JPH077840B2 - Method for manufacturing photoelectric conversion semiconductor device - Google Patents

Description

The present invention relates to a photoelectric conversion element provided with a non-single crystal semiconductor including an amorphous semiconductor that generates a photoelectromotive force by light irradiation on a substrate having an insulating surface. The present invention relates to a method for manufacturing a photoelectric conversion semiconductor device which is electrically connected in series and can generate a high voltage.

[Conventional technology and its problems]

Conventionally, many examples of a photoelectric conversion device, that is, a device in which a plurality of elements are arranged on the same substrate and integrated or hybridized, are well known.

For example, JP-A-55-4994, JP-A-55-124274, and Japanese Patent Application No. 54-90097 / 9009 filed by the present inventor.
8/90099 (Showa 54.7.16 application) is known.

For example, the patent application for becoming the inventor is a semiconductor SixC _1- x
-Si heterojunction is used, which is different from the case where only other amorphous Si is used. Furthermore, as a semiconductor, at least one PN or PIN junction to which hydrogen or a halogen element containing a microcrystalline structure is added in addition to an amorphous structure is used.
A non-single crystal semiconductor having a junction is integrated or hybridized.

In the above-mentioned conventional technique, the integrated structure is manufactured by using a mask, and there is a problem in productivity and practicability.

Furthermore, during this integration, an extra step was required to manufacture the external extraction electrode of the photoelectric conversion device, and it was difficult to achieve the same step as the integration step of the photoelectric conversion part. In order to improve the drawbacks of the production of the photoelectric conversion device by mask alignment as described, by achieving the external extraction electrode region of the photoelectric conversion device in the same process as the integration process using the production method by the laser scribing method, An object is to obtain a photoelectric conversion device with high productivity and high practicality.

[Structure of Invention]

A method for manufacturing a photoelectric conversion semiconductor device of the present invention is a non-single electrode capable of generating a photovoltaic force by a first electrode formed on a light-transmitting substrate having an insulating surface and light irradiation formed on the first electrode. Method for manufacturing photoelectric conversion semiconductor device in which a plurality of photoelectric conversion elements having a crystalline semiconductor and a second electrode formed on the non-single-crystal semiconductor are electrically connected in series to each other and arranged on the translucent substrate In the step of forming a first conductive film on the translucent substrate having the insulating surface, and forming a groove in the first conductive film by a laser scribing method to form a first electrode of the photoelectric conversion element. And a step of forming an external lead electrode region, a step of forming an opening by a laser scribing method in a side end portion of the first conductive film, the opening being orthogonal to the opening formed in the first conductive film. On the first conductive film, the first conductive film Forming a non-single-crystal semiconductor that generates a photoelectromotive force by light irradiation on the groove formed in the film and on the groove formed orthogonal to the groove formed in the first conductive film; Forming a groove in the single crystal semiconductor and the first conductive film by a laser scribing method in parallel with the groove formed in the first conductive film; and the non-single crystal semiconductor and the first conductive film. A second conductive film is formed in an opening formed in the film to form a connecting portion, and a laser scribing method is performed in parallel to the opening formed in the first conductive film with respect to the second conductive film. Forming a groove to form a second electrode of the photoelectric conversion element and an external connection pad in the external extraction electrode region, the first conductive film, the non-single-crystal semiconductor, and the second conductive film. It was formed on the side edge of the first conductive film with respect to the conductive film. The method for manufacturing a photoelectric conversion semiconductor device characterized by having the steps of forming a open groove by laser scribing in parallel to the groove.

〔Example〕

FIG. 1 shows from above the panel (50) of a photoelectric conversion device using the manufacturing method of the present invention. In FIG. 1, the panel (50) includes a plurality of photoelectric conversion elements (31), (11).
Are connected in series via a connecting portion (12) to be integrated. External lead electrode regions (5) and (45) are provided at both ends.

Separation grooves (62) formed by a laser scribing method described later are provided at the upper and lower ends of the panel (50) so as not to electrically short-circuit with a frame described later with reference to FIG.

The size of the panel (50) in Fig. 1 is 20 cm ×
Any size such as 60 cm, 40 cm × 120 cm, 40 cm × 60 cm can be obtained by design.

Hereinafter, a method for manufacturing the photoelectric conversion device of the present invention will be described with reference to FIGS. 2, 3, and 4.

FIG. 2 shows a vertical sectional view of (A-A ') in FIG. In addition, the vertical cross-sectional view of (BB ') in FIG.
FIG. 3 (B) is a vertical sectional view of the same (CC ') of FIG.
Is shown in. Further, a vertical sectional view of the same (DD ') is shown in FIG.
FIG. 4 (B) is an enlarged view of the location (E) in FIG. 4 (A). Further, the reference numerals are assigned correspondingly.

FIG. 2 is a longitudinal sectional view of FIG. 1 (A-A '), but at the same time shows the manufacturing process of this embodiment. Therefore, to be precise, FIG. 2 (D) corresponds to FIG. 1 (A-
A ') is a longitudinal sectional view.

Hereinafter, a part of the manufacturing process of this embodiment will be described with reference to FIG.

In this embodiment, a glass plate (for example, a thickness of 1.2 mm, a length (horizontal direction in the drawing) 60 cm, and a width 20 cm) which is a transparent substrate (1) having an insulating surface is used as the substrate.

First, a transparent conductive film, for example, ITO (about 1500Å) + SnO ₂ (200), which is the first conductive film (2) forming the first electrode of the photoelectric conversion device, is formed over the entire upper surface of the glass substrate (1).
~ 400 Å) or a transparent conductive film (1500 to 2000 Å) containing tin oxide as a main component to which a halogen element is added was formed by a vacuum deposition method, an LPCVD method, a plasma CVD method or a spray method.

The first conductive film (2) is unnecessary in the external extraction electrode regions (5) and (45), but may be present in order to avoid an increase in manufacturing cost using a mask.

Thus, a transparent conductive film is also formed on the external lead electrode regions (5) and (45).

Then, from below or above the translucent substrate (1),
An output of 0.5 to 3 W was applied by a YAG laser processing machine (manufactured by Nippon Laser). The laser spot diameter was set to 30 to 70 μmφ, typically 50 μmφ by controlling a microcomputer to irradiate the laser beam.

By scanning with this laser light, scribe is performed to form the first open grooves (13) and (13 '), and the photoelectric conversion elements (31),
The space (11) and the external extraction electrode region (5) are divided. Thus, the first electrode (37) was produced.

The first open grooves (13) and (13 ') formed by this first laser scribing have a width of about 50 μm and a length of 20 cm, and the first electrode (37) is completely cut and separated to a depth. I went so I could.

This length was passed from the upper end to the lower end of the substrate (1) in FIG. 1, and the scanning speed for forming the open groove was increased to 5 m / min.

Thus, the external extraction electrode region (5), the first photoelectric conversion element (31) and the second photoelectric conversion element (11) were constituted. The width of these elements was 10 to 20 mm.

Then, plasma CVD is performed on the upper surface of the transparent conductive film (2).
Method, LPCVD method, photo CVD method, LTCVD method (also referred to as HOMO CVD method) to form a non-single crystal semiconductor that generates a photoelectromotive force by light irradiation, especially a non-single crystal semiconductor layer (3) having a PN or PIN junction 0.2-1.0 μm, typically 0.4-0.6 μm
Was formed to a thickness of.

Typical examples of the non-single-crystal semiconductor layer (3) are a P-type semiconductor (42) (SixC _1- x, X = 0.8, 50 to 150Å), an I-type amorphous or semi-amorphous silicon semiconductor (43).
(0.4-0.6μm), N-type microcrystal (100-200Å) or
SixC _1- x (0 <x <1 eg x = 0.9) semiconductors (44)
Is a non-single-crystal semiconductor having a single PIN junction.

Furthermore, as this semiconductor layer, a P-type semiconductor (SixC _1- x),
I-type Si semiconductor, N-type Si semiconductor, P-type Si semiconductor, I-type SixG
A tandem PINPIN ... PIN junction having two PIN junctions made of an e1 _- x semiconductor and an N-type semiconductor and one PN junction may be used.

The non-single crystal semiconductor layer (3) was formed with a uniform film thickness on the entire surface of the transparent conductive film (2) and the first grooves (13) and (13 ').

Further, as shown in FIG. 2 (B), a second open groove (1) is formed over the photoelectric conversion element (31) side of the first open groove (13).
8) was formed by laser scribing over a width of 50 μm over a distance (17) of 100 to 500 μm.

Laser scribing for forming the second open groove (18) was performed by irradiating a laser beam from below or above the glass plate (1) as a substrate.

By the second open groove (18) thus formed,
A structure was obtained in which the side surfaces (8) and (9) of the first electrode (37) were exposed.

The presence of the right side surface (9) of the first electrode formed by the second open groove (18) means that the side surface (1) of the first electrode (37) is
It is provided over the first electrode of the photoelectric conversion element (31) on the left side of 6).

Then, as shown in FIG. 2 (B), by entering the inside of the photoelectric conversion element (31), the side surfaces (8) and (9) of the first electrode are exposed. As a result, a part of the first electrode (37) of the photoelectric conversion element remains on the right side of the second open groove (18). If there is no such remaining region, the semiconductor filled in the first open groove (13) which is much easier to process than the transparent conductive film (2) due to high heat of laser light (up to 2000 ° C.) It blows away. Therefore, isolation between the first electrodes of the photoelectric conversion elements (31) and (11) becomes impossible. As a result, as shown in FIG. 2 (B), the second open groove (18) has the first groove (18).
It is very important that it is installed inside the electrode (37).

The translucent conductive film remaining on the side surface (9) is 50-50.
It had a width of 0 μm. The laser light is too strong at 1 to 5 W to remove all of the transparent conductive film (37) in the depth direction, and as a result, the side surface (8) is shown in FIG. 2 (C). There is no problem in practice even if the second electrode (38) is brought into close contact with each other. That is, it has a feature that a margin can be given to the intensity of the output pulse of the laser light, which is extremely important in industrial application.

In FIG. 2, a translucent conductive film (4) forming a second electrode (38) serving as a back electrode was further formed on the upper surface of the semiconductor layer (3).

Translucent conductive film (4) forming the second electrode (38)
ITO (indium tin oxide) with a thickness of 700-1400Å
Then, a reflective metal such as silver, aluminum or chrome was formed thereon to a thickness of 300 to 3000Å. Further, a two-layer film of aluminum, copper or aluminum and nickel was formed on the upper surface thereof. For example
It has a three-layer structure of 1500 Å ITO, 500 Å chromium, 1000 Å copper, and 1500 Å nickel.

The ITO and chrome are for promoting reflection of incident light (10) on the back side and effectively photoelectrically converting long wavelength light of 600 to 800 nm. Further, nickel is for improving the adhesion between the external connection pad (49) and the external connection body (23) in the external extraction electrode region (5). These were formed at a temperature of 300 ° C. or lower which does not deteriorate the semiconductor layer (3) by using the electron beam evaporation method or the plasma CVD method. This ITO is a semiconductor layer (3) and a second electrode (38)
It is also useful for preventing the deterioration of reliability due to a chemical reaction with, that is, improving reliability.

Then, the translucent conductive film (4) forming the second electrode (38) which is the back surface electrode is cut and separated by irradiating the laser beam from above, and the third open groove (20) having a width of 50 μm. Was formed.

This laser light is applied to the semiconductor, especially N or P which is in close contact with the upper surface.
The type semiconductor layer is dug out as shown by (40), and the residual metal or conductivity in the groove between the first photoelectric conversion element region (31) and the second photoelectric conversion element region (11) adjacent to each other The generation of crosstalk (leakage current) due to the conductive semiconductor was prevented.

For example, the semiconductor (3) has one PIN junction with the P-type semiconductor layer (42), the I-type semiconductor layer (43), and the N-type semiconductor layer (44), and the N-type semiconductor is microcrystalline or polycrystalline. When it has a structure, its electric conductivity has a high value of ¹ to 200 (Ωcm) ⁻¹ .

Therefore, the N-type semiconductor layer is dug out and removed,
It was extremely important to provide an intrinsic semiconductor in the recess to prevent the generation of leak current. Further, when the bottom portion (40) of the I-type semiconductor layer was oxidized to silicon oxide, the leak current could be further reduced. It is preferable that the dug out exceeds the I-type semiconductor layer (43) and does not reach the transparent conductive film (2) for the first electrode (37).

Therefore, not only the second electrode (38) is formed with a groove by laser light, but also the I-type semiconductor layer (4 μm) below the second electrode (38) having a thickness of 0.2 μm or more.
It is important to give a margin for the thickness of 3) to the working process of forming the third open groove (20).

Thus, as shown in FIG. 2 (C), the plurality of photoelectric conversion elements (31) and (11) were connected in series at the connecting portion (12). At the same time, it was possible to obtain a low-cost photoelectric conversion device using laser scribing without adding any extra step to the external extraction electrode region (5).

FIG. 2 (D) shows that this embodiment has been completed as a photoelectric conversion device that can withstand practical use. That is, a silicon nitride film (21) having a thickness of 500 to 5000 Å is formed as a passivation film by a plasma vapor phase method to prevent generation of a leak current between each element. Then, an external lead terminal (23) was further provided in the external lead electrode region (5). Then, a photoelectric conversion device was completed by filling these with an organic resin (22) such as polyimide, polyamide, Kapton or epoxy.

Next, the external extraction electrode region when the photoelectric conversion element and the external extraction electrode region are simultaneously formed will be described.

FIG. 3 shows the external lead electrode regions (5) and (45), and FIG. 3 (A) is a vertical cross-sectional view taken along line (BB ′) of FIG. ) Are vertical sectional views of (C-C ') of FIG. 1, respectively.

The portion shown in FIG. 3 (A) shows the structure of the external extraction electrode region (5) and has the manufacturing process corresponding to FIG.

In FIG. 3 (A), the external extraction electrode region (5)
External connection pad (49) that contacts the external connection body (47)
This external connection pad (49) is connected to the conductive film (4) forming the second electrode of the adjacent photoelectric conversion element (31). At this time, even if the external connection pad (49) is pressed too strongly and the semiconductor (3) penetrates through the first conductive film (53) thereunder, the external connection pad (49) is short-circuited. An open groove (13 ') is provided by laser scribing so as not to short-circuit with the first electrode (37) in the photoelectric conversion element region, and is electrically connected to the external connection pad (49) in the external extraction electrode region (5) and its adjacent area. The photoelectric conversion element (31) located is separated from the first electrode (37).

The outer portion is the end portion of the substrate (1), and the conductor and the semiconductor are cut and separated at the side surface (20 ').

Further, FIG. 3B shows the second extraction electrode region (4
The structure of 5) is shown. This second extraction electrode region (45) is the first electrode (37) below the adjacent photoelectric conversion element.
Connected with.

A non-single crystal semiconductor (3) is formed on the upper surface of the first electrode (37).
Are formed. Further, an opening groove (18 ″) is formed in the same step as the step of forming the second opening groove (18) by laser scribing.
The side surface (55) of the first electrode (37) was exposed. Further, as described in the manufacturing process of FIG. 2, the second conductive film (4) was formed, and at the same time, the pad (48) and the side contact (55) were formed. Thus, the external connection pad (48) is secondly provided on the side surface (55) of the first electrode (37) of the photoelectric conversion element.
And the external connection pad (48) is electrically connected to and connected to the external connection body (46). .
Again, in FIG. 2, the groove (20 ″) formed by the same process as the formation of the third groove (20) formed by laser scribing, the pad (48) is completely different from the edge (20). It is electrically separated from the photoelectric conversion element.

Next, FIG. 4 shows the separation structure of the side end portion, and FIG.
FIG. 4 is an enlarged view of (E) in FIG. 1, and FIG. 4 (B) is an enlarged view of (DD ′) in FIG. 1.

The portion shown in FIG. 4 (A) has two photoelectric conversion elements (31) and (11) and a connecting portion (12).

On the other hand, the conductor (69) such as the transparent conductive film (59) and the second conductive film (58) remains at the side end portion (61) as shown in FIG. 4 (B). Even if these conductors remain, the characteristics of the photoelectric conversion elements (31) and (11) should not be deteriorated, and even if these conductors (69) remain, they should be fixed to the outer frame (60) at this part. It has a structure that allows it. That is, the fourth open groove (56) formed by laser scribing is formed in the first conductive film (2) along the side edge of the substrate (1). Further this fourth open groove (56)
A semiconductor (3) and a second conductive film (4) are formed so as to cover the film. Thereafter, a fifth open groove (57) is provided by laser scribing over the end side of the fourth open groove (56).
The first conductive film (2) and the semiconductor (3) by the open groove (57) of
And the second conductive film (4) is cut. That is, the conductive film (61), the semiconductor (3)
All the conductive films (4) are cut to have the same shape. Then, even if the second conductive film (4) and the conductive film (61) are short-circuited, the fourth open groove (56) of the separation groove (62) causes the first conductive film (2) and the second conductive film (61) to separate. It is possible to prevent a short circuit between the conductive films (4). Further, the carbon fiber frame (60) pressurizes the conductor (69), and even if a short circuit occurs, the photoelectric conversion element (3
1) and (11) have no characteristic deterioration.

That is, since the side end portion has the separation groove (62) formed by the two open grooves (56) and (57), the photoelectric conversion element is not deteriorated by being fixed to the outer frame, and the resin ( Even if the frame (60) and the photoelectric conversion device are fixed in 63), the device can be made sufficiently reliable. Of course, the conductor (69) need not be partially present.

The photoelectric conversion device manufactured by the present invention is a substrate (60 cm x 20 cm)
In, the width of each element area is 14.35 mm, the width of the connecting part is 150 μ
m, width of external extraction electrode area 10 mm, peripheral area 4 mm,
Effective area (192 mm × 14.35 mm × 40 steps) 1102 cm ² or 91.8%
I was able to get As a result, if the segment has a conversion efficiency of 10.6%, 9.7% on the panel (100mW / AMI for AMI)
It was possible to obtain a conversion efficiency of cm ² ) with an output power of 11.6W.

The spot diameter of the YAG laser used for laser scribing is 30 μmφ at an output of 0.3 to 5 W and 50 μmφ at 0.5 to 8 W.
However, by further reducing the spot diameter, the area required for the connecting portion 12 can be further reduced, and the effective area of the photoelectric conversion device can be further improved.

Furthermore, by using a microcomputer together in the scribing step, the manufacturing cost of the device can be reduced, which is extremely simple and highly accurate.

In addition, this panel is also used, for example 40 cm × 20 cm or 60
Packaged by combining 6 or 4 cm x 20 cm in series in an aluminum sash frame, N of 120 cm x 40 cm
It is also possible to make a panel for high power of EDO standard.

In addition, this NEDO standard panel is formed by laminating another glass plate to the reflection side (upper side in the drawing) of the photoelectric conversion device of the present invention by seaflex to form a laminated glass, and the photoelectric conversion device is arranged between them to wind, rain, etc. On the other hand, it is also effective to increase the mechanical strength.

In FIGS. 1 to 4, light is incident on the lower glass plate, but the light incident side is not limited to the lower side.

That is, a substrate having a flexible insulating surface, for example, anodized aluminum is used, and the second upper surface is used.
It is also possible to perform photoelectric conversion by incidence from the upper surface by making the electrode of ITO the transparent conductive film ITO.

〔The invention's effect〕

(1) Since the photoelectric conversion device manufacturing method of the present invention does not use a metal mask at all, there is no industrial hindrance in the manufacturing process of a large-area panel, and a large-area, low-cost integrated photoelectric conversion for generating large power. Very suitable for mass production of equipment.

(2) With respect to the connecting portion between the photoelectric conversion elements of the photoelectric conversion device obtained by the manufacturing method of the present invention, by connecting the second electrode of the photoelectric conversion element adjacent to the side surface of the first electrode, The required area of this connecting part is 1/10 compared to the conventional method
It can be sufficiently reduced to the following, which can help improve the effective area of the panel.

(3) Since the photoelectric conversion device obtained by the manufacturing method of the present invention is further provided with the open groove at the side end portion orthogonal to the first open groove, the photoelectric conversion device can be stably fixed to the outer frame. You can

[Brief description of drawings]

FIG. 1 is a panel of a photoelectric conversion device according to the present invention. FIG. 2 is a vertical sectional view showing a manufacturing process of the photoelectric conversion device of the present invention. 3 and 4 are vertical cross-sectional views showing an enlarged panel of the photoelectric conversion device of FIG. 1 of the present invention.

Claims (1)

[Claims] 1. A first electrode formed on a translucent substrate having an insulating surface, a non-single-crystal semiconductor formed on the first electrode and capable of generating a photoelectromotive force by light irradiation, and the non-single crystal semiconductor. A method for manufacturing a photoelectric conversion semiconductor device, wherein a plurality of photoelectric conversion elements each having a second electrode formed on a crystalline semiconductor are electrically connected in series to each other and arranged on the transparent substrate, wherein the insulating surface is Forming a first conductive film on the translucent substrate, and forming a groove in the first conductive film by a laser scribing method to form a first electrode and an external extraction electrode region of the photoelectric conversion element. Forming a groove on the side edge of the first conductive film by a laser scribing method at right angles to the groove formed on the first conductive film; and forming a groove on the first conductive film. On the opening formed in the first conductive film and Forming a non-single-crystal semiconductor that generates a photoelectromotive force by light irradiation on the groove formed orthogonal to the groove formed in the first conductive film; and the non-single-crystal semiconductor and the first conductive material. Forming a groove in the film in parallel with the groove formed in the first conductive film by a laser scribing method, and forming a groove in the groove formed in the non-single-crystal semiconductor and the first conductive film. A second conductive film is formed to form a connecting portion, and an opening groove is formed in the second conductive film in parallel to the opening formed in the first conductive film by a laser scribing method to form the photoelectric conversion layer. A step of forming a second electrode of the conversion element and an external connection pad in the external lead electrode region; and a step of forming the first conductive film, the non-single-crystal semiconductor, and the second conductive film with respect to the first conductive film. A laser scan is performed parallel to the groove formed on the side edge of the conductive film. The method for manufacturing a photoelectric conversion semiconductor device characterized by having the steps of forming a open groove by law.