphide film is annealed at a temperature within the range of 600 to 700 C. for a time period ranging from 2 to 50 hours for the purpose of removing defects in the film so deposited.
  • the duration of heating is dictated by considerations relating to film thickness, the shorter time periods corresponding with the smaller thicknesses and the converse.
  • EXAMBLE A sputtering apparatus similar to that shown in FIG. 1 was used to produce the gallium phosphide layer.
  • the cathode consisted of a wafer of gallium phosphide of 99.99 percent purity which had been diced and ground flat for use therein.
  • the gallium phosphide wafer was mounted by means of a conductive epoxy adhesive on a cooling block that forms a part of the cathode member. in the apparatus actually employed, the anode was grounded, the potential difference being obtained by making the cathode negative with respect to ground.
  • a glass microscope slide, approximately 1% inch 3 inch in length was selected as a substrate member. The slide was first washed in a detergent such as Alconox to remove large particles of dirt and grease.
  • a direct current voltage of 3000 volts was then impressed between the cathode and anode and sputtering initiated at a rate of 260 angstroms per minute. Sputtering was continued for a time period of approximately 10 minutes, thereby resulting in a film 2600 angstroms in thickness. Following the sputtering treatment, the specific resistivity in ohm-centimeters was measured and found to be approximately 100. Next, the sputtered film was annealed for 3 hours at a temperature of approximately 600 C. and the resistivity again measured. Subsequent to annealing the resistivity of the material was found to be approximately 10 -10 ohm centimeters.
  • a technique for the decomposition of stoichiometric gallium phosphide films comprising the steps of depositing polycrystalline gallium phosphide at a rate within the range of to 380 angstroms per minute upon a substrate member heated to a temperature within the range of 25 to 650 C., the lower rates corresponding with the higher temperatures and the converse, substantially as shown in FIG. 3, by sputtering from a target of gallium phosphide and annealing the resultant deposited film at a temperature within the range of 600 to 700 C.
  • the thickness of said deposited film ranges from 2500 to 80,000 angstroms.

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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)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Cold Cathode And The Manufacture (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
US848612A 1969-08-08 1969-08-08 Technique for the deposition of gallium phosphide resistive films by cathodic sputtering Expired - Lifetime US3607699A (en)

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US84861269A 1969-08-08 1969-08-08

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US (1) US3607699A (fr)
JP (1) JPS50513B1 (fr)
BE (1) BE754400A (fr)
DE (1) DE2039514A1 (fr)
FR (1) FR2056548A5 (fr)
GB (1) GB1253779A (fr)
NL (1) NL7011436A (fr)
SE (1) SE351789B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894893A (en) * 1968-03-30 1975-07-15 Kyodo Denshi Gijyutsu Kk Method for the production of monocrystal-polycrystal semiconductor devices
US3928092A (en) * 1974-08-28 1975-12-23 Bell Telephone Labor Inc Simultaneous molecular beam deposition of monocrystalline and polycrystalline III(a)-V(a) compounds to produce semiconductor devices
US4147573A (en) * 1977-04-05 1979-04-03 Futaba Denshi Kogyo K. K. Method of depositing III-V compounds on group IV element wafers by the cluster ion technique
US4761300A (en) * 1983-06-29 1988-08-02 Stauffer Chemical Company Method of vacuum depostion of pnictide films on a substrate using a pnictide bubbler and a sputterer
US5473456A (en) * 1993-10-27 1995-12-05 At&T Corp. Method for growing transparent conductive gallium-indium-oxide films by sputtering
US6258620B1 (en) 1997-10-15 2001-07-10 University Of South Florida Method of manufacturing CIGS photovoltaic devices

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894893A (en) * 1968-03-30 1975-07-15 Kyodo Denshi Gijyutsu Kk Method for the production of monocrystal-polycrystal semiconductor devices
US3928092A (en) * 1974-08-28 1975-12-23 Bell Telephone Labor Inc Simultaneous molecular beam deposition of monocrystalline and polycrystalline III(a)-V(a) compounds to produce semiconductor devices
US4147573A (en) * 1977-04-05 1979-04-03 Futaba Denshi Kogyo K. K. Method of depositing III-V compounds on group IV element wafers by the cluster ion technique
US4761300A (en) * 1983-06-29 1988-08-02 Stauffer Chemical Company Method of vacuum depostion of pnictide films on a substrate using a pnictide bubbler and a sputterer
US5473456A (en) * 1993-10-27 1995-12-05 At&T Corp. Method for growing transparent conductive gallium-indium-oxide films by sputtering
US6258620B1 (en) 1997-10-15 2001-07-10 University Of South Florida Method of manufacturing CIGS photovoltaic devices

Also Published As

Publication number Publication date
JPS50513B1 (fr) 1975-01-09
SE351789B (fr) 1972-12-11
NL7011436A (fr) 1971-02-10
BE754400A (fr) 1971-01-18
DE2039514A1 (de) 1971-02-18
FR2056548A5 (fr) 1971-05-14
GB1253779A (en) 1971-11-17

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