JPH06112514A - Manufacture of photoelectric conversion semiconductor device - Google Patents

Abstract

PURPOSE:To sharply reduce the occurrence of leakage and short-circuiting at a connecting section forming the serial connection of photoelectric conversion devices to be manufactured by laser scribing by separating an opened groove formed on the surface of a non-single-crystal semiconductor from another opened groove formed in the surface of a conductive film on a substrate by a specific distance or longer. CONSTITUTION:A photoelectric conversion device in which a plurality of photoelectric conversion elements are electrically connected in series on an insulating substrate 1 is provided with a first conductive film 2 formed in the substrate 1 and first opened groove 13 for making the film 2 to be constituted as the first electrode of each photoelectric conversion element. In addition, the photoelectric conversion device is also provided with a non-single-crystal semiconductor 3 which coats the film 2 and has a PIN junction, second opened groove 18 for making the semiconductor 3 to be constituted as the semiconductor of each photoelectric conversion element, second conductive film 4 on the semiconductor 3, and third opened groove 20 for making the film 4 to be constituted as the second electrode of each photoelectric conversion element. The second groove 18 is separated from the side face of the first groove 13 by >=30mum.

Description

Detailed Description of the Invention

The present invention relates to a photoelectric conversion element (also simply referred to as an element) in which a non-single crystal semiconductor including an amorphous semiconductor having at least one junction capable of generating a photoelectromotive force by light irradiation is provided on a translucent insulating substrate. The present invention relates to a method for manufacturing a photoelectric conversion device in which a plurality of cells are electrically connected in series to generate a high voltage.

The present invention relates to a method of manufacturing a connecting portion which connects two elements by using a laser scribing method (hereinafter referred to as LS) in a maskless process.

The layout, size and shape of the elements in the device of the present invention are determined by design specifications. However, in order to simplify the content of the present invention, in the following detailed description, the first electrode on the lower side (substrate side) of the first element and the second electrode of the second element arranged on the right side of the first electrode will be described. It is described based on the case where the electrode (on the semiconductor, that is, the side away from the substrate) is electrically connected in series.

In such a structure, the second open groove for connecting the first element and the second element is the transparent electrode which is the first electrode of the first element while removing the non-single-crystal semiconductor. The photoconductive film (hereinafter referred to as CTF) was produced without being removed by LS. As a result, the conductive film forming the second electrode of the second element is extended and brought into contact with the upper surface of the first electrode of the first element to form the connecting portion.

The present invention provides heat resistance on the upper surface of a non-single crystal semiconductor,
When a conductor having a low thermal conductivity, for example, a metal containing chromium as a main component or an insulator such as silicon nitride is provided and the semiconductor thereunder is selectively removed by LS, CTF is used.
Is a connection part of a photoelectric conversion device manufactured by utilizing the fact that it can be manufactured without any damage.

In the photoelectric conversion device of the present invention, particularly in the thin film photoelectric conversion device, the conductive layers for electrodes, which are thin film layers, and the semiconductor layers are both 500 Å to 1 μm,
It is 0.2 to 1.0 μm thin, and it has been found that it is possible to manufacture by an automatic mask alignment mechanism of a computer control system by using the LS system.

As a result, instead of the conventional mask aligning process, the present invention is a maskless process which does not use a mask at all, which is extremely simple and highly accurate, and leads to a reduction in the manufacturing cost of the device. An object of the present invention is to provide an extremely epoch-making photoelectric conversion device in which W can be manufactured, and the expansion of the manufacturing scale enables 100 to 200 yen / W.

The details of the present invention will be described below with reference to the drawings.
FIG. 1 is a vertical sectional view showing a manufacturing process of the present invention. Translucent substrate having insulating surface in the drawing (1) For example, glass plate (eg, thickness 0.6 to 2.2 mm, eg 1.2 mm, length [left and right in the drawing] 60 cm, width 20 cm) translucent organic resin or resin A composite organic resin having a silicon nitride film formed to a thickness of 300 to 2000 Å was used. Further, a transparent conductive film such as ITO (a mixture of indium oxide and tin oxide, that is, a film in which 10% by weight of tin oxide is added to indium oxide) (about 1500Å) + SnO ₂ (200 to 400Å) or A transparent conductive film (1500 to 20000Å) containing tin oxide as a main component, to which a halogen element such as fluorine was added, was formed by a vacuum deposition method, an LPCVD method, a plasma CVD method or a spray method.

After that, a YAG laser beam machine (manufactured by Nippon Laser Co., Ltd., wavelength 1.06 μm or 0.58 μm) outputs 1-3 W.
(Focal length 40 mm) was added, and a spot diameter of 20 to 70 μm, typically 50 μφ, was controlled by a microcomputer.
Further, the irradiation laser light is scanned to form the first open groove (13) which is a scribe line, and the inter-element region (3
A first electrode (2) was prepared on (1) and (11).

The first open groove (13) formed by the first LS has a width of about 50 μm and a length of 20 cm, and the electrodes of the first CTF are completely cut to electrically separate the electrodes. After this, a known plasma CV is formed on the upper surface of the groove (13) of the electrode (2).
A non-single crystal semiconductor layer (3) for generating a photoelectromotive force by light irradiation was formed by D method or photo CVD method to a thickness of 0.2 to 1.0 μm, typically 0.5 μm. A typical example is a P-type semiconductor (Si _x C _1-x x = 0.8 about 100 Å) -I-type amorphous or semi-amorphous silicon semiconductor (about 0.5
μm) -Semiconductor silicon having N-type microcrystals (about 500 Å), and Si _x C _1-x x = 0.9 about 50 Å stacked on the silicon, or a non-single-crystal semiconductor having one PIN junction, or P
Type semiconductor (Si _x C _1-x ) -I type, N type, P type Si semiconductor-I type Si _x Ge _1-x semiconductor _- T type tandem having one PN junction composed of N type Si semiconductor Type PINPIN ... PIN junction semiconductor (3). The non-single-crystal semiconductor (3) was formed with a uniform film thickness over the entire surface, covering all of the first electrode and the trench.

Further, a film containing chromium as a main component (hereinafter referred to as chromium) (C) was formed on the upper surface of the semiconductor by an electron beam vapor deposition method to a thickness of 300 to 4000 Å. This chromium is a typical example of one that is sublimable and has a low thermal conductivity among metals. Further, make ohmic contact with the semiconductor, and add room temperature to 150
Since it is stable at high temperatures of ℃ for long-term use, it does not deteriorate at the electrode-semiconductor interface.

Next, as shown in FIG. 1B, the first
The second groove over the left side (first element side) of the open groove (13) of
The open groove (18) was formed by the second LS process. This second groove is formed from the side surface (16) of the first electrode of the second element (11).
It is only required to be on the left side of 30 μm or more, and it is shifted to the first element side of 30 to 200 μm. That is, it is characterized in that it is provided over the position of the first electrode of the first element, and a part (9) of the first electrode is left so as to give a manufacturing margin. In such a structure, that is, in CTF (2)-semiconductor (3)-chromium, the semiconductor containing silicon as a main component has sublimation property, and chromium on this has heat resistance and oxidation resistance. In addition, since the reflected light with respect to the laser light is small, the irradiation light can raise the temperature of the chromium itself and the semiconductor therebelow to a sufficiently high temperature. In addition, since the heat conductivity is low, this heat may be laterally propagated and dissipated, and silicon in the irradiation portion is vaporized to a temperature equal to or higher than the vaporization temperature and splashes outwardly. At this time, CTF, which is less likely to be vaporized than silicon, remains as it is by exposing the surface thereunder. In addition, this backside is exposed due to the heat of vaporization of silicon vaporization.
(8) The CTF was not altered by the temperature. Thus, as shown in FIG. 1, the upper surface (8) of the CTF (2)
It became possible to expose.

Thus, the second open groove (18) was formed in the inside (9) of the first electrode (37) of the first element (31) as shown in FIG. 1 (B). In this drawing, the first and second
The centers of the open grooves (13) and (18) are shifted by 100 μm. Thus the second groove (18) exposed the upper surface (8) of the first electrode. Of course, it is also possible to expose the CTF to the side surface or the side surface and the upper surface end portion with a width of 1 to 5 μm by increasing the average output in the LS and removing the CTF. Furthermore, dilute hydrofluoric acid (48%
1/10 HF, which is obtained by diluting HF with 10 times water, is used here) for 10 seconds to 1 minute, typically 30 seconds for ultrasonic wave may be applied for etching.

That is, as is conventionally known, when LS is performed without simply forming any heat-resistant material on the semiconductor, oxygen in the atmosphere reacts with silicon, and the surface of the CTF is A good contact cannot be made, because the mixture of CTF and the compound of lower silicon oxide makes it insulating. However, the present invention has been found out experimentally. When a heat-resistant non-oxidizing material such as chromium having a high heat insulating property and a low thermal conductivity is formed on this semiconductor, a chemical reaction by LS occurs. It did not occur between silicon and CTF, and it was found that it is possible to selectively vaporize only silicon by heat depending on the conditions.

Therefore, the upper surface of the CTF can be made to have conductivity without any damage. In addition, in FIG. 1, this chrome was left as it was, and a part of the second electrode was formed. Further, as shown in FIG. 1C, a second electrode (6) and a connecting portion (connector) (30) on the back surface were formed on the upper surface. Conductive oxide films (hereinafter referred to as CO) (45) and (45 ') were formed as the conductors forming the connecting portion. As this CO (7), here, a mixture (45) containing ITO (indium oxide tin oxide as a main component) was formed. It is also possible to form indium oxide as a main component as this CO.
If TO is formed to a thickness of 500 to 3000Å, for example 1500Å, by electron beam evaporation, CVD, or PCVD, a wraparound is more likely to occur during film formation than other metals. For this reason, the CTF is sufficiently inserted into the second groove (18),
It was possible to form a contact structure by making good electrical connection with the bottom surface (8) of (37). That is, since the conductor which constitutes the connector (30) constitutes a compound as an oxide from the beginning, CO does not migrate through the connecting portion in the semiconductor (3), and the CTF (37) and CO It was possible to provide high reliability without producing an insulator at the interface with (30) due to the oxidation reaction. Nickel 100-1000 on this CO
It is effective to vacuum-deposit to a thickness of Å to promote external connection.

In an embodiment of the present invention, a reflective metal such as silver or aluminum is used at the interface with the semiconductor under the chromium.
It was effective to reduce the thickness to 500 Å to improve the conversion efficiency of the photoelectric conversion device. Next, in the present invention, in order to form this second electrode, the third groove (20) is formed.
Over the first element region (31). That is, the laser beam (20 to 100 μmφ, typically 50 μmφ) is separated from the second open groove (18) by electrical separation between the electrodes (39) and (38) where the open circuit voltage of the first element is generated. The layers were formed with a spacing of 50μ. That is, the center of the third groove (20) is provided at a depth of 30 to 200 μm, typically 100 μm, over the first element side as compared with the center of the second groove (30). Second electrode (4)
Shows the case where the open groove (20) is formed by irradiating the third LS laser beam from above and cutting and separating. In the third groove as well, since the heat energy applied to silicon is trapped by the heat-resistant conductor chromium (46), all the semiconductor is removed at the same time when the second groove is formed, and the surface of the first electrode is removed. Is exposed. At this time, since the vaporization of silicon is performed so as to burst, the periphery of the third trench on the semiconductor side becomes polycrystalline and the element (31) can be normally formed without causing a short circuit. As exposure of this semiconductor, it is effective to oxidize the side surface and passivate it. Thus, as shown in FIG. 1C, a photoelectric conversion device in which a plurality of elements (31) and (11) are connected in series at the connecting portion (12) can be manufactured.

FIG. 1D shows the photoelectric conversion device of the present invention completed, that is, a silicon nitride film 21 is formed as a passivation film by a plasma vapor phase method.
A uniform thickness of 0 to 2000Å was formed to further prevent the generation of leak current between each element due to adsorption of moisture.

Further, an external lead terminal is provided at the peripheral portion (5). These were filled with an organic resin (22) such as polyimide, polyamide, Kapton or epoxy. Thus, the photoelectromotive force generated by the irradiation light (10) flows from the bottom contact to the second electrode of the second element from the first electrode of the first element as shown by the arrow (32), and can be connected in series. did it.
And if the segment has a conversion efficiency of 10.3% (1.05 cm), it is 8.6% (theoretically) on a 10 cm x 10 cm panel.
Although it was 9.4%, the effective conversion efficiency decreased due to the resistance of 12-stage connection) (AMl [100 mW / cm ² ]), and it was possible to have an output power of 0.83 W. Furthermore, when this panel is subjected to a high temperature storage test of 150 ° C, it will be 10% after 1000 hours.
For example, with 20 panels, the worst was 4% and X = 1.5%. This was a surprising value, considering that when the reliability test is performed under the same conditions using the conventional mask method, the number of inoperable panels reaches 16 in 10 hours.

FIG. 2 shows a method of manufacturing another photoelectric conversion device of the present invention. The process is abbreviated in correspondence with FIG. Figure 2
In (A), the CTF (2) first open groove on the substrate (1),
Further, a non-single crystal semiconductor was manufactured by a method similar to that in FIG. Next, in FIG. 1 (A), a material for accumulating the heat of laser light, that is, a material having a low thermal conductivity and hardly reacting with a semiconductor was formed as a coating film (4) on this upper surface. Coating (4)
In the conductor, a metal containing chromium as a main component is used as an electron beam.
In the vapor deposition method and the insulator, silicon nitride was formed by the plasma vapor phase method. Further, as in FIG. 1 (B), a second open groove (18) was formed by LS to expose the surface (8) of the first electrode (37). In addition, the coating film (4) as shown in FIG. 2 (B) was removed by the etching method. The etching of chromium was carried out with a mixed solution of nitric acid, second ceramium, ammonium and perchloric acid and water, and the etching of silicon nitride was carried out with hot phosphoric acid. Thus, FIG. 2B was obtained.

Further, conductive oxides (45) and (45 ') were formed as a second electrode on this upper surface by an electron beam evaporation method of ITO. Further, metals (46) and (46 ') containing chromium as a main component were prepared. Instead of chromium, a reflective metal such as aluminum or silver, which is more conductive than chromium, may be formed on the upper surface as a silicon nitride insulating film. After that, FIG.
A third open groove as shown in (C) was formed. Then, the vicinity of the third open groove (20) could be selectively removed without damaging the semiconductor. In addition, this surface thinly oxidizes the upper part of the trench of the semiconductor, and the oxidation enables passivation of the insulator (34).

2D, the drawing shown in FIG. 1D and the silicon nitride film for passivation and the coating insulating film (22) were prepared. Also, this panel, for example, 40 cm x 60
cm or 60cm x 20cm, 40cm x 120cm are packaged by combining 2 pieces, 4 pieces or 1 piece in an aluminum sash or carbon fiber frame, and a 120cm x 40cm NEDO standard high power panel can be provided. Is. Further, in this NEDO standard panel, a fluorine-based protective film is attached to the reflection surface side (upper side in the drawing) of the photoelectric conversion device of the present invention by seaflex to increase mechanical strength against wind pressure, rain, etc. Is also effective.

Embodiment 1 This embodiment will be described with reference to the drawing of FIG. That is, a transparent substrate
(1) Chemically tempered glass thickness 1.1 mm, length 10 cm, width 10
cm was used. On top of that, a textured CTF (having a fiber structure) is added to ITO 1600Å + SnO ₂ 300 Å
Was manufactured by an electron beam evaporation method. After that, the first open groove was manufactured at a scanning speed of 3 m / min by controlling a YAG laser having a spot diameter of 50 μm and an output of 1 W by a microcomputer. Laser light output from the edge of the panel
At 1 W, the first electrode semiconductor was scanned in a rectangle 1.5 mm inside the glass edge (corresponding to FIG. 1 (13 ')) to prevent electrical short circuit between the panel frame and the device. Element area (31), (11) is 8mm
Width After that, a non-single crystal semiconductor having one PIN junction shown in FIG. 2 was manufactured by a known PCVD method. Its thickness was about 0.6 μm. Furthermore, chromium (4) was prepared by electron beam evaporation to a thickness of 3000Å. After that, the first element (31) is shifted by 100 μm from the first groove, and the second groove (18) is formed by LS in the atmosphere at an output of 1 W with a spot diameter of 50 μmφ as shown in FIG. It was prepared as shown in B). Further, soak the whole substrate in 1/10 HF for 30 seconds,
The oxide insulator in the groove was removed to expose the surface (8) of CTF. Further, ITO was used as CO on the whole by electron beam vapor deposition to form an average film thickness of 1050Å by electron beam vapor deposition, and part of the second electrodes (38), (39) (45), (4)
5 ') was formed and in addition the connector (30) was constructed.

Further, the third open groove (20) is similarly provided with the third LS.
To the depth of 100 μm from the second groove (18)
2C was formed by shifting to the element (31) side of FIG. The output of the laser light was 1 W, and the other conditions were the same as those for producing the second groove. After this, passivation film (21) is
A silicon nitride film was formed by the CVD method to a thickness of 1000Å at a temperature of 200 ° C. Then, 12 layers of elements were connected to a 10 cm x 10 cm panel, and an effective area of 88% could be made. The effective efficiency of the panel is 8.6% at AMl (100mW / cm ² ),
We were able to obtain an output of 0.83W.

As the transparent substrate (1) of the present invention, a transparent organic resin such as Smirato 1100 manufactured by Sumitomo Bakelite Co., Ltd.
In addition, by stacking the protective organic resin (22) on the upper side as well, it is possible to have a structure in which the photoelectric conversion device is sandwiched between the organic resin sheets, and it has flexibility, is extremely inexpensive, and is mass-produced. Became possible. The second open groove in the present invention removes the metal of the non-single crystal semiconductor. However, it is not possible to form a part of the hole or leave the semiconductor in the peripheral part of the panel and form an open groove only inside so as to prevent a short circuit between the elements in the peripheral part of the connecting part. It is valid.

In FIGS. 1 and 2, light is incident from the lower transparent insulating substrate. However, in the present invention, the light incident side is not limited to the lower side, and it is possible to perform light irradiation from the upper side using ITO for the upper electrode, and the substrate is not a glass substrate but a flexible light-transmitting organic resin. It is possible to use a substrate.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view showing a manufacturing process of a photoelectric conversion device of the present invention.

FIG. 2 is a vertical cross-sectional view showing a manufacturing process of the photoelectric conversion device of the present invention.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 2, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

This invention uses a non-single crystal semiconductor.
And a method for manufacturing a photoelectric conversion device. This invention relates to a photoelectric conversion element (also simply referred to as an element) in which a non-single crystal semiconductor including an amorphous semiconductor having at least one junction capable of generating a photoelectromotive force by light irradiation is provided on a translucent insulating substrate.
The present invention relates to a method for manufacturing a photoelectric conversion device in which a plurality of cells are electrically connected in series to generate a high voltage.

The present invention also relates to a method of manufacturing a connecting portion which connects two elements using a laser scribing method in a maskless process.

[0003]

2. Description of the Related Art Conventionally, photoelectric conversion is performed by laser scribing.
When making a device, change its effective area by increasing it
Grooves formed in the first electrode to improve efficiency
And an opening formed in the semiconductor on the first electrode, or
The groove formed in the semiconductor on the first electrode and the second electrode
The formed grooves have a very small distance between them.
I was there.

However, at such a small interval, the laser beam
If the spot diameter of the
It was easy to grow and was not suitable for mass production.

[0005]

OBJECT OF THE INVENTION The present invention is manufactured by laser scribing.
To provide a method for manufacturing a photoelectric conversion semiconductor device suitable for
With the goal.

[0006]

In order to achieve the above object, the present invention
Is a series of photoelectric conversion elements electrically connected on an insulating substrate.
A photoelectric conversion device arranged in a linked manner, the photoelectric conversion device comprising:
The exchange device includes a first conductive film formed on the insulating substrate.
And connecting the first conductive film to the first conductive film of each of the photoelectric conversion elements.
A first open groove for forming an electrode and P for covering the conductive film
A non-single crystal semiconductor having at least one IN junction;
A semiconductor is each semiconductor of the plurality of photoelectric conversion elements.
And a second trench on the non-single-crystal semiconductor for
And a conductive film, and the conductive film is connected to each of the plurality of photoelectric conversion elements.
And a third groove for forming the second electrode,
The groove is provided at a distance of 30 μm or more from the side surface of the first groove.
It is characterized by being scraped.

The invention of the present application also provides a plurality of photoelectric devices on an insulating substrate.
A photoelectric conversion device in which conversion elements are electrically connected in series and arranged.
A photoelectric conversion device, wherein the photoelectric conversion device is on the insulating substrate.
The formed first conductive film and the first conductive film are
First open groove for forming a first electrode of each of the conversion elements
And has at least one PIN junction covering the conductive film.
And a plurality of photoelectric conversions of the non-single crystal semiconductor
A second groove for forming each semiconductor of the device,
A second conductive film and a plurality of the conductive films on the single crystal semiconductor.
The third electrode for forming the second electrode of each photoelectric conversion element of
An opening, and a center of the third opening and the second opening.
Characterized by a distance of 30 μm or more from the center of
There is.

With the above structure, photoelectric conversion by laser light is performed.
A method for manufacturing a device, comprising a series of photoelectric conversion devices to be manufactured.
Avoid leaks and shorts at the connections that form the connection
It can be drastically reduced, which makes it suitable for mass production.
A photoelectric conversion device could be manufactured. The present invention is described below.
An example is shown.

[0009]

[Embodiment 1] The arrangement, size, and shape of elements in the device of the present invention are determined by design specifications. However, in order to simplify the content of the present invention, in the following detailed description, the first electrode on the lower side (substrate side) of the first element and the second electrode of the second element arranged on the right side of the first electrode will be described. It is described based on the case where the electrode (on the semiconductor, that is, the side away from the substrate) is electrically connected in series.

In such a structure, the second opening for connecting the first element and the second element is the transparent electrode which is the first electrode of the first element while removing the non-single crystal semiconductor. The photoconductive film was produced without being removed by laser scribing . As a result, the upper surface of the first electrode of the first element by extending the conductive film forming the second electrode of the second element allowed contact was allowed constituting the connecting portion.

In a photoelectric conversion device, particularly in a thin film type photoelectric conversion device, the conductive layers for electrodes, which are thin film layers, and the semiconductor layer are respectively 500Å to 1 μm and 0.2 to 1.
0 [mu] m is the thinness, by using a laser scribing method, it is possible to produce an automatic mask alignment mechanism of the computer control system.

The present invention is based on laser scribing.
This is a maskless process that uses no mask, is extremely simple and highly accurate, and reduces the manufacturing cost of the device. Therefore, it is possible to manufacture 500 yen / W.
It is possible to provide an extremely epoch-making photoelectric conversion device in which the production scale can be increased to 100 to 200 yen / W.

In this embodiment , a heat-resistant, low thermal conductivity conductor such as a metal containing chromium as a main component or an insulator such as silicon nitride is provided on the upper surface of a non-single-crystal semiconductor, and this is used as a mask to select the semiconductor below. The connecting portion of the photoelectric conversion device was manufactured by utilizing the fact that the transparent conductive film can be manufactured without any damage when the film is removed by laser scribing .

The present invention will be described in detail below with reference to the drawings.
FIG. 1 is a vertical sectional view showing a manufacturing process of the present invention. Translucent substrate having insulating surface in the drawing (1) For example, glass plate (eg, thickness 0.6 to 2.2 mm, eg 1.2 mm, length [left and right in the drawing] 60 cm, width 20 cm) translucent organic resin or resin A composite organic resin having a silicon nitride film formed to a thickness of 300 to 2000 Å was used. Further, a transparent conductive film such as ITO (a mixture of indium oxide and tin oxide, that is, a film in which 10% by weight of tin oxide is added to indium oxide) (about 1500Å) + SnO ₂ (200 to 400Å) or A transparent conductive film (1500 to 20000Å) containing tin oxide as a main component, to which a halogen element such as fluorine was added, was formed by a vacuum deposition method, an LPCVD method, a plasma CVD method or a spray method.

Thereafter, the output is 1 to 3 W by a YAG laser beam machine (wavelength 1.06 μm or 0.58 μm manufactured by Nippon Laser Co., Ltd.)
(Focal length 40 mm) was added, and a spot diameter of 20 to 70 μm, typically 50 μφ, was controlled by a microcomputer.
Further, the irradiation laser light is scanned to form the first open groove (13) which is a scribe line, and the inter-element region (3
A first electrode (2) was prepared on (1) and (11).

The first open groove (13) formed by this first laser scribing has a width of about 50 μm, a length of 20 cm and a depth of the first.
The extent to which each electrode of the transparent conductive film of
Then, each element was electrically decomposed to form a first electrode.
After that, a non-single crystal semiconductor layer (3) for generating a photoelectromotive force by light irradiation by a known plasma CVD method or a photo CVD method on the upper surface of the groove (13) of the electrode (2) is 0.2 to 1.0 μm typically Was formed to a thickness of 0.5 μm.

A typical example thereof is a P-type semiconductor (Si _x C _1-x x
= 0.8 to about 100 Å) -I-type amorphous or silicon semiconductor (approximately 0.5 [mu] m semi-amorphous) -N-type microcrystalline (about 500 Å) Si _x on the semiconductor silicon Further this with
C _1-x x = 0.9 About 50Å are stacked to form a non-single crystal semiconductor having a single PIN junction or a P-type semiconductor (Si _x C
_1-x ) -I type, N type, P type Si semiconductor-I type Si _x Ge
_1-x semiconductor _- tandem PIN PIN with two PIN junctions and one PN junction made of N-type Si semiconductor
... PIN junction semiconductor (3). The non-single-crystal semiconductor (3) was formed with a uniform film thickness over the entire surface, covering all of the first electrode and the trench.

Further, a film containing chromium as a main component (hereinafter referred to as chromium) (C) was formed on the upper surface of this semiconductor by an electron beam vapor deposition method to a thickness of 300 to 4000 Å. This chromium is a typical example of one that is sublimable and has a low thermal conductivity among metals. Further, make ohmic contact with the semiconductor, and add room temperature to 150
Since it is stable at high temperatures of ℃ for long-term use, it does not deteriorate at the electrode-semiconductor interface.

Next, as shown in FIG. 1B, the first
The second groove over the left side (first element side) of the open groove (13) of
The open groove (18) was formed by the second laser scribing process. This second groove may be on the left side of the side surface (16) of the first electrode of the second element (11) by 30 μm or more, 30 to 200 μm.
m was shifted to the first element side. That is, the first of the first element
It is characterized in that it is provided over the electrode position of, and part of the first electrode (9) is left to give a manufacturing margin. Such a structure, that is, a transparent conductive film (2)
-Semiconductor (3) -In chromium, a semiconductor containing silicon as a main component has sublimation properties, and chromium on this has heat resistance and oxidation resistance. In addition, since the reflected light with respect to the laser light is small, the irradiation light can raise the temperature of the chromium itself and the semiconductor therebelow to a sufficiently high temperature. In addition, since the heat conductivity is low, this heat may be laterally propagated and dissipated, and silicon in the irradiation portion is vaporized to a temperature equal to or higher than the vaporization temperature and splashes outwardly. At this time, the translucent conductive film, which is less likely to be vaporized than silicon, remains as it is by exposing the surface thereunder. In addition, the back surface was exposed (8) by the heat of vaporization of silicon, and the translucent conductive film was not altered by the temperature. Thus, as shown in FIG. 1, the upper surface (8) of the transparent conductive film (2) can be exposed.

Thus, as shown in FIG. 1 (B), the second groove (18) was formed in the inside (9) of the first electrode (37) of the first element (31). In this drawing, the first and second
The centers of the open grooves (13) and (18) are shifted by 100 μm. Thus the second groove (18) exposed the upper surface (8) of the first electrode. Of course, the average output in the laser scribing is increased to remove the transparent conductive film to expose the side surface of the transparent conductive film or the side surface and the end of the upper surface with a width of 1 to 5 μm. It is also possible. Furthermore, this substrate was diluted with diluted hydrofluoric acid (48% HF diluted with 10 times water 1
/ 10 HF was used here) for 10 seconds to 1 minute
It may be etched by applying ultrasonic waves for 30 seconds.

That is, as is well known in the art , the laser scanning is simply performed without forming any heat resistant material on the semiconductor.
When the etching is performed, oxygen in the atmosphere reacts with silicon, and in addition, the surface of the transparent conductive film becomes insulating due to the mixed compound of the transparent conductive film and lower silicon oxide. I can't make good contacts. However, the present invention has been found experimentally, and if a heat-resistant non-oxidizing material such as chromium having a high heat insulating property and low thermal conductivity is formed on this semiconductor, laser scribe < It has been found that a chemical reaction due to silicon does not occur between the silicon and the translucent conductive film, and it is possible to selectively vaporize only silicon by heat depending on the conditions.

Therefore, the upper surface of the translucent conductive film can be rendered electrically conductive without any damage. In addition, in FIG. 1, this chrome was left as it was, and a part of the second electrode was formed. Further, as shown in FIG. 1C, the second electrode on the back surface is formed on the upper surface.
(6) and the connecting part (connector) (30) were formed. A conductive oxide film ( oxide) is used as a conductor forming the connecting portion .
Conductive films ) (45) and (45 ') were formed. This oxide conductive film (7)
As a result, here, a mixture (45) containing ITO (indium oxide tin oxide as a main component) is formed. It is also possible to form indium oxide as a main component as the oxide conductive film . 500 to 3000 Å ITO, for example 1500 Å
If the electron beam evaporation method, the CVD method, or the PCVD method is used to form the film having a thickness of 1, the wraparound is more likely to occur when forming the film, as compared with other metals. For this reason, it is possible to make a contact configuration by sufficiently entering the inside of the second open groove (18) and electrically connecting well with the bottom surface (8) of the transparent conductive film (37). That is, oxidation
Since the conductor forming the connector (30) forms a compound as an oxide from the beginning in the conductive film, the semiconductor (3)
There is no migrating due to the connecting part, and it is transparent.
It was possible to provide high reliability without forming an insulator due to an oxidation reaction at the interface between the photoconductive film (37) and the oxide conductive film (30). 100% nickel is deposited on this conductive oxide film.
It is effective to vacuum-deposit to a thickness of ~ 1000Å to facilitate external connection.

In an embodiment of the present invention, a reflective metal such as silver or aluminum is used in an amount of 50 to 50 at an interface with a semiconductor under chromium.
It was effective to reduce the thickness to 500 Å to improve the conversion efficiency of the photoelectric conversion device. Next, in the present invention, in order to form this second electrode, the third groove (20) is formed.
Over the first element region (31). That is, the laser beam (20 to 100 μmφ, typically 50 μmφ) is separated from the second open groove (18) by electrical separation between the electrodes (39) and (38) where the open circuit voltage of the first element is generated. The layers were formed with a spacing of 50μ. That is, the center of the third groove (20) is provided at a depth of 30 to 200 μm, typically 100 μm, over the first element side as compared with the center of the second groove (30). Second electrode (4)
Shows the case where the open groove (20) is formed by irradiating the laser beam of the third laser scribe from above and cutting and separating.
In the third groove as well, since the heat energy applied to silicon is trapped by the heat-resistant conductor chromium (46), all the semiconductor is removed at the same time when the second groove is formed, and the surface of the first electrode is removed. Is exposed. At this time, since the vaporization of silicon is performed so as to burst, the periphery of the third trench on the semiconductor side is polycrystallized and the element (31) is normally formed without short-circuiting.
It became possible to make. As exposure of this semiconductor, it is effective to oxidize the side surface and passivate it. Thus, as shown in FIG. 1C, a plurality of elements
It was possible to make a photoelectric conversion device in which (31) and (11) were connected in series at the connecting part (12).

FIG. 1D shows the photoelectric conversion device of the present invention completed, that is, a silicon nitride film 21 is formed as a passivation film by a plasma vapor phase method.
A uniform thickness of 0 to 2000Å was formed to further prevent the generation of leak current between each element due to adsorption of moisture.

Further, an external lead terminal is provided at the peripheral portion (5). These were filled with an organic resin (22) such as polyimide, polyamide, Kapton or epoxy. Thus, the photoelectromotive force generated by the irradiation light (10) flows from the bottom contact to the second electrode of the second element from the first electrode of the first element as shown by the arrow (32), and can be connected in series. did it.
And if the segment has a conversion efficiency of 10.3% (1.05 cm), it is 8.6% (theoretically) on a 10 cm x 10 cm panel.
Although it was 9.4%, the effective conversion efficiency decreased due to the resistance of 12-stage connection) (AMl [100 mW / cm ² ]), and it was possible to have an output power of 0.83 W. Furthermore, when this panel is subjected to a high temperature storage test of 150 ° C, it will be 10% after 1000 hours
For example, with 20 panels, the worst was 4% and X = 1.5%. This was a surprising value, considering that when the reliability test is performed under the same conditions using the conventional mask method, the number of inoperable panels reaches 16 in 10 hours.

FIG. 2 shows another method for manufacturing a photoelectric conversion device of the present invention. The process is abbreviated in correspondence with FIG. Figure 2
In (A), a transparent conductive film (2) on a substrate (1), a first groove, and a non-single-crystal semiconductor were prepared by the same method as in FIG. Next, in FIG. 1 (A), a material for accumulating the heat of laser light, that is, a material having a low thermal conductivity and hardly reacting with a semiconductor was formed as a coating film (4) on this upper surface. Film
In the case of (4), a metal containing chromium as a main component was formed by an electron beam evaporation method in the conductor, and silicon nitride was formed in the insulator by a plasma vapor phase method. Similarly to further FIG 1 (B) laser
The second open groove (18) is formed by scribing , and the first electrode
The surface (8) of (37) was exposed. In addition, the coating film (4) as shown in FIG. 2 (B) was removed by the etching method. The etching of chromium was carried out with a mixed solution of nitric acid, second ceramium, ammonium and perchloric acid and water, and the etching of silicon nitride was carried out with hot phosphoric acid. Thus, FIG. 2B was obtained.

Further, conductive oxides (45) and (45 ') were formed as a second electrode on this upper surface by electron beam evaporation of ITO. Further, metals (46) and (46 ') containing chromium as a main component were prepared. Instead of chromium, a reflective metal such as aluminum or silver, which is more conductive than chromium, may be formed on the upper surface as a silicon nitride insulating film. After that, FIG.
A third open groove as shown in (C) was formed. Then, the vicinity of the third open groove (20) could be selectively removed without damaging the semiconductor. In addition, this surface thinly oxidizes the upper part of the trench of the semiconductor, and the oxidation enables passivation of the insulator (34).

2D, the drawing shown in FIG. 1D and the silicon nitride film for passivation and the coating insulating film (22) were prepared. Also, this panel, for example, 40 cm x 60
cm or 60cm x 20cm, 40cm x 120cm are packaged by combining 2 pieces, 4 pieces or 1 piece in an aluminum sash or carbon fiber frame, and a 120cm x 40cm NEDO standard high power panel can be provided. Is. Further, in this NEDO standard panel, a fluorine-based protective film is attached to the reflection surface side (upper side in the drawing) of the photoelectric conversion device of the present invention by seaflex to increase mechanical strength against wind pressure, rain, etc. Is also effective.

[Specific Example] A specific example will be described with reference to FIG. That is, as the translucent substrate (1), chemically strengthened glass with a thickness of 1.1 m
An m 2, a length of 10 cm and a width of 10 cm were used. Further, a light-transmitting conductive film having a texture (having a fiber structure) is further formed thereon.
TO1600Å + SnO ₂ 300Å was prepared by the electron beam evaporation method. After this, the spot diameter of the first groove is 50μ.
A YAG laser with m and output of 1 W was controlled by a microcomputer at a scanning speed of 3 m / min. Furthermore, the edge of the panel is scanned with a laser light output of 1 W in a rectangular shape 1.5 mm inside the glass edge of the semiconductor for the first electrode (Fig. 1 (1
Corresponding to 3 ')) Prevents electrical short circuit between the panel frame and the device. The element regions (31) and (11) were 8 mm wide. After that, a non-single crystal semiconductor having one PIN junction shown in FIG. 2 was manufactured by a known PCVD method. Its thickness was about 0.6 μm. Furthermore, chromium (4) was
It was made to a thickness of 00Å. After this, 100 from the first opening
μm The first element (31) is shifted, and the spot diameter is 50 μm.
A second open groove (18) was produced by laser scribing in the air at an output of 1 W at φ and as shown in FIG. 1 (B). Further, the whole substrate was dipped in 1/10 HF for 30 seconds to remove the oxide insulator in the groove and expose the surface (8) of the transparent conductive film . Further, ITO was formed as an oxide conductive film on the whole by electron beam evaporation method to an average film thickness of 1050Å by electron beam evaporation method, and part of the second electrodes (38), (39) (4
5) and (45 ') were formed, and in addition, the connector (30) was constructed.

Further, the third open groove (20) is similarly provided with a third laser.
By using the scribe , a shift depth of 100 μm from the second open groove (18) toward the first element (31) side is formed, and then, as shown in FIG.
(C) was obtained. The output of the laser light was 1 W, and the other conditions were the same as those for producing the second groove. After that, the passivation film (21) is formed into a silicon nitride film with a thickness of 1000Å by PCVD method.
It was prepared at a temperature of 200 ° C. Then, 12 layers of elements were connected to a 10 cm x 10 cm panel, and an effective area of 88% could be made. The effective efficiency of the panel was 8.6% at AM1 (100 mW / cm ² ), and the output was 0.83 W.

As the transparent substrate (1) in the present invention, a transparent organic resin such as Smirato 1100 manufactured by Sumitomo Bakelite Co., Ltd.
In addition, by stacking the protective organic resin (22) on the upper side as well, it is possible to have a structure in which the photoelectric conversion device is sandwiched between the organic resin sheets, and it has flexibility, is extremely inexpensive, and is mass-produced. Became possible. The second open groove in the present invention removes the metal of the non-single crystal semiconductor. However, it is not possible to form a part of the hole or leave the semiconductor in the peripheral part of the panel and form an open groove only inside so as to prevent a short circuit between the elements in the peripheral part of the connecting part. It is valid.

In FIGS. 1 and 2, light is incident from the lower transparent insulating substrate. However, in the present invention, the light incident side is not limited to the lower side, and it is possible to perform light irradiation from the upper side using ITO for the upper electrode, and the substrate is not a glass substrate but a flexible light-transmitting organic resin. It is possible to use a substrate.

[0033]

According to the present invention, photoelectric conversion by laser light is performed.
Connection part forming a series connection in the fabrication of a semiconductor device
Can significantly reduce leaks and shorts in
To produce a photoelectric conversion device suitable for mass production.
We were able to.

Claims (2)

[Claims] 1. A photoelectric conversion device having a plurality of photoelectric conversion elements electrically connected in series on an insulating substrate, the photoelectric conversion device comprising a first photoelectric conversion device formed on the insulating substrate. Non-single crystal having at least one PIN junction covering the conductive film and a first opening for making the first conductive film the first electrode of each photoelectric conversion element. A semiconductor, a second opening for using the semiconductor as a semiconductor of each of the plurality of photoelectric conversion elements, a second conductive film on the non-single-crystal semiconductor, and the conductive film for the plurality of photoelectric conversion elements. A third groove for providing a second electrode for each of the elements,
The photoelectric conversion device, wherein the second open groove is provided at a distance of 30 μm or more from a side surface of the first open groove. 2. A photoelectric conversion device having a plurality of photoelectric conversion elements electrically connected in series on an insulating substrate, wherein the photoelectric conversion device is a first photoelectric conversion device formed on the insulating substrate. Non-single crystal having at least one PIN junction covering the conductive film and a first opening for making the first conductive film the first electrode of each photoelectric conversion element. A semiconductor, a second opening for using the semiconductor as a semiconductor of each of the plurality of photoelectric conversion elements, a second conductive film on the non-single-crystal semiconductor, and the conductive film for the plurality of photoelectric conversion elements. A third groove for providing a second electrode for each of the elements,
The photoelectric conversion device, wherein the distance between the center of the third groove and the center of the second groove is 30 μm or more.