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Publication numberUS2738762 A
Publication typeGrant
Publication dateMar 20, 1956
Filing dateJul 20, 1953
Priority dateOct 8, 1951
Publication numberUS 2738762 A, US 2738762A, US-A-2738762, US2738762 A, US2738762A
InventorsPeter Pawlyk
Original AssigneeOhio Commw Eng Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Apparatus for the deposition of nonconductive copper coatings from vapor phase
US 2738762 A
Abstract  available in
Previous page
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Claims  available in
Description  (OCR text may contain errors)

Mardi 20 1956 P. PAWLYK y A 2,738,762


APPARATUS FOR THE DEPOSITION OF NON-CONDUCTIVE COPPER COATINGS FROM VAPOR PHASE Original Filed Oct. 8, 1951 2 Sheets-Sheet 2 2o a 11,2 ma@ O LL( @empoli N l o-@ew (Il v n I v f 2 INVENTOR i-IE E I E PETER PAwLYK BYwgmf/;

ATTORNEYS United States Patent O APPARATUS FOR THE DEPOSITION OF NON- CONDUCTIVE COPPER COATINGS FROM VAPOR PHASE Peter Pawlyk, Dayton, Ohio, assigner to The Commonwealth Engineering Company of Ohio, Dayton, Ohio, a corporation of Ohio Original application October 8, 1951, Serial No. 250,302. and this application July 20, 1953, Serial No.

4 Claims. (Cl. 118-49) This invention relates to means and methods of obtaining uniform concentrations of mixed gases at constant temperatures. More particularly the invention relates to the control of gaseous mixtures, one of the gases of which is a metal-bearing compound decomposable under the influence of heat to deposit metal.

This application is a division of co-pending application Serial No. 250,302, tiled October 8, 1951, and assigned to the same assignee as the present invention.

This application is related to co-pending applications, Serial Nos. 250,301; 250,303; 250,304; 250,305; 250,306 and 250,307; all led October 8, 1951, and by the same inventor as the present application.

The efficient plating of objects with metals, by the pyrolysis of gaseous metal-bearing compoundsand the deposition of the metallic component of the gas requires close control of decomposition conditions in order that a tine uniform deposit may be obtained. Premature heating of the metal-bearing gas above the decomposition point induces uncontrolled decomposition in the gas plating apparatus, and thus deprives the process of etticiency, since the concentration of metal inthe gas striking the object to be plated will then be uncontrolled and in some cases insufficient to provide a uniform, adherent coat on the workpiece.

An inert carrier gas may be used together with the metal-bearing gas and serves as an effective diluent aiording means ot' control of the concentration of the metalbearing gas. Such inert gases are carbon dioxide, nitrogen, helium and argon.

This invention contemplates subjecting the metal-bear-V ing compound in the liquid or solid state to the action of a carrier gas under controlled conditions `of temperature, and effecting vaporizaton of the metal-bearing compound under the controlled, conditions to provide a plating gas mixture uniform in concentration and of predetermined temperature characteristics. v

The invention also contemplates particular structural arrangements for the handling of the solid or liquid metal-bearing compound, which arrangements facilitate the contact with the carrier gases to accomplish intimate contact between these primary components. Thus, for example, fusing together of the solid particles of-metalbearing compound may be prevented by the arrangements of the invention.

The invention further contemplates `the provision of novel procedural steps to assist `in the attainment of the desired plating gas of uniform characteristics.

These and other allied purposes of the invention are attained by providing apparatus for the passage of the inert carrier gas through a pre-heating coil, maintained at a constant temperature, immediately prior to contacting the solid or liquid metal-bearing component with the carrier gas, the metal-bearing component itself being held at constant temperature conditions. The contact of the carrier gas withcthe metal-bearing 'component is facilitated by dispersing the particles of metal-bearing solid in a carburetor or gas mixing chamber `in layers, andv in- -in the openingS (Figure 2) of the carburetor.

.stances `befitself of a heat insulation material.


2 terspersing glass beads or ceramic material with the metalbearing solid to facilitate the dispersement. Glass wool and/ or metal screening may be employed to support the metal-bearing solid compounds, and both are effective to cleanse the gases as well as to assist in contact thereof with the solid compound.

Where the metal-bearing compound is in the liquid state the inert` carrier gases may be lbubbled through the material, a procedure which is facilitated by the employment of horizontal screens spaced along the vertical axis of the carburetor. The screens are in this instance eiective to prevent the entraining of the gas in restricted paths, and the minor turbulence created by the screen is suicient to insure of adequate liquid contact by the gas.

In accordance with the process of this invention the passage of the carrier gas under controlled conditions to the similarly controlled metal-bearing compound results in controlled temperature conditions in the gas mixture flowing from the carburetor to the plating chamber. This gas mixture may be subjected to a further heating step before entering the plating chamber and such a step is particularly eliective where the desired gas temperature in the chamber is higher than the temperature which may be effectively employed in the carburetor.

The invention will be more fully understood by reference to the following detailed description and accompanying drawings wherein:

Figurell is a schematic View of one embodiment of the invention; i

Figure 2 is a longitudinal sectional view of the carburetor of the embodiment of Figure l;

Figure 3 illustrates a modification ofthe carburetor system of Figure 1;

Figure 4 illustrates another embodiment of the invention; v

l Figure 5 illustrates a method of packing the carburetor with solids; and l Figure 6 illustrates a modification of the structure of Figure 5.

Referring to Figure l there is shown at 10 a tank of liquitied carbon dioxide provided with a valve 28 and from which extends a short copper conduit 9 having therein a gauge 36 which measures gas flow. The inner end of conduit 9 is formed into a coil 7which surrounds the carburetor 4, the lower end of the coil being secured The coil 7 and kcarburetor 4v are immersed in oil 3 contained in tank 2 and this assembly, indicated generally at 1, is adapted to be maintained at an elevated temperature by electric .heater 'element 29 secured beneath container 2. Heater element 29 may be provided with `thermostatic means, including element 37 secured to the heater by conductor 38,vv for automatically controlling the temperatbure of the oil 3 but where the volume of the oil is relatively large in comparison with the carburetor volumeand the temperature'of the oil not greater than about C. manual control is fully effective since electric heaters are readily obtainable which supply a substantially constant heat input. v e

vAt the upper opening 6- (Figure 2) of the carburetor 4 there is secured a conduit 12 which connects with plating chamber 24. Conduit 12 is provided with asbestos or other heat insulatingmaterial 33 and may in given ininterposed between the carburetor 4 and the plating chamber, and surrounding conduit 12 is a heater 11. f

The plating chamber 24 may be adapted tocontain an object to be plated or may itself( be the object which or pipe member'24 is provided withend flanges 30, 31.

Flange 30 secures the member 24 to conduit 12 while tlange 31 secures the chamber to an outlet line 32 provided with a vacuum 27 which exhausts to the atmosphere or a recovery apparatus as desired.

Chamber 24 is surrounded with a thin layer of asbestos 25 surmounted by an electric heating coil 26 powered from a source (not shown).

In Figure 2 the carburetor 4 is shown provided with vertically arranged layers 13 of chromium carbonyl, supported on screens 15 which are separated by layers of glass Wool 14. As shown in Figure 2 the screens are in pairs spaced apart and the glass wool is between adjacent pairs, each pair being adapted for supporting therebetween the chromium carbonyl. Metal screens 16 are positioned adjacent the inlet and outlet 6 to provide a thoroughly dispersed gas flow. The metal screens and 1.6 are approximately 100 mesh and the powder particles thereon vary from about 2 to 5 times the size of the screen openings.

In the modification of Figure 3 the coil 7 and carburetor 4 are euch immersed in oil 3 but the carburetor is not enclosed by the coil as in Figure l but is separated from it by a short length of connecting coil 17 which is also immersed in the bath. Such an arrangement is particularly useful where the temperature variation throughout the bath is negligible and the arrangement is desirable due to the simplified mechanical connections. This structure is particularly useful in connection with liquid metalbearing compounds as the carburetor may be readily recharged.

Figure 4 illustrates an embodiment of the invention in which the mixture of gases emanating from the carburetor 4 and heat jacket 11, as in the embodiment of Figure 1, are passed through a second coil 34, maintained in a constant temperature bath 18 containing oil 19 heated by element This arrangement is particularly suited for complete stabilization of the temperature of the gases, the mixture emanating from this constant temperature bath then being subject to the heat of heating jacket 20 prior to entry to the plating chamber'. This mode of raising the temperature in controlled steps is particularly effective where the temperature of decomposition of the metal bearing gases is relatively high.

Figures 5 and 6 set forth arrangements of solid metalbearing compounds which are particularly suited for establishing good contact with the carrier gases. Numeral 21 of Figure 5 indicates glass beads interspersed with fragments 22 of solid chromium carbonyl. Numeral 23 in Figure 6 indicates beads of chromium carbonyl supi ported by screens 35.

ln the operation of the apparatus the usual precautions are observed of providing a clean workpiece and flushing of the apparatus free of air prior to entry of the plating gases. Referring particularly to Figure l, carbon dioxide gas is bled from cylinder 10 into coil 7 through end 9 and attains a temperature substantially equal to that of the oil bath before entering the carbureting chamber 4 at 5. The carburetor is, as noted, packed with chromium carbonyl fragments which also are at substantially the temperature of the oil bath, in the present case 170 C. Preferably the temperature of the oil bath and gases entering the carburetor is between about 10 to 40 C. higher than that required` for vaporization of the carbonyl. Thus the slight tendency of the gases to cool as they expand into the carburetor is not a serious factor in the operation of the equipment.

lt will be clear that the particular temperature of the entering gases is a variable factor depending upon the physical dimensions of the carburetor and coil, the method of packing the carburetor and the particular compound to be volatilized. However, it will not generally be necessary to raise the temperature vof the incoming gases more than 40 C. above that required for vaporization of the carbonyl. v

The hot carrier gas contacting the carbonyl vaporizes the same and the mixture of gases flows upwardly, under the influence-of the pressure of the carrier gas, to the heating jacket 11, where additional heat is supplied to the gases, the temperature of which however is still below the decomposition point of the chromium carbonyl.

The packing of the carburetor in the indicated manner tends to eliminate any tendency of the metal bearing compounds to fuse together and consequently uniform gas flow to the plating chamber is secured with the apparatus of invention.

The metal-bearing gas entering the plating chamber 24, at flow rates of the carbon dioxide measured at the tank 10 of between about l liter to 8 liters per minute, will fill the chamber uniformly with plating gas which decomposes under the influence of the heat of the cham- ,ber depositing chromium on the interior Walls of the chamber. The pressure of the gases in the chamber may be maintained by the vacuum pump 27 at a pressure of 5 to 7 pounds absolute, although this pressure may be varied upwardly to speed the plating time, or lowered to achieve deposits of very fine metal. The temperature of the chamber wall in the present instance is about 600 F. and may be varied between about S50-700 F. to change the rate of deposition of metal. However, under the conditions noted, and a pressure of 5-7 pounds, a uniform plating having a thickness of approximately .003 may be obtained lin about 50 to 60 minutes over the interior length of a 5 tube.

The attainmentof a uniform mixture of carrier and metal-bearingy gas at the entrance to the plating chamber is essential to the uniform deposition of the metal and leads to the result noted above. However, in instances where the temperature of the carburetor is considerably below that desired for optimum plating of the workpiece, the uniform gas mixture emanating from the carburetor may be additionally heated with the apparatus of Figure 4 while maintaining uniformity in the gas mix.

The feature of pre-heating above the vaporization point of the metal-bearing compound insures of maximum and uniform vaporization at a given internal temperature of the carburetor. Where the carburetor and coil are exposed to the same oil bath a vapor pressure of carbonyl will of course exist over the fragments but the physical arrangement of the system is such that little carbonyl will iiow until the carrier gas sweeps away the carbonyl allowing more of the material to vaporize.

All metal-bearing gases which are subject to decomposition by heat to result in the deposition of the metallic component may be suitably employed in the process and apparatus of invention. Thus the solid metalbearing compounds such as molybdenum carbonyl, tungsten carbonyl and cobalt carbonyl, as well as liquids, for example, the nickel carbonyl and iron penta carbonyl, may be employed. The 'hydiides of antimony and tin, chromyl chloride, copper nitroxyl and cobalt nitrosyl carbonyl are other effective agents.

lt will be understood that this invention is susceptible to modification in order to adopt it to different usages and conditions and accordingly, it is desired to comprehend such modifications within this invention as may fall within the scope of the appended claims.

I claim:

1. In apparatus for gasplating, the structure comprising la plating chamber having an inlet and outlet, a hollow conduit secured at one end to said inlet, a heater element surrounding said conduit, a constant temperature source of plating gas secured to the other end of said conduit, and means including a source of vacuum connected to the outlet of said plating chamber for lthe passing of plating vgases through said apparatus.

J '2. 'In apparatus for gas plating with heat decomposable gaseousmetal-bearing compounds, the combination of a gas plating chamber having an inlet and an outlet, Witha gas mixing chamber communicating with the inlet of said gasrplating chamber for intermixing the gaseous metal-bearing compound with inert carrier gas, and means comprising solid discrete particles in said gas mixing chamber to facilitate intimate contact of the inert carrier gas with the gaseous metal-bearing compound.

3. In apparatus for gas plating with heat decomposable gaseousmetal-bearing compounds, the combination of a gas plating chamber having an inlet and an outlet, with a gas mixing chamber communicating with the inlet of said gas plating chamber for intermixing the gaseous metal-bearing compound with inert carrier gas, and means comprising multiple layers of solid discrete particles supported on foraminous material disposed in said mixing chamber tol facilitate intimate contact of the inert carrier gas with the gaseous metal-bearing compound.

4. In apparatus for gas plating with heat decomposable gaseous metal-bearing compounds,` a gas plating chamber having an inlet and an outlet, a gas mixing chamber communicating with said inlet, said gas mixing chamber containing spaced screens for supporting a solid gasiable metal-bearing compound, means for heating said gas mixing chamber to a substantially uniform temperature throughout, and means including a source of vacuum connected to the outlet of said plating chamber for withdrawing the gaseous mixture from said gas mixing chamber and into said plating chamber.

References Cited in the le of this patent UNITED STATES PATENTS 1,848,346 Griswold Mar. 8, 1932 2,333,534 Lang Nov. 2, 1943 2,344,138 Drummond Mar. 14, 1944

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1848346 *Feb 1, 1927Mar 8, 1932Dow Chemical CoApparatus for conducting chemical reactions
US2333534 *Aug 19, 1942Nov 2, 1943Sigmund Cohn & CoFirst surface mirror
US2344138 *Jan 16, 1941Mar 14, 1944Chemical Developments CorpCoating method
Referenced by
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US3226942 *Dec 22, 1961Jan 4, 1966United Aircraft ProdHeat transfer means
US3858548 *Feb 19, 1974Jan 7, 1975Corning Glass WorksVapor transport film deposition apparatus
US4947790 *Jan 10, 1989Aug 14, 1990U.S. Philips CorporationArrangement for producing a gas flow which is enriched with the vapor of a low-volatile substance
US5019423 *Dec 21, 1988May 28, 1991Mitsui Toatsu Chemicals, Inc.Equipment and method for supply of organic metal compound
US8272626Oct 12, 2006Sep 25, 2012Sigma-Aldrich Co. LlcBubbler for the transportation of substances by a carrier gas
US8309173 *Dec 9, 2010Nov 13, 2012Asm International N.V.System for controlling the sublimation of reactants
US8343583Jul 7, 2009Jan 1, 2013Asm International N.V.Method for vaporizing non-gaseous precursor in a fluidized bed
US9297071Oct 21, 2010Mar 29, 2016Sigma-Aldrich Co. LlcSolid precursor delivery assemblies and related methods
US20080251016 *Oct 12, 2006Oct 16, 2008Hugh CunningBubbler For the Transportation of Substances By a Carrier Gas
US20100009080 *Jul 7, 2009Jan 14, 2010Asm International N.V.Fluidized bed evaporator
US20110076402 *Dec 9, 2010Mar 31, 2011Asm International N.V.System for controlling the sublimation of reactants
U.S. Classification118/726, 427/252
International ClassificationC23C16/448
Cooperative ClassificationC23C16/4481
European ClassificationC23C16/448B