O

|||||||||||| US005328668A
United States Patent (19) (11 Patent Number: 5,328,668
Sabacky et al. 45 Date of Patent: "Jul. 12, 1994
(54) SYNTHESIS OF SEMICONDUCTOR GRADE (56) References Cited
TUNGSTEN HEXAFLUORDE U.S. PATENT DOCUMENTS
(75) Inventors: Bruce J. Sabacky, Westminster; 2,926,074 2/1960 Berger ................................. 422/235
Robert E. Doane, Springs, both of 2,929,690 3/1960 Bennet ... 422/235
Colo. 3,981,684 9/1976 Mavrovic ... 422/235
4,404,180 9/1983 Drum et al..... ... 422/235
(73) Assignee: Bandgap Chemical Corporation, 4,788,042 11/1988 Marsh et al. ........................ 422/235
Longmont, Colo. OTHER PUBLICATIONS
(*) Notice: The portion of the term of this patent Perry et al., "Chemical Eng. Handbook, 5th Ed.," pp.
subsequent to Oct. 12, 2009 has been 23-56, 1973.
disclaimed.
Primary Examiner-Timothy M. McMahon
(21) Appl. No.: 528,716 Attorney, Agent, or Firm-Hopgood, Calimafde, Kalil &
(22 Filed: May 24, 1990 Judlowe
(57) ABSTRACT
Related U.S. Application Data Semiconductor grade tungsten hexafluoride (WF6) is
62) Division of Ser. No. 476,232, Feb. 7, 1990 produced by reacting tungsten metal with a recirculat
i v W. T. ways/ass a sua - ing flow of gaseous WF6 containing a small concentra
51) Int. Cl. ................................................ F28D 7/00 tion of fluorine in a heated reactor. The high purity
52 U.S. C. .................................... 422/235; 422/232; WF6 produced is useful for deposition of tungsten met
422/234; 42.3/53; 423/59; 42.3/462 allization in fabricating VLSI integrated circuitry.
58) Field of Search ....................... 422/232, 234, 235;
423/53, 59, 462, 489 1 Claim, 1 Drawing Sheet

5
COOLER
6
4
REACTOR CONDENSER

PUMP

HEAT WAPORIZER

RESERVOIR

PRODUCT
COLLECTOR Y19
U.S. Patent July 12, 1994 5,328,668

5
COOLER
6
4 REACTOR CONDENSER

PUMP

HEAT WAPORIZER
25
2

RESERVOIR
20

PRODUCT
COLLECTOR 9.
 1.
5,328,668
2
SYNTHESIS OF SEMCONDUCTOR GRADE DETAILED DESCRIPTION OF THE
TUNGSTEN HEXAFLUORDE INVENTION
In carrying out the invention it is preferred to employ
This is a division of copending application Ser. No. 5 a reactor, which is preferably made of nickel, provided
476,232, filed Feb. 7, 1990. with means for circulating gas to and through the reac
tor and recirculating the product gas in a closed system.
BACKGROUND OF THE INVENTION Means for removing product tungsten hexafluoride,
It is known that deposition of metallic tungsten on preferably as a liquid, and means for introducing
semiconductor materials in the fabrication of VLSI 10 makeup fluorine are provided.
It is essential, in accordance with concepts of the
integrated circuitry is useful. For this application, the invention, that the circulating gas stream contain as its
tungsten metal deposited should be, to the highest de principal ingredient
gree possible, devoid of alpha-particle emitting impuri sten a major proportion of gaseous tung
ties such uranium and thorium which can cause soft 15 Preferably, the fluorinea content
hexafluoride and minor proportion of fluorine.
of the gaseous mixture
error generation in memory circuits. Impurities such as is about 5% to about 40%, by volume. More preferably,
sodium also must be eliminated from the tungsten used the fluorine content is about 10% to about 30%, by
for this purpose to avoid diffusion thereof from the volume, e.g., about 20%, by volume. No other ingredi
tungsten metal layer into active regions of the circuit, ents are needed in the circulating gas stream, although,
an event which could destroy or degrade circuit perfor 20 if desired up to about 10%, by volume of helium or
aCC. argon may be present. In practice, the fluorine content
Industrial production of high purity tungsten traces of the gaseous mixture is controlled to adjust the kinet
back to the development of tungsten wire for use in ics of the reaction to provide acceptable rates of pro
incandescent lamp filaments since it was found that 25 duction, to control the evolution of heat by the exother
mic reaction of fluorine with tungsten and to insure the
certain impurities, such as iron, rendered tungsten bil overall
lets brittle and unworkable. The development of the tungstenreaction is sufficiently slow to allow the metallic
technology is recounted in Smithells book Tungsten, A rities that may be present inpreferentially
to be fluorinated
the metallic
to other impu
tungsten.
Treatise On. Its Metallurgy, Properties And Applications The tungsten reactant is preferably particulate form,
published by Chapman & Hall Ltd., London, 1952. 30 ranging in size from pellets, prills and granules to a
In providing a tungsten product for use in semicon powder initially having a particle size of about 5 to 20
ductors it is found that impurity levels in the tungsten microns diameter. For best results, the initial powder
must be far lower, i.e., orders of magnitude lower, than should be of high purity, e.g., should contain no more
that required merely to make tungsten ductile. The than 5 ppm total impurities excluding oxygen. Oxygen
present invention is directed to means and methods of 35 content is preferably less than 500 ppm. In particular, it
providing a tungsten product which may be employed is preferred that uranium, thorium, iron, chromium,
in treating semiconductor materials without producing sodium, copper molybdenum and potassium should not
adverse or destructive effects in circuits produced using exceed about 1, 1,300, 100, 200, 800, 200 and 150 ppb
such a tungsten product. each, respectively.
The invention is particularly directed toward the ingThe reaction is carried out at a temperature exceed
production of tungsten hexafluoride of ultra-high purity e.g.,the boiling temperature of tungsten hexafluoride,
which may be employed to deposit metallic tungsten on about 600 C.,thepreferably
within temperature range of about 300 to
about 350 to about 450° C.,
semiconductor materials without producing the afore e.g., about 400 C. The pressure
mentioned deleterious effects on the resulting circuits. 45 atmospheric to slightly elevated, e.g.,ofabout
reaction may be
1.1 to about
Deposition of tungsten from tungsten hexafluoride 2.0 atmosphere.
offers practical advantages as compared to deposition of The reaction is carried out in a closed system con
tungsten by the sputtering method as has been practiced prising a reactor chamber and gas circulating means,
in the semiconductor industry. with provisions for removing product tungsten hexaflu
50 oride, preferably as a liquid, and means for introducing
SUMMARY OF THE INVENTION
fresh reactant fluorine as required. Means for flushing
The invention is directed to the production of tung the system attendant upon the introduction of fresh
sten hexafluoride (WF6), a compound having a boiling reactant tungsten may also be provided. Gases such as
point of about 17.5 C. by reacting tungsten metal, usu helium, argon or nitrogen may be used for this purpose.
ally as powder, with a gas stream containing major 55 Helium and argon are advantageously used. In order to
amounts of tungsten hexafluoride and minor amounts of and minimize product contamination, the reactor chamber,
fluorine at a temperature exceeding the boiling point of preferably the remaining apparatus as well, are
made
tungsten hexafluoride. Advantageously, the process is and forms of nickel. Nickel reacts only slowly with fluorine
carried out continuously by recirculating the gas stream containingaatmosphere.
protective film when exposed to a fluorine
past the reactant tungsten metal in a closed system with product contamination This by
action aids prevention of
the apparatus. It is to be
removal of product tungsten hexafluoride and addition appreciated in this connection that fluorine is an ex
of reactant fluorine to the reactant gas mixture as re tremely aggressive element. A preferred apparatus for
quired. conducting the process is a horizontal tube reactor since
65 such apparatus permits convenient batch introduction
DESCRIPTION OF THE DRAWING
of reactant tungsten without rotating seals or other
The drawing is a flow sheet describing the process of moving parts and minimizes recirculation of particulate
the invention schematically. tungsten in the system.
 5,328,668
3 4.
The process will now be described in conjunction 330, 200 and 130 ppb, respectively. The process of calci
with the flow sheet shown in the drawing; in which nation, dissolution, and partial crystallization can be
reservoir 11 is adapted to contain liquid WF6 which repeated if desired to provide tungsten metal of even
flows from reservoir 11 to heated at 25 vaporizer 12 higher purity.
through pipe 21, producing a stream of WF6 gas which The resulting tungsten powder was fed to a horizon
then flows to the nozzle of a venturi pump 13 via pipe tal tube reactor where it was converted to tungsten
22. The height of the liquid column of WF6 in reservoir hexafluoride by reaction with a gas stream consisting of
11, the temperature of vaporizer 12, and the configura tungsten hexafluoride containing 20%, by volume, of
tion of the venturi nozzle of pump 13 primarily deter fluorine. Temperature in the reactor was maintained
mine the pressure and flowrate of WF6 through the 10 between 395 C. and 405 C. during the run and the
pump and into the reactor 14 thence to cooler 15 and recirculation rate was 20,000 standard liters of gas per
condenser 16. Pump 13 serves to circulate any non-con kilogram of tungsten per hour. Tungsten hexafluoride
densable gases, including unreacted F2, from the vapor of high purity was condensed from the gas stream and
space of condenser 16 back through the reactor via withdrawn as product at the rate of 0.2 kilograms per
by-pass 23. The pressurized stream of WF6 generated by 15 hour of operation. Tungsten hexafluoride obtained by
the reservoir 11 and vaporizer12 and entering the pump this process contained no more than 1000 ppb total
nozzle serves as the motive fluid for the pump. The impurities with typical concentrations of specific impu
combined streams of non-condensable gases and WF6 rities at the following levels:
then exit the pump 13 and enter the reactor 14 contain
ing tungsten powder or granules. Fluorine injected into
the suction port 17 of the pump then reacts with tung ppbw
sten metal in reactor 14 yielding additional WF6. The Cr O
reactor temperature is controlled carefully through use Fe
K
10
10
of external heaters, through control of the quantity of Na 10
F2 injected at 24 into stream 17, and through vaporizer 25 Th
temperature and reservoir inventory which, in turn, U
control the flowrate of WF6 into the reactor. Gases
exiting the reactor pass through a cooler 15 and then In summary, the invention embodies several unique
enter condenser 16 where WF6 vapor is condensed to features as follows:
liquid WF6. Liquid WF6 then flows via stream 18 to 30 1. The system is completely closed and contains no
reservoir 11, thereby completing the circuit. When major components other than the two reactants, F2
sufficient WF6 has been generated in the system and W, the product, WF6, and the preferred mate
through addition of F2 and reaction with W, the level of rial of construction, nickel. Introduction of impuri
liquid WF6 in reservoir 11 reaches an overflow level ties such as oxygen and water vapor are therefore
and exits the system into product collector 19 via con 35
nector pipe 20. minimized since no diluent gases are used for tem
In summary then, fluorine gas injected into the sys perature control in the reactor.
tem at the suction port of recirculating pump 13 reacts 2. The system contains no moving parts, eliminating
with tungsten metal contained in reactor 14 to produce contamination from leaking seals on rotating shafts,
WF6 that collects as a liquid product in collection vessel etc. and contamination from erosion of the interior
19. The recirculation of WF6 occurs continuously, with surfaces of the containment vessels.
or without F2 addition. As F2 is added, additional WF6 3. The reaction of F2 with W is forced to proceed at
is generated as long as tungsten metal is available in low controlled temperatures, thereby minimizing
reactor 14. contamination from hot reactor walls, etc.
Control of the system is achieved through adjustment 45 4. The low reaction temperatures eliminate the intro
of the condenser and vaporizer temperatures as well as duction of significant quantities of many impurities
the inventory level of WF6 liquid in reservoir 11. F2 is contained in the tungsten metal feedstock by pre
injected into the system based on a continuously noni venting their volatilization and subsequent intro
tored system pressure. When the system pressure is at or duction into the liquid WF6 product stream. This is
below a determined set point, F2 is injected until the 50 the case, for instance, for fluorides of alkali and
system pressure reaches a second control point, at alkaline earth metals, many transition metals, and
which time the F2 flow is stopped. As the F2 in the thorium.
system is consumed and liquid WF6 is produced, the 5. Because of the continuous recirculation of WF6
system pressure falls, reaching the first control point. over tungsten metal in the reactor, impurity species
This F2 addition cycle then begins again. 55 that can be reduced by tungsten metal to species of
An example will now be given: lower relative volatility can be effectively removed
440 kilograms of commercial ammonium paratung from or prevented from entering the product
state (APT) containing no more than about 500 ppm of stream. The impurities remain with the tungsten
impurities with the principal impurities being Si, Fe, metal in the reactor. This is the case, for instance,
Mo, and Na with no single impurity exceeding 300 ppm, 60 for uranium.
were decomposed by heating at about 650 C., dissolved Although the present invention has been described in
in cold concentrated ammonia solution and partially conjunction with preferred embodiment, it is to be un
crystallized by boil off of water and ammonia to yield derstood that modifications and variations may be re
300 kilograms of high purity APT. The resulting APT sorted to without departing from the spirit and scope of
was hydrogen reduced to metallic tungsten powder 65 the invention, as those skilled in the art will readily
which upon analysis was found to contain no more than understand. Such modifications and variations are con
5 ppm total impurities with no impurity from the group sidered to be within the purview and scope of the inven
consisting of U, Th, Fe, Na and K exceeding 0.5,0.5, tion and appended claims.
 5
5,328,668
6
What is claimed is: ered thereto from said pump; cooler means for cooling
1. A closed reactor system particularly adapted for gaseous products from said reactor; condenser means
reacting metallic tungsten with fluorine, comprising: a coupled to said cooler means, means leading from said
reservoir for holding liquid tungsten hexafluoride; a condenser means to said reservoir; product collector
vaporizer for vaporizing liquid tungsten hexafluoride means for collect liquid tungsten hexafluoride over
from said reservoir; heat supply means for supplying flowing said reservoir; and bypass means between said
heat to said vaporizer; a pump for mixing gaseous fluo condenser and said pump to bypass said reservoir and
rine with tungsten hexafluoride vapor; fluorine supply said vaporizer with non-condensable gases from said
means coupled to said pump; reactor means for contain condenser.
ing particular tungsten for reaction with fluorine deliv O is a sk

15

20

25

30

35

45

50

55

65
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. . . 5,328,668
DATED July 12, 1994
INVENTOR(S) : Barry J. Sabacky et al.
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby
Corrected as shown below:

Claim 1, column 5, line 10, "particular"

Signed and Sealed this

Attest: (a (eam
BRUCELEMAN
Attesting Officer Commissioner of Patents and Trademarks