JPH0566754B2 - - Google Patents

Description

Detailed Description of the Invention The present invention provides a plurality of photoelectric conversion elements (also simply referred to as elements) in which a non-single-crystal semiconductor including an amorphous semiconductor that generates a photovoltaic force upon irradiation with light is provided on a substrate having an insulating surface. A structure and fabrication of a separation groove provided so that the electrical characteristics of the element are not deteriorated by the frame by providing a frame at the end of a photoelectric conversion device that is electrically connected in series and can generate high voltage. Regarding the method.

The present invention is characterized by using a laser scribing (hereinafter referred to as LS) method in order to reduce the area required for connecting multiple elements to 1/10 to 1/100 of the conventional mask alignment method.

This invention shows a structure for manufacturing without using any mask by providing a separation groove with an open groove for the first frame and an open groove for the second frame using the LS method.

In the present invention, the separation grooves are formed in the same process as that of the photoelectric conversion element, that is, without using any extra process.

Furthermore, in the present invention, even if the connection between the aluminum sash and the carbon fiber frame of this photoelectric conversion device is misaligned in the separation groove at the two ends, the characteristics of the element will not deteriorate, and the formation of the ends The feature is that it was manufactured without using any kind of mask.

That is, this invention is a maskless LS method,
The present invention relates to a photoelectric conversion device that makes it possible to more reliably connect an external lead-out electrode part, which is particularly susceptible to reliability deterioration.

In this invention, by using a laser beam scribing method, the address to be scribed is stored in advance in the memory of a computer (microcomputer) using the alignment laser as a reference, which is necessary for the conventional mask alignment method. It is characterized by eliminating at once all causes of price increases and yield decreases in manufacturing, such as mask misalignment, warping, and decreases in manufacturing yields due to alignment accuracy.

Conventionally, many examples of photoelectric conversion devices (hereinafter simply referred to as devices), that is, devices in which a plurality of elements are arranged on the same substrate and are integrated or hybridized, are known.

For example, JP-A No. 55-4994, JP-A No. 55-124274, and Japanese Patent Application No. 54-90097 filed by the present inventor.
90098/90099 (July 16, 1972) is known.

For example, in the patent application filed by the present inventor, the semiconductor is a heterojunction of Si _x C _1-x -Si, which is different from the case where other amorphous silicon semiconductors are simply used, and furthermore, this semiconductor has an amorphous structure. In addition, it is an integrated or hybridized non-single crystal semiconductor having at least one PN or PIN junction to which hydrogen or halogen elements containing a microcrystalline structure are added.

The present invention is achieved without using such an integrated structure as a mask, but during this integration, the manufacturing of the peripheral part of the connecting part with the outer frame, which tends to require extra steps, is the same as the integration process. It is achieved through the process.

Therefore, in the photoelectric conversion device of the present invention, particularly in the thin film type photoelectric conversion device, both the conductive layer for electrodes and the semiconductor layer, which are each thin film layer, are
It has a thickness of 500 Å to 1 μm, and by using a laser scribing method, it has become possible to manufacture it without the need for mask alignment.

In this LS method, 10 to 100 μm, for example 50 μm
It is possible to separate the two regions by a linear groove with a width of . However, in this LS method,
Selective surface removal is extremely unproductive. Furthermore, in the LS method, having a straight line increases productivity, but scanning a curved line in a complicated manner slows down the scanning speed, resulting in an increase in price. For this reason, when creating an integrated structure in the LS method, it is industrially extremely important to achieve this with straight and linear open grooves. The present invention relates to a structure and manufacturing method of a peripheral portion, that is, a side end portion, of a photoelectric conversion device by making full use of such features.

In the present invention, this scribing process is extremely simple and highly accurate due to the combined use of a microcomputer, resulting in a reduction in the manufacturing cost of the device. Therefore, it is possible to manufacture products for 500 yen/W, and by expanding the manufacturing scale, 100 to 200
This is by providing an extremely innovative photoelectric conversion device that enables conversion of yen/W.

Furthermore, in the present invention, in addition to using this laser scribing process, it is important to provide a degree of redundancy (margin) in the alignment accuracy of the scribe lines. Therefore, the first electrode (lower side) between adjacent elements and the second electrode (upper electrode) of the other element are electrically connected to the first electrode and its side surface by the lead extending from the second electrode. By connecting it to the scribe line, it was possible to provide redundancy in the position of the open groove of the scribe line.

FIG. 1 shows a panel 50 of a photoelectric conversion device using the present invention from above. That is, in the drawing, the photoelectric conversion elements 31 and 11 are connected in series via the connecting portion 12 and integrated. Both ends of the external lead electrode are provided at 5.

Separation grooves 62 are provided at the upper and lower ends of the panel to prevent electrical contact with the frame. By specifically providing the separation groove of the present invention, it is possible to precisely define the effective area of the photoelectric conversion device, and furthermore, even if a conductive film exists outside the separation groove (i.e., since no mask is used, the It has now become possible to completely electrically isolate this remaining conductive film (which is generally formed over the entire surface of the substrate) and the device.

In the panel shown in Figure 1, its size is 20cm x
Any size such as 60 cm, 40 cm x 120 cm, 40 cm x 60 cm, etc. can be obtained by design.

The vertical cross-sectional view of (A-A') in Figure 1 is shown in Figure 2.
As shown in the figure. The vertical cross-sectional view of (B-B') is shown in Figure 3
-C') is shown in FIG. 3B.

Further, the structure of the end portion of the present invention is shown in FIG. 4B as a vertical sectional view taken along line (D-D'), and in FIG. 4A as enlarged view E. The numbers correspond to each other.

FIG. 2 shows a longitudinal sectional view of FIG. 1 along line A-A'. That is, it is a longitudinal cross-sectional view showing the manufacturing process of the photoelectric conversion device.

In FIGS. 2 and 4, a substrate having an insulating surface, such as a transparent substrate 1 or a glass plate (for example, a
1.2mm, length (left and right in the drawing) 60cm, width 20cm)
was used. Furthermore, a transparent conductive film such as ITO (approximately 1500 Å) + SnO ₂ (approximately 1500 Å)
A transparent conductive film (1500 to 2000 Å) mainly composed of tin oxide or tin oxide doped with a halogen element was formed by vacuum evaporation, LP CVD, plasma CVD, or spraying. Although this first conductive film is not necessary in the external lead-out electrode portion, patterning using a mask is not performed in order to avoid an increase in manufacturing cost when a mask is used. Therefore, the transparent conductive film CTF is also formed in the peripheral portion 59 in FIG. 1.

After this, a YAG laser processing machine (manufactured by Nippon Laser) is used to output 0.5 to 3W from the bottom or top of this board.
Add output, and the spot diameter is typically 30 to 70μmφ.
A microcomputer is controlled to irradiate 50μmφ, and the scanning creates the opening groove 1 for the scribe line.
3 and 13' were formed to divide each element region and the external lead electrode region. Then, a first electrode was produced.

Open groove 13,1 formed by this first LS
3' had a width of about 50 μm and a length of 20 cm, and the depth was such that each of the first electrodes was completely cut and separated. This length passes through the board from the top end to the bottom end in FIG.

In this way, the external extraction electrode region 5, the first element region 31, and the second element region 11 were constructed. The width of these elements was 10 to 20 mm.

Furthermore, an opening groove for the first frame was made in a direction perpendicular to the first opening grooves 13, 13' as shown at 56 in FIG. Open groove 56 for this first frame
was provided inside the end portion 70 with a width of 1 mm.

After this, plasma CVD method or LP is applied to this upper surface.
CVD method, optical CVD method, optical plasma CVD method, LT
A non-edge crystal semiconductor layer 3 having a PN or PIN junction is formed by CVD method (also called HOMO CVD method) at 0.2
It was formed to a thickness of ~1.0 μm, typically 0.4 to 0.6 μm. A typical example is a P-type semiconductor (Si _x C _1- x
0.850~150Å) 42-I type amorphous or semi-amorphous silicon semiconductor (0.4~0.6μm)
A non-single-crystal semiconductor 3 having one PIN junction made of a semiconductor 44 having 43-N type microcrystals (100 to 200 Å) was formed. This semiconductor consists of two PIN junctions consisting of a P-type semiconductor (Si _x C _1-x ) - type Si semiconductor - N-type Si semiconductor - P-type Si semiconductor - type Si _x Ge _1-x semiconductor - N-type semiconductor, and The semiconductor 3 may be a tandem type PINPIN having two PN junctions...a PIN junction semiconductor 3.

The non-single crystal semiconductor 3 was formed to have a uniform thickness over the entire surface of the first grooves 13 and 13' on the CTF 2 and also on the first frame groove 56. Furthermore, as shown in FIG. 2B, a second open groove 18 is formed on the left side of the first open groove 13 with a width of 50 μm and a width of 100 to 500 μm.
The second LS process was performed over a distance 17 of m. The laser may be applied either from below the glass 1 or from above the substrate.

The second open groove 18 thus exposed the side surfaces 8, 9 of the first electrode. The presence of the right side surface 9 of the first electrode formed by the second groove causes the first electrode of the first element on the left side of the side surface 16 of the first electrode 37 to
It is characterized by being provided over the electrode positions. Then, as shown in FIG. 2B, by entering the inside of the first electrode 31,
The side surfaces 8 and 9 of the first electrode are exposed.
By doing so, the first electrode 37 of the first element
A part of it remains on the right side of the second open groove. If there is no such residual area, the high heat of the laser light (~2000
CTF2 is much easier to process than the CTF2, so the semiconductor filled in the first groove 13 is blown away. Therefore, isolation between the first electrodes of the first and second elements becomes impossible. As a result, as shown in Figure 2B, the second
It is very important that the groove is provided inside the first electrode. The CTF remaining in this portion 9 had a width of 50 to 500 μm. This laser beam is 1~5W, which is a little too strong, so this CTF3
7 in the depth direction, and as a result, there is no practical problem even if the second electrode 38 is brought close to the side surface 8 as shown in FIG. 2C. That is, it is extremely important for the industrial application of the present invention to be able to provide a margin for the intensity of the output pulse of the laser beam.

In FIG. 2, a second electrode 4 on the back surface is further formed on this top surface as shown in FIG. 2C,
Furthermore, a third open groove 20 for cutting and separation was provided by the third LS method.

This second electrode 4 is made of a transparent conductive film with a thickness of 700 to 1400
It is formed of ITO (indium tin oxide) to a thickness of 300 to 3000 Å on its upper surface. Furthermore, a two-layer film of copper, aluminum, or aluminum and nickel was formed on the upper surface. For example, ITO at 1050Å, chromium at 500Å
It has a three-layer structure of 1,000 Å of copper, and 1,500 Å of nickel. This ITO and reflective metal promote reflection of incident light 10 on the back surface side and effectively photoelectrically convert long wavelength light of 600 to 800 nm. Furthermore, nickel is used to improve the adhesion between the pad 49 and the external connector 23 in the external lead electrode portion 5. These were formed using an electron beam evaporation method or a plasma CVD method at a temperature of 300° C. or lower, which does not deteriorate the semiconductor layer 3.

This ITO is also useful for preventing a decrease in reliability due to a chemical reaction between the semiconductor 3 and the back electrode 4, that is, improving reliability.

The back electrode is irradiated with a laser beam from above to cut and separate the second electrode to form a third open groove 20.
(width 50 μm) is shown. This laser light is applied to N or P which is in close contact with the semiconductor, especially the top surface.
By hollowing out the semiconductor layer of the mold 40, generation of crosstalk (leakage current) due to residual metal or conductive semiconductor in the open groove between the adjacent first element 31 and second element 11 was prevented.

In particular, this semiconductor 3 has a P-type semiconductor layer 42, a N-type semiconductor layer 43, an N-type semiconductor layer 44, and, for example, one
When the N-type semiconductor layer has a PIN junction and has a microcrystalline or polycrystalline structure, it has a high electrical conductivity of 1 to 200 (Ωcm) ⁻¹ . For this reason, it is extremely important to hollow out and remove the N-type conductive semiconductor layer and provide an intrinsic semiconductor in the recessed portion to prevent leakage current generation. It is preferable that this gouging does not go beyond the mold semiconductor layer and do not reach the CTF for the first electrode. When the surface of this I layer was oxidized to silicon oxide, the leakage current could be further reduced.

Furthermore, as shown in FIG. 4, an opening groove 57 for the second frame is formed on the end side of the opening groove 56 for the first frame,
A separation groove 62 was formed. It is important that at least the second conductive film 4 is hollowed out in the opening groove for the second frame. The surface may be formed with the same laser output as the third groove in FIG. 2C. However, as shown in FIG. 4B, it is extremely easy to make the semiconductor 3 and the first conductive film 2 below it at the same time.
It has a gap of 50 to 500 μm between the opening groove 56 for the frame,
The CTF 61 was left here to prevent the semiconductor filled in the first groove from scattering by forming it in the second groove.

Thus, as shown in FIG.

At the same time, the external extraction electrode 5 can be manufactured without adding any extra steps, making it possible to match the photoelectric conversion device at low cost using the LS method.

FIG. 2D and FIG. 4B show the present invention further completed as a photoelectric conversion device, that is, a silicon nitride film 21 is formed as a passivation film to a thickness of 500 to 2000 Å by plasma vapor phase method. ,
This prevents leakage current between each element. These were filled with an organic resin 22 such as polyimide, polyamide, Kapton or epoxy.

Thus, for the irradiation light 10, the width of each element on the substrate (60 cm x 20 cm) as in this example is
The effective area (192 mm x 14.35 mm x 40 stages 1102 cm ² , or 91.8%) was obtained by 14.35 mm, the width of the connecting portion 12 of 150 μm, the width of the external extraction electrode portion 5 of 10 mm, and the peripheral portion of 694 mm. As a result, the segment is 10.6
% conversion efficiency, 9.7% at panel
(AM1 (100 mW/cm ² )) was able to provide an output power of 11.6 W.

Furthermore, since no metal mask is used, there is no industrial problem in the manufacturing process of large-area panels, making it extremely suitable for large-area, low-cost mass production for generating large amounts of power.

The spot layer of the YAG laser with more than 3 outputs
~5W (30μm) and 5~8W (50μm), but by further reducing the spot diameter based on the technical concept, this connection part can be made smaller and the effective area as a photoelectric conversion device can be further increased. It has an inventive step in that it can be improved.

FIG. 3 shows the external extraction electrodes 5, 41 of the present invention in a longitudinal sectional view corresponding to FIGS. 1 (B-B') and (C-C').

FIG. 3A shows the structure of the first externally drawn electrode section and corresponds to FIG. 2, but the externally drawn electrode section 5 has a pad 49 that contacts the external connector 47, It is connected to the second electrode (upper electrode) 4 of the adjacent element. At this time, even if the pressure applied to the external connector 47 is too strong and the pad 49 shoots through the semiconductor 3 to the first conductive film 53 underneath, it will not shoot with the first electrode 2 of the adjacent element. An open groove 13' is provided to electrically separate the first pad 49 of the electrode section 5 from the first electrode 2 of the element located next to it. Also, the outer part is the edge of the substrate 1, and the side surface 2 for both conductors and semiconductors.
It is cut and separated by 0'.

Furthermore, FIG. 3B shows the structure of the second external extraction electrode section. This second electrode portion is provided with a pad 48 connected to the side surface 55 of the first electrode 2 under the adjacent photoelectric conversion element at 18' by a second conductive material. Furthermore, the pad 48 is in electrical connection contact with the external connection 46. Here again, the pad 48 is electrically isolated from other photoelectric conversion elements by the opening groove 20'' and the end portion 20, making it possible to create a photoelectric conversion device in one panel without using a matching mask. It has the characteristic of being able to

FIG. 4 is an enlarged view of D-D' and E in FIG. 1 of the present invention.

In FIG. 4A, it has two elements 31, 11 and a connecting part 12. Also in the side end portion 70 and its vicinity, as shown in FIG. 4B,
The CTF 59 and the second conductive film 58 remain.
Therefore, even if these conductors remain, the elements 31,
In addition, even if this conductor 69 remains, this part should be removed from the outer frame 6.
It has a structure that can be fixed at 0. That is, the first conductive film 2 forms an opening 56 for the first frame along the side edge of the substrate. Further, a semiconductor 3 and a second conductive film 4 are formed to cover this first frame groove. Thereafter, an open groove 57 for the second frame is formed across the end side of the open groove 56 for the first frame.
, make this open groove with LS, and connect conductors 2 and 4.
The semiconductor 3 is cut and separated. Then, even if the second conductive film 4 and the first conductive film 61 are shot, the opening between the electrodes 2 and 4 can be prevented by the opening groove 56 for the first frame. Moreover, even when the conductor 69 is pressurized and shot by the frame 60 made of aluminum sash, carbon fiber, etc., the characteristics of the elements 31 and 11 do not deteriorate in any way. That is, the side end portions could be stably mechanically reinforced by the outer frame etc. for the first time due to the separation groove 62 formed by the two frame opening grooves 56 and 57. The outer frame does not cause deterioration of the element, and even if the frame and the photoelectric conversion device are solidified with the resin 63, it has become possible to obtain a sufficiently reliable device.

Furthermore, this panel for example 40cm x 20cm or
A package is made by combining 60cm x 20cm into 6 or 4 pieces in series within a frame, and 120cm x 40
It is possible to install a panel for high power consumption according to the NEDO standard of cm.

In addition, this NEDO standard panel is made by laminating another glass plate using Seaflex on the opposite side (upper side in the drawing) of the photoelectric conversion device of the present invention, and the photoelectric conversion device is placed between them, so that wind pressure, rain, etc. It is also effective to increase mechanical strength.

In FIGS. 1 to 4, light was incident from the lower glass plate. However, the present invention does not limit the light incident side to the lower side.

That is, by using a substrate with a flexible insulating surface, such as anodized aluminum, and using only ITO as the second electrode on the top surface, it is possible to perform electro-optical conversion by incidence from the top surface. shall be.

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1. A first conductive film provided on a substrate having an insulating surface, a non-single crystal semiconductor provided on the conductive film, and a second conductive film provided on the non-single crystal semiconductor. A photoelectric conversion device in which a plurality of photoelectric conversion elements each having a conductive film are connected in series, wherein the first conductive film includes a first frame that electrically isolates only the conductive film from a peripheral portion of the photoelectric conversion device. There is an opening groove for
The first conductive film, the non-single crystal semiconductor, and the second conductive film are electrically connected to the first conductive film, the non-single crystal semiconductor, and the second conductive film from the periphery of the photoelectric conversion device. The opening groove for the second frame to be separated is provided along the opening groove for the first frame and closer to the periphery of the photoelectric conversion device than the opening groove for the first frame. Photoelectric conversion device. 2. A photovoltaic device having a first conductive film provided on a substrate having an insulating surface, a non-single crystal semiconductor provided on the conductive film, and a second conductive film provided on the non-single crystal semiconductor. A method for manufacturing a photoelectric conversion device in which a plurality of conversion elements are connected in series, wherein the first conductive film includes a first frame for electrically isolating only the conductive film from a peripheral portion of the photoelectric conversion device. a step of forming an open groove; and a step of forming an open groove between the first conductive film, the non-single crystal semiconductor, and the second conductive film; A step of forming an opening groove for a second frame to electrically isolate it from the peripheral area along the opening groove for the first frame and closer to the peripheral area of the photoelectric conversion device than the opening groove for the frame. A method for manufacturing a photoelectric conversion device, comprising: