JPS59152673A - Manufacture of photoelectric converter - Google Patents

Abstract

PURPOSE:To improve the efficiency and the reliability by providing a sawtooth- shaped surface having an angle of 70 deg. or near 70 deg. by pressing (closely contacting) a base material having a sawtooth-shaped surface, then forming a blocking layer by baking, and forming the first electrode made of a light transmission conductive film on the blocking layer and the second electrode on a non-single crystal semiconductor. CONSTITUTION:A base material 40 is arranged upward, pressure is applied to press (closely contact) on a glass plate 2 to deform the surface to a sawtooth- shaped surface. Then, since an insulator 3' is temporarily baked, it is deformed by this pressure, deformed as in the shape of the base material to provide a sawtooth-shaped uneven surface. Then, the insulator 3' on the surface is thermally oxidized and integrated with a substrate. The main surface of the light transmission substrate has an angle of 70 deg. or near 70 deg.. A CTF which forms the first electrode by an LPCVD method or a PCVD method is formed on the surfaces of the recess 14 and the projection 13. The second CTF9 is formed by an electron beam depositing method or the PCVD or LPCVD method similar to the first CTF from ITO.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves forming a coating layer of a pre-sintered insulating material or a conductive material on a transparent substrate, and pressing (adhering) a base material having a serrated surface onto the applied layer. After forming a serrated surface at or near the angle of 70 degrees, firing is performed to form a blocking layer, and a first electrode made of a light-transmitting conductive film is formed on the blocking layer. and a non-single crystal semiconductor which has at least one PIN or PN junction on the electrode and which generates photovoltaic force upon irradiation with light, and a second electrode (back electrode) formed on the semiconductor to perform photoelectric conversion. The present invention relates to a method for manufacturing a device (hereinafter referred to as PVC).

In the present invention, by providing the main surface of this light-transmitting insulating substrate with a serrated uneven surface, the surface area is increased (and the optical path becomes long for light, and it becomes substantially difficult for carriers, especially holes). The purpose is to improve the photoelectric conversion efficiency on the light irradiation surface side by making the optical path shorter.

Since the present invention has sawtooth irregularities, the angle of the sawtooth is particularly 70° or its vicinity <+2s', = within), and the substrate and the transparent conductive film are It is characterized in that the interface between one electrode and the antireflection film is irradiated with incident light at least twice, thereby reducing reflection loss at that interface.

The present invention enables mass production by deforming the blocking bottom using a stamping method so that the convex/concave portions are approximately 1 m, and the pitch thereof is 0.1 to IV (height difference is 0.05 to ?). is intended to do. .

By doing this, the irradiated light is double reflected on the surface on the incident light side, thereby forming an interface between the transparent conductive film (hereinafter referred to as CTF) constituting the first electrode on the transparent substrate and the semiconductor. In addition, it is possible to reduce the total amount of reflection at the interface between the substrate and the CTF. As a result, the amount of reflected incident light has been reduced by 6-8% compared to the previous 20-30%.
As a result, the conversion efficiency of the photoelectric conversion device could be improved by 10 to 15%.

In the present invention, it is possible to use simple soda glass or white plate glass as the translucent substrate, but in addition, by using chemically strengthened glass whose mechanical strength is 3 to 5 times higher, it is possible to use chemically strengthened glass with a thickness of 0.65 to 50%. It is characterized by the use of a thin substrate of 2.2 mm.

Generally, the glass used for chemical strengthening is
After the photoelectric conversion device is completed, alkaline metals such as potassium impregnated to a depth of ~3 cm will diffuse back into the CTF and
This lowers the electrical conductivity of the metal, which in turn lowers its reliability.

In order to prevent this drawback, the present invention provides an insulating coating between the chemically strengthened glass and the CTF of the first electrode, which is made of silicon oxide or phosphorus glass or a mixture thereof, which has a blocking (mask) effect against potassium. Alternatively, indium oxide, tin oxide, or a mixture thereof is provided as a coating layer with an average thickness of 0.1 to 5/AA on these insulating materials, and then this insulating material or conductive material is coated with a saw. The blocking layer is characterized by having irregularities in the form of a shape.

Furthermore, the present invention is characterized by improving the quantum efficiency of light incident on the semiconductor at short wavelengths.

That is, by lengthening the optical path for short wavelengths of 500 nm or less,
In addition, by shortening the drifting diffusion length of one of the electron/ball pairs generated by this photoexcitation, particularly preferably the hole, the CTF can be reached in a time sufficiently shorter than the carrier lifetime, thereby increasing the quantum efficiency by 4.
The conventional values of 60% at 00 nm and 80% at 500 nm were increased to 85% at 400 nm and 95% at 500 r+m.

These effects combine to make the conventional structure 8M1 (10
Under irradiation of 0 mW/c♂), only 7% could be obtained, but this could be increased to 10.2-11.5%.

The present invention is based on the (100) plane or a plane near it (generally (100)
1n) plane and fi>3 For example, when n=5, (1
15) is the neighborhood) Preferably (100
) by etching the surface of a silicon single crystal with a PW (mixture of ethylenediamine, pyrocatechol, and water) to form a V-shaped groove (the angle of the ■-shaped groove is 70.5), i.e. creating a base material (here single crystal silicon) with a serrated surface at or near an angle of 70″′;
A "mold" for deforming this translucent substrate-like insulator or a conductive material on an insulating material or a coating layer made of a conductive material into a saw shape.
By integrating this insulator with a translucent substrate by firing, the substrate itself has a serrated surface, and all of its irregularities have a serrated shape with approximately the same shape. A substrate (substrate) is formed.

Furthermore, the present invention provides subsequent processes such as electron beam evaporation, spraying, and plasma vapor deposition (PCVD) on the serrated main surface.
The CTF forming the first electrode is formed using a low pressure vapor phase method (referred to as PCV D method) or the reduced pressure vapor phase method (referred to as PCV D method), and a non-single crystal semiconductor film is further formed on this CTF. It is a feature.

Conventional PvC, whose vertical cross-sectional view is shown in Figure 1, is a CTF (4) made of ITO on a glass substrate (1) with a flat surface.
It is known to form one or two layers of lSnO, etc. by electron beam evaporation or spraying. When forming CTF using a spray method, ITO (insium oxide to tin oxide compound) is formed to an average thickness of 150 to 200 OA, and tin oxide is further applied to the top surface of this to an average thickness of 200 to 500 Å.
It is formed to a thickness of 00λ. Then, the surface of this CTF is 0
．． Concave (14), convex (1
3) (However, the difference in height can only be 200 to 500'A, which is about 1/10 of the particle size at most). Therefore, the semiconductor part t3p
type semiconductor e.g. 5ixC+<(0<x<1)(6)
When a non-single crystal semiconductor (5) having an l''IN junction consisting of an I-type semiconductor (7) and an N-type semiconductor (8) is laminated, and a second electrode is formed, the incident light (10) is Among them, it is possible to make a slight difference as shown in (2I).

However, in such a conventional example, a smooth scale-like shape (resembling fish scales when viewed under an electron microscope) with an uneven surface formed by clusters of devotion simply by spraying on a transparent substrate (3) having a flat surface has been proposed. It had only a scaly curved surface, which was completely unsatisfactory.

Therefore, it is required to use this shape even more actively. Furthermore, in such a conventional method, the substrate (3
), CTF (4) was found to be completely ineffective against reflection at the interface (20).

In such conventional methods, the photoelectric conversion efficiency (hereinafter simply referred to as efficiency) is up to 7% (7 to 7.9%), and the maximum is 7.93.
I could only get up to %.

The present invention not only improves the quantum efficiency of long-wavelength light of 600 nm or more by diffusely reflecting such long-wavelength light, but also effectively uses short-wavelength light. The optical path length/carrier diffusion length of short-wavelength light is further increased to 1.5 to 7 from the conventional value l by using a double repulsion agent to prevent reflection due to the difference in refractive index.

Especially 300. Short wavelength light of ~500 nm is 20 nm in semiconductors.
More than 90% of light is absorbed up to 00 Å and photoelectrically converted, but
Among these balls, which are carriers, cannot reach the flat surface electrode (4). At optical path length (OL)/carrier diffusion length (DL), that is, O/D1, carriers generated by photoexcitation must diffuse to the electrode the same length as the light entered. Must not be.

However, in the present invention, since this O,/D=1.5 to 5 can generally be set to 2 to 3, the resulting 3
It became possible to improve the quantum efficiency in the range of 00 to 500 r+m.

FIG. 2 shows a vertical sectional view of the PVC of the present invention. In the drawings, glass is used here as the transparent substrate (2).

That is, the glass plate (2) has a thickness of 0.65 to 2.2 mm, and is further made of chemically strengthened glass to which an alkali metal element such as potassium is added at a depth of 20 to 3 mm near the surface. Using.

The thickness of such a glass substrate is conventionally known 3,
It has the same mechanical strength as 3mm thick glass and is lightweight.

However, it has been found that when the potassium used for reinforcement diffuses back into the CTF, this potassium reduces the electrical conductivity of the CTF.

Therefore, in addition to improving efficiency, the blocking layer having serrated irregularities also has the feature of improving reliability due to the blocking effect of the alkali metal.

That is, a transparent conductive film on a chemically strengthened glass (2), a transparent insulating material mainly composed of silicon oxide phosphorous glass, or a mixture thereof, or a transparent conductive film on a transparent insulating material. A blocking layer (3) was provided to prepare a substrate.

Furthermore, the main surface of this board has a convex part (13) and a concave part (14).
It consists of an insulator (13) having a saw-like shape, the angle of which is 7
0' or its vicinity (within +25.-15, 55 to 9
5'). Furthermore, the tip of the convex portion or the bottom of the concave portion has a curved surface (circular cross section, radius of curvature of 200 i to 200 g). Also, the pitch (distance between the convex part and the adjacent concave part) of this 1 is 0.1 to 107 (height difference is 0.05 to 2)
Preferably, the pitch height difference is 0.3 to 0.8. u (0,
3-0,? ) or 2-5/14 (1,5-ri).

Furthermore, CTF (4), which constitutes the first electrode and also serves as an anti-reflection film, is applied along this serrated surface with a thickness of 1500 to 200.
The thickness of the CTF is 0^, and the surface of the CTF is mainly composed of tin oxide.

Furthermore, closely related to this CTF, PCVD method or Ll'C
P-type non-single crystal semiconductor obtained by the VD method, for example, about 10
5iXc, -L (0 < x < 1 e.g. x = 0.8) (6) with a thickness of
Summer-type semiconductor doped with y10 to 1 to 10c7 (7) For example, a silicon semiconductor made by a glow discharge method or a silicon semiconductor having a semi-amorphous structure was made to have an average thickness of 0.4 to 0.7.

This summer-type semiconductor contains 1 meter 10'2'IO'c of boron.
In order to improve the properties, it is very important that m' is added and that the amount of oxygen added is less than 5'IO'cm', preferably less than 5〆10'cm'.

In this way, the crystal structure could have a semi-amorphous semiconductor rather than an amorphous one.

Furthermore, one PIN made of N-type polycrystalline or microcrystalline silicon semiconductor (8) with an average thickness of 100 to 200'A.
A non-single crystal semiconductor (5) having a junction is provided.

This semiconductor has an oxygen concentration of 540cm or less, preferably 5y.
10 cm' or less.

Furthermore, a second electrode (9) is formed on this upper surface using the I'CVD method.
Second CTF by PCV D method or electron beam evaporation method
(11) For example, ITO is formed to have an average thickness of 900 to 1300 -V uniform thicknesses or 1050 mm, and the reflective electrode (12) on the top surface is provided with aluminum or silver as the main component. It is being

A comparison of the characteristics of the present invention obtained in such a structure with the conventional structure shown in FIG. 1 is as follows.

Conventional example Invention open circuit voltage (V,) 0.81 0.9
2 Short circuit current (mA/cQ)' 13.9.
18.9 Fill factor (%) '58.3
68.0 Conversion efficiency (%), 6.56
40.6 The above efficiency is based on an area of 1.05 cm (3.5 m
mx3cm), AMI (100mW/
This is the characteristic when irradiated with irradiation light of cm). From this, the present invention has the great feature of being able to improve its efficiency by 80% compared to the conventional method.

FIG. 3 is a principle diagram showing the effect of the present invention.

In the drawing, the main surface of the glass substrate is chemically strengthened glass (1)
This is a substrate (1) consisting of a blocking M (3) having two saw-shaped protrusions (13) and four parts (14).

On the top surface of the substrate (1) are CTF (4), two layers (6) I
Jt (7'), a semiconductor (5) having at least one PIN junction made of an N layer (8), and a back electrode (9).

In the drawing, the incident light (10) passes through the blocking layer (3)
=CTF (4) The first reflection (20) occurs at the interface, but
It reaches another blocking N (3)-CTF (4) interface again and undergoes a second reflection (23). Due to these two irradiations, (21) and (21') are incident on the semiconductor,
More than 95% of the light was able to enter the semiconductor. Furthermore, since the back surface of the substrate (35) is glass treated with ^R treatment (manufactured by Nippon Sheet Glass Co., Ltd.), reflections are caused by atmospheric radiation.
It was effective because the glass interface (the entire surface of which was statically treated) could be substantially reduced to 1% from the usual 5%.

Since the angles of the saw-shaped irregularities of this substrate are all the same, and the angle (30) is approximately 70', all incident light is incident twice, so that it can be controlled as in the conventional example. It has the great feature of being extremely efficient in utilizing irradiated light compared to a structure that does not have any irregularities, where the incident light is diffusely reflected only on the surface.

Furthermore, since the structure of the present invention is controlled so that this serrated shape is the same at all locations, there is no possibility of short circuits between the upper and lower electrodes due to product variations, which will reduce the yield. Has characteristics. Furthermore, even if the light entering the CTF (4) is reflected (22') at the CTF-semiconductor interface, it ends up entering the semiconductor (21), which has a higher refractive index.

Also, in semiconductors, electrons generated by photoexcitation (16)
, of the hole (17) pair, the electron passes through the center part (15) of the recess (14) (the most stable energy level) and reaches the second electrode (9) by a drift distance.

The diffusion length of the electron (16) is 100 times longer than that of the hole (17).
0 times, so 1 layer (6) averages 0.3 to 0.87M
For example, even if 0.57<, there is no problem with the drift distance.

Furthermore, since these electrons reach the recess (14) on the back surface (9), the drift distance could be effectively further shortened.

On the other hand, holes, which are only about 1/1000th the size of electrons, have an extremely short drift distance of (27), so they are captured by recombination centers and prevented from disappearing. For this reason, it has been found that the present invention, which sets OL/DL>1, especially 2 to IO, is extremely important.

In other words, the main surface of this substrate having a sawtooth shape can shorten the drift length of both holes and electrons, and furthermore, the semiconductor (7) and electrode (4) can shorten the drift length of both holes and electrons.
) has another feature that the contact resistance at the electrode-semiconductor interface can be reduced by increasing the contact area with the electrode.

Furthermore, the serrated surface of this substrate is produced by plasma CVD.
Alternatively, similar unevenness is induced on the surface of the semiconductor (4) (semiconductor (7) - electrode (8) interface) made by LPCV D, and this uneven surface lengthens the optical path due to diffused reflection. can do.

Therefore, the unevenness on the back electrode can ultimately promote even better efficiency. In particular, it was possible to confine long wavelength light of 600 nm or more in the semiconductor for a longer time (long optical path), and it was possible to promote improvement in quantum efficiency in the long wavelength region.

Also, the angle (33) of the sawtooth shape of the substrate (1) is constant at approximately 70° because angle selective etching is performed on a silicon substrate having a base material (100), and its pitch ( 33
), the height difference (34) can be made substantially uniform over all of the substrates. Therefore, some of the protrusions are extremely large, and another feature is that there is no reduction in yield due to shorts between the upper and lower electrodes there.

Regarding this long wavelength light, as shown in Figure 2, the back electrode has an uneven back surface like the front surface, and is further used as a CTF and a reflecting electrode to promote diffuse reflection of long wavelength light and increase its reflection efficiency. It has the characteristic of being able to

FIG. 4 shows the manufacturing process for making the PVC of the present invention.

Example 1 A manufacturing process as an example of the present invention is shown according to the drawings.

A silicon single crystal having a (100) plane was used as the base material (40). Furthermore, this upper surface was thoroughly cleaned and U2 and natural oxides were removed. Furthermore, silicon oxide was selectively formed on this curved surface in the form of dots or networks.

To create a dot-like appearance, the glass (M silicon oxide glass) solution used in the coating method is diluted with an organic solvent such as alcohol, and the dots are scattered and applied using a spray method. The length is 100λ~0. For example, the particle spacing (pitch 0.1 to 0, for example about 20
Formed as 0OA. Further, add this to 500~600'
It was fired in air at C to obtain silicon oxide particles.

After this firing, the silicon oxide film with a thickness of 10 to 50 mm in the part without grains is removed with 1/10 hydrofluoric acid (hydrofluoric acid diluted with 10 times as much water) to form a so-called island shape. A silicon oxide film was formed in a cluster shape and used as a starting material.

Then, the silicon matrix material on which the silicon oxide mask was selectively formed was subjected to anisotropic etching using APW.

That is, for example, in a solution of 17 cc of ethylenediamine, 3 gr of pyrocatechol, and 8 cc of water, the base material shown in FIG. 1) is (100) plane (
35), we have (111) and (36), and we were able to obtain the angle (30) of 70.5. (10
0) is slightly shifted, this angle becomes 70.5', l
:, the angle of the rim deviation is around 70°.

After washing this APW with water, the silicon oxide on the mask was removed with a hydrofluoric acid solution. After this, etching may be performed again in an AI'W chamber for 0.1 to 2 minutes to remove the flat portion of the mask portion, if necessary.

Next, in Figure 1, a glass plate with a thickness of 0.65 to 2.2 mm, for example, a glass plate with a thickness of
) was dissolved in an organic solvent such as alcohol and applied with siliconization to form a coating layer (3).

Here, we use a solvent manufactured by Tokyo Ohka Co., Ltd. (OCD 5i-1100
(for silicon oxide) was used.

When the refractive index was desired to be higher than that of glass, titanium oxide was mixed into silicon oxide.

Actually, after applying the solution, the coating was applied by rotating at a speed of 10 times/minute using a spinner to form 41 coated layers.

In this way, an insulator (3) was formed.

Furthermore, after this, beta was carried out for 10 to 30 minutes at so-, 3orfc, for example, 15 (1'c) in the air, and the solvent such as alcohol was vaporized and removed. ), the base material (40) is placed above and pressed (adhered) onto the glass plate (2) by applying pressure like a stamp to transform its surface into a serrated surface. It was.

Then, since the insulator (3') has only been pre-fired, it is deformed by this pressure and deforms like the shape of the base material to have a saw-like uneven surface.

(Figure 4 was obtained.

After this, in order to vitrify the insulator (3') on this surface,
It was heated and oxidized at a temperature of 400 to 8006C, for example 600C, and was integrated with the substrate.

Then, when vitrifying this insulator, the volume becomes 15~30
%, the convex portion becomes smaller than the base material and its tip becomes slightly rounded.

To make this serrated surface even sharper, increase the angle of the base material by 7
65r~55' instead of '0, 5'! :do it.

Thus, the main surface of the transparent substrate (1) is coated with the blocking layer (
3) has a serrated concave (14) and convex (13) surface, and the angle is 70.5 or its vicinity (12t, -10
(within 0).

In addition, it was possible to prevent the impregnation (back diffusion) of stream and force into the CTF from the glass substrate, and as a result, a decrease in the transmittance of the CTF and an increase in the sea resistance were prevented. FIG. 4(B) shows a light-transmitting substrate (1) whose main surface has an angle of 70° or its vicinity. Moreover, on the surface of this concave (14) and convex (13), LPCV D
CTF constituting the first electrode by method or PCvD method
formed.

That is, in the LPCV D method, 300 to 55σC
InCl, and 5nC- or 5bCl, were used as indium tin or antimony reactive gases at a temperature of . For example, to make tin oxide, 5nC11
and air, which is an oxide gas, are mixed, and 0.1 to 10 to
The substrate was placed in a reactor maintained at, for example, 1 torr.

This substrate was heated to 300 to 6 ocfc, for example, 450°C, and the above-mentioned reactive gas was passed through it. Since this is under reduced pressure, the mean free path of the reactive gas becomes large, and a uniform blackened tin oxide film of 1000 to 30
I was able to make it as thick as 00 people. In ITO (indium oxide to which 5% tin oxide is added), indium chloride may be added simultaneously with tin chloride in a ratio of 20=1 as a reactive gas.

When performing the pcvo method, the temperature is 0.01 to 2 torr, and the same starting materials as in the LI"cvp method are heated at room temperature to 1601C.
The signal was applied at a high frequency, for example, 13.56 MHz.

Thus, it is important to create a uniform film thickness on the serrated surface.

(7) CTF is 400 to 600”C after Kono, for example, 50
(Calcination in air (30 minutes to 3 hours) at 1'c was effective for increasing the electrical conductivity.

During the firing of °CTF (4) at 500 °C, this blocking M (3) had a very large effect because it prevented back-diffusion of the potassium from the substrate glass (2) into the CTF.

That is, in this example, it was possible to have a C I-resistance of 20 to 25 cubic A and a transmittance of 95% in the region of 400 to 600 nm. However, if CTF is formed by the method described above on chemically strengthened glass without this blocking layer,
Sheet resistance is 70-150 due to back-diffusion of potassium.
-'='El+, and the lot variation became large, and the resistivity also became high. In addition, a devitrification phenomenon occurred in addition to reflection at the surface, and a transmittance of only 70% could be achieved.

(Thus, in the heating beta process, blocking N(3) can prevent back diffusion of alkali metals from glass, preventing devitrification and increase in sheet resistance, and the present invention improves conversion efficiency as PvC. was able to make a major contribution.

Note that for the formation of CTF, 5nCI containing CF2Or,
together with oxide gas at 400-600'C, e.g. 500'C.
It may be formed to a thickness of 1000 to 250 OA at 6C, 1 to 3 torr.

Furthermore, as shown in Fig. 4(C), P-type 5tX containing silane and methane as main components was obtained by plasma vapor phase method.
c+-, (0<x<1) was formed to a thickness of about 100 people. Further, by adding 0.5 to IPPM of BJI, silane or IIF is subjected to a reaction with silane using a known plasma vapor phase method to obtain an average reflection thickness of 0.4 to 0, for example, an average of 0.
It was formed to a thickness of about 100 yen. At this time, the back surface of the non-single crystal semiconductor (7) has a sawtooth curved surface with unevenness, and the height difference is 0.1 to 0.
゜It was close to two houses. Furthermore, N-type semiconductor is 5/5 yen
It was made by microcrystallization to an average thickness of 100 to 200 by plasma vapor phase method with iH9-1%, Si H,/H, > 10.

After this, the second CTF (9) is applied to ITO by known electron beam evaporation method or by PCVO or LP similar to the first CTF.
The CVD method was used to form an average thickness of 900 to 1300 Å, for example, 1050 Å. Further, on this CTFJ 2, a reflective electrode (19) mainly composed of aluminum was formed by a vacuum evaporation method or an LPCVD method using TMA (+-remethylaluminum).

In this way, the structure shown in Figure 4 ('C) was obtained.

The characteristics obtained in Fig. 4(C) are briefly summarized as follows: open circuit voltage 0.92V, short circuit current 18.9mA/c♂, fill factor 6
The conversion efficiency was 1.0% and the conversion efficiency was 10.6%.

Example 2 This example was shown in accordance with FIG. 4 with the same steps as Example 1.

However, the method for manufacturing the base material (40) was as follows.

In addition, as another structure, the serrated main surface can be formed in a mesh shape or a sag shape as follows.

The width of the Zunawara net is 0.3~57, and the opening (pitch) of the rectangular serrations or comb-shaped serrations is 0.3~? Upon binding, this mesh (comb opening) was oriented in the <110> direction. Zunawachi (10
0) After cleaning the surface of the silicon substrate, 1100'C
A silicon oxide film with a thickness of 500 to 1000 wafers was formed by thermal oxidation in oxygen. Thereafter, a photoresist was applied to the upper surface, and a mesh-like or comb-like (also called sag-like) pattern was formed by the first etching method. Furthermore, using this resist I film as a mask, the remaining silicon oxide film was removed with 1/1O hydrofluoric acid. Thus the net or comb
A silicon oxide film was formed with an orientation of 110>.

Thus, using the crystallization method of the (100) substrate, it was possible to make molds of rectangular sawtooth or comb-like sawtooth structures.

The rest was carried out in the same manner as in Example 1.

This method has the disadvantage of requiring a notching process, but on the other hand, the difference in height of the sawtooth is even smaller than in the embodiment, and there is almost no difference in height between the -L and lower electrodes.1. No decrease in manufacturing yield was observed at all, and we were able to achieve a composite integrated structure for a calculator with a manufacturing yield of 85% or more.

Example 3 In this example, the coating layer is a conductive layer.

That is, a silicide coating solution, which is the first coating layer, was applied onto chemically strengthened glass with a thickness of 1.1 mm using a solvent (OC) manufactured by Tokyo Ohka Co., Ltd.
D 5i-41000>0. It was formed to a thickness of y4.

Furthermore, after removing the alcohol component of this coated layer by calcining by heating oxidation, the second coated layer was similarly coated with a solution of indium compound, stannide, or a mixture thereof for ITO. It was formed using Indium Film (Indium Film or CG, -3). This conductive coating layer was formed and similarly prebaked at 200'C for 130 minutes in the air.

In this way, I was able to explore the structure shown in Figure 4 (A).

The subsequent steps are the same as in Example 1.

In this example, since a part of the first CTF is configured in this sawtooth region, the electrical conductivity of this CTF is increased from 40 to 50n10 in Example 1 to 20n10.
It was possible to lower the FF (fill factor) as a photoelectric conversion device by 14%.

As a result, the characteristics of the photoelectric conversion device are as follows: the open circuit voltage is 0.
91 V, short circuit current 17.4 m8 cm'', fill factor 1
0% efficiency of 11.1% could be obtained.

As described above, according to the present invention, since the first coating film blocks the sludge and lume in the glass substrate, the sheet resistance of the CTF decreases by 450 to 50%.
Baking in 506C1 air (effective for increasing CTFO transmittance and conductivity) was not observed at all in terms of characteristics.

As is clear from the above description, in order to create saw-shaped irregularities on a transparent substrate, the present invention uses a base material having an irregular surface like a stamp and transfers it to the coating layer on the surface of the glass substrate. By firing the attached layer and integrating it with the substrate, the substrate (substrate and blocking layer) itself on the side of the incident light surface was able to have an uneven surface.

In the present invention, a saw-shaped silicon plate having a (100) plane was used as the base material.

However, a stainless steel plate or cylindrical roll is ``scored'' with a diamond needle to form a comb, rectangle or triangle at an angle of 706 or around 60'', for example 0.4 to 1.
．． For example, 0. It is extremely effective to make it from Tobisochi and use it as the base material.

In the present invention, instead of using a semiconductor having one P■N, it is also effective as a Kundem structure having an r1NPIN...PIN junction.

The semiconductor was a non-single-crystal semiconductor whose main component was silicon by plasma vapor phase method. But 5ixGel((0<x
< 1), 5ixSnl, ((0<x< 1), Si,
It is also possible to set N4J3<X4).

As is clear from the above description, in the present invention, a glass plate having a thickness of 0.65 to 2.3 mm is used as a transparent substrate. However, it is also effective to use flexible glass or quartz with a thickness of 0.1 to 107 m as the substrate.

Furthermore, as this substrate, transparent polyimide, Bo 1, S □
゛? ? A mid-organic In resin may be used, and a blocking layer may be formed on this organic resin by the method of the present invention.

[Brief explanation of the drawing]

FIG. 1 shows a vertical Itli plane view of a conventional photoelectric conversion device. FIG. 2 shows a longitudinal cross-sectional view of the photoelectric conversion device of the present invention. FIG. 3 does not show the principle of the photoelectric conversion device of the present invention and does not show a longitudinal view. FIG. 4 shows a method for manufacturing the photoelectric conversion device of the present invention. Patent applicant mouse 2 ('3 ]] □□-yoL □-zu0 r3 'lt/ 15 no-9 Do I! B m-5' □Goooo (-9 5 1ε ([λ 14 is also 4C Ko

Claims (1)

[Scope of Claims] (1) An insulating material whose main component is a silicide or a mixture thereof dissolved or mixed in an organic solvent, or a conductive material whose main component is an indium compound, a stannic compound, or a mixture thereof, on a transparent substrate. After forming a coating layer on the material, the organic solvent is vaporized by heating and oxidizing at 50 to 300'C to form an insulator mainly composed of silicon oxide or a mixture thereof, or indium oxide, tin oxide, or forming a conductive coating layer containing the mixture as a main component on the substrate;
a step of compressing or closely adhering a base material having a serrated surface with an angle of 0 or around 0 to the coating layer, thereby deforming the surface of the coating layer into a serrated shape, and the substrate and the deformed coating. By heating and baking the layer at 400 to 800 tons, the applied layer is integrated onto the substrate as a fronting layer that is translucent and has a serrated surface having an angle of 70' or around 70'. a step of forming a first electrode of a transparent conductive film on the surface of the transparent insulator;
A method for manufacturing a photoelectric conversion device, comprising the steps of: forming a non-single crystal semiconductor that generates a photovoltaic force by irradiating light on the conductive film; and forming a second electrode on the semiconductor. 2. A method for producing a photoelectric conversion device according to claim 1, characterized in that chemically strengthened glass to which potassium is added on the front and back surfaces is used as the light-transmitting substrate.