U.S. patent application number 10/968625 was filed with the patent office on 2005-03-10 for fibers and ribbons for use in the manufacture of solar cells.
Invention is credited to Carroll, Alan F., Roach, Christopher John.
Application Number | 20050051207 10/968625 |
Document ID | / |
Family ID | 34225824 |
Filed Date | 2005-03-10 |
United States Patent
Application |
20050051207 |
Kind Code |
A1 |
Carroll, Alan F. ; et
al. |
March 10, 2005 |
Fibers and ribbons for use in the manufacture of solar cells
Abstract
This invention is directed to a process for the fabrication of
features on a silicon wafer utilizing fibers comprising organic
polymer and inorganic material.
Inventors: |
Carroll, Alan F.; (Raleigh,
NC) ; Roach, Christopher John; (Apex, NC) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY
LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
34225824 |
Appl. No.: |
10/968625 |
Filed: |
October 18, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10968625 |
Oct 18, 2004 |
|
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|
10428284 |
May 2, 2003 |
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Current U.S.
Class: |
136/256 ;
438/98 |
Current CPC
Class: |
H01L 31/022425 20130101;
H01L 31/068 20130101; Y10T 428/29 20150115; Y02E 10/547
20130101 |
Class at
Publication: |
136/256 ;
438/098 |
International
Class: |
H01L 031/00 |
Claims
What is claimed is:
1. A process to attach fibers to a substrate for use in solar cell
manufacture comprising the steps of: a) affixing a fiber comprising
an organic polymer and an inorganic material to a substrate in a
desired orientation forming an article; and b) heating the article
to a temperature sufficient to effect removal of the organic
polymer resulting in the inorganic material affixed to the
substrate in the desired orientation.
2. The process of claim 1 further comprising forming a fiber
comprising an organic polymer and an inorganic material destined
for deposition on a substrate.
3. The process of claim 1 wherein the inorganic material is
conducting metal particles selected from Au, Ni, Au/Cr, Au/Cu,
Au/Ta, Cu/Cr, Au/indium tin oxide, Cu, Ag and Ni.
4. The process of claim 2 wherein the substrate is a silicon
wafer.
5. The process of claim 1 further comprising a step of heating the
article to a temperature above the melting point of the organic
polymer.
6. The process of claim 1 wherein the fiber is deposited as an
electrode.
Description
FIELD OF THE INVENTION
[0001] This invention is directed to a fiber or ribbon comprising
organic polymer and inorganic materials. The invention is further
directed to a process for the fabrication of features on solar cell
structures utilizing such fibers or ribbons.
BACKGROUND OF THE INVENTION
[0002] A conventional solar cell structure with a p-type base has a
negative electrode that is typically on the front side or sun side
of the cell and a positive electrode on the backside. The solar
cell has a carrier-collecting junction close to its front surface.
The front surface is contacted with parallel fingers which are
currently about 140 microns wide per finger. The fingers are
connected by two bus bars that are perpendicular to the fingers.
Typically, a five-inch square cell has about 55 fingers separated
by about 2.1 mm spaces. The electric current collected for storage
by the solar cell is gathered by metal contacts to a doped region
on the front surface and by a second contact to the oppositely
doped region on the back surface.
[0003] It is difficult to obtain very fine line and space
resolution for the formation of the negative electrodes when
applied by conventional patterning techniques such as screen
printing, sputtering or chemical etching methods. The present
invention will allow for the use of fibers or ribbons, wherein
conductive metal particles are integrated into the fiber or ribbon,
to form such electrodes on the front surface of the solar cell
structure. The fibers or ribbons will allow narrower lines with
increased height thickness which will increase the cell power by
decreasing cell shadowing loss without increasing resistance of the
lines. Currently shadowing loss accounts for about 9% loss in a
solar cell structure. Narrower lines will substantially decrease
such loss.
[0004] U.S. Pat. Nos. 3,686,036, 4,082,568, 4,347,262, and
4,235,644 disclose various solar cell devices and methods of
manufacture.
SUMMARY OF THE INVENTION
[0005] This invention provides a process for the manufacture of
electrodes on a solar cell structure comprising the steps of
affixing a fiber or ribbon comprising an organic polymer and a
conductive material to a substrate such as a silicon wafer in a
desired orientation forming a solar cell structure; heating the
structure to a temperature above the melting point of the organic
polymer; and heating the structure to a temperature to sufficiently
effect the essentially complete removal of the organic polymer
resulting in the inorganic material affixed to the substrate in the
desired orientation.
[0006] The invention is also directed to a fiber or ribbon for use
in the manufacture of electrodes on the front surface of a solar
cell structure comprising conductive particles, dielectric
particles or mixtures thereof combined with a polymer suitable for
forming a spinnable dispersion.
BRIEF DESCRIPTION OF THE DRAWING
[0007] FIG. 1 is an illustration of a top surface metallization of
a solar cell.
[0008] FIG. 2 is a cross sectional illustration of FIG. 1 with a
press plate.
[0009] FIG. 3 is an illustration showing fiber placement after
processing.
[0010] FIG. 4 is an illustration of the solar cell structure after
firing.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The present invention is directed to methods for the
manufacture of solar cell structures utilizing fibers or ribbons
bearing conductive metal particles combined with a spinnable
fiber-forming dispersion.
[0012] Examples of applications for the fibers or ribbons include
the manufacture of features on a solar cell structure, for example,
negative electrodes or emitters when the inorganic material of the
fiber or ribbon are conductive metal particles.
[0013] Polymers suitable for use in the present invention include
those that form a spinnable dispersion with particles of inorganic
materials such as conducting metal particles. The polymer must be
soluble in a suitable solvent so that a dispersion comprising
polymer and inorganic material particle can be prepared. The
resulting inorganic material bearing polymer dispersion must be
capable of being spun into flexible fibers or extruded into
flexible ribbons. As used herein, the term "fiber" means a single
flexible filament; a group of flexible filaments twisted together
or bundled together; or a group of flexible filaments lying
parallel to each other forming a bundle. The bundle may or may not
be coated to afford protection to the fiber. Cross sectionally, the
fiber or bundle may be circular, oblong, square, rectangular,
triangular and any other shape. The term "ribbon" means a flexible
strip and may be one homogeneous ribbon; or may be constructed by
laying more than one fiber in the same plane; or may be several
homogeneous ribbons or planes of fibers or combinations thereof
layered on top of one another to form a ribbon-like structure.
Although preferred that each fiber or ribbon have the same chemical
properties, there are some applications that may deem an
intermingling of different chemistries of the individual fibers or
ribbons. Fiber diameters typically range from 20 microns to 100
microns, but may extend beyond the range for some applications.
Ribbon size typically ranges up to 200 microns in width to 100
microns in height but may extend beyond the range for some
applications. Length of fiber or ribbon is preferred to be
continuous, but noncontinuous fiber or ribbon lengths for forming
components is suitable. Further, the polymer must be selected so as
to soften and melt cleanly; for example, the polymer must burn out
cleanly without leaving behind any residue. The polymer, in the
presence of the inorganic material, must exhibit a melting point
prior to decomposition. The polymer melt that results from the
chosen polymer must wet out the material on which the solar cell is
constructed. Examples of polymers that meet the above selection
procedure include ethylene/vinyl acetate copolymers, obtainable
from the DuPont Company (Wilmington, Del.) under the trade name
ELVAX.RTM.. Also, polymethylmethacrylate polymers may be suitable
in the present invention and are available from the DuPont Company
(Wilmington, Del.) under the trade name ELVACITE.RTM.. Additional
suitable ethylene/vinyl acetate copolymers and
polymethylmethacrylate polymers are available from manufacturers
such as Dow and Exxon.
[0014] Organic solvents for use in the preparation of the spinnable
inorganic material/polymer dispersion are characterized by high
solubility for the polymer and by high vapor pressure at spinning
temperatures to facilitate spinning of the inorganic material into
polymer fiber or ribbon. Some examples of suitable solvents include
tetrachloroethylene, toluene, and xylenes. Dry spinning is a
preferred technique for forming a fiber or ribbon. However, wet
spinning, melt or gel spinning can be employed. All techniques are
well known by those in the art of fiber technology.
[0015] Wet spinning is the oldest process. It is used for
fiber-forming substances that have been dissolved in a solvent. The
spinnerets are submerged in a chemical bath and as the filaments
emerge they precipitate from solution and solidify. Because the
solution is extruded directly into the precipitating liquid, this
process for making fibers is called wet spinning.
[0016] Dry spinning is also used for fiber-forming substances in
solution. However, instead of precipitating the polymer by dilution
or chemical reaction, solidification is achieved by evaporating the
solvent in a stream of air or inert gas. The filaments do not come
in contact with a precipitating liquid, eliminating the need for
drying and easing solvent recovery.
[0017] In melt spinning, the fiber-forming substance is melted for
extrusion through the spinneret and then directly solidified by
cooling.
[0018] Gel spinning is a special process used to obtain high
strength or other special fiber properties. The polymer is not in a
true liquid state during extrusion. Not completely separated, as
they would be in a true solution, the polymer chains are bound
together at various points in liquid crystal form. This produces
strong inter-chain forces in the resulting filaments that can
significantly increase the tensile strength of the fibers. In
addition, the liquid crystals are aligned along the fiber axis by
the shear forces during extrusion. The filaments emerge with an
unusually high degree of orientation relative to each other,
further enhancing strength. The process can also be described as
dry-wet spinning, since the filaments first pass through air and
then are cooled further in a liquid bath.
[0019] Conductive metal materials in powder form usable in the
process of the present invention are those known by those in the
electronics industry. Examples of suitable conducting metals,
include those commonly used in solar devices, are as follows: Au,
Ni, Au/Cr, Au/Cu, Au/Ta, Cu/Cr, Au/indium tin oxide, Cu, Ag and Ni.
Ag is the preferred conducting metal.
[0020] Fibers or ribbons comprising 70-80% conductive metal
particles by weight are preferred; although, inorganic particle
loading up to 90% by weight is suitable. Maximizing the inorganic
solids loading will minimize shrinkage of the fibers during firing.
However the polymer content must be kept high enough to form a
flexible and uniform fiber or ribbon.
[0021] The method of affixing the formed fiber or ribbon to the
solar cell surface (substrate) may be any method ranging from
manual placement to mechanized placement means. The solar cell
surface may be any surface suitable for use in solar cell
manufacturing, but the preferred surfaces are processed Si wafers,
CuInSe substrates, or substrates covered with thin films of
amorphous silicon, CD-In--Ga--Se, CdS, ZnS, or CdTe.
[0022] After placement of the fiber or ribbon, the first heating
stage heats the solar cell structure that holds the affixed fiber
or ribbon to a temperature above the melting point of the organic
polymer component of the fiber or ribbon. This adheres the
inorganic material/polymer fiber or ribbon to the substrate
material. In one embodiment the heating source may be incorporated
into a press plate. In another embodiment the heating source may be
independent of the press plate.
[0023] A second heating stage which substantially to completely
burns out the organic polymer from the fiber or ribbon results in
the inorganic material adhering to the substrate material. It is
preferred that the conductive inorganic materials are sintered. The
firing temperature profile may be the two heating stages carried
out in one continuum of heating or two discretely staged heating
events. For example, the fiber and/or ribbon placement and initial
heating stage can be combined. Heating either the substrate and/or
fiber/ribbon during the placement step can be used to secure the
fiber/ribbon in the required position on the substrate. This would
be the preferred positioning method to create functional features
where there is no mechanical support structure to hold the fiber
and/or ribbon in place. Another alternative method to tack fibers
and/or ribbons in place without heating would be to wet the fiber
or substrate surface with solvent vapors immediately before
positioning (to make the fiber stick to the substrate).
[0024] More specifically, FIG. 1 illustrates a top surface
metallization by the placement of multiple fine fibers (101) of
conductive material onto a solar cell.
[0025] The fibers are very narrow having dimensions of about 20 to
80 microns in width. The fibers can be extruded as either circular
rods or rectangular shaped ribbon. Their aspect ratio may typically
be about 1.
[0026] The fibers may be placed by a fixture such as a loom (102)
and positioned over the solar cell substrate such as a processed
crystalline Si wafer (103). Proper positioning will need to be done
accurately (X-Y positioning shown in FIG. 1). A cross-sectional
view of FIG. 1 is shown in FIG. 2. FIG. 2 positions the fibers
close to the Si wafer surface prior to pressing with a heated
TEFLON.RTM. plate (201).
[0027] Fiber number and spacing will vary as a function of solar
cell design. Some designs may have close spaces between lines as
illustrated in FIG. 1. Some designs may have wider spaces between
lines.
[0028] The placement of fibers is a critical operation. The narrow
fibers will need support, as they may be fragile. They will need to
be positioned accurately with repeated performance.
[0029] Once the fibers are placed onto or above the cell, a press
plate may both press and heat the fibers to stick them to the cell
surface (FIG. 2). The TEFLON.RTM. plate will not grip the fibers
thereby allowing the plate to be removed without pulling on the
fibers. Prior to lifting the plate the fibers will typically be
cut. In another embodiment, an independent heating source may be
used from the underside of the cell.
[0030] The cell has a thin film antireflective coating of SiNx
(202) on its upper surface. Under the SiNx is a diffused layer of
n+Si (203)(typically Si with high concentration of P n-type dopant
[for a negative emitter]). The base of the cell is p-type Si
(103).
[0031] FIG. 3 shows the cell cross section of FIG. 2 after the
press plate is removed. The fibers (101) have been deformed
slightly during pressing and heating and have been made to adhere
to the top of the SiNx layer (202) (the outermost surface of the
cell).
[0032] FIG. 4 illustrates the cell cross section of FIG. 3 but
after firing the fibers (101). The fibers contact the n+Si layer
(203) by penetrating the SiNx layer (202). This is necessary, as
the SiNx is a non-conducting layer. FIG. 4 also illustrates the
fibers remaining in the same X-Y position after firing.
EXAMPLES
Example 1
[0033] A smooth fiber forming paste containing silver particles was
made as follows. 5.0 g ELVAX.RTM. 265 ethylene vinyl acetate resin
(DuPont, Wilmington, Del.) was first soaked with 30 ml
tetrachloroethylene (TCE) in a 100 ml beaker for one half hour. The
beaker wrapped with a round band heater was enclosed in a bell jar.
An air-driven stirrer was situated at the center of the bell jar
for stirring the mixture in the beaker. The mixture was heated to
100.degree. C. until the polymer dissolved. To the solution, 15.0 g
silver powder (silver powder, nominal size .about.2 um D50
[.about.0.5 um D10, .about.7 um D90] available from E. I. du Pont
de Nemours and Company, Wilmington, Del.) and 0.4 g glass frit were
added. It was stirred for about four hours. Once the mixture looked
very smooth, vacuum was applied to the bell jar to thicken the
mixture until an extensible viscosity was obtained. The mixture was
then tested with a spatula to ascertain that fiber could be pulled
from the smooth, thick paste. Once a smooth, fluid mixture was
achieved, it was transferred to a plastic syringe having a
.about.0.5 mm diameter hypodermic needle for extrusion. The paste
had to be kept at .about.80.degree. C. while it was being extruded
to TEFLON.RTM. fluoropolymer sheets (DuPont, Wilmington, Del.) for
forming continuous fibers. Fibers ranging from 100 to 300 microns
were obtained. The obtained fibers were elastic and could be
handled easily without breaking, which makes it possible for
further processing. Thin ribbons down to 50 microns in thickness
were obtained if the extrudates came into contact with the
TEFLON.RTM. fluoropolymer sheets (DuPont, Wilmington, Del.) before
the skin of the extrudate had solidified.
1 Glass Frit Composition (given in weight %) Bi.sub.2O.sub.3 82.0
PbO 11.0 B.sub.2O.sub.3 3.5 SiO.sub.2 3.5 Milled to nominal S.A. of
5.5 m.sup.2/g
Example 2
[0034] The silver fibers from Example 1 were affixed to a silicon
wafer and fired at 900C (set point) in an IR furnace. The fibers
did not retain their original dimensions. The fired fibers measured
40 microns.times.8 microns high.
* * * * *