Method and apparatus for depositing film on a substrate, and products produced thereby

Method and apparatus for using emitting, ionizing, accelerating and collecting elements in a high vacuum to implant a hard film on a plastic substrate or the like. In preparation, a slug of a selected material to be deposited as a film is placed in the emitter. The specimens or articles to be implanted are placed on supports in the vicinity of the collector. A cover enclosure is then placed in position and the region enclosed by the cover is exhausted to a high vacuum. Selected potentials are applied to various elements of the apparatus and an accelerating/directing field which may be developed electrostatically, magnetically or by a combination of both, is developed in the acceleration structure. The electrostatic field causes electron emission from the ionizing elements to develop an increased charge on the emitted ionized particles. When implantation is to begin, a shutter control is moved out of beam blocking position and ionized particles from the emitter pick up additional charge from the ionizing elements and are accelerated to high velocity for bombarding the specimens. The collector is provided near the end of the enclosure beyond the specimen support region. The specimens are discharged regularly to eliminate the build-up of surface charge from the stream of bombarding ions.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to film deposition methods and apparatus, and more 
particularly, to such apparatus and methods for depositing a thin 
transparent hard film on a substrate, the properties of which may be 
enhanced by transformation of its surface in such manner. The invention is 
particularly applicable to film implantation in plastics. 
2. Description of the Prior Art 
With the increasing use of plastic and other non-glass lenses in eyeglasses 
and other items, it has become increasingly important to develop hardened 
surfaces on such relatively soft materials which resist scratching and 
abrasion. This is particularly true since the recent introduction of laws 
requiring the discontinuance of glass lenses in all but a few types of 
eyeglasses. Various methods of developing such hardened surfaces have been 
employed, but with less then complete success. These methods include the 
dipping of plastic lenses, the wiping on of a film, the use of harder 
plastics themselves, the provision of a laminated lens and similar 
approaches. Ideally, of course, such a product should have the resilience 
of the better plastics for protection against impact from hard objects 
while having surfaces that are as effective as glass or more so in 
resisting scratching and abrasion. 
Similarly the surface properties of many materials and objects may be 
enhanced by the provision of an extremely thin surface coating of a 
suitable material which may serve to protect the surface underneath from 
corrosion, wear and the like or provide a surface hardness not attainable 
by the substrate alone. Thus for example, razor blades which are said to 
suffer more from corrosion than wear, may be made to last many times 
longer than at present with suitable protection of the fine cutting edge 
from corrosion. If at the same time the cutting edge may be hardened, then 
the effects of wear will be reduced as well, both factors acting together 
to provide a much longer lasting blade. 
In addition, surface alloys may be developed on metal substrates and 
surface layers of various dopings of impurities and the like on 
semiconductor substrates may be possible through the use of appropriate 
deposition and implantation techniques. The accomplishment of such 
developments would greatly economize on the use of rare and expensive 
materials where only surface effects are needed. 
Efforts have been made to develop such products by particle bombardment. 
Examples of such may be found in U.S. Pat. Nos. 3,117,022 of G. A. Bronson 
et al, 3,494,852 of M. Doctoroff, 3,371,649 of H. E. T. Gowen, 3,409,529 
of K. L. Chapra et al, 3,472,751 of W. J. King, 3,562,141 of J. R. Morley, 
and others. However, whether through ineffective focusing or direction of 
the beam, emission and control of the ionized particles of for whatever 
reason unknown, such approaches have not resulted in truly acceptable and 
satisfactory products which realized the potential of the theories 
underlying such bombardment techniques. 
SUMMARY OF THE INVENTION 
The invention is generally set forth in the abstract above, which is 
incorporated by reference. In brief, the invention comprises methods and 
apparatus for developing emission of ionized molecular particles of a 
selected material and further ionizing the particles and accelerating them 
in a predetermined path toward a collector region for implantation on a 
plastic or other substrate positioned in the vicinity of the collector 
region. The entire particle bombardment structure is positioned within a 
vacuum chamber during operation. Predetermined electrical potentials are 
maintained at the various elements of the structure employed in the 
apparatus. Either electrostatic or magnetic ion beam directing apparatus 
may be employed for beam control or some combination of the two systems 
may be utilized. An electrostatic field is required, however to develop 
electron emission from ionizing elements positioned adjacent the path of 
the beam so as to "super-ionize" the beam, thus permitting effective 
acceleration. The beam is directed over a sufficient extent and controlled 
to such a degree by apparatus in accordance with the invention as to 
permit bombardment of specimen substrate over a considerable area. Where 
the specimen substrate is non-conducting, provision is made for the 
dissipation of surface charge carried to the substrate by the bombarding 
ions. Those ionized particles which do not impact the specimen materials 
are caught on a collecting grid and removed from the system. 
Material which has been successfully implanted in apparatus in accordance 
with the invention comprises minerals such as are set forth in the 
above-identified patents, selected for their properties of hardness, 
elasticity, heat resistance and optical clarity. The materials may include 
trace amounts of minute impurities such as may be found in commercial 
grade materials. In one example these materials are implanted onto various 
types of plastic lenses with implantation occurring to a depth of 
approximately 10,000 Angstroms (1 micron) within the preferred range from 
several hundred Angstroms to a few microns and the process of implanting 
and depositing continuing until a film layer is built up to a preferred 
thickness of approximately 2 microns. The result is an eyeglass lens or 
other product which has the shatter-resistance of the plastic substrate 
under the surface film with abrasion-resistant properties equal to or 
better than those of glass. 
In one particular arrangement in accordance with the invention, an electron 
beam gun emitter was employed with a paste mixture of such known minerals 
selected for their properties of hardness, elasticity, heat resistance and 
optical clarity, positioned in the electron beam gun target region. This 
electron beam gun is water-cooled, has a filament for emitting electrons 
and utilizes electromagnetic fields to cause the emitted electron beam to 
curve and bombard the target material. As a result, the target material 
and its molecules are bombarded off the surface as ionized molecular 
particles where they become accelerated by the field of the particle 
accelerator. A removable shutter is positioned in the region between the 
emitter and the accelerator to block or pass the beam as desired. 
The accelerator structure has interspersed ionizing elements which further 
ionize the molecular particles of the beam. This structure accelerates, 
directs and shapes the beam in its path to the specimen and collector 
region. In one particular arrangement of the invention, the accelerator 
structure comprises a series of spaced and insulated flat rings of varying 
diameters, increasing in the direction of beam traversal. Selected ones of 
these rings were fashioned as ionizing elements by silver soldering sharp 
needles with their points directed inward and generally equally spaced 
about the circumference of the rings. These sharp points serve as electron 
emitters for further ionizing particles as they pass through the rings. 
The accelerator structure is suspended from insulated wires extending to a 
support structure which also holds a target frame on which various lenses 
may be mounted. The collector screen extends over the specimen support 
brackets, physically and electrically separated therefrom, and is 
positioned across the divergent beam region so as to collect those 
particles that do not impact the specimens. 
In operation, a bell jar type cover is placed over the entire structure and 
the region thus enclosed is evacuated to a high vacuum. The insulators and 
interconnecting conductors are arranged to develop various potentials at 
various elements of the structure. A DC power supply has been employed for 
developing these potentials with selected RF modulation of certain 
electrode elements being developed from an RF generator. 
In one preferred arrangement in accordance with the invention, the electron 
beam gun emitter is maintained at the negative power supply voltage which 
is 10 kv. The first, third and fifth rings of the accelerator structure 
(counting from the bottom nearest the electron beam gun emitter) are 
preferably maintained at neutral potential, although these may have their 
potentials controlled, if desired, to exert minor control on the particle 
beam. The second and fourth rings are the ionizing elements with the 
needles attached. These are maintained at a negative potential range of 
approximately -3,000 to -15,000 volts, modulated with an RF signal of 
approximately 25 to 100 volts rms at 400 megahertz. The sixth and final 
ring is maintained at a slight positive potential, although this is not 
critical and this ring may be left to float and assume the potential of 
the beam, if desired. The specimen support frame is maintained at a 
positive 4 to 10 kilovolts. This can also be modulated with an RF signal 
at an amplitude of approximately 25 to 100 volts rms which serves to 
develop a controlled plasma that periodically discharges the plastic or 
other nonconducting material of the specimen substrate. The lenses or 
other products to be filmed are mounted in clips secured to the support 
frame. As an alternative to using a controlled plasma for discharging the 
substrate, isotope bodies may be mounted near the support frame for 
discharging the plastic substrate by radioactive bombardment. The 
collector screen is also maintained at a positive potential of from 4 to 
10 kilovolts, thus providing a strong positive force drawing the 
negatively ionized beam particles toward the specimens being bombarded. 
It has also been found possible to develop a beam which results in film 
deposition and implantation by reversing the polarity of potentials 
applied to the various elements of the structure. In such event, of 
course, the effectiveness of the ionizing elements is limited but the 
accelerating, beam shaping and directing, and collecting elements operate 
with positive ions essentially as described for negatively ionized 
particles. 
In alternative embodiments of the invention, various types and 
configurations of accelerating and ionizing structures may be employed. 
One such structure utilizes a series of vertical vanes fixed to the 
various horizontal rings by insulator mounts. The vanes are preferably of 
stainless steel and fashioned with all surfaces made extremely smooth, as 
by electropolishing, except the inner edge which is sharpened to an 
extreme degree. As explained previously, the succeeding rings increase in 
diameter and the vanes are angled along their inner sharp edges to match 
the gradient of ring inner diameter. The shape of such accelerating vanes 
influences the rate of acceleration of the beam particles. It may also be 
related to the shape of the specimen being coated. The shape of the beam 
may be varied by using rings which are elliptical or which present other 
shapes rather than circular. 
Still another alternative arrangement of the accelerating ionizing 
structure may utilize the stacked rings as first described but with the 
ion emitting rings being fashioned with extremely sharp inner edges 
instead of having the needles mounted thereon as heretofore described. 
Still another embodiment may utilize a series of tubular rings with the 
accelerating rings being rounded and polished while the electron emitter 
(ionizing) tubular elements are provided with a radially inward knife 
edge. 
The potentials applied to the various elements of the accelerating 
structure may be stepped and varied as desired. A varying effect on the 
shape, density and velocity of the beam can be achieved by varying the 
potentials of the accelerating/ionizing structure as a function of 
distance from the emitter, for example. As already mentioned, other beam 
shaping and directing structures may be employed utilizing magnetic field 
control of beam shape and particle distribution. 
Various arrangements and configurations of accelerating and beam directing 
elements may be employed to separate different particles in the beam so 
that bombardment of the specimens occurs only with the particles of 
desired size and velocity. Particular arrangements in accordance with the 
invention include structure for developing oriented magnetic fields which 
curve the desired particles along selected paths to the specimens while 
other particles that might have a deleterious effect upon the specimens 
being bombarded are directed along paths which impact shields or otherwise 
miss the specimens altogether. 
The benefits provided by the present invention are particularly useful in 
developing suitable low-cost lenses for eyeglasses and other applications 
from materials and fabrication processes formerly unsuitable. For example, 
it now becomes practical to form lenses by injection molding processes 
with the lenses in the final fabrication step being coated with films 
implanted by means of the present invention. 
Moreover, arrangements in accordance with the present invention may be used 
for implanting films on substances and articles other than plastic lenses. 
For example, one or a plurality of beam ionizing and accelerating 
arrangements in accordance with the present invention may be used on a 
mass production basis to implant a film having the desired properties of 
hardness, resistance to abrasion, and the like on a thin sheet of plastic 
or other material suitable for lamination with other sheets of plastic or 
the like to develop a desired combination of properties for an overall 
article. Such a laminated article may comprise an automobile windshield, 
for example, with the principal layer of the article being a thicker sheet 
of plastic having desirable properties of resistance to breakage and the 
like with the outer surfaces being covered with thin laminations of 
plastic implanted with a film in accordance with the present invention. 
The resultant article develops, by virtue of the implanted film, the 
necessary properties of hardness and resistance to surface abrasion which 
are not provided by the inner sheet constituting the principal material of 
the article. 
Mass production of such a film may be accomplished by feeding a thin sheet 
passing between respective storage rolls through an evacuated chamber in 
which the beam accelerating and ionizing structures of the present 
invention are located. It may also be possible to treat fabrics of various 
type in similar fashion. It has been found that the implantation of a 
particular material as a film has a beneficial result insofar as 
improvement of fire resistant or fire retardant properties is concerned. 
It is believed that the implantation of such a film tends to prevent 
oxidation by keeping air from reaching the combustible material 
underneath. It may be possible to treat fabrics in such fashion to develop 
fire retardant properties. Materials which are useful for this purpose 
comprise minerals which are non-combustible and which present a very small 
temperature coefficient of expansion, thus permitting the film to avoid 
rupture and remain intact as a protective coating over a considerable 
temperature range. Where multiple constituents of the protective film are 
present, they may be selected to compensate for their respective 
temperature coefficients so that the coefficient of expansion overall is 
approximately stabilized. Thus, the application of heat does not have the 
effect of fracturing the implanted film. As long as the implanted film, 
which itself is non-combustible, maintains its integrity, the oxidizable 
material underneath is prevented from combination with oxygen.

Description of the Preferred Embodiments 
As is shown in FIG. 1, a complete system 10 in accordance with the 
invention may comprise a high voltage power supply 12, a high vacuum 
system 14 and an RF power supply 16. The vacuum system 14 comprises a bell 
jar housing or cover 18 having one or more viewing windows 19 and a vacuum 
control console 20. Suitable interconnections between the various 
components of the overall system are provided via cables 22 and 24. 
FIG. 2 depicts a bombardment apparatus mounted within the housing 18 of the 
vacuum system 14 of FIG. 1. The apparatus 15 is shown comprising 
upstanding frame support rods 30 mounted to a base plate ring 32 in 
position on the control console table 20. Recessed within the base plate 
ring 32 is an electron beam gun emitter 34, shown partially broken away in 
section. Such a unit may comprise a Model 2" SFIH-270.degree. electron 
beam source with a Model CV-14 power supply, both of Airco Temescal 
Division of Air Reduction Company, Inc. and, as represented in FIG. 2, may 
be water-cooled by means of tubes 36 and have a centrally located target 
region 38 in which slug 40 of material to be evaporated is positioned. A 
filament (not shown) is positioned within the cavity 42. Suitable magnetic 
field generating coils are located within the structure adjacent the 
cavity 42. Various leads 44 are provided for carrying current to the 
filament and to the field generating coils. In operation of the electron 
beam gun emitter 34, electrons are emitted by the filament within the 
cavity 42 and directed outward and downward upon the target slug 40 under 
the influence of the generated electromagnetic field where they bombard 
and heat the slug 40 to cause emission of ionized molecular particles 
therefrom. A pivotable shutter 46, controllable from outside the vacuum 
housing, is provided to either block the cloud of emitted ionized 
particles or, alternatively when pivoted out of the way, to permit the 
ionized particles to respond to the field of the accelerating structure 
48. 
A specimen support or mounting frame 50 is shown mounted by means of 
insulators 52 atop the support rods 30. It is this frame 50 upon which the 
various articles, such as plastic lenses, may be secured for deposition of 
the film. A collector screen 54 is shown in position above the frame 50. 
It will be understood that the collector screen 54 is actually mounted to 
the top of the housing 18 (FIG. 1) but it is shown in position here as it 
is normally located when the housing 18 is in position, for a more 
complete understanding of the apparatus. The potential of the screen 54 
may be determined by connections (not shown) to the inside of the housing 
18. 
The accelerating/ionizing structure 48 is suspended from the support rods 
30 by means of wires 60 and insulators 62. The details of the 
accelerator/ionizer 48 are better shown in FIG. 3. It will be seen to 
comprise a plurality of flat rings, increasing in both inner and outer 
diameter from bottom to top. The first, third and fifth rings 66 serve as 
guard rings and principally serve to isolate the field of the intermediate 
ionizing or emitting rings 68, although they may contribute to the 
electric field for particle acceleration and direction. An accelerating 
ring 70 is the uppermost ring in the structure 48. Thus, six rings are 
shown in the structure, although a greater or lesser number may be 
provided if desired. Adjacent rings are separated from one or another by 
means of insulators such as 72. The emitter rings are provided with a 
plurality of needles 74 spaced generally equidistantly about the rings 68, 
and soldered thereto, as by silver solder. The points of the needles 74 
are sharpened to a fine degree and point radially inward. Thus, the points 
of the needles 74 readily emit electrons under the influence of an 
electric field which serves to further ionize the modecular particles that 
are being acted upon by the accelerator structure 48 and drawn toward the 
specimen/collector region by the positive potentials applied thereto. 
The potential of the various elements of the apparatus of FIG. 2 may be 
controlled by means of conductors and feed-through insulators 80 extending 
through the base plate ring 32. Thus, a conductor 82 is connected to the 
specimen frame 50. A conductor 84 is connected to a lower wire 60 to 
control the potential of the accelerating ring 70. Conductors 86 extend to 
respective ones of the guard rings 66, while the potential of the emitter 
rings 68 is controlled by conductors 88. These are connected to the 
associated high voltage power supply 12 and RF power supply 16 (FIG. 1). 
In one particular mode of operation of the apparatus, radioactive isotope 
blocks 90 may be utilized to discharge the build-up of surface charge on 
the specimens being filmed through radioactive bombardment. Such 
radioactive isotope blocks may also be suitably positioned at other points 
within the housing 18 in locations suitable for effectively discharging 
the specimens, if desired. Alternatively microwave RF energy may be beamed 
at the specimens from suitably positioned slotted lossy wave-guide 
elements to produce a local plasma for discharging surface charge. 
FIGS. 4 and 5 illustrate respectively plan and sectioned elevational views 
of one alternative type of accelerator/ionizing structure which may be 
substituted for that shown in FIGS. 2 and 3. This structure, designated 
48A, comprises a plurality of rings 101, of which three are shown, 
electrically isolated from one another and from interconnecting vertical 
vanes 102 by means of insulators 103. The vanes 102 are angled to follow 
the contour of the inner diameters of the respective rings 101 and are 
sharpened to a fine razor edge along this portion of the vanes 102. The 
remainder of the structure is smooth, as by electropolishing. Thus the 
vanes 102 serve to emit electrons copiously along their sharpened inner 
edges under the influence of an electric field. Suitable connections (not 
shown) may be provided to control the potentials of the vanes 102 and 
rings 101. 
FIG. 6 is a schematic plan view of accelerating structure 48 and FIGS. 7A 
and 7B are partial sectional elevations of alternative arrangements for 
the structure 48. FIG. 7A illustrates a plurality of tubular rings of 
which the emitter rings 104 have been fashioned with an extended and 
sharpened inner edge. The remainder of the rings 106 are perfectly rounded 
and electropolished to develop a smooth surface. The rings 104 under the 
influence of the applied electric field serve to discharge electrons 
inwardly from the sharpened inner edges. 
FIG. 7B represents a structure similar to that shown in FIG. 3, except that 
the needles 74 have been eliminated and the two emitter rings 68A have 
been provided with a sharply honed inner edge to accomplish the emission 
of electrons inwardly under the influence of the electric field. The 
remainder of the rings 68 are smoothed, as by electropolishing, as are the 
other surfaces and edges of the rings 68 apart from the sharpened inner 
edge thereof. 
Other accelerator and ionizing structural configurations may be devised to 
accomplish the results achieved by the accelerator/ionizer structure 48 
and alternative arrangements shown and described herein. In particular, 
the structure may be substituted or modified by the inclusion of apparatus 
for generating magnetic fields, either in place of or in addition to the 
electric fields generated by certain of the elements herein shown, in 
order to accomplish the desired result of directing and shaping the 
particle beam to fit the particular specimen on which the film is being 
deposited. 
FIG. 8 is a representation of a particular lens 110 which has been 
espcially coated in the apparatus shown and described herein. Lens 110 on 
its left half 112 and the small circles 114 has been coated with an 
implanted film comprising principally minerals such as those referred to 
hereinabove selected for their properties of hardness, elasticity, heat 
resistance, and optical clarity. Except for the small circular areas 114, 
the right half 116 is uncoated. This was accomplished by first masking the 
right half 116 with a perforated foil layer before implanting the film. As 
a test, the lens 110 was then rubbed with various abrasive materials, 
including emery paper and steel wool. The coated areas 112 and 114 were 
unmarked by these abrasive materials and the lens remains clear and 
transparent in these areas. Over the remainder of the right half 116, 
however, the lens was severely scratched to the point where it was no 
longer transparent, as indicated by the stippling shown thereon. Similar 
experiments with soft lenses coated by other methods known in the art 
served to scratch and mar the lens face but did not affect the films and 
filmed lenses produced by the present invention. 
Various other uses besides the coating of eye glass lenses and the like may 
be realized from the practice of the present invention. FIGS. 9 and 10 
illustrate another extensive area of use where the present invention will 
be most important. FIG. 9 illustrates a continuous system utilizing a 
plurality of particle bombardment units of the present invention arranged 
for a continuous film deposition process to implant a hard film on a 
cellulose plastic sheet. Facilities are known in the art for developing 
and maintaining a high vacuum chamber through which continuous materials 
may be fed for vacuum processing. The combination schematic and block 
diagram of FIG. 9 is intended to represent such a system. It is shown 
comprising a large chamber 120 through which a plastic sheet 122 is fed 
between rolls 124 and 126 at opposite ends of the chamber. Successive 
vacuum barriers 128 are provided at each end of the chamber 120. The film 
may be fed through suitable sealing arrangements 130, here represented as 
rollers between which the sheet 122 passes in going between outside 
ambient pressure and the high vacuum inside the chamber 120. Air passages 
or ports 132 are provided to connect the various regions within the 
chamber 120 with a plenum chamber 134 which is maintained at a high vacuum 
by an associated vacuum system 138. Alternatively the reels 124, 126 may 
be positioned within the chamber 120, in which case the need for the 
sealing elements for admitting the plastic 122 through the chamber walls 
is unnecessary. Within the chamber 120 and adjacent the sheet 122 which is 
supported on rollers or guides 136 is shown a plurality of units 15 (FIG. 
2) mounted on a base 148. These units 15 are shown as being connected to a 
power supply unit 139 which may include both the high voltage power supply 
and RF generator supply used in the system of the invention. 
In operation of the system represented in FIG. 9, the sheet 122 is 
transferred from roll 124 to roll 126, passing through the vacuum chamber 
120 and past the ionized particle deposition units 15. One or more of the 
units 15 may be operated to implant the desired film on one or both sides 
of the sheet 122 so as to develop the film in the desired areas and to the 
desired thickness. If deposition on both sides of the sheet 122 is 
desired, it can easily be arranged, either by mounting additional units 15 
on opposite sides of the sheet (possibly by using deflecting fields to 
develop the desired particle trajectories) or simply by doubling back the 
sheet 122 so that it traverses one or more of the units 15 with the 
opposite side of the sheet in position to be bombarded by the ionized 
particles therefrom. 
An outstanding benefit of implanting film on plastic sheet in this fashion 
is the opportunity which develops for fabricating a variety of articles 
which have heretofore been limited to fabrication from glass because of 
the need for surface protection by providing extreme resistance to 
abrasion. One such item is the automobile windshield. Such is represented 
in FIG. 10 as being formed of plastic sheet, preferably injection molded 
to a suitable thickness and shape, to which a sheet 142, cut from a sheet 
122 which has been implanted with a hard film in accordance with the 
invention as described in connection with FIG. 9, may be bonded. In FIG. 
10, only one such sheet 142 is shown in conjunction with the base layer 
140, although it will be understood that a sheet 142 may be provided on 
each side of the base layer 140. 
FIG. 11 represents a cross-section of an article, such as the windshield of 
FIG. 10 or an injection-molded lens, for example, in which a base layer 
150 is laminated between two layers 152. Each of the layers 152 is 
implanted with a hardened film in the manner described hereinabove along 
its outer surface. Thus, the laminated structure will provide the desired 
combination of toughness and resilience that may correspond to the base 
layer 150 and still provide the resistance to abrasion along all surfaces 
that are subject to abrasive forces as is provided by the protective film 
implanted in the manner described herein. One method of producing such an 
article is illustrated in FIG. 12. The more generalized methods of 
operating apparatus in accordance with the invention as described in 
conjunction with FIGS. 1-7 and 9 are illustrated in FIG. 13. 
Thus far the invention has been described in the context of deposition of a 
clear transparent film on a plastic substrate. However, it will be 
understood that other films may be deposited and that the substrate need 
not necessarily be plastic or, indeed, non-conducting. Various materials 
or compositions may be used as a source of the particles for deposition. 
One type of particular interest for sunglasses and windows for filtering 
the sun's rays is the deposition of a colored film. This may be 
accomplished by the inclusion of the oxides or other substances which 
impart the desired color to the film as deposited. Since the colors and 
tints achieved thereby have a tendency to fade, proportionally on exposure 
to ultraviolet light, it is desirable to implant a film of a deeper shade, 
color or tint than that which is ultimately desired and thereafter by 
exposure to ultraviolet rays or a similar treatment fade the deposited 
film to the intended hue. With controlled rates of deposition of a colored 
film, the ultraviolet rays which are present in the plasma during the 
deposition process may develop the desired fading so that the ultimate 
level of tinting is already present when the deposition process is 
completed. Such methods are illustrated in FIG. 14. 
An alternative arrangement in accordance with the present invention for use 
in the system of FIG. 1 is illustrated in FIG. 15, which is a partial 
elevational view showing the details of particular features, partially in 
section and partially broken away. In FIG. 15, apparatus 150 is shown 
having many of its basic structural elements similar to the structure of 
the apparatus 15 of FIG. 2; and where corresponding elements of structure 
are shown, the same reference numerals are employed. Thus, the apparatus 
150 is shown comprising a base 32 mounted on a table 20, a combination 
accelerating and ionizing structure 48 suspended by wires 60 and 
insulators 62 from support members 30, a shutter 46 mounted for pivotal 
movement above the base 32, and a bell jar cover 18a corresponding to the 
bell jar 18 of the vacuum apparatus of FIG. 1. 
In the configuration of FIG. 15, while the ionized particle beam is 
generated, accelerated and ionized in the same fashion as with the 
apparatus of FIG. 2, the beam is subsequently directed through a curved 
path to impact the mounted specimens. The purpose of directing the beam in 
such fashion is to achieve a separation of particles of various sizes and 
weights, thus avoiding a deleterious effect on the specimen being coated 
which might be caused by the impacting of larger particles that are 
sputtered off the material which is the source of the film particles. It 
has been found that the impact upon the specimens being filmed of 
relatively large particles tends to produce pitting of the implanted film. 
As a consequence, the film is fractured or the larger particles are 
embedded in the specimen and there is a tendency for absorption of 
moisture with a consequent lifting of film in the vicinity of the pits. In 
an extreme case the larger particles may develop undesirable surface 
irregularites. It has been found that the tendency to emit larger 
particles along with the smaller ones which are desired for the implanting 
process is diminished if the material comprising the source of the film is 
heated to a molten form before emission is initiated. However, applying 
this much heat to the system has an adverse effect in cases where the 
specimens are plastic or some other soft material since the heat tends to 
soften and melt the specimens and spoils the entire process. 
A preferable arrangement for overcoming this problem is represented in FIG. 
15 wherein the apparatus 150, in addition to comprising the elements 
already mentioned, includes means for establishing particularly oriented 
magnetic fields for directing the smaller particles to the specimens that 
are placed out of the path of the larger particles. This apparatus is 
shown additionally comprising a cylinder 164 containing magnetic field 
coils 165 for establishing a vertically directed magnetic field. The 
cylinder 164 is suspended from the support rods 30 by means of wires 160 
and insulators 162. Above the cylinder 164 is shown a second magnetic 
field means 166 for establishing a magnetic field which is horizontally 
directed. Means 166 may comprise individual magnets 168 which may be in 
the form of permanent magnets or the magnets 168 may be the pole pieces of 
electromagnetic coil magnets. In one configuration, means 166 may be in 
the form of a generally flat plate mounted to the wall of the housing 18a 
on the far side thereof, with a corresponding magnetic field means of 
opposite magnetic polarity (not shown) on the near side of the beam path 
through the center of the housing 18a. 
Above the magnetic field producing apparatus is an arrangement for 
suspending the specimens about the sides of the housing 18a. This 
mechanism is represented as a cylinder 170 having an extended upper lip 
adapted to be supported on a ring 172 by means of ball bearings 174 to 
permit rotation of the cylinder 170. A motor 176 with a drive roller 178 
bearing against the cylinder 170 serves to drive the cylinder 170 in 
rotation within the housing 18a. Specimens in the forms of lenses 180 are 
shown positioned on mounting racks 182 pivotably mounted in supports 184. 
The racks 182 are arranged to be pivoted through 180.degree. at a 
particular point in the cycle of rotation of the cylinder 170 in order to 
rotate the lenses 180 relative to the cylinder 170 so that they may be 
coated on both opposite surfaces. As shown in FIG. 15, this pivoting 
mechanism comprises a block 186 having a rod 188 extending to engage a 
trip lever 190 at the lower ends of the racks 182. Thus as each individual 
rack 182 passes the rod 188, the trip lever 190 is engaged by the rod 188 
and caused to rotate so as to turn the lenses 180 around and expose the 
other side to bombardment on further rotation of the cylinder 170. 
In the operation of the apparatus of FIG. 15, emitted particles are 
accelerated and ionized by means of the apparatus 48 as already described 
in connection with FIG. 2. As the particle beam passes through the 
apparatus 48, the larger particles pick up a lesser negative charge in 
proportion to their mass than do the smaller particles. In fact, the 
particles may have a positive charge upon emission which, in some 
instances, is not even neutralized by the emitted electrons during passage 
of the particles through the apparatus 48. As is known, the ballistic 
trajectory of a charged particle through a magnetic field may be dependent 
on the charge-to-mass ratio. Particles having a larger charge-to-mass 
ratio are deflected more by an orthogonal magnetic field than particles 
which have zero net charge or a smaller charge-to-mass ratio. Thus, the 
magnetic field directing and deflecting means of FIG. 15 serve to separate 
the particles which are larger than desired and those which are 
inadequately ionized from the particles of proper size and ionization to 
produce the desired film implantation on the lens specimens 180. 
For apparatus such as is shown in FIG. 15, a collector and suitable surface 
charge discharging means may be positioned across the top underneath the 
dome of the housing 18a in the manner indicated in FIG. 2. Such a 
collector, in addition to being effective as an element establishing an 
electrostatic field, may also serve to collect and trap the charged 
particles of larger size or lesser charge-to-mass ratio which are not 
directed by means of the magnetic field of the magnetic field means 166 to 
the specimens 180. As an alternative to the arrangement as depicted in 
FIG. 15, the specimens may be mounted in the manner shown in FIG. 2 with 
magnetic field deflecting means such as a baffle being provided to cause 
the particles to follow a dog-leg curved path which ultimately directs the 
appropriate particles to the specimen while deflecting or trapping the 
undesired particles outside the region of the specimens being implanted. 
As another alternative to the arrangement represented in FIG. 15 wherein 
the specimens are physically revolved by the cylinder 170 about the 
interior of the housing 18a during the film deposition process, the 
position of the specimens 180 may be fixed by holding the cylinder 170 
stationary and the magnetic field of the magnetic field means 166 may be 
rotated to cause the particle beam to sweep the specimen area. In such 
case, the magnetic field means 166 may itself comprise a cylindrical ring 
with the individual magnet field elements 168 being selectively magnetized 
by electromagnetic fields established by selective and successive 
energization of the respective electromagnetic coils to develop a 
horizontal magnetic field which rotates in controlled fashion in a plane 
generally orthogonal to the longitudinal axis of the apparatus 150. Such a 
swept field may selectively film any particular specimen as desired. At 
the same time it is effective in the manner already described at 
separating the desired particles from the undesired particles in order to 
provide an improved resultant filmed product. Also, if desired, the 
structure comprising the mounting racks 182 may be electrostatically 
charged so that these racks 182 serve additionally as a collector to 
attract the charged particles passing through the accelerating and 
ionizing structure 48 and the magnetic field means 164, 166. 
Still another embodiment of the invention is represented in FIG. 16 which 
shows apparatus 200 such as may be employed in the system of FIG. 1. 
Apparatus 200 is similar to that shown in FIG. 2 with certain notable 
modifications. As shown in FIG. 16, the apparatus 200 comprises the vacuum 
chamber within a housing 18a having a table 20, a base 32, a particle 
emitter 34, a shutter 46 and the ionizing, accelerating and directing 
structure 48. The elements 34, 46, and 48 are positioned off-center within 
the vacuum chamber of the apparatus 200. Above the elements 34, 46 and 48, 
and aligned therewith, is a particle diverting and directing structure 202 
suspended from support rods 204 by means of wires 206 and insulators 208. 
As shown in FIG. 16, the structure 202 includes a plurality of toroidal 
ring magnets 210 mounted within an outer housing or baffle 212. The 
respective ring magnets 210 are successively positioned along the intended 
path of the selected ionized particles and so oriented as to direct the 
particles by means of an electromagnetic field from the vicinity of the 
apparatus 48 upward and sideways to establish a stream of ionized 
particles generally centrally located and symmetrically disposed about the 
longitudinal axis of the housing 18a. The baffle or shield 212 is so 
arranged as to prevent any line-of-sight path from the structure 48 to the 
specimens above the apparatus 200. In this arrangement in accordance with 
the invention, the upper portion of the apparatus may correspond to the 
upper part of FIG. 2 with the specimens symmetrically disposed across the 
upper end of the chamber 18a. In this arrangement, the particles which do 
not have the appropriate velocities and charge-to-mass ratio will not 
follow the same path through the apparatus 202 as do the selected 
particles, but instead will tend to impact the baffle or shield comprising 
the housing 212 and thus be removed from the stream of ionized particles 
directed toward the specimens at the top of the apparatus. 
Although FIG. 16 shows the diverting and directing apparatus 202 as 
including a plurality of ring magnets 210, it will be understood that this 
structure may be formed of a single solenoidal coil in place of the 
individual magnets 210. Alternatively a plurality of permanent magnets, 
suitably fixed in a series of rings, may be used as the magnets 210. Such 
an arrangement has the advantage of developing the desired 
particle-diverting field without the application of electrical power, thus 
reducing the power requirements of the apparatus 200 and avoiding the heat 
otherwise generated within the housing 18a by the electromagnet system. 
Apparatus in accordance with the present invention may also be utilized to 
implant metal surfaces with desired compounds. Certain compounds may have 
the effect of changing the surface properties of the metallic article, 
similar to the hardening provided for plastic lenses and the like already 
described. In other circumstances, apparatus in accordance with the 
present invention may be utilized to implant surface films on selected 
portions of semiconductors in order to facilitate the fabrication of 
entire solid state circuits on single semiconductor chips. Various other 
applications of the methods and apparatus of the present invention will 
occur to those skilled in the art without departing from the concepts of 
the invention. 
Thus, there have been described and shown herein various particular 
arrangements in accordance with the present invention which illustrate the 
application thereof to a variety of uses. Variations of the structures 
shown and described herein, all within the basic concept of the invention, 
will occur to those skilled in the art. For example, other configurations 
of ionizing elements may be employed, as for an example the use of 
specific electron guns for directing electrons into the particle stream 
for further ionization thereof. 
Although there have been described above specific methods and apparatus for 
depositing film on a substrate, and products produced thereby, in 
accordance with the invention for the purpose of illustrating the manner 
in which the invention may be used to advantage, it will be appreciated 
that the invention is not limited thereto. Accordingly, any and all 
modifications, variations or equivalent arrangements which may occur to 
those skilled in the art should be considered to be within the scope of 
the invention.