BACKGROUND OF THE INVENTION
[0001] This invention relates to a method and apparatus for tuning microwave transmission
windows and more particularly for maximizing the power transmitted through the windows.
The invention has application with any microwave power transmission into a plasma,
but has particular applicability for plasma-type systems, such as those incorporating
amorphous semiconductor alloys. The invention includes to a method and apparatus for
making such devices by plasma deposition from reaction gases wherein the plasmas are
excited by microwave energy. The invention has one of its most important applications
in making commercial electrophotographic devices having a cyclindrical or drum configuration
with the amorphous semiconductor alloys coated or deposited on the outer surfaces
thereof. The present invention enhances the commercial mass production of electrophotographic
drums incorporating amorphous semiconductor alloys.
[0002] Silicon is the basis of the huge crystalline semiconductor industry and is the material
which has produced expensive high efficiency (18 percent) crystalline solar cells
for space applications. When crystalline semiconductor technology reached a commercial
state, it became the foundation of the present huge semiconductor device manufacturing
industry. This was due to the ability of the scientists to grow substantially defect-free
germanium and particularly silicon crystals, and then turn them into extrinsic materials
with p-type and n-type conductivity regions therein. This was accomplished by diffusing
into such crystalline material parts per million of donor (n) or acceptor (p) dopant
materials introduced as substitutional impurities into the substantially pure crystalline
materials, to increase their electrical conductivity and to control their being either
of a p or n conduction type. The fabrication processes for making p-n junction crystals
involve extremely complex, time consuming, and expensive procedures. Thus, these crystalline
materials useful in solar cells and current control devices are produced under very
carefully controlled conditions by growing individual single silicon or germanium
crystals, and when p-n junctions are required, by doping such single crystals with
extremely small and critical amounts of dopants.
[0003] In summary, crystal silicon devices have fixed parameters which are not variable
as desired, require large amounts of material, are only producible in relatively small
areas and are expensive and time consuming to produce. Devices based upon amorphous
silicon can eliminate these crystal silicon disadvantages. Amorphous silicon has an
optical absorption edge having properties similar to a direct gap semiconductor and
only a material thickness of one micron or less is necessary to absorb the same amount
of sunlight as the 50 micron thick crystalline silicon. Further, amorphous silicon
can be made faster, easier and in larger areas than can crystalline silicon.
[0004] Accordingly, a considerable effort has been made to develop processes for readily
depositing amorphous semiconductor alloys or films, each of which can encompass relatively
large areas, if desired, limited only by the size of the deposition equipment, and
which could be readily doped to form p-type and n-type materials where p-n junction
devices are to be made therefrom equivalent to those produced by their crystalline
counterparts. For many years such work was substantially unproductive. Amorphous silicon
or germanium (Group IV) films are normally four-fold coordinated and were found to
have microvoids and dangling bonds and other defects which produce a high density
of localized states in the energy gap thereof. The presence of a high density of localized
states in the energy gap of amorphous silicon semiconductor films results in a low
degree of photoconductivity and short carrier lifetime, making such films unsuitable
for photoresponsive applications. Additionally, such films could not be successfully
doped or otherwise modified to shift the Fermi level close to the conduction or valence
bands, making them unsuitable for making p-n junctions for solar cell and current
control device applications.
[0005] In an attempt to minimize the aforementioned problems involved with amorphous silicon
and germanium, W.E. Spear and P.G. Le Comber of Carnegie Laboratory of Physics, University
of Dundee, in Dundee, Scotland, did some work on "Substitutional Doping of Amorphous
Silicon", as reported in a paper published in Solid State Communications, Vol. 17,
pp. 1193-1196, 1975, toward the end of reducing the localized states in the energy
gap in amorphous silicon or germanium to make the same approximate more closely intrinsic
crystalline silicon or germanium and/or substitutionally doping the amorphous materials
with suitable classic dopants, as in doping crystalline materials, to make them extrinsic
and of p or n conduction types.
[0006] The reduction of the localized states was accomplished by glow discharge deposition
of amorphous silicon films wherein a gas of silane (SiH₄) was passed through a reaction
tube where the gas was decomposed by a radio frequency (RF) glow discharge and deposited
on a substrate at a substrate temperature of about 500-600°K (227-327°). The material
so deposited on the substrate was an intrinsic amorphous material consisting of silicon
and hydrogen. To produce a doped amorphous material, a gas of phosphine (PH₃) for
n-type conduction or a gas of diborane (B₂H₆) for p-type conduction was premixed with
the silane gas and passed through the glow discharge reaction tube under the same
operating conditions. The gaseous concentration of the dopants used was between about
5 x 10⁻⁶ and 10⁻² parts per volume. The material so deposited included supposedly
substitutional phosphorous or boron dopant and was shown to be extrinsic and of n
or p conduction type.
[0007] While it was not known by these researchers, it is now known by the owrk of others
that the hydrogen in the silane combines at an optimum temperature with many of the
dangling bonds of the silicon during the glow discharge deposition, to substantially
reduce the density of the localized states in the energy gap toward the end of making
the electronic properties of the amorphous material approximate more nearly those
of the corresponding crystalline material.
[0008] The incorporation of hydrogen in the above RF deposition method not only has limitationns
based upon the fixed ratio of hydrogen to silicon in silane, but, more importantly,
various Si:H bonding configurations introduce new antibonding states which can have
deleterious consequences in these materials. Therefore, there are basic limitations
in reducing the density of localized states in these materials which are particularly
harmful in terms of effective p as well as n doping. The resulting density of states
of the RF silane deposited materials leads to a narrow depletion width, which in turn
limits the efficiencies of solar cells and other devices whose operation depends on
the drift of free carriers. The RF method of making these materials by the use of
only silicon and hydrogen also results in a high density of surface states which affects
all the above parameters.
[0009] After the development of the glow discharge deposition of silicon from silane gas
was carried out, work was done on the sputter depositing of amorphous silicon films
in the atmosphere of a mixture of argon (required by the sputtering deposition process)
and molecular hydrogen, to determine the results of such molecular hydrogen on the
characteristics of the deposited amorphous silicon film. This research indicated that
the hydrogen acted as an altering agent which bonded in such a way as to reduce the
localized states in the energy gap. However, the degree to which the localized states
in the energy gap were reduced in the sputter deposition process was much less than
that achieved by the silane deposition process described above. The above-described
p and n dopant gases also were introduced in the sputtering process to produce p and
n doped materials. These materials had a lower doping efficiency than the materials
produced in the glow discharge process. Neither process produced efficient p-doped
materials with sufficiently higher acceptor concentrations for producing commercial
p-n or p-i-n junctions devices. The n-doping efficiency was below desirable acceptable
commercial levels and the p-doping was particularly undesirable since it reduced the
width of the band gap and increased the number of localized states in the band gap.
[0010] Greatly improved amorphous silicon alloys having significantly reduced concentrations
of localized states in the energy gaps thereof and high quality electronic properties
have been prepared by glow discharge as fully described in U.S. Patent No. 4,226,898,
Amorphous Semiconductors Equivalent to Crystalline Semiconductors, Stanford R. Ovshinsky
and Arun Madan which issued October 7, 1980, and by vapor deposition as fully described
in U.S. Patent No. 4,217,374, Stanford R. Ovshinsky and Masatsugu Izu, which issued
on August 12, 1980, under the same title. As disclosed in these patents, which are
incorporated herein by reference, fluorine is introduced into the amorphous silicon
semiconductor to substantially reduce the density of localized states therein. Activated
fluorine especially readily diffuses into and bonds to the amorphous silicon in the
amorphous body to substantially decrease the density of localized defect states therein,
because the small size of the fluorine atoms enables them to be readily introduced
into the amorphous body. The fluorine bonds to the dangling bonds of the silicon and
forms what is believed to be a partially ionic stable bond with flexible bonding angles,
which results in a more stable and more efficient compensation or alteration than
is formed by hydrogen and other compensating or altering agents. Fluorine is considered
to be a more efficient compensating or altering element than hydrogen when employed
alone or with hydrogen because of its exceedingly small size, high reactivity, specificity
in chemical bonding, and highest electronegativity. Hence, fluorine is qualitatively
different from other halogens and so is considered a super-halogen.
[0011] As an example, compensation may be achieved with fluorine alone or in combination
with hydrogen with the addition of these elements(s) in very small quantities (e.g.,
fractions of one atomic percent). However, the amounts of fluorine and hydrogen most
desirably used are much greater than such small percentages so as to form a silicon-hydrogen-fluorine
alloy. Such alloying amounts of fluorine and hydrogen may, for example, be in the
range of 1 to 5 percent or greater. It is believed that the new alloy so formed has
a lower density of defect states in the energy gap than that achieved by the mere
neutralization of dangling bonds and similar defect states. Such larger amount of
fluorine, in particular, is believed to participate substantially in a new structural
configuration of an amorphous silicon-containing material and facilitates the addition
of other alloying materials, such as germanium. Fluorine, in addition to its other
characteristics mentioned herein, is believed to be an organizer of local structure
inthe silicon-containing alloy through inductive and ionic effects. It is believed
that fluorine also influences the bondign of hydrogen by acting in a beneficial way
to decrease the density of defect states which hydrogen contributes while acting as
a density of states reducing element. The ionic role that fluorine plays in such an
alloy is believed to be an important factor in terms of the nearest neighbor relationships.
[0012] About forty-five years ago, C. Carlson developed the first electrophotographic process
based on a sulfur material. Other chalcogenides such as selenium and selenium alloys
were thereafter suggested for such applications together with organic substances such
as polyvinyl carbazole (PVK). These materials, however, exhibited certain deficiencies.
They were toxic, and therefore difficulty to handle, soft, and therefore subject to
wear, and had poor infrared light photoresponse.
[0013] In view of the above noted deficiencies of these materials, silicon based amorphous
semiconductor alloys were investigated for possible applications in electrophotographic
processes. These materials were considered likely to be useful because of the hardness
of amorphous silicon alloys, because of their nontoxic nature, and because of their
improved photoresponse to infrarred light. Also, as previously mentioned, these materials
could be made with a density of states reduced to a point where charging of the materials
to the potentials required for electrophotographic replication was considered possible.
Thus, amorphous semiconductor alloys made by the processes hereinabove described have
demonstrated photoresponsive and structural characteristics which are suited for electrophotographic
applications. These prior art processes, however, have suffered from relatively slow
deposition rates and low conversion efficiency of the reaction gas feed stock which
are important considerations from the standpoint of using amorphous semiconductor
materials on a commercial basis.
[0014] A new and improved process for making electrophotographic devices incorporating amorphous
semiconductor alloys is disclosed in U.S. application Serial No. 580,081, filed February
14, 1984 for "An Improved Method Of Making A Photoconductive Member And Improved Photoconductive
Members Thereby", filed in the names of Annette G. Johncock and Stephen J. Hudgens,
which is incorporated herein by reference. The process described therein is a microwave
glow discharge deposition process which provides substantially increased deposition
rates and reaction gas feed stock utilization. Among the many applications for amorphous
semiconductor alloys, high deposition rates and reaction gas feed stock conversion
efficiency and utilization are most essential for the commercial viability of electrophotographic
devices utilizing such materials. High deposition rates and reed stock conversion
efficiency and utilization are necessary because layer thicknesses of about 15 microns
or more of amorphous semiconductor alloy are required in such devices to enable sufficient
surface potential, about 350 volts, to be applied thereto. As a result, amorphous
semiconductor alloys can be deposited at sufficient rates and have desired photoresponsive
characteristics to enable the commercial utilization of such materials in electrophotographic
devices.
[0015] The electrophotographic devices used in commercial practice usually take the form
of cylindrical or dum members. An apparatus and method which facilitates the deposition
of amorphous semiconductor alloys uniformly over the entire outer surface of such
drums to form electrophotographic devices thereon is disclosed in U.S. Application
Serial No. 580,086, also filed February 14, 1984, for "Method and Apparatus For Making
Electrophotographic Devices", filed in the names of the current inventors, Eugene
W. Fournier, Erik J. Bjornard, Annette G. Johncock and Joachim Doehler, which is incorporated
herein by reference. At the same time, all of the advantages of microwave glow discharge
processes including high reaction gas feed stock utilization can be realized. The
present invention provides a method and apparatus to maximize and stabilize the power
transmitted through the microwave window into the deposition chamber to enhance the
microwave glow discharge process which can be utilized in making the above electrophotographic
devices.
SUMMARY OF THE INVENTION
[0016] The invention provides a method and apparatus for turning a microwave transmission
window to maximize and stabilize the power transmitted through the window into a microwave
plasma. The window is tuned to transmit the power required to achieve the plasma conditions
desired. The power transmission through the window is tuned by adding a pair of tuning
structures to the window. The tuning structures can be formed by stacking a plurality
of small disks or other shaped pieces of dielectric material, such as alumina, adjacent
the outer edge of the window. The width or diameter and the height of the tuning structures
are adjusted to achieve both a high transmission coefficient as well as a consistent
plasma excitation to provide stability in the plasma, for example, in a glow discharge
deposition process. One particular utilization of the invention is with making electrophotographic
devices incorporating amorphous semiconductor alloys as described in the above-referenced,
copending applications.
[0017] Copending application Serial No. 580,086 provides a method and apparatus for depositing
a layer of material onto the outer surface of at least a pair of cylindrical members.
The method includes the steps of forming an inner chamber including the pair of cylindrical
members by aligning the members with the longitudinal axes thereof disposed substantially
parallel and the outer surfaces of the members closely spaced apart to form the inner
chamber and a narrow passage communicating with the inner chamber between the members.
The method further includes the steps of introducing at least one reaction gas into
the inner chamber through the narrow passage, wherein, the at least one reaction gas
includes at least one element to be deposited, and forming a plasma from the at least
one reaction gas within the inner chamber to deposit the layer of material containing
the at least one element onto the outer surface of the cylindrical members.
[0018] The inner chamber can be formed by forming a substantially closed loop of a plurality
of the cylindrical members by aligning the members with the longitudinal axes thereof
disposed substantially parallel and the outer surfaces of adjacent members closely
spaced apart to form the inner chamber substantially closed and a narrow passage between
adjacent members communicating with the inner chamber. The at least one reaction gas
is then introduced into the inner chamber through at least one of the narrow passages.
[0019] The reaction gases can include silane (SiH₄), silicon tetrafluoride (SiF₄), germane
(GeH₄), germanium tetrafluoride (GeF₄), diborane (B₂H₆), boron trifluoride (BF₃),
phosphine (PH₃), phosphorus pentafluoride (PF₃), ammonia (NH₃), nitrogen (N₂), oxygen
(O₂) and methane (CH₄) or combinations thereof. The plasma within the inner chamber
can be formed by coupling microwave energy or radio frequency energy into the inner
chamber through a microwave transmission window.
[0020] Serial No. 580,086 provides an apparatus for depositing a layer of material onto
the outer surfaces of at least a pair of cylindrical members. The apparatus includes
a substantially closed deposition chamber, means for aligning the members with the
longitudinal axes thereof disposed substantially parallel with the outer surfaces
of the members closely spaced apart to form a substantially closed inner chamber within
the deposition chamber and a narrow passage communicating with the inner chamber between
the members. The apparatus further includes means for introducing at least one reaction
gas into the inner chamber through the narrow passage wherein the at least one reaction
gas includes at least one element to be deposited onto the outer surfaces of the members.
The apparatus further includes means for forming a plasma from the at least one reaction
gas within the inner chamber to deposit the layer of material containing the at least
one element onto the outer surface of the cylindrical members.
[0021] The apparatus can include means for aligning a plurality of the cylindrical members
in a substantially closed loop with the longitudinal axes thereof disposed substantially
parallel and the outer surfaces of adjacent members closely spaced apart to form the
substantially closed inner chamber and a narrow passage between each pair of members
communicating with the inner chamber. The reaction gas introducing means are arranged
to introduce the reaction gas into the inner chamber through at least one of the narrow
passages.
[0022] The plasma-forming means includes means for coupling microwave energy into the inner
chamber through a microwave transmission window. To facilitate the uniform deposition
onto the outer surfaces of the cylindrical members, the apparatus can further include
means for rotating the cylindrical members about their own longitudinal axes and means
for rotating the microwave energy polarity. The reaction gas introducing means preferably
include means for introducing the reaction gas into the inner chamber through at least
one of the narrow passages and means for pumping unused reaction gases from the inner
chamber through at least one narrow passage other than the narrow passage through
which the reaction gas is introduced into the inner chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023]
Fig. 1 is a partial cross-sectional view of a cylindrical member having materials
deposited thereon in accordance with Serial No. 580,086 wherein the deposited materials
adapt the cylindrical member for used as an electrophotographic device which can embody
the present invention;
Fig. 2 is a side view partly in cross section of an apparatus in accordance with Serial
No. 580,086 which can embody the present invention;
Fig. 3 is a cross-sectional view taken along lines 3-3 of Fig. 2;
Fig. 4 is a side view, partly in cross section, of another apparatus in accordance
with Serial No. 580,086 which can embody the present invention;
Fig. 5 is an explanatory sketch of the microwave power reflected by one transmission
window;
Fig. 6 is an explanatory sketch of the microwave power transmitted by the window of
Fig. 5;
Fig. 7 is a graph illustrating the reflected power versus plasma intensity relationship;
Fig. 8 is a side diagrammatic view of an embodiment of the present invention; and
Fig. 9 is a top plan diagrammatic view of the embodiment of Fig. 8.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Figs. 1 through 4 describe the method and apparatus claimed in copending application,
U.S. Serial No. 580,086 with one radio frequency embodiment, Fig. 5 deleted. The applicability
of Serial No. 580,086 to the present invention is described with respect to Figs.
1 through 4 and the additional new disclosure and structures of the present invention
are more particularly described with respec to Fig. 5 and the figures and specification
thereafter.
[0025] Referring now to Fig. 1, it illustrates, in partial cross-sectional side view, an
electrophotographic device 10 of the type which can be formed utilizing the present
inventin by depositing various materials onto the outer surface of a cylindrical member
12. The cyclindrical member 12 forms the substrate of the electrophotographic device
10. The device 10 includes a first blocking layer 14 deposited onto the substrate
12, a photoconductive layer 16 deposited onto the first blocking layer 14, and a second
blocking layer 18 deposited onto the photoconductive layer 16. The photoconductive
layer 16 preferably is formed from an amorphous semiconductor alloy and more particularly,
an amorphous silicon alloy containing silicon and hydrogen and/or fluorine. Depending
upon the type of blocking layers 14 and 18 selected, and the type of charge utilized
in charging the device 10, the photoconductive region 16 can also include small amounts
of a dopant such as boron to provide the region 16 with substantially intrinsic properties.
Similarly, the photoconductive region 16 can be rendered slightly n-type without any
dopant included.
[0026] The bottom blocking layer 14 is provided to preclude charge injection from the substrate
12 into the photoconductive region 16. To that end, the bottom blocking layer 14 can
be made insulative when formed from an amorphous alloy including silicon and carbon,
silicon and oxygen, or silicon and nitrogen. In forming such bottom blocking layers,
reaction gas mixtures of silane (SiH₄) and/or silicon tetrafluoride (SiF₄) with methane
(CH₄), ammonia (NH₃), nitrogen (N₂) or oxygen can be used. Such blocking layers are
suitable for both positive and negative charging of the electrophotographic device
10.
[0027] If positive charging of the electrophotographic device 10 is desired, the bottom
electron blocking layer 14 can be, for example, a p-type amorphous silicon alloy formed
from reaction gas mixtures including silane and/or silicon tetrafluoride with a p-type
dopant-containing compound such as diborane (B₂H₆) or boron trifluoride (BF₃). In
this case, it is also preferred that the photoconductive region 16 be formed from
an amorphous silicon alloy which includes a small amount of p-type dopant achieving
substantially intrinsic properties.
[0028] If negative charging is desired, the bottom hole blocking layer can be, for example,
an amorphous silicon alloy which is n-type. To form such a blocking layer, reaction
gas mixtures of silane and/or silicon tetrafluoride with an n-type dopant-containing
compound, such as phosphine (PH₃) or phosphorus pentafluoride (PF₅) can be used. In
this case, the photoconductive layer 16 is preferably formed from an amorphous silicon
alloy which is slightly n-type.
[0029] The top blocking layer 18 can be formed from any of the materials mentioned with
respect to the bottom blocking layer 14. Hence, the top blocking layer can be formed
from an insulative material or a p-type or n-type amorphous semiconductor alloy as
previously described above. For further details with respect to specific examples
of some of the configurations and materials of electrophotographic devices of the
type which can be made by utilizing the present invention, reference can be had to
the aforementioned copending U.S. patent application Serial No. 580,081.
[0030] As disclosed in the above-mentioned copending application the photoconductive region
16 preferably is thick in dimension, being on the order of 10 to 25 microns thick
to facilitate a sufficient surface potential characteristic of the device. As also
disclosed in that application, in order to make such devices on a commercial basis,
it is necessary to deposit the materials forming the photoconductive region 16 by
a method which exhibits high deposition rates. Conventional radio frequency glow discharge
deposition techniques are not suitable for forming the entire 10 to 25 microns thick
photoconductive region 16. However, as disclosed in the aforementioned copending application,
microwave energy excited glow discharge plasmas facilitate the deposition of the photoconductive
region 16 at deposition rates which render such devices commercially viable. The apparatus
and method of the present invention contemplate an improved utilization of microwave
energy for forming a plasma from which the materials of the electrophotographic device
can be deposited at such commercially viable rates and with gas feed stock utilization
no heretofore possible.
[0031] The photoconductive region 16 can be formed from both microwave and radio frequency
glow discharge plasmas or radio frequency energy could be utilized to ignite the plasma.
In the case of utilizing radio frequency to deposit a portion of the region 16, the
major portion of the photoconductive region 16 can be formed from the microwave energy
glow discharge plasma and the remaining or top portion of the photoconductive region
16 can then be formed from the radio frequency glow discharge plasma. The apparatus
and method accommodates both modes of operation in order to facilitate the making
of electrophotographic copier drums having desired photoresponsive and charge retention
characterisitics to render the devices especially useful for electrophotographic copying.
[0032] Referring now to Figs. 2 and 3, they illustrate an apparatus 20, which can embody
the present invention adapted for depositing a layer or layers of material, preferably
amorphous semiconductor alloys, onto a plurality of drums or cylindrical members 12.
The apparatus 20 includes a deposition chamber 22. The chamber 22 includes a pump-out
port 24 adapted for suitable connection to a pump for pumping out reaction products
from the chamber and to maintain the interior of the chamber at an appropriate pressure
to facilitate the deposition process therein. The chamber 22 further includes a plurality
of reaction gas input ports 26, 28, and 30 through which reactin gases are introduced
into the depositon environment in a manner to be described hereinafter.
[0033] Within the chamber 22, there are supported a plurality of cylindrical members or
drums 12. The drums 12 are arranged to form a substantially closed loop with the longitudinal
axes of the drums being disposed substantially parallel and the outer surfaces of
adjacent drums being closely spaced apart to form an inner chamber 32. For disposing
the drums 12 in this manner, the chambe 22 includes a pair of upstanding walls 34
and 36 which support thereacross a plurality of stationary shafts 38. Each of the
drums 12 is mounted for rotation on a respective one of the shafts 38 by a pair of
disc-shaped spacers 40 and 42. The spacers 40 and 42 have an outer dimension corresponding
to the inner dimension of the drums 12 to thereby make frictional engagement with
the inner surfaces of the drums 12 for accurately positioning the drums with respect
to one another. The spacers 40 include a sprocket 44 arranged to engate a drive chain
46. The drive chain 46 makes a continuous loop around the sprockets 44 and a drive
sprocket 48 of a motor 50. Although the drums 12 are illustrated as having the support
and drive mechanisms within the chamber 22, this structure can be external to the
chamber 22 with appropriate vacuum feedthrough seals where desired. As a result, and
as will be further explained hereinafter, during the deposition process the motor
50 is energized to cause each of the drums 12 to be rotated about its onw longitudinal
axis. This facilitates a uniform deposition of the material being deposited over the
entire outer surface of each of the drums 12.
[0034] As previously mentioned, the drums 12 are disposed so that the outer surfaces thereof
are closely spaced apart to form the inner chamber 32. As can be noted in Fig. 3,
the reaction gases from which the deposition plasma is formed are introduced into
the inner chamber 32 through at least one of a plurality of narrow passages 52 formed
between one pair of adjacent drums 12. Preferably, the reaction gases are introduced
into the inner chamber 32 through every other one of the narrow passages 52.
[0035] Referring to Fig. 3, it can be seen that the plasma is confined within the inner
chamber 32. The plasma changes in intensity as the surfaces of the drums 12 are rotated
into and then out of the chamber 32. This can result in defects being formed in the
weaker plasma regions in or adjacent the narrow passages 52. To avoid the possibility
of a large plurality of defect regions or defect layers being formed as the material
is deposited on the surface of the rotating drums 12, the drums 12 can be rotated
a single or several revolutions to achieve a deposited high quality material of the
thickness desired. For example, the drums 12 can only be rotated a single revolution
to deposit the required material thickness to form the bottom blocking layer 14.
[0036] In Fig. 3, it can be noted that each pair of adjacent drums 12 is provided with a
gas shroud 54. Each shroud 54 is connected to one of the reaction gas inlets 26, 28,
and 30 by a conduit 56. Each shroud 54 defines a reaction gas reservoir 58 adjacent
the narrow passage through which the reaction gas is introduced. The shrouds 54 further
include lateral extensions 60 which extend from opposite sides of the reservoirs 58
and along the circumference of the drums 12 to form narrow channels 62 between the
shroud extensions 60 and the outer surfaces of the drums 12.
[0037] The shrouds 54 are configured as described above so that the gas reservoirs 58 permit
relatively high reaction gas conduction while the narrow channels 62 provide a high
resistance or low conduction of the reaction gases. Preferably, the vertical conductance
of the reaction gas reservoirs 58 is much greater than the conductance of the narrow
passage 52 between the drums. Further, the conductance of the narrow passages 52 is
much greate than the conductance of the narrow channel 62. This assures that a large
percentage of the reaction gas will flow into the inner chamber 32 and uniform gas
flow along the entire lateral extent of the drums 12.
[0038] The shrouds 54 further include side portions 64 which overlap end portions of the
drums 12 and spacers 42 and 44. The side portions 64 are closely spaced from the end
portions of the drums 12 and spacers 42 and 44 to continue the narrow channels 62
across the ends of the drums. The side portions 64 thereby impede reaction gas flow
around the ends of the drums. It has been discovered by Applicants that the apparatus
20 can be utilized withoug the shrouds 54.
[0039] As can also be noted Fig. 3, in accordance with this embodiment, the narrow passages
66 which are not utilized for reaction gas introduction into the inner chamber 32
are utilized for conducting reaction products from the inner chamber 32 and the chamber
22. When the pump which is coupled to the pump-out port 24 is energized, the interior
of the chamber 22 and the inner chamber 32 is pumped out, with the inner chamber being
pumped out through the narrow passages 66. In this manner, reaction products can be
extracted from the chamber 22 and the interior of the inner chamber 32 can be maintained
at a suitable pressure for deposition.
[0040] To facilitate the formation of the deposition plasma identified by reference character
68 in Fig. 2, the apparatus 20, in accordance with this preferred embodiment, further
includes a first microwave energy source 70 and a second microwave energy source 72.
Each of the microwave energy sources 70 and 72 includes an antenna stub 74 and 76,
respectively. The microwave energy sources 70 and 72 can be, for example, microwave
frequency magnetrons having an output frequency of, for example, 2.45 GH
z. The magnetrons 70 and 72 are mounted to a cylindrical waveguide structure 78 and
80, respectively. The stubs 74 and 76 are spaced from back walls 79 and 81 of the
waveguides 78 and 80 by a distance of about one-quarter of the waveguide wavelength.
This spacing maximizes the coupling of the microwave energy from the stubs to the
waveguides. The waveguide structures 78 and 80 are mounted for rotation onto another
waveguide 82 and 84, respectively. The waveguides 82 and 84 project into the chamber
22 and terminate in close proximity to the edge portions of the drums 12. The end
portions of the waveguides 82 and 84 include a lip portion 86 and 88. Against each
of the lip portions 86 and 88 is disposed a sealing O-ring 90 and 92 each of which,
together with the lip portions 86 and 88, supports a respective microwave transmission
window 94 and 96. The transmission windows 94 and 96 together with the drums 12 define
the substantially closed inner chamber 32. The present invention can be utilized to
maximize and stabilize the microwave power transmitted through the windows 94 and
96.
[0041] The waveguides 78 and 82 form a coupling means for coupling the microwave energy
generated by the magnetron 70 into the inner chamber 32. Similarly, the waveguides
80 and 84 define a coupling means for coupling the microwave energy generated by magnetron
72 into the inner chamber 32. The microwave energy generated by the magnetrons 70
and 72 is radiated by the antenna stubs 74 and 76, which determine the polarization
of the radiated microwave energy. In order to avoid interaction between the stubs
74 and 76, the antenna stubs preferably are displaced from each other by an angle.
In accordance with this preferred embodiment, the angle between the stubs is about
60°. However, for systems incorporating a greater number of drums than the six drums
illustrated herein, the angle of displacement between the antenna stubs 74 and 76
will vary. The reason for this is that it is preferred that the antenna stubs be disposed
with respect to the drums 12, so that each stub forms an identical and uniform microwave
energy field within the inner chamber 32.
[0042] The windows 94 and 96, in addition to enclosing the inner chamber 32, protect the
magnetrons 70 and 72 from the reaction gases. They further serve to preclude the formation
of a plasma at the magnetron probes 74 and 76 and they also provide a low loss coupling
of the microwave energy into the inner chamber 32. To that end, the windows 94 and
96 can be formed from a material such as alumina, and have a thickness which provides
low reflected power into the waveguides 82 and 84.
[0043] To further diminish the interaction between the magnetrons 70 and 72, each magnetron
can be energized sequentially. For example, if alternating current is being utilized
to energize the magnetrons, the magnetrons can be energized during alternate half
cycles of the alternating current. In this manner, the interaction between the magnetrons
can be further diminished.
[0044] As previously mentioned, the waveguides 78 and 80 are mounted for rotation on their
respective waveguides 82 and 84. As a result, each of the magnetron sources 70 and
72 can be rotated about the longitudinal axis of the waveguides 82 and 84 to rotate
the polarity of the microwave energy to even out the microwave field. Such rotation
assures that the time average density of depositing species is radially uniform. The
polarization could also be circular to even out the field.
[0045] In utilizing the apparatus 20 of Figs. 2 and 3 for depositing a material onto the
outer surfaces of the drums 12, and more particularly for depositing layers of materials
to form electrophotographic copier drums, the drums 12 are first mounted as illustrated
and as described above. Thereafter, reaction gases are introduced through the inlet
ports 26, 28, and 30 while the chamber 22 is pumped out by the pump coupled to the
outlet 24. With the reaction gases introduced into the inner chamber 32, the magnetrons
70 and 72 are then energized to couple microwave frequency energy into the inner chamber
32 to form a glow discharge plasma therein. The microwave energy is readily coupled
into the inner chamber 32, because the inner chamber itself defines a waveguide structure
at microwave frequencies.
[0046] The motor 50 is then energized to cause the drums 12 to be rotated about their own
longitudinal axes. The magnetrons 70 and 72 can then also be rotated about the waveguides
82 and 84 as previously described. As a result of the foregoing, a uniform deposition
of material will ensue upon the entire outer surfaces of the drums 12.
[0047] During the deposition process, it may be desirable to heat the drums 12. To that
end, the apparatus 20 further includes a plurality of heating elements 100 which are
mounted to the stationary shafts 38 by spacers 102. Since the shafts 38 are stationary,
the heating elements 100 will also be stationary within the drums 12. The heaters
100 can take the form of resistance heating elements or incandescent lamps. for the
deposition of amorphous semiconductor alloys, the drums are preferably heated to a
temperature between 20°C and 400°C, and preferably, about 300°C. It can also be desirable
to preheat the reaction gases prior to introduction thereof into the inner chamber
32. This can be accomplished, for example, by heating the shrouds 54 to about 300°C
by slug heaters incorporated therein or lamps disposed adjacent the shrouds 54 external
to the deposition region.
[0048] For making an electrophotographic drum as illustrated in Fig. 1, the first blocking
layer 14 as previously described can be formed from an insulative material, a p-type
amorphous silicon alloy, or an n-type amorphous silicon alloy. When the blocking layer
14 is formed from an insulative material such as silicon nitride, silicon carbide,
or silicon dioxide, the reaction gases introduced into the inner chamber during the
deposition process can be silane (SiH₄) and /or silicon tetrafluoride (SiF₄) with
methane, nitrogen, ammonia, or oxygen. Such a blocking layer can be utilized for both
positive and negative charging of the electrophotographic drum.
[0049] When the blocking layer 14 is a p-type amorphous silicon alloy, the reaction gases
introduced into the inner chamber 32 can be silane and/or silicon tetrafluoride with
diborane or boron trifluoride. Such a blocking layer is suitable for an electrophotographic
drum to be positively charged.
[0050] When the blocking layer 14 is to be formed from an n-type amorphous silicon alloy,
the reaction gases introduced into the iner chamber can be silane and/or silicon tetrafluoride
and phosphine or phosphorus pentafluoride gas. Such a blocking layer is suitable for
an electrophotographic device to be negatively charged.
[0051] For making the photoconductive region 16, the photoconductive region 16 can be an
amorphous silicon alloy incorporating silicon, hydrogen, and/or fluorine. Such a material
can be deposited from reaction gases of silane, and/or silicon tetrafluoride, and
hydrogen. If the photoconductive region is to be rendered substantially intrinsic,
boron trifluoride or diborane gas can also be utilized. If it is to be slightly n-type,
no dopant is utilized.
[0052] In some instances, as fully described in cross-reference Serial No. 580,081, it may
also be desirable to incorporate a layer of material in the photoconductive region
16 towards the top thereof which has a more narrow band gap than the bulk of the photoconductive
region. To deposit such a material, germane (GeH₄) or germanium tetrafluoride (GeF₄)
gas can also be introduced into the inner chamber 32. The germane or garmanium tetrafluoride
together with the silane and/or silicon tetrafluoride will form an amorphous silicon
germanium alloy having a reduced band gap for infrared photoresponsive applications.
Also, as fully described in cross-referenced Serial No. 580,081, a top blocking enhancement
layer can be deposited before the top blocking layer 18 by RF deposition.
[0053] Lastly, for forming the top blocking layer 18, any of the materials and gas mixtures
previously referred to form the bottom blocking layer 14 can be utilized. During the
deposition of any one of the layers 14, 16, or 18, it may be desirable to introduce
a plasma-sustaining gas such as argon. Also, the pressure within the inner chamber
should be about .05 Torr or less.
[0054] Referring now to Fig. 4, it illustrates another apparatus 110 which can embody the
present invention. The apparatus 110 in the major respects thereof is essentially
identical to the apparatus 20 of Fig. 2. Therefore, the apparatus 110 will be described
only to the extent of the difference between the apparatus 110 and the apparatus 20
of Fig. 2.
[0055] As can be notd from Fig. 4, the apparatus 110 includes a single source of microwave
energy, magnetron 70. The other magnetron has been removed and a plate 112 is substituted
therefor. The plate 112 makes contact with a cylindrical tube 114 which supports the
window 96 at its end opposite the plate 112 and a wall 116 intermediate its ends.
As a result, a single magnetron 70 can be utilized for coupling microwave energy into
the inner chamber 31. Again, during the deposition, the magnetron 70 can be rotated
about the waveguide 82 to rotate the polarization of the microwave field.
[0056] As will also be noted in Fig. 4, the apparatus 110 includes a cylindrical waveguide
structure 120 formed from a wire mesh or screen. The waveguide structure 120 is disposed
within the inner chamber 32 and preferably is closely spaced with respect to the drums
12. The waveguide structure 120 can be utilized to provide a more uniform and continuous
waveguide structure and thereby provide more efficient propogation of the microwave
energy within the inner chamber 32. However, the waveguide structure 120 will decrease
the gas utilization efficiency of the system by a small amount inasmuch as deposition
will take place on the waveguide structure 120.
[0057] Referring now to present invention, Applicants have discovered that the tuning of
the power transmitted through a transmission window is not as simple as might first
be assumed. Applicants have discovered that there are a number of important conditions
which must be taken into account.
1. The frequency of the microwave power generator or magnetron is not fixed. The frequency
depends on the magnetron output power and therefore oscillates in a band (about 50MHz)
in synchronism with the power supply output ripple. The frequency also varies in accordance
with the magnetron temperature and fluctuates as the magnetron cooling water temperatures
and pressure varies.
2. There are unavoidable dimensional changes in the deposition chamber as the glow
discharge process proceeds due to the changes in temperature of the transmission window
structure which cause the window to expand.
3. A separate conventional tuner can, in principle, compensate for any dielectric
discontinuity introduced in the waveguide by the transmission window. Applicants,
however, have determined that such a separate tuner (such as a 4-stub unit) absorbs
more power as the mismatch increases. In some cases, the separate conventional tuner
has resulted in power absorption of greater than ninety percent.
4. The microwave power or radiation transmitted through the window into the process
gas must both ignite the glow discharge plasma and maintain the plasma. A single,
high-Q, tuner configuration cannot tune the deposition system for both the plasma
off and plasma on conditions, since the complex dielectric constant of the ignited
plasma is not the same as the complex dielectric constant of the gas in the deposition
system with the plasma off. A compromise must be made.
5. The tuning for the plasma on condition is not necessarily stable when various process
gases are utilized, since the complex dielectric constant of the plasma and the microwave
power absorbed by the plasma couple to each other through changes in the microwave
transmission. The plasma conditions, such as the species existing from the various
reaction gases, are in part dependent upon the amount of power transmitted into the
plasma and in turn the reflected power is related to the plasma conditions which the
microwave energy sees.
[0058] Applicants have discovered that item 3, above, requires that the window structure
must have low-loss tuning elements, close to the window to reduce the standing wave
current in the tuner. Items 4 and 5, above, do not require further changes in the
tuning configuration once an acceptable compromise has been found.
[0059] Applicants originally assumed that the window only needed to be matched for one parameter,
that being a suitable transmission over an acceptable broad band. After further investigation,
a second parameter was formed which must be dealt with. Referring now to the power
reflected by a window illustrated in Fig. 5 and the power transmitted by the window
illustrated in Fig. 6, there are two major reflection peaks 150 and 152. (It should
be noted that a difference in measuring instrumentation resulted in a reversal of
the X and Y axis directions between Fig.5 and Fig.6). The peaks 150 and 152 have the
following characteristics:
(1) The peaks are extremely narrow, on the order of 2MHz. In order even to be found,
the instrumentation must be precisely adjusted. Because of their narrow width, the
peaks at first were not even discovered.
(2) The frequency at which the peaks occur depends upon the diameter of the transmission
window. The peaks hence can drift into the magnetron frequency band as windows are
changed or as the various fluctuations described above occur.
(3) The peaks introduce a large discontinuity in the matching of the window to the
plasma.
[0060] Applications have interpreted the peaks 150 and 152 as mode shifts in the transmission
window. Because of the high dielectric constant of the window material, such a alumina,
the optical size of the window (in this example, four inches in diameter) is large
enough to sustain four propagation modes. The magnetron operating frequency is, in
the examples illustrated, 2.45 GHz. Other frequencies can be utilized in accordance
with the invention. The cut-off frequency of the fifth propagation mode was determined
to be substantially at the operating frequency. The deposition or other plasma system
can be operated satisfactorily with whatever number of modes are propagated through
the window, however, it appears that the system does not operate properly if the microwave
propagation energy switches randomly from one mode to another. This can cause an unstable
plasma condition which can vary the deposition parameters and can result in the plasma
going into the off condition.
[0061] A further operating condition which must be taken into account is illustrated in
the graph of Fig. 7. The plasma intensity (1) is related to the reflected power (R)
by an operating curve 154. A point of minimum R 156 would appear to be the optimum
operating condition, since the point 156 is the lowest lost R point. However, if the
plasma conditions move toward a lesser intensity, i.e. the plasma becomes weaker for
any reason, the R increases in a runaway or unstable type of condition and hence the
plasma will go off. Therefore, a compromise operating region 158 is chosen in which
to operate the system, which is a slightly higher R loss region, but which is a stable
plasma operating region.
[0062] To compensate for the above discovered conditions, Applicants have invented the following
tuning method and apparatus. Referring to Figs. 8 and 9, a microwave transmission
window 160 is mounted in one end of a microwave transmission system 162. A plasma
(not shown) will exist on the free side of the window 160. A pair of tuning structures
164 and 166 embody the present invention. As illustrated, each of the structures 164
and 166 are formed from a plurality of separate segments 168, which preferably are
formed from the same dielectric material as the window 160 to provide the required
low loss tuning structures. The segments can be disks 168 or can be any other shape
such as a rectangle 168ʹ. The size of the segments 168 and the heights of the tuning
structures 164 and 166 are adjusted to achieve both high transmission through the
window and a stable plasma mode excitation. The structures 164 and 166 then are fixed
such as by tape or other adhesive and the window 160 is then tuned for the desired
system operation.
[0063] The segments 168 and tape or adhesive are selected to have minimum microwave absorption
properties and can be formed from the same materials as the window 160 or from other
suitable dielectric material. The system is tuned for a compromise between the plasma
off and on conditions, but at a level which will still allow for the plasma to be
ignited, although a separate RF or other signal could be utilized to ignite the plasma.
The tuning structures 164 and 166 provide substantially the lowest possible power
loss, because the structures are placed onto the surface of the window 160 itself.
Any tuning structure, such as the conventional stub which is placed close to, but
separate from the window 160, will result in power being reflected between the stub
and the window resulting in heating of the system and hence a power loss. Referring
to Figs. 5A, 5B, 6A and 6B, the widths of the segments 168 are chosen to move the
magnetron operating frequency to a midpoint between the peaks 150 and 152 to provide
a stable operating region between the peaks. Further, the height of the tuning structures
164 and 166 is selected to move the operating R point towards a minimum amount (Figs.
5A and 5B).
[0064] In addition, although the present invention has been particularly described with
respect to the formation of electrophotographic drums, it can be appreciated by those
skilled in the art that the method and apparatus of the present invention can be utilized
with any type of microwave transmission window and any type of plasma. Although alumina
is a preferably window material when depositing silicon, other types of plasma which
do not contain silicon, such as a plasma etching system could use other dielectric
materials, such as quartz. Applicants have discovered that quartz is not a preferable
material when utilizing silicon, since the window 160 must be cooled to prevent the
silicon deposited on the window surface from crystallizing, which can cause thermal
runaway and hence require a shut down of the system operation. Alumina or another
dielectric material with high thermal conductivity is thus preferred for utilization
with a silicon depositing plasma. As a result of the foregoing, it can be seen that
the present invention can be practiced in a manner otherwise than as specifically
described herein.
1. A method of tuning a microwave transmission window (160), comprising:
providing microwave generating means (74, 76);
providing a plasma chamber (22);
coupling said chamber to said generating means through a dielectric microwave transmission
window; and
tuning said window to maximize the power generated by said generating means and transmitted
through said window into said chamber by providing at least two tuning structures
(164, 166) and placing said structures adjacent the outer edges of said window.
2. The method as defined in claim 1 wherein said tuning includes forming each of said
tuning structures from a plurality of dielectric segments (168) placed on top of one
another.
3. The method as defined in claim 2 wherein said tuning includes sizing said segments
as to width and adjusting the height of said structures to maximize said transmitted
power.
4. The method as defined in claim 3 further including tuning said segments to stabilize
the modes transmitted into said chamber.
5. The method as defined in claim 1 including introducing a least one reaction gas
into said chamber and forming a plasma from said reaction gas prior to tuning said
window.
6. The method as defined in claim 5 wherein said at least one reaction gas is a semiconductor
containing compound.
7. The method as defined in claim 6 wherein said at least one reaction gas includes
silicon.
8. The method as defined in claim 1 further including the step of maintaining the
pressure within said inner chamber at about .05 Torr or less.
9. The method as defined in claim 1 further including the step of adjusting the power
density of said microwave energy between about .1 to 1 watt per cubic centimeter.
10. The method as defined in claim 1 wherein the frequency of said microwave energy
is 2.45 Gigahertz.
11. An apparatus for tuning a microwave transmission window (160), comprising:
generating means (74, 76);
a plasma deposition chamber (22);
said chamber coupled to said generating means through a dielectric microwave transmission
window; and
means for tuning said window to maximize the power generated by said generating means
and transmitted through said window into said chamber, said tuning means including
at least two tuning structures (164, 166) located adjacent the outer edges of said
window.
12. The apparatus as defined in claim 11 wherein each of said tuning structures is
formed from a plurality of dielectric segments (168) placed on top of one another.
13. The apparatus as defined in claim 12 wherein said segments are sized as to width
and the height of said structures is adjusted to maximize said transmitted power.
14. The apparatus as defined in claim 12 wherein said segments are utilized to stabilize
the modes transmitted into said chamber.
15. The apparatus as defined in claim 12 wherein said window and said segments are
formed from alumina.
16. A tuned microwave transmission window (160) for a plasma deposition system, said
system including microwave generating means (74, 76) coupled to a plasma deposition
chamber (22) through the transmission window, said tuned window comprising:
a dielectric window member coupling and separating the microwave generating means
from the deposition chamber, means for tuning said dielectric window member to maximize
the power generated by said generating means and transmitted through said dielectric
window member into said chamber, said tuning means including at least two tuning structures
(164, 166) located adjacent the outer edges of said dielectric window member.
17. The apparatus as defined in claim 16 wherein each of said tuning structures is
formed from a plurality of dielectric segments (168) placed on top of one another.
18. The apparatus as defined in claim 17 wherein said segments are sized as to width
and the height of said structures is adjusted to maximize said transmitted power.
19. The apparatus as defined in claim 18 wherein said segments are utilized to stabilize
the modes transmitted into said chamber.
20. The apparatus as defined in claim 17 wherein said dielectric window member and
said segments are formed from alumina.