Solar 2

llllllllllllllIllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll ,
US005538903A
United States Patent [19]
[11]
Aramoto et al.
[45]
[54] METHOD OF MANUFACTURING SOLAR
Patent Number:
Date of Patent:
60-33278
62-30318
l-2351l6
4-188623
5-154441
CELL
[75] Inventors: Tetsuya Aramoto, Osaka; Nobuo
Nakayama, Hirakata; Kuniyoshi

Omura, Higashiosaka; Mikio
Japan ....................................... .. 437/9
7/1992
6/1993
Japan .
Japan .
Japan .
Japan ....................................... .. 437/9
Matsushita News, Feb. 1, 1983, pp. 1-5.

T. Arita et a1, Solar Energy Materials, vol. 23, pp. 371379
(Dec. 1991).
[57]
ABSTRACT
Japan .................................. .. 5-314478
A method of manufacturing a solar cell, comprising the steps

of forming a layer of n-type compound semiconductor, a
layer of p-type compound semiconductor, and an electrode
Int. Cl.6 ................................................... .. H01L 31118
layer on a glass substrate, wherein at least one of said steps
US. Cl. ............................ .. 437/5; 136/260; 136/264;
of forming a layer of compound semiconductor layer com

prises preparing a paste by mixing a semiconductor raw
material and a viscous agent, applying said paste to said
substrate, drying said paste to harden it, and ?ring the dried
paste, and vibrating said substrate during or after the appli
cation of the paste, to remove the bubbles in the paste,
Nov. 18, 1993
[JP]
136/265; 427/74; 427/76; 427/346; 437/9;

-
[58]
2/1985
2/1987
9/1989
Primary ExaminerAaron Weisstuch

Attorney, Agent, or FirmRatner & Prestia
[21] Appl. No.: 342,445

Nov. 18, 1994
[22] Filed:
Foreign Application Priority Data
[30]
[51]
[52]
Jul. 23, 1996
OTHER PUBLICATIONS
Murozono, Hirakata, all of Japan
[73] Assignee: Matsushita Electric Industrial Co.,

Ltd., Osaka, Japan
5,538,903
437/234
Field of Search .................................. .. 437/5, 9, 234;
427/74-76, 346; 136/260, 264, 265
[56]
References Cited
FOREIGN PATENT DOCUMENTS
47-5880
48-26976
resulting in a semiconductor layer which is smooth, dense,

and having good adhesion, thus realizing a solar cell with
improved and uniform characteristics.
3/1972 Japan.
8/1973
Japan ....................................... .. 437/9
24 Claims, 3 Drawing Sheets
LIGHTW 4x;
//
US. Patent
Jul. 23, 1996
Sheet 1 of 3
FIG. I
5,538,903
US. Patent
Jul. 23, 1996
Sheet 2 of 3
5,538,903
{MS SFNTEREB
.LiWER
QM @EASS'
wasrmwa
X599
US. Patent
Jul. 23, 1996
Sheet 3 of 3
5,538,903
LOG
lO4~
Voc
L02 ~
LOO
FIG. 3A
L04
C
.2
'
l .00
PG
Q)
FIG. 3B
FIG._3C
EFF
I.
00
FIG. 3D
ITI
5,538,903
1
METHOD OF MANUFACTURING SOLAR

CELL
conventionally, to obtain such a layer, a paste made of the

powdered compound semiconductor or elements therefor, an
eletroconducting agent, and a viscous agent nrixed together

was kept under reduced pressure to remove bubbles therein
and, after the deposition, the substrate was held horizontally

BACKGROUND OF THE INVENTION
at about 50 C., which was lower than the drying tempera

ture of the viscous agent, to reduce the viscosity of the
viscous agent and uniformly precipitate the raw material
1. Field of the Invention

This invention relates to a method of manufacturing a
solar cell of compound semiconductors by way of coating

and ?ring.
2. Description of the Prior Art
powders in order to obtain a high density layer. However, if

10
sometimes happened in the coating process by screen print

ing that bubbles were introduced from the surrounding
atmosphere, resulting in uneven deposition or pin-holes.
Also, with the heat treatment only after coating, the raw
In recent years, expectations for solar cells as a clean
energy source have been raised, in view of the global

warming, acid rain, ozone layer destruction, and other such
environmental destruction. For the wide usage of solar cells
to occur, improvement of the photo-electric conversion
e?iciency and reduction of the cost are most important. that
material powders did not always uniformly precipitate, and

the bubbles were not sufficiently removed, resulting in the
layer not being ?at, or of uniform thickness. The pin-holes
left after coating and ?ring of the layers caused an increase
of the sheet resistance. Especially, if pin-holes were formed
in the p-type CdTe layer, the carbon particles of the carbon
purpose, solar cells made of compound semiconductors of .
Group l]1V materials such as GaAs, InP, Group H-VI

materials such as CdSICuZS, CdS/CdTe, and Group I-H
electrode layer formed thereon penetrated into the pin-holes

up to the CdS layer under the CdTe layer, causing internal
short circuiting or current leakage, fatally damaging the
solar cell performance.
I-VI2 materials such as CuInS2, CuInSe2, as well as crys

talline and amorphous silicon solar cells, have been inves
tigated in many countries of the world. Among these, solar

cells made of compound semiconductor heterojunctions of
n-CdS/p-CdTe have been produced commercially, with rela
tively low material cost, conversion efficiency as high as
10%, less deterioration over long time periods, and a rela
tively simple manufacturing process suitable for mass pro
duction consisting of printing, drying, ?ring (sintering or
the bubbles were removed from the paste before coating, it
25
SUMMARY OF THE INVENTION

It is an object of the present invention to provide a new
30
baking), resulting in a high density arrangement on a glass

plate and realization of high voltage without outer wire
connection, as well as large area cells.
A typical solar cell of Group lI-VI semiconductor, of

which a sectional view is shown in FIG. 1, comprises a glass
substrate 1 of high light transmittance and electrical insu
lation provided on one surface thereof with an n-type CdS
layer 2, a p-type CdTe layer 3, a current collecting carbon

electrode layer 4, an Agln electrode which is the positive
terminal 5, and an Ag.In electrode which is the negative
terminal 6 formed by laminating with printing and baking of

each layer. Usually, although not shown in the ?gure, the
thus prepared solar cell element is provided, on both the
Ag-In electrodes, with a copper paste layer deposited, dried,

and baked for easy soldering of lead wires. The cell is then
covered all over with a passivation layer of a therrnosetting
resin such as epoxy and baked.
Light, including that of the sun, falls on the surface of the

glass substrate 1 opposite to the surface having the above
solar cell element layers, to generate electrical power by
method of manufacturing compound semiconductor solar

cells comprising n-type and p-type compound semiconduc
tors and electrode layers having improved performance,

uniform characteristics, and low production cost, brought
about by formation of the layers without pin-holes and with
uniform thicknesses and smooth surfaces.
To obtain the above object, a method of manufacturing a
solar cell according to the present invention comprises the
steps of forming a layer of an n-type compound semicon
ductor, a layer of a ptype compound semiconductor, and an
electrode layer on a glass substrate, wherein at least one of
said steps of forming a layer of compound semiconductor

comprises preparing a paste by mixing a semiconductor raw
material and a viscous agent, applying said paste to said
substrate, drying said paste to harden it, and ?ring said dried
paste, and vibrating said substrate during or after the appli
cation of the paste.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic sectional view of a Group II-VI
compound semiconductor solar cell of n-CdS/p-CdTe type.
FIGS. 2(A)2(B) are microphotographs of sections of

sintered CdS layers on a glass substrate.
As the substrate, a heat-resistant barium borosilicate glass
FIGS. 3A-3D are graphs of the open circuit voltages,
is employed, which has very low alkali metal content and a
short circuit currents, ?ll factors, and intrinsic photoelectric
high softening point.
55 conversion efficiencies of solar cells fabricated according to
In the manufacturing of the compound semiconductor
the present invention, as well as by the conventional method.
photo-electric conversion.
solar cell by the coating and ?ring method, it is important

that each of the n-type compound semiconductor layer,
p-type compound semiconductor layer, and electrode layer
DETAILED DESCRIPTION OF THE

INVENTION
have uniform thickness, a smooth surface, and no pin-holes. 60
An example of the method of manufacturing a Group

H-VI compound semiconductor solar cell according to the
directly on the substrate is uniform, smooth, and non
present invention is now explained by referring to FIG. 1.
porous, the adherence of the layer to the substrate is
improved, resulting in an increase of the light transmittance,
A paste was prepared by mixing a ?ne powder of cad
decrease of the sheet resistance, and, further, an increase of 65 mium sulphide (CdS), cadmium chloride (CdCl2), and pro
Especially, if the n-type CdS semiconductor layer formed
the photo-current and improvement of the characteristics of
pylene glycol (PG), the CdCl2 being a ?ux, and the PG being
the cell.
a viscous agent.
5,538,903
3
The paste was applied to a substrate of barium borosili
turing process of a compound semiconductor solar cell, the
cate glass by screen printing to form a coating layer of 60 run

thickness.
The glass substrate was subjected to vibration of 20 pm
pastes made of the mixtures of the respective powdered

n-type and p-type compound semiconductor materials, ?ux
agent, and viscous agent were applied to form the n-type and
p-type layers and electrode layers on the substrate.
A: A sample cell fabricated with the semiconductor and
electrode layers dried and ?red after the application of
amplitude and 28 kHz ultrasonic frequency by contacting

the output end of a piezoelectric vibrator on the outer end of
the substrate for 5 seconds, whereby the roughness of the

deposited layer due to the screen net disappeared and the
the paste on the substrate without vibration, i.e. accord
bubbles in the layer were removed. The substrate with the

vibrated layer was then dried in the atmosphere at 120 C.
(PG was removed by vaporization), and sintered at 690 C.
A comparison substrate coated with a CdS layer was
fabricated by a similar method but without the application of
vibration.
The light transmittance and sheet resistance of the two
ing to the prior art.

B: A sample cell fabricated with vibration given to the
substrate only after the application of CdS paste, i.e. no
vibration during the other processes.
C: A sample cell fabricated with vibration given only after
the application of CdTe, i.e. no vibration during the
other processes.
kinds of samples were then measured and rnicrophoto graphs

of sections thereof (X500) were taken. The results are shown
in Table 1 and FIGS. 2(A)2(B).
TABLE 1
D: A sample cell fabricated with vibration given only after

the application of the carbon paste, i.e. no vibration
20
CdS layer formed

according to the
CdS layer formed
present invention
without vibration
Light transmittance (%)
63
60
(7t = 0-7 um)

Sheet resistance
28
33
25
during the other processes.

E: A sample cell prepared with vibration given to the
substrate after application of the CdS paste, CdTe paste,
and carbon paste, with further drying and ?ring.
The vibration was given at 20 pm amplitude and 22 kHz
frequency for 10 seconds by contacting the output end of the
ultrasonic oscillator to the reverse side of the glass substrate;
the reverse side being the surface on which the semicon
ductor layers were not applied. The other conditions were
(?lcrnz)
the same.
For the solar cells of these samples, the open circuit
As is observed in FIG. 2(B), the CdS layer on the
substrate prepared without vibration has projections and

depressions on the surface, void spaces and/or pin-holes, and
the thickness is not uniform. Moreover, it is not su?iciently
adherent to the substrate. On the contrary, the CdS layer of
the sample shown in FIG. 2(A) fabricated with vibration has
few voids and/or pin-holes, uniform thickness, and a smooth
30
35
surface, fully adherent to the substrate. Numerically, Table 1

indicates improvements of the light transmittance by 5% and
reduction of the sheet resistance by 15%. Thus it is expected
the CdS layer formed with the vibration would have superior
characteristics as the window layer of a solar cell.
Next, Cd.Te paste was prepared by kneading well an

equi-mol mixture of cadmium (Cd) and tellurium (Te)
powders with addition of CdCl2 and PG, and the paste was
applied in a 30 pm thickness on the above CdS sintered layer
by screen printing, dried in the atmosphere, and sintered at
620 C., to form a CdTe layer.
Then, a carbon paste, prepared by kneading carbon pow
adhesion between the CdS layer and the substrate, resulting

in an increase in light transmittance, and a reduction in
40
45
der and a viscous agent made of a solution of a resin in an
electricity collecting electrode 4 on the n-CdS/p-CdTe het

Further, the carbon electrode layer 4 and the CdS layer 2
were provided with a positive terminal 5 and a negative
terminal 6 of Ag.In by depositing Ag.In paste by screen

printing and drying and baking, the Ag.ln paste being
prepared by kneading of silver (Ag) and indium (In) pow
ders with a viscous agent made of a solution of a resin in an
organic solvent.
measured, with the results shown in FIGS. 3A3D as values

relative to the values for sample cell A taken as 1.00.
From the measurements of the sample cell B as shown in
FIGS. 3A-3D, it is seen that the vibration after the CdS
application has caused, by removing the paste bubbles,

smoothing the ?lm surface, and by improvement of the
organic solvent was applied on the CdTe layer, to form an
erojunction.
voltage (Voc), short circuit current (Isc), ?ll factor (FF), and
intrinsic photo-electric conversion e?iciency (EFF) were
50
surface resistance, an improvement of Isc, and, through the

reduction of the number of pin-holes at the junction,
improvements of Voc and FF.
From the data for the sample cell C, it is seen that the
vibration after the Cd. Te paste application has led to the
improvement of Voc, Isc, and FF as a result of CdTe grain
size or orientation or other improvement in the ?lm quality.
The measurements of the sample cell D show the contri
bution of the vibration after the carbon paste application to
the improvement of Isc, FF, and EFF. It is thought that the
contact resistance between the carbon electrode layer and
the CdTe layer is reduced by the vibration.
Lastly, from the data of the sample cell E, it is clear that
an about 10% increase of EFF compared to sample cell Ahas
been obtained by the combined e?ect of the vibrations after
each of the applications of CdS, Cd.Te, and carbon pastes.
Thus, it is understood that the characteristics of the solar
cells are improved by the simple measure of vibrating the
glass substrate after the applications of the pastes, without
requiring any signi?cant change of the process or manufac
. On the positive and negative electrodes 6 and 5 of Ag.In, 60 turing installation.
copper paste was applied by screen printing, and dried and

baked. Further, on the other parts of the cell a passivation
layer was likewise applied by printing, and dried and baked,

to complete the cell. The sinterings or bakings in the above
processes were made in a nitrogen atmosphere.
The following describes the effect of vibration given to
the glass substrate when, in the above described manufac~
The method of application of the various pastes is not

con?ned to the screen printing as referred to in the above
examples. Various other methods can be employed; nozzle

printing of paste from a nozzle, including printing of a ?gure
in a desired pattern on a glass substrate by adjusting the
distance between the tip of the nozzle and the surface of the
substrate to change the paint thickness; relief and intaglio
5,538,903
5
printing; and spray printing of paste with a spray gun while

shielding the non-printed areas by a mask.
Table 2 shows how the spread of unevenness of the
surface (the difference between the maximum thickness and
printing, nozzle printing, relief printing, intaglio printing,
the minimum thickness) and the yields in production change
and spray printing.
3. A method of manufacturing a solar cell according to
claim 2, wherein the application of the paste is performed by

a method selected from the group consisting of screen
depending upon whether or not the ultrasonic treatment is
employed on every layer of the cells. As is observed, by the
claim 3, wherein the powdered raw materials for the layers

of n-type and ptype semiconductors comprise elements of
vibration after the paste application similar effects can be

obtained as with the screen printing.
10
TABLE 2
Printing
Without ultrasonic
With ultrasonic
treatment
treatment
Spread of
unevenness (pm)
Yield
(%)
Spread of
unevenness (urn)
Yield
(%)
35
15
21
26
92
85
72
82
74
8
9
4
9
12
9S
89
82
90
91
Screen
Nozzle
Relief
lntaglio
Spray
groups II and VI or a compound thereof.

claim 4, further comprising a step of forming a passivation

layer of resin over said cell except for the positive and
negative output terminals thereof.
claim 3, wherein said n-type compound semiconductor layer

comprises CdS, and said p-type compound semiconductor
layer comprises one of CdTe and CuInSe2.
For the application of such ultrasonic vibration, 5 to 10

seconds are su?icient, so that the application of paste with

claim 3, further comprising a step of fornring a passivation
claim 2; wherein the powdered raw materials for the layers
of n-type and p-type semiconductors comprise elements of
the vibration and further vibration thereafter of a short time
Instead of vibrating the outer circumference or the outer
surface after the application of the pastes as explained

above, vibration during printing of the paste may have the
same effects.
less than 5 seconds is su?icient; therefore substantial elon

gation of manufacturing time does not occur.
Although ultrasonic vibration given to the glass substrate
25

30
during or after the pastes of the n-type and p-type compound

semiconductor layers and electrode layer were applied was
effective, vibration given during or after application of the
pastes for the formation of the terminal or passivation layer
did not bring about remarkable effects on the cell charac
teristics.
It is added that the method of the present invention, thus
far explained with reference to CdS/CdTe compound semi
conductor solar cells, can be applied to the formation of
other compound semiconductor layers of solar cells includ

claim 2, wherein said n-type compound semiconductor layer
comprises CdS, and said p~type compound semiconductor


ing Group I-III-VI2 compounds, for example CuInSe2, in
the place of CdTe, provided the layer is formed by coating

and ?ring.

As explained above in detail, when a solar cell is fabri
cated by forming a laminate of n-type and p-type compound

semiconductor layers and electrode layers on a glass sub
strate, the layers become free of bubbles, and the surfaces
?at, if vibration is given to the glass substrate during or after
the paste of the raw material and viscous agent for the layer
are applied; and drying and ?ring thereafter provide dense
layers of uniform thickness and in good contact with the next
layer, and a solar cell with improved, uniform characteris
45
claim 1, wherein the application of the paste is performed by

a method selected from the group consisting of screen
printing, nozzle printing, relief printing, intaglio printing,

and spray printing.
50

of n-type and p-type semiconductors comprise elements of
tics.
What is claimed:
1. A method of manufacturing a solar cell, comprising the 55 claim 15, further comprising a step of forming a passivation
steps of forming a layer of n-type compound semiconductor,
a layer of p~type compound semiconductor, and an electrode
layer on a glass substrate, wherein at least one of said steps
of forming a layer of compound semiconductor comprises:

preparing a paste by mixing a powdered semiconductor
60
claim 14, wherein said n-type compound semiconductor

layer comprises CdS, and said p-type compound semicon
raw material and a viscous agent, applying said paste to
ductor layer comprises one of CdTe and CuInSe2.
said substrate, drying said paste to harden it, and ?ring

said paste, and vibrating said substrate during or after
the application of the paste.


claim 1, wherein said vibration is of an ultrasonic pulse
form.
65

5,538,903
7
comprises CdS, and said p-type compound semiconductor

of n-type and p-type semiconductors comprise elements of 5

10 negative output terminals thereof.
22. A method a manufacturing a solar cell according to
claim 1, wherein said n~type compound semiconductor layer

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llllllllllllllIllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll ,

United States Patent [19]

[54] METHOD OF MANUFACTURING SOLAR

[75] Inventors: Tetsuya Aramoto, Osaka; Nobuo

Nakayama, Hirakata; Kuniyoshi

Japan ....................................... .. 437/9

Matsushita News, Feb. 1, 1983, pp. 1-5.

Japan .................................. .. 5-314478

A method of manufacturing a solar cell, comprising the steps

Int. Cl.6 ................................................... .. H01L 31118

layer on a glass substrate, wherein at least one of said steps

US. Cl. ............................ .. 437/5; 136/260; 136/264;

of forming a layer of compound semiconductor layer com

Nov. 18, 1993

136/265; 427/74; 427/76; 427/346; 437/9;

Primary ExaminerAaron Weisstuch

[21] Appl. No.: 342,445

Jul. 23, 1996

Murozono, Hirakata, all of Japan

[73] Assignee: Matsushita Electric Industrial Co.,

Field of Search .................................. .. 437/5, 9, 234;

427/74-76, 346; 136/260, 264, 265

resulting in a semiconductor layer which is smooth, dense,

Japan ....................................... .. 437/9

24 Claims, 3 Drawing Sheets

Jul. 23, 1996

Jul. 23, 1996

Jul. 23, 1996

METHOD OF MANUFACTURING SOLAR

conventionally, to obtain such a layer, a paste made of the

eletroconducting agent, and a viscous agent nrixed together

and, after the deposition, the substrate was held horizontally

at about 50 C., which was lower than the drying tempera

1. Field of the Invention

solar cell of compound semiconductors by way of coating

powders in order to obtain a high density layer. However, if

sometimes happened in the coating process by screen print

In recent years, expectations for solar cells as a clean

energy source have been raised, in view of the global

material powders did not always uniformly precipitate, and

purpose, solar cells made of compound semiconductors of .

Group l]1V materials such as GaAs, InP, Group H-VI

electrode layer formed thereon penetrated into the pin-holes

I-VI2 materials such as CuInS2, CuInSe2, as well as crys

tigated in many countries of the world. Among these, solar

duction consisting of printing, drying, ?ring (sintering or

the bubbles were removed from the paste before coating, it

SUMMARY OF THE INVENTION

baking), resulting in a high density arrangement on a glass

A typical solar cell of Group lI-VI semiconductor, of

layer 2, a p-type CdTe layer 3, a current collecting carbon

terminal 6 formed by laminating with printing and baking of

Ag-In electrodes, with a copper paste layer deposited, dried,

Light, including that of the sun, falls on the surface of the

method of manufacturing compound semiconductor solar

tors and electrode layers having improved performance,

said steps of forming a layer of compound semiconductor

compound semiconductor solar cell of n-CdS/p-CdTe type.