JPS59144181A - Manufacture of photoelectric converter - Google Patents

Abstract

PURPOSE:To improve the reliability in a high temperature condition test by forming an electrode contacted closely with a non-single crystal conductor of a light transmission conductive film made of an oxide. CONSTITUTION:A light transmission conductive film 2 is formed on a glass substrate 1. A non-single crystal semiconductor having at least one PIN or P-N is laminated on the film 2. Then, an oxidized indium ITO is formed. The non- single crystal semiconductor of SixC1-x as a P type semiconductor is closely contacted with the oxidized tin 2, and an N type non-single crystal semiconductor is closely contacted with the ITO. Then, a heat fusible light transmission filler such as polyvinyl butyral is arranged on an element 6. A light transmission insulating substrate 8 is arranged thereon. Then, it is installed in an autoclave furnace, which is then evacuated in vacuum. Thereafter, it is heated and pressurized. As a result, the filler has insulating property, and filled on the back surface side of a photoelectric conversion element. Accordingly, the polyvinyl butyral is not deteriorated, thereby providing light reliability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a photoelectric conversion device using a non-single crystal semiconductor, and more particularly to a method for manufacturing a semiconductor device that seeks high efficiency and high reliability.

This invention includes a first translucent insulating substrate, a first electrode having a first translucent conductive film (hereinafter simply referred to as CTFI) on the substrate, and a photovoltaic film formed on the electrode by light irradiation. At least one that generates electrical power.

A non-single crystal semiconductor having a PN or PIN junction, and a second transparent conductive film on the semiconductor (hereinafter simply referred to as CrF2)
The present invention relates to a method for manufacturing a photoelectric conversion device having a structure in which a photoelectric conversion element (hereinafter simply referred to as PvC or element) provided by a second electrode made of the following is provided and this is formed into a panel. In the present invention, the second electrode (also referred to as the back electrode) of the photoelectric conversion element is C
By setting it to rF2, 600% of the irradiation light such as sunlight
It has an electrode structure that allows long wavelength light of nm or more to be emitted backward from the second electrode.

That is, the present invention provides first and second
Both electrodes are not metal (CTF made of oxides such as indium tin oxide, insium tin oxide, etc.)
The conventionally known metal constituting the electrode, generally aluminum, undergoes migray l- (abnormal diffusion) in the semiconductor and does not cause a decrease in reliability in high-temperature storage tests at temperatures above 150"C. The purpose is to prevent

Furthermore, by using both the first and second electrodes as CTF, the laser scribing method (simply referred to as LS) can be adopted when forming a composite integrated structure, resulting in high productivity and a - Another feature is that it can reduce the required area, that is, improve the effective conversion efficiency.

In addition, the present invention further provides 6
The device is characterized in that long-wavelength light with a wavelength of 00 nm or more is provided on the back surface and further diffused to the outside from the second light-transmitting insulating substrate via the light-transmitting filler.

By doing so, it was possible to prevent the temperature of the photoelectric conversion device itself from increasing, and thereby prevent a decrease in efficiency.

Furthermore, in addition to radiating long-wavelength light including infrared light to the outside, it becomes possible to install a solar water heater adjacent to the glass substrate on the back side.

That is, the present invention performs photoelectric conversion using short wavelength light and photothermal conversion using long wavelength light, and by integrating them and installing them on the roof of a general house, the total conversion and utilization rate of sunlight is 9. Another feature is that it can be made extremely high.

In other words, utility model registration application 53-83 filed by the inventor
838 (filed on June 19, 1978) "Solar cells", by making the front tempered glass part of a solar water heater into a laminated glass structure that includes a photoelectric conversion device, solar energy can be generated. It also has the feature of increasing the overall utilization efficiency of.

The present invention has a structure in which the front and back surfaces of the device are sandwiched with an inorganic material made of glass, particularly hardened glass, and a structure in which a plurality of devices are integrated on one substrate. By having this, we were able to achieve high quality and high reliability.

The organic substance, which is a heat-meltable light-transmitting filler, is not exposed to short wavelength light, but is only exposed to long wavelength light of 600 nm or more that has passed through the device.

Therefore, this organic material has another feature that it does not undergo photodeterioration and can have high reliability.

In addition, since no metal material is used for the electrodes, it is possible to
In the LS using high temperature, abnormal diffusion does not occur at the same time as scribing (and high reliability can be achieved even in the manufacturing process of multiple integration).

Furthermore, unlike conventional mask methods that use vapor deposition masks, screen printing, etc., by using LS, which is a maskless process, when compounding the entire panel, it is possible to The proportion could be set to 10% or less, generally 5 to 7% of the total.

Therefore, it also has another feature of being able to achieve high efficiency at the panel level.

As shown in the vertical cross-sectional view of FIG.
, etc., and further form a PIN junction, PIN PIN... Next, the back electrode is made of aluminum metal with a thickness of 0.3~
It was formed to have a thickness of V. Furthermore, the epoxy resin (5) was coated and produced.

Sunlight or the like is used as the irradiation light (10). However, such a conventional structure is not sufficient in terms of reliability. A detailed investigation into the cause revealed that the metal constituting the back electrode (4) did not form an alloy with the semiconductor (3) and was abnormally diffused into the semiconductor during a high temperature storage test of 10σ or more, typically 150'C. , 0.51 in about 12-50 hours
It was found that the particles were mixed in at a depth of as much as I, degrading characteristics such as conversion efficiency from 6% to less than 1%, and causing a substantial short circuit between the two electrodes.

For this reason, in non-single-crystal semiconductors that use amorphous or semi-amorphous silicon as the main component, it is most important that the material in close contact with the semiconductor is not a metal but a conductor of a compound such as a metal oxide or metal nitride. It turns out that there is something.

The present invention has been made based on such experimental facts, and when the semiconductor (3) forms one PIN junction, the P-type semiconductor is closely coated with CTF containing soot oxide to form an electrode. Moreover, the first feature is that indium oxide or ITO (oxide indium containing 10% by weight or less of soot oxide) is closely attached to the N-type semiconductor, resulting in a structure that does not use metal.

FIG. 2 shows a vertical LMj plane view of a photoelectric conversion device manufactured by the method of the present invention.

This photoelectric conversion device is a device in which a plurality of elements are integrated on the same light-transmitting substrate and framed in a panel structure.

In the drawing, ITO is placed on the transparent substrate (1) at 1500 ~
Provided with a thickness of 2500×, and further coated with tin oxide of 200×
A CTI'1(2) with a thickness of 50071 mm is provided.

Furthermore, a non-single crystal semiconductor (3) having a PIN junction is converted into a P-type s+Xc, -, ('O< x < 1 e.g. x = o,
s ><1oo7+>-■ type Si (approximately 0.nl-
The structure of N-type microcrystalline Si (particle size 100-200"A) was fabricated by plasma vapor phase method. Furthermore, ITO in close contact with this N-type semiconductor was
CTF 2 (4) was set for human thickness.

This composite is performed by forming a CTFI on the entire surface of the substrate (1), and then scribing the CTFI to about 2 +1J using LS to divide it into multiple regions (17), and then forming the semiconductor (3). After forming on the entire surface, semiconductor (3) and C
TFI was separated again by LS (113). Furthermore, after CTF2 (4) was formed on the entire surface, it was separated into a plurality of regions (19) by LS. Thus, the first
It is divided into an element (20), a second element (21), a third element (22), etc. For example, the connection part is connected to the first external extraction electrode base (15) connected to the external connection electrode 16), and the first external electrode (15) is connected to the second electrode of the first element. was connected to the second electrode of the second element at (18) and connected in series. Furthermore, the first electrode of the third element (22) is connected to another external connection electrode (16')
')It has become.

In this way, a plurality of elements are combined on the same substrate (1). Furthermore, this element is made of a heat-melted PVB (also known as Seaflex) translucent heat-melted filler (7) (thickness of 0.2 to 1 mm, generally 0.5 mm).
filled with.

Furthermore, a back glass (8), which is a second light-transmitting substrate, is provided on the upper surface, and has a laminated glass structure with (1) and (8).

Therefore, the long wavelength light on the PVB
(7) It passes through the glass substrate (8) and is emitted to the outside of the back surface.

In the drawing, the panel has an aluminum sash frame (13
), (13'), and this and the substrate (1
) (8) is Futhilcom, (14), (14
) The can is filled and the substrate is fixed to the frame.

Furthermore, in the drawing, on the opposite side of the irradiation light (10),
The dashed line indicates that a solar water heater (30) having a water cooling pipe (31) can be provided.

This water heater is located on the roof side and heats the inside of the water cooling pipe by supplying long wavelength light (10) from the back of sunlight, and can raise the temperature of water to 60-80'C. Solar heat can be used.

Such a structure does not occupy a large area of the roof, which is advantageous in that it can increase utilization efficiency.

FIG. 3 shows manufacturing steps related to the method for manufacturing a photoelectric conversion device of the present invention.

That is, in FIG. 3(A), a glass substrate (1), preferably glass, was used as the glass substrate. CTFI (2) is placed on this board (1).
) by known electron beam evaporation method, spray method or CVD method.
It was formed to a thickness of 0.15 to 0.25) A by the method. This CTF is ITO (0,15~0.25/14) +
It was set as SnO□ (200 to 500λ). It may also be 5nOt to which a nitrogen element is added.

Furthermore, a non-single crystal semiconductor having at least one PIN or PN junction is deposited on top of this by PCVD (plasma vapor deposition method).
Laminated by. In general, a P-type semiconductor is formed by 5ixC1 ((0< x <l x =
0.8. ) to a thickness of about 100 mm. As a type 2 semiconductor, silicon doped with hydrogen or fluorine was formed to a thickness of about 0.5 by PCVD of silane or 5iF.At this time, the oxygen in the silicon was
m'J), preferably 5λ10cm. Further, a silane obtained by diluting an N-type semiconductor 10 to 20 times with hydrogen was mixed with phosphin by the PCVD method.

As a result, it becomes microcrystalline, which not only reduces its light absorption properties but also increases its electrical conductivity ')'''>10
(fLcm) can be obtained. This N-type silicon is 10
It is very important to have a thickness of 0-200/l and to be polycrystalline so that no light is absorbed in this region.

Next, ITO is removed by electron beam evaporation or CVD.
．． 1~0. P is generally formed to a thickness of o,'2/14. In order to increase the open-circuit voltage, in the present invention, the P-type semiconductor, here 5ixC74, is brought into close contact with the tin oxide CTFI, and the N-type non-single crystal semiconductor (here, microcrystalline silicon) is made of CrF2. It was brought into close contact with indium oxide or ITO. After a long time, it was possible to obtain an open circuit voltage of 0.92V with one element. If this combination was reversed, only 0.78VL could be obtained.

Thus, Figure 3(A) was obtained.

Next, the procedure was as shown in FIG. 3(B). That is, in the drawing, a heat-meltable and translucent filler was placed on the element (6). PVB (polyvinyl butyral) was used as this filler. That is, since powdered baking soda was sprinkled on the surface of this PVB at room temperature, it was first washed with water to remove this baking soda (bicarbonate trine), and then thoroughly dried. This was done at 20-25°C. Next this PV
The B foil was arranged in the shape of an element (6). Further, a glass plate (8), which is a light-transmitting insulating substrate, was disposed on the upper surface thereof.

In this way, Figure 3 (B) was obtained.

Furthermore, these were placed in an autoclave furnace, and the inside of this crepe furnace was evacuated.

Then, the air between this element and the PVB and between the PVB and the second glass substrate was removed, that is, deaerated.

Thereafter, the heated air is heated in the crepe oven to 100 to 170'C, generally 120 to 150'C, and a pressure of 7 to 12 atm/atm, for example, 10 atm/C, is applied to the heated air inside the crepe oven. This was achieved by filling the

In this way, the PVB is melted and the whole is integrated as shown in Figure 3 (C
) was obtained.

That is, this light-transmitting filling material has an insulating property, and is filled on the back side where the photoelectric conversion element is installed. Therefore, this PVB did not deteriorate due to irradiation with ultraviolet rays, etc., and was able to have optical reliability.

Furthermore, due to the presence of PVB of 9, there is no reduction in conversion efficiency as a photoelectric conversion device, and it is simply resistant to wind pressure, rain pressure,
It has a major feature of being useful for improving reliability such as humidity resistance. That is, the present invention improves the manufacturing yield by providing the PVB on the back side of the photoelectric conversion element, rather than on the light irradiation side, which is most sensitive to the characteristics.

As is clear from the drawing, the element (6) has a transparent substrate made of glass (inorganic material) on the irradiation light side, and is covered with glass (R1fA-free material) on the back side, so it has a so-called laminated glass structure. Inside the device, elements are provided in close contact with one of the substrates in a composite arrangement.

By adopting such a structure, it was possible to have an ideal structure in which moisture and the like do not enter into the interior, and furthermore, there is no reaction between the semiconductor (3) and the metal.

Examples of the present invention will be added below to supplement the content.

Example 1 FIG. 2 is a longitudinal sectional view of an embodiment of the invention.

In the drawing, the glass substrate has dimensions of 20 cm x 60 cm. One element has a size of 15 mm x 20 cm and has a 40-stage series connection structure.

The comparison of conversion efficiency is as follows.

Conventional example Present invention 1 Present invention 2 Present invention 3 Open circuit voltage (V)
0.82 0.9j 32 32 Short circuit current (mA/cm) 13.1 15.2 336
340 Fill factor (%) 58 65
54' 54 efficiency (%) 6.3 9.
0 4.84 4.9011Ts (hours)
3 >1000 >1000 >11
000HU (hour) ~200~200 ~200
> 1000 In the table above, the conventional example has the structure shown in Figure 1 and has an area of 3mm x 3cm (Icmt)
This is the structure when . The present invention 1 has the structure shown in FIG. 3(A), in which the back electrode is CTF2 and is made of ITO. Yes, the area is 3mm x 3cm (Ic
mt). The present invention 2 has the structure shown in FIG. 2, and has characteristics when 40 stages are connected in series on a 20 cm x 60 cm substrate, and the filler (7) and back surface protector (8) are not provided. Furthermore, the efficiency is ΔM
1 (100 mW/cm). Further, IITs indicates the time until the efficiency changes by 10% or more from the initial value in a high temperature storage test at 150'C in the atmosphere. Also +1U11 is 65°cRn9o
It shows the time required to show an efficiency change of 10% or more in a humidity test in an atmosphere of 10%.

As is clear from the above results, by using CTF2 on the back side, the efficiency could be improved from 6.3% in the conventional example to 9%.

As described above, the first and second electrodes of the present invention are formed using CTF.
By doing so, in addition to being able to improve efficiency, it was also possible to have stable characteristics for over 1000 hours in HTS, whereas the conventional example had characteristics for only 3 hours.

Furthermore, when the present invention was applied to a composite cell as shown in FIG. 2, an effective conversion efficiency of 4.84% and a voltage of 32V were obtained. Even in HTS, 100
However, [(IIM is still around 20
It turned out that 0 hours was still not enough.

For this reason, if the device is made to have a Zandwisochi structure using PVB and a glass substrate on the back side, and (, 7) and (8) in FIG.
90%, which is approximately the same as Invention 2, but the optical axis property could be maintained for more than 1000 hours in IIUM.

Due to the laminated glass structure, it is even more resistant to wind pressure (50 m).
The structure shown in FIG. 2 of the present invention was able to have the highest reliability even in the case of wind speed of 1-1 rain pressure test (1-1 rain pressure test).

In addition, in the embodiment of the present invention, the conventional example has a conversion efficiency of 6.3.
%, but this suggests that other means such as glass-CT
If it is possible to improve the characteristics by 8 to 10% by making the F interface Tescutia to reduce the reflection of light on the incident light side, the characteristics can be similarly improved in Invention L2 and 3 in Example 1. Needless to say, it is possible to achieve this.

Further, in the present invention, the case where one PIN junction is mainly shown is shown. But this is PINPIN...P
It is sufficient to make only one IN junction and one PN or PIN junction, and from this point of view, it has been found that the present invention has an extremely important feature that will further promote commercialization as a photoelectric conversion device panel. did.

In addition, for example, four 20cm x 60cm NEDO standard panels of 40cm x 7120cm, and 20cm
x 40cm x 6 pieces, 20cm x 20cm x 12 pieces, 4
It is possible to frame aluminum sash etc. by combining three pieces of 0cm x 40cm.

[Brief explanation of the drawing]

FIG. 1 shows a longitudinal cross-sectional view of a conventional photoelectric conversion device. Figure 2 shows the composite integrated patent applicant manufactured by the method of the present invention.

Claims (1)

[Scope of Claims] 1. A first light-transmitting insulating substrate, a first electrode that applies Th' to a light-transmitting conductive film on the substrate, and generating a photovoltaic force by irradiating light on the electrode. at least one PN or PI that occurs
A step of forming a non-single-crystal semiconductor forming an N-junction and a second electrode made of a transparent conductive film on the semiconductor, arranging a transparent heat-meltable filling layer, and further comprising forming the filling material. The method includes a step of forming a second light-transmitting substrate thereon, and a step of melting and integrating the filler by applying heat and pressure after degassing by evacuation. A method for manufacturing a photoelectric conversion device characterized by: 2. In claim 1, the first and second transparent substrates are made of glass, and the heat-melted filler is made of PV.
B (monovinyl fluoride, also known as Tetra), heated to 120-150°C, 8-12 atm/c
A method for manufacturing a photoelectric conversion device, characterized in that a pressure of 100 m” is applied.A photoelectric conversion device.