U.S. patent number 3,604,970 [Application Number 04/767,170] was granted by the patent office on 1971-09-14 for nonelectron emissive electrode structure utilizing ion-plated nonemissive coatings.
This patent grant is currently assigned to Varian Associates. Invention is credited to Robert D. Culbertson, Russell C. McRae, Harold P. Meyn.
United States Patent |
3,604,970 |
Culbertson , et al. |
September 14, 1971 |
NONELECTRON EMISSIVE ELECTRODE STRUCTURE UTILIZING ION-PLATED
NONEMISSIVE COATINGS
Abstract
A nonemissive electrode structure is disclosed together with a
method for fabricating same. The nonelectron emissive electrode
structure includes a core member which may be made of any one of a
number of different metals such as molybdenum, copper, tantalum or
tungsten. A nonelectron emissive material is deposited over the
core metal. The nonemissive deposited layer may be any one of a
number of different materials which will provide electron emission
inhibiting characteristics in the presence of surface contamination
by barium and/or strontium. Examples of such electron emission
inhibiting materials include titanium, chromium, zirconium, or
silicon. An outer coating of carbon is formed over the emission
inhibiting layer to further enhance the nonelectron emissive
characteristics of the electrode. Alternatively, the nonemissive
deposited layer and carbon coating may be codeposited into a single
covering layer deposited over the core material. The electrode
structure is especially suitable as a grid structure in an electron
discharge device employing either an oxide coated cathode or a
dispenser cathode of the type containing barium and/or
strontium.
Inventors: |
Culbertson; Robert D.
(Campbell, CA), McRae; Russell C. (Cupertino, CA), Meyn;
Harold P. (Palo Alto, CA) |
Assignee: |
Varian Associates (Palo Alto,
CA)
|
Family
ID: |
25078693 |
Appl.
No.: |
04/767,170 |
Filed: |
October 14, 1968 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
666802 |
Sep 11, 1967 |
|
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Current U.S.
Class: |
428/560;
204/298.05; 313/107; 422/186; 427/124; 428/564; 428/656; 428/661;
313/106; 313/355; 427/122; 428/552; 428/641; 428/934 |
Current CPC
Class: |
H01J
19/30 (20130101); Y10T 428/12111 (20150115); Y10T
428/12674 (20150115); H01J 2893/002 (20130101); Y10S
428/934 (20130101); Y10T 428/12056 (20150115); Y10T
428/12778 (20150115); Y10T 428/12812 (20150115); Y10T
428/12139 (20150115) |
Current International
Class: |
H01J
19/00 (20060101); H01J 19/30 (20060101); H01j
043/00 () |
Field of
Search: |
;313/106,107,355
;29/155.5 ;204/298,312 ;117/216,217,218 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Huckert; John W.
Assistant Examiner: James; Andrew J.
Parent Case Text
DESCRIPTION OF THE PRIOR ART
This is a continuation-in-part of our copending application Ser.
No. 666,802, filed Sept. 11, 1967 and now abandoned.
Claims
What is claimed is:
1. An electrode for an electron tube comprising a metallic core and
an emission-inhibiting outer layer on said core, said layer
comprising carbon and a material selected from the group consisting
of titanium, chromium, zirconium and silicon, said material being
intimately commingled with said carbon.
Description
Heretofore, nonemissive grid structure for electron discharge tubes
have been proposed wherein the grid structure was made of a wire
material having a core of a refractory metal such as molybdenum,
tungsten or tantalum which was carburized on its outside surface
and then plated with a metal of group 8 of the periodic table such
as platinum, rhodium, or iridium which serves to produce an
electron emission inhibiting layer which in turn was covered by a
carbide of a metal selected from a class of zirconium, tantalum,
molybdenum and tungsten. Such an electron nonemissive electrode
structure is described and claimed in U.S. Pat. No. 2,497,090
issued Feb. 14, 1950 and assigned to the same assignee as the
present invention. The problem with this prior art electrode
structure is that the coating layers are carburized in a furnace at
about 1,350.degree. C. to 1,400.degree. C. in order to form the
various carbide layers. This heat treatment of the electrode
produces embrittlement which makes the wire difficult to work into
a grid structure or, if the grid structure is formed before
carburizing, tends to make the resultant grid electrode structure
relatively brittle and, therefore, relatively easy to fracture in
use.
Other prior art nonemissive electrode structures for electron tubes
have been made of a molybdenum wire coated with a nickel coating
which in turn was coated with carbon. One of the problems with this
electrode structure was the same as that previously mentioned with
regard to the first electrode structure, namely, that the carbon
coating had to be carburized to the electrode structure in order to
form a tightly adherent layer to prevent flaking and the like and
that the carburization of the electrode was obtained at relatively
high temperatures such that the resultant electrode structure was
relatively brittle and therefore prone to fracture in use.
Still other prior art nonemissive electrode structures have
included a core wire of molybdenum or other refractory metal coated
with an electron emission inhibiting material such as platinum,
iron, cobalt, iridium or osmium with an outer coating of carbon
which is then heated to a relatively high temperature in a hydrogen
atmosphere until the surface is shiny and clean. In the case of a
platinum emission inhibiting layer, this indicates that the carbon
has diffused through the platinum to form a carbide layer with the
core material such that the shiny platinum is left on the outside
surface. Such a nonelectron emissive grid structure is described in
U.S. Pat. No. 2,282,097 issued May 5, 1942. Such a grid structure
may be utilized to advantage in electron discharge devices
employing a thoriated tungsten cathode but the electrode structure
does not exhibit the desired nonelectron emissive characteristics
when employed with oxide cathodes or with dispenser cathodes
incorporating barium or strontium and operating at relatively low
temperatures, as of less than 1,000.degree. C.
Recently methods have been developed for ion plating carbon and
other materials from a glow discharge onto structures to be coated.
Such coatings are relatively adherent and are produced at
essentially room temperature. Such methods for depositing carbon
and other materials are disclosed and claimed in copending U.S.
application Ser. No. 632,361 filed Apr. 20, 1967 and now abandoned
and assigned to the same assignee as the present invention.
SUMMARY OF THE PRESENT INVENTION
The principal object of the present invention is the provision of
an improved nonelectron emissive electrode structure and of
improved methods for fabricating same.
One feature of the present invention is the provision of a
nonelectron emissive electrode structure for use in environments
subject to surface contamination by barium and/or strontium and
comprising a core material having a covering layer comprising
carbon and one or more materials selected from the class consisting
of titanium, chromium, zirconium, and silicon, whereby the
electrode structure has improved nonelectron emissive
properties.
Another feature of the present invention is the provision of a
nonelectron emissive electrode structure for use in the just-stated
environments and comprising a core material having an outer layer
of carbon and an intermediate layer made of a material selected
from the class consisting of titanium, chromium, zirconium, and
silicon, whereby the electrode structure has improved nonelectron
emissive properties.
Another feature of the present invention is the method for
fabricating a nonelectron emissive electrode structure comprising
the step of simultaneously ion plating carbon and an electron
emissive inhibiting material selected from the class consisting of
titanium, chromium, zirconium, and silicon from a glow discharge
onto the electrode core. The coated wire may then be heated to a
temperature between 750.degree. C., and 1,000.degree. C.
Yet another feature of the present invention is the method for
fabricating a nonelectron emissive electrode structure comprising
the steps of coating a core metal of the electrode structure with
an electron emissive inhibiting material and ion plating carbon
from a glow discharge over the layer of nonelectron emissive
material to form the composite nonelectron emissive electrode
structure, whereby the carbon coating forms a tightly adherent
coating and is produced at a relatively low temperature which will
not adversely affect the ductility of the electrode structure.
Another feature of the present invention is the same as the
preceding feature wherein the electron emissive inhibiting layer is
ion plated from a glow discharge onto the core material to provide
a uniform tightly adherent intermediate layer.
Other features and advantages of the present invention will become
apparent upon a perusal of the following specification taken in
connection with the accompanying drawings wherein:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary perspective view, partly broken away, of an
electron tube incorporating an electrode structure of the present
invention,
FIG. 2 is an enlarged fragmentary perspective view of a wire
electrode structure incorporating features of the present
invention,
FIG. 3 is a schematic diagram of an apparatus for performing the
ion plating method of the present invention,
FIG. 4 is an enlarged fragmentary perspective view of another wire
electrode structure incorporating features of the present
invention,
FIG. 5 is a schematic diagram of an alternative apparatus for
performing the ion plating method of the present invention; and
FIG. 6 is a flow diagram in block form of a series of specific
steps which may be taken in fabricating the wire electrode
structure shown in FIG. 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, there is shown a typical electron tube
employing nonelectron emissive electrode structures of the present
invention. More specifically, the electron tube 1 includes a hollow
cylindrical cathode electrode structure 2 which is heated to
thermionic emission temperature by means of a filamentary heater 3
contained within the cylindrical emitter 2. A hollow cylindrical
anode structure 4 is disposed surrounding the cathode emitter 2 for
collecting the electrons emitted from the emitter 2. A control grid
structure 5 is disposed surrounding the cathode 2 between the
cathode 2 and the anode 4 for controlling the beam current passed
through the control grid 5 from the emitter 2 to the anode 4. A
screen grid structure 6 is disposed surrounding the control grid 5
between the control grid 5 and the anode 4 for reducing the control
grid to anode capacity. The screen grid structure 6 operates near
the anode potential and will intercept some of the beam current. It
is desirable that the screen grid should be as nonelectron emissive
as possible. The screen and control grids 6 and 5 are typically
cylindrical cagelike structures supported at their bases from
conical support structures 7, as of nickel.
The cathode emitter 2 need not be of the indirectly heated type as
shown but may also be made of a directly heated configuration
wherein the emitter is formed by a thoriated tungsten wire through
which the heating current is passed for heating same to its
operating temperature of approximately 1,500.degree. C. Emitter 2,
as shown in FIG. 1, is of the oxide coated variety wherein a nickel
base material is coated by carbonates of barium and strontium and
has an operating temperature of 850.degree. C.
Referring now to FIG. 2, there is shown a section of nonelectron
emissive wire 11 incorporating features of the present invention
and which may be employed for fabricating the grid structures 5 and
6 as described with regard to FIG. 1. The grid wire 11 includes a
cylindrical central core member 12 as of molybdenum, tungsten,
tantalum or copper, as of 0.010 inch in diameter. The core 12 is
coated with a layer of material, which will inhibit electron
emission in the presence of surface contamination by barium or
strontium at temperatures less than 1,000.degree. C., such as
titanium, chromium, zirconium or silicon to a thickness as of 0.003
inch to form an intermediate layer 13 of the wire 11. An outer
coating of carbon 14 is formed over the intermediate layer 13 to
provide a dark coating for the electrode and to further inhibit
electron emission. The carbon layer 14 is preferably on the order
of 2 microns thick. FIG. 4 illustrates an alternative configuration
in which core 12 of nonelectron emissive wire 15 is coated with but
a single covering layer of material 16. Layer 16 consists of both
one of the just-listed emission-inhibiting materials and
carbon.
Referring now to FIG. 3, there is shown an apparatus for
fabricating the electrode structures of the present invention. More
specifically, the preformed electrode structures of core material
may be plated with layers 13 and 14 or the core wire 12 may be
coated with layers 13 and 14 and then fabricated with the control
electrode configuration. Briefly, the method for fabricating the
nonelectron emissive electrode structures comprises the steps of
ion plating the emission-inhibiting layer 13 onto the core material
12 from a glow discharge and then ion plating the carbon layer 14
from the glow discharge to produce the composite electrode
structure. The structure may finally be heated in an inert gas or a
vacuum.
The ion plating apparatus includes an evacuable glow discharge
chamber 21, such as a bell jar, which is evacuated to a relatively
low pressure of 10.sup..sup.-6 torr via exhaust tubulation 22,
chemical trap 23 and vacuum pump 24 in order to remove undesired
gases and substances from the chamber 21. The chamber 21 is then
backfilled with a glow discharge gas, preferably a noble gas such
as argon, through a variable leak 25 to a pressure of 1 to 5
.times. 10.sup..sup.-2 torr. The glow discharge gas is supplied
from a source 26 and fed into the chamber 21 via inlet tubulation
27 containing a glow meter 28 and a metering valve 29. Within the
chamber 21 the gas inlet tubulation includes a porous tungsten plug
31 through which the gas enters the chamber 21 and which also
serves as the positive electrode for producing the glow discharge.
The inlet tubulation 27 is insulated from the bottom wall of the
bell jar 21 via insulator 32. A sputter shield 33 shields the
insulator 32 from material sputtered within the chamber 21.
A second glow-discharge-forming electrode 34 projects toward the
first electrode 31 from the top wall of the chamber 21. A
feedthrough insulator 35 supports the second electrode 34 from the
top wall. A sputter shield 36 surrounds the feedthrough insulator
35 to prevent the insulator 35 from being shorted out due to
condensation of conductive materials over the insulator 35. A
high-voltage DC power supply 37 provides a potential as of 1 to 5
kv. between the glow discharge electrodes 31 and 34 with a negative
potential being applied to the upper electrode 34.
An evaporator element 38 such as a resistive filament coated with
one of the aforementioned electron emission inhibiting materials is
disposed in the vicinity of the glow discharge electrodes 31 and 34
for evaporating the electron emissive inhibiting material into the
glow discharge. In one form, the evaporator 38 comprises a
filamentary element having one terminal connected to the porous
tungsten block 31 and having the other terminal connected to a
filament supply 39 via a switch 40. The filament supply 39 has one
terminal connected to the porous tungsten block and supplies
heating current through switch 40 to the evaporating element 38 for
evaporating the emission inhibiting material into the glow
discharge.
The electrode structure made of the core material to be coated such
as, for example, performed grid structure 5 or 6 to core wire 12 is
mechanically abraded, rinsed and dried, and placed on the negative
electrode 34. The glow discharge is started by applying the
operating potentials, as of 1 to 5 kv., to the electrodes 31 and 34
and maintaining the glow discharge gas pressure at about 1 to 7
.times. 10.sup..sup.-2 torr with a glow discharge current as of 10
to 80 ma. Gas is continuously pumped by pump 24 and new gas is
continuously leaked into the chamber 21 via inlet tubulation 27.
The glow discharge ionizes the argon gas and drives the argon ions
into the surface of the electrode structure 5, 6 or 12 to be
coated, thereby cleaning the surface of the electrode structure at
a relatively low temperature as of 50.degree. C. The cleaning glow
discharge is maintained for 5 to 45 minutes in order to thoroughly
clean the surface to be coated.
After the cleaning step, and while the glow discharge is
maintained, switch 40 is closed to energize the evaporator 38 and
the electron emission inhibiting material is evaporated from the
evaporator 38 into the glow discharge to ionize the electron
emission inhibiting material. Suitable electron emission inhibiting
materials for use where subjected to barium or strontium
contamination of less than 1,000.degree. C. include titanium,
chromium, gold, platinum, zirconium and silicon. Platinum is a
useful electron emission inhibiting material for thoriated
emitters. Ions of the electron emission inhibiting material are
electrodeposited (ion plated) onto the surfaces of the electrode
structure to be coated, thereby forming the intermediate electron
emission inhibiting layer 13. The intermediate layer is deposited
to a suitable thickness preferably less than a few microns thick.
When the intermediate layer has reached a sufficient thickness
switch 40 is opened and the evaporation ceases.
After depositing the intermediate layer 13, a suitable hydrocarbon
such as acetylene, C.sub.2 H.sub.2, is introduced into the glow
discharge. Other suitable hydrocarbon gases include methane and
ethane. The hydrocarbon gas is leaked into the glow discharge from
a source 41 via flow meter 42 and metering valve 43 in the inlet
tubulation 27.
The acetylene is dissociated by the glow discharge and most of the
carbon atoms are ionized to form positive carbon ions. Positive
carbon ions are electrodeposited (ion plated) by the electric field
between the electrodes 31 and 34 onto the surface of the electrode
structure 5, 6 or 12 to be coated, thereby plating same. The
acetylene gas will sustain the glow discharge. Thus, as the
acetylene is introduced, the argon is slowly valved off such that
within 5 minutes the discharge is operating on pure acetylene. The
glow discharge is maintained for 5 to 45 minutes to produce a
carbon coating of suitable thickness after which the leak 25 is
closed to extinguish the discharge and the high potential removed
from the electrodes 31 and 34. The system is then allowed to cool,
opened to air, and the coated articles removed. The coated articles
are then placed in a vacuum furnace and fired at 975.degree. C. for
15 minutes to drive off any hydrogen which may not have dissociated
from the acetylene during the ion plating step, and any plated
material from the evaporator other than the electron emission
inhibiting matter.
FIG. 6 illustrates the preferred sequential steps to be taken in
producing the electron-emissive inhibited structure shown in FIG.
4. In performing these steps the apparatus of FIG. 5 is preferably
used. This apparatus is the same as that shown in FIG. 3 with the
exclusion of porous block 31, evaporator 38 and filament supply 39.
Instead titanium is introduced to chamber 21 through inlet
tubulation 47, containing a flow meter 45 and a metering valve 46,
which communicates with a volatile supply of titanium tetrachloride
44. If desired, this alternate means for supplying titanium to
chamber 21 may also be used in forming the three layer electrode
structure shown in FIG. 2.
In forming the two layer electrode structure shown in FIG. 4, the
specific steps shown in FIG. 6 are preferably taken. Following the
abrading and argon bombardment steps as hereinbefore explained in
fabricating the structure of FIG. 2, valve 29 is closed and valves
43 and 46 are opened while the flow discharge is maintained. This
allows gaseous acetylene, C.sub.2 H.sub.2, and titanium
tetrachloride, TiCl.sub.4, to be introduced into the glow discharge
within chamber 21. Here the titanium is dissociated from the
chlorine, and the carbon is dissociated from the hydrogen. The
chlorine and hydrogen gases are pumped out of the chamber to
chemical traps 23 while the particulate carbon and titanium ions
are drawn by cathode 34 to structures 6, 7 and 12 mounted thereon.
This step is maintained for 10 minutes following which period
high-voltage source 37 is disconnected and valves 43 and 46 are
closed. After this the chamber is evacuated and cooled and the
coated wire removed. The wire electrode is then vacuum-fired for 5
to 45 minutes at between 750.degree. C. and 1,000.degree. C.,
preferable for 15 minutes at 975.degree. C.
The exact character of the ion plated coatings is not precisely
known. For example, an electron nonemissive electrode structure
fabricated by the aforedescribed method and comprising a molybdenum
core with a carbon outer coating and a titanium intermediate layer
was subjected to both X-ray diffraction and emission spectroscopy
analysis. The X-ray diffraction showed no carbon, titanium or
carbides of titanium or molybdenum. Emission spectroscopy showed
titanium as a major constituent. The conclusion is that the
coatings and interface compounds, if any, are amorphous or
extremely small crystallites in structure or they are very
thin.
Referring now to the table below, there is shown a comparison
between the primary electron emission characteristics of the prior
art grid structures compared to grid structures of the present
invention. ##SPC1##
More specifically, the grid structures were tested in a
tetrode-type tube similar to that shown in FIG. 1 which employs an
oxide coated nickel base cathode 2 and commercially available as
the Eimac 4X150A tube type. A series of these tubes was constructed
wherein the screen grid 6 was made of wire having the configuration
as indicated in column 1 of the table. The primary electron screen
grid emission current was measured for the screen grid as a
function of the power dissipated by the screen grid under two
conditions. Namely, an initial condition just after tube processing
when the screen grid is uncontaminated and a second condition 500
hours later after substantial contamination of the screen grid by
barium and/or strontium evaporated from the nickel oxide cathode
2.
As seen from the table, screen grid electrodes employing ion plated
carbon were initially much superior to the electrodes employing
gold-plated molybdenum, carburized molybdenum and bare molybdenum
wire. More specifically, the latter three screen grid materials
could collect only 30, 18 and 16.5 watts, respectively, before they
emitted 100 microamperes of screen grid current. On the other hand,
the screen grids employing ion plated carbon on gold and ion plated
carbon on ion plated titanium could dissipate 55 watts while
producing only 18 microamperes and between 12 and 40 microamperes,
respectively, of primary screen grid current. These grid structures
were employed in a tube having an oxide coated cathode on a nickel
base material wherein the operating temperature of the cathode is
about 850.degree. C. The grids become contaminated after many hours
of use by barium and/or strontium evaporated from the oxide cathode
and which condense upon the screen grid structure. This barium
and/or strontium coating reduces the work function of the surface
of the screen grid electrode structure causing it to become more
electron emissive substantially counteracting the nonelectron
emissive layer and carbon coating placed upon the electrode
structure.
The screen grid electrode structure No. 5 having ion-plated carbon
on ion-plated titanium on molybdenum core material has substantial
advantage over the gold plated molybdenum wire, identified as
sample No. 1, and the ion plated carbon on gold plated molybdenum
grid identified as sample No. 4, in that the titanium is less
expensive than the gold and, in addition, permits grids to have a
much higher power-handling capability because the titanium has a
lower vapor pressure than the gold. Thus, grid No. 5 utilizing the
ion plated carbon on ion plated titanium on a molybdenum core
permits the screen grid electrode to dissipate much higher power
than would be possible with a gold plated screen grid electrode
structure. Evaporated gold will also poison the cathode causing the
tube to become inoperative.
Since many changes may be made in the above construction and many
apparently widely different embodiments of this invention could be
made without departing from the scope thereof, it is intended that
all matter contained in the above description or shown in the
accompanying drawings shall be interpreted as illustrative and not
in a limiting sense.
* * * * *