JPS6094781A - Manufacture of semiconductor device - Google Patents

Abstract

PURPOSE:To eliminate a damage at all in a thin organic resin film while scribing the first CTF by dividing the CTF via LS into a plurality of element regions, forming the first groove for forming the first electrodes of the elements, and coating the groove and the first electrodes of the elements with a nonsingle crystal semiconductor. CONSTITUTION:A light transmission conductive film is formed on the upper surface of a light transmission substrate 1 of organic resin having insulating surface, a YAG laser is emitted by controlling with a microcomputer to form a scribing groove 13, the first electrode 2 is formed between elements, thereby forming the first element 31 and the second element 11. Then, a nonsingle crystal semiconductor layer 3 having a PN or PIN junction is formed by a plasma CVD method on the upper surface over the first groove 13 and the electrodes of the elements. Thus, the groove 13 is filled with the semiconductor 13, thereby electrically isolating the first electrode 2 of the elements.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a non-single crystal semiconductor (2) comprising an amorphous semiconductor having at least one PIN or PN junction; The present invention relates to a method for manufacturing a photoelectric conversion device capable of generating high voltage by electrically connecting a plurality of photoelectric conversion elements (also simply referred to as elements) provided on a thin film in series.

This invention consists of an organic resin thin film and a transparent conductive film (
When carrying out laser scribing (hereinafter referred to as LS) using CTP, we have experimentally discovered that there are conditions under which the organic resin thin film is not damaged at all while scribing the CTF, and we have utilized this fact. This method is intended to produce semiconductor devices, particularly photoelectric conversion devices.

In this invention, the first CTF is connected to a plurality of elements using LS □
The purpose is to divide the semiconductor into regions, form a first groove for configuring the first electrode of each element, and cover this groove and the first electrode of each element with a non-single crystal semiconductor. .

Furthermore, the second groove for electrically connecting the first and second elements is removed simultaneously with the non-single crystal semiconductor having a PN or PIN junction and the first electrode thereunder (3). The purpose is to connect the conductor of the second electrode of the second element to the side surface of the first electrode of the first element or the upper surface and side surface having 111 of 0.1 to 5 μ at the end of the electrode. .

The use of flexible organic thin films as substrates for inexpensive, mass production of photoelectric conversion devices has been encouraged.

According to the present invention, when a laser beam is irradiated to a transparent OF that allows light irradiation from the OF side and a CTF above it,
When we experimentally investigated the conditions under which the CTF could be removed without damaging or damaging the OF, we found that the laser beam could not be irradiated in one place for a long time (several tens of milliseconds), and that the CTF could be removed without damaging the OF. By optimizing the scanning speed,
It has been found that it is possible to selectively remove only CTP.

That is, due to laser beam irradiation, OF has a low thermal conductivity (generally 1 to 7 XI (1'''4 cal/sec)
/CIA/ ``C/cm) Therefore, if a laser pulse is repeatedly applied to the same position, this organic resin will deteriorate, carbonize, and be cut.However, if this is repeated once or several times, the OF heat Conductivity is 1/1 of CTI'
0:I(4), it has been found that conversely, only the CTF can be selectively removed from the area irradiated with the laser beam.

In this invention, the electrical connection at the connecting portion is
By extending the second electrode of the second element to the side surface of the transparent conductive film (CTF) constituting the electrode, and using the second electrode in close contact with the side surface, the required surface area at the connecting portion is reduced. It is characterized by

For this reason, an opening groove separating the semiconductors of the first and second elements is provided over the first electrode position of the first element, and L
It is characterized by providing manufacturing redundancy (margin) due to fluctuations in the scanning of S.

In manufacturing the photoelectric conversion device of the present invention, particularly a thin film type photoelectric conversion device, each of the thin film layers, the conductive layer for the electrode and the semiconductor layer, each has a thickness of 500 to 1 μm, and a laser scribing method is used. This makes it possible to fabricate without the need for mask alignment at all.

The details of the embodiment will be shown below according to the drawings.

(5) FIG. 1 is a longitudinal sectional view showing the manufacturing process of the present invention.

In the drawings, an organic phase 111-i with an insulating surface, a thin 11Q substrate, for example Sumilite manufactured by Sumitomo Bakelite Co., Ltd. (continuous use temperature 150-300°C, light transmittance 80-92
% (thickness 100μ), thermal conductivity 3-7 X 10'
4Col/sec/ci/'C/clll
) was used as a light-transmitting substrate (1) (for example, thickness 100μ, length in left and right direction in the drawing) 60 cm, 1320 cm). Furthermore, a light-transmitting conductive film such as ITO (approximately 1500) +SnO, (200
~400 people) or a translucent conductive film whose main component is tin oxide added with a halogen element (1500-2000 people)
was formed by a vacuum evaporation method, a plasma CVD method, or a spray method. For example, Sumilite FS 71300 manufactured by Sumitomo Bakelite Co., Ltd. was used as the OF. This OF has a continuous use upper limit temperature of 180℃ and a thermal conductivity of 4.3 xlO', C
al/sec/cJ/℃/cm, light transmittance 86.3
% (with a thickness of 100μ), surface resistivity 5.4 X1
014Ω, volume resistivity 1.7×1016ΩCl11 as a representative example.

ITO was formed on this OF to a thickness of 700 mm by sputtering6). Its sheet resistance then had 200Ω/hole.

After that, a YAG laser processing machine (Nippon Laser W) is used to output 0.5 to 1.5 mm from the upper side of this substrate (1). (1), a spot diameter of 30 to 70 μΦ, typically 50 μΦ, is irradiated under the control of a microcomputer, and by scanning it, an opening groove (13) for a scribe line is formed, and a first electrode (2 ) was created.

That is, a YAG laser (emission wavelength 1.06μ, focal length %lt 50mm, light diameter 50μ) was irradiated here. The conditions are: 6KI (z, average output 1.3W) at the same time repeatedly
, scanning speed (scanning speed, hereinafter referred to as SS) 6
The speed was set at 0 cm/min.

The open groove (13) formed by scribing has a width of about 1
20μ (generally 1 if the diameter of the laser beam is 50μ)
Each of the first electrodes was completely cut and separated by a length of 20 cm and a depth of 0.0 to 150 μm.

The width of the first element (31) and the second element (11) was 10 to 20 mm.

At this time, the range examined using an electron microscope showed that the back surface of the OF7) No damage or local deterioration was observed.

It is estimated that this laser beam has a temperature of 1600℃ or more, but it does not cause any damage to the leaves, which have only a low heat resistance of about 180℃ (i (e.g. t1.3) after continuous use). Ta.

That is, selectively opening the groove (10) with respect to the CTF on the OF,
It was found that (10') can be produced.

Moreover, it was possible to obtain a resistance greater than IMΩ (with a width of 1 cm) between the two probes.

FIG. 2 shows the electrical resistance when the repetition frequency of the laser beam is varied and an open groove is formed.

In the drawings, scan speed (hereinafter referred to as SS)
60cm/min average output 0. Death, light f, ¥i50 It
(7) A YAG laser was used. Then, when the frequency is lowered below 10KIIz, the curve (6) becomes 7Kll.
It has been found that electrical isolation can be performed discontinuously at 1 MΩ or more (6') below z.

However, when this frequency is lower than 4 Kllz, in addition to this CTI', the underlying OF is also affected at its center (Gaussian distribution energy (
8) Damage occurred in the region with the highest density.

As a result, the range shown in (7) was suitable for LS (laser scribing) of CTF on the OF.

Furthermore, CTF can be applied without damaging the underlying OF.
When we investigated the range in which only 30% of the sample was removed, we obtained Figure 3.

That is, SS 0 to 15001117 minutes, average output 0 to 3
W.

Repetition frequency 6K II z, focal length 50cm,
If the laser beam is a YAG laser with a diameter of 50μ, area 1
9, that is, point A.

The areas surrounded by B, C, D, E, and F had no damage to the OF and could be removed using CTF alone.

Further, in region (17), even the CTF could not be removed, and in region (16), the pulsed light was not continuous on the CTF, and only a discontinuous large groove was obtained as shown by the broken line. Area (18) was an area where damage was caused not only to the CTF but also to the underlying OF.

As a result, it was found that there is a region (19) where only CTP can be selectively removed as an open groove (1) without damaging the underlying OF.

(9) Using the above laser scribing method, the CTF (2) constituting the first electrode was cut and separated to form open grooves. A PN layer is formed on the upper surface of the shallow box 1 by plasma CVD or Lll CVII method, covering the grooves of the shallow box 1 and the electrodes of each element.
In addition, the non-single crystal semiconductor layer (3) having a PIN junction is
．． It was formed to a thickness of 2 to 1.0 microns, typically 0.4 to O-577.

In this way, the first trench was filled with a non-single crystal semiconductor, making it possible to electrically isolate the first electrodes of each element.

A typical example of the semiconductor layer (3) is a P-type semiconductor (S1xCl-x
x ~0.850~150 people) = Type I amorphous or semi-amorphous silicon semiconductor (0.4~0.5
μ) - a non-monocrystalline semiconductor with one PIN junction consisting of a semiconductor with N-type microcrystals (100-200);
or P-type semiconductor (SixC+-x) -1 type, N type,
A tandem-type PINFIN having two PIN junctions and one PN junction made of a pzst semiconductor, an I-type 5ixGel-X semiconductor, and an N-type Si semiconductor is a PIN junction semiconductor (3).

(10) Such a non-single crystal semiconductor (3) was formed to have a uniform thickness over the entire surface. Furthermore, as shown in FIG. 1(B), there is a semiconductor on the left side of the first groove (13) and a C below it.
TF and scribe at the same time to make the second open groove (18) 5
A second laser scribing process was performed to form the wafer over a distance of 100 to 500 .mu. within 0 .mu.m.

(Thus, the second open groove (18) exposed the side surfaces (8) and (9) of the first electrode without damaging the surface of the OF.

At this time, as a result of exposing the upper end of the CTF to a width of 0 to 5 μm, the side and upper surfaces of the CTF constitute contacts of the connecting portion. The conditions for forming this second open groove are the same as the conditions for forming the first open groove. That is, the presence of the semiconductor can be substantially ignored, and the characteristics shown in FIGS. 2 and 3 can be used.

What is clear from the drawings <1. It can be seen that the left side surface (8) of the first electrode formed by LS is present. As shown in FIG. 1(B), the first electrode (37
), the side surface of the first electrode (11) may be exposed to (8)t(9).

In this step, the surface (14) of the first electrode (37)
Instead of exposing only the CTF (37), the laser beam was a little too strong at 0.5 to 2 degrees and removed all of this CTF (37) in the depth direction, and as a result, the first
In Figure (C), even if the second electrode (38) is closely connected, the contact resistance is practically small and there is no problem ε11. 1111 It is extremely important in industrial application of the present invention that a margin can be given to the intensity of the output pulse of the laser light.

In FIG. 1, a second electrode (4) on the back surface is further formed on this two surface as shown in FIG. Open t'M (20) was established.

This second electrode (4) has a transparent conductive film of 700 to 14
Formed with ITO (indium tin oxide) to a thickness of 0.00 mm, and then coated with 1:1 μm of 300 to 30 mm on the surface.
It was formed to a thickness of 0.00 people. For example, 1150 people (45) for rTO and 1500 people (46) for chromium.

The two-layer film of ITO (12) and chromium was important to prevent the laser beam applied during the formation of the third groove from scribing the semiconductor surface. These methods do not degrade semiconductor layers using electron beam evaporation or plasma CVD methods3.
It was formed at a temperature below 00°C. External extraction electrode (23
) is selectively coated with nickel using electroless plating.
Improved adhesion there.

This ITO also serves to prevent a decrease in reliability due to a chemical reaction between the semiconductor (3) and the back electrode (4), that is, to improve reliability.

The back electrode is irradiated with a laser beam from above to cut and separate the second electrode, forming a third open groove (20) (50 μm in diameter).
) is formed. When the heat of this laser light is applied to the semiconductor, the amorphous semiconductor becomes polycrystalline, so a two-layer film of ITO-Cr was used to block the laser light. In order to increase the reflection of incident light on the back surface, it may be ITO (1050 people) -Ti (20 people) -Ag (200 people) -Cr (1500 people). Furthermore, the P(13) or N-type semiconductor layer under this trench is left for 1 to 1 week at room temperature to 150°C to oxidize and form an insulator (40), and any residual metal or conductive material in the trench is removed. The occurrence of crosstalk (leakage current) due to magnetic semiconductors has been reduced to 1.

In particular, this semiconductor (3) is a P-type semiconductor layer (42), a 1-type semiconductor layer (43), an N-type semiconductor layer (44) and, for example, 1
This N-type semiconductor layer has a microcrystalline or polycrystalline structure. Its electrical conductivity is 1-200 (
When the conductivity is as high as Ωcm), it is extremely important to prevent pansivation and leakage current by oxidizing the N-type semiconductor layer of the present invention at a temperature of room temperature to 150°C and making it an insulator. Met.

Thus, as shown in FIG. 1(C), a plurality of elements (
We were able to create a photoelectric conversion device in which 31) and <11) were connected in series through a connecting section.

FIG. 1(D) shows an attempt to further complete the present invention as a photoelectric conversion device, that is, a silicon nitride film (21) with a thickness of 500 to
Formed to a thickness of 2000-1, the capacitor (14) prevented the occurrence of premature leakage current. Furthermore, an external lead-out terminal (23) was provided at the peripheral portion (5). These were filled with an organic resin (22) such as polyimide, polyamide, Kapton or epoxy.

Thus, for the irradiation light (10), each element is
．． The effective area (19
2 mm x 14.35 mm x 40 stages 1102C (ie, 91.8%) could be obtained. As a result, if a segment has a conversion efficiency of 9.6%, then 7
．． 8.4 at 9% (AMI (100mW/cJ))
It was possible to have an output power of W.

As is clear from the above embodiments, by cutting and separating using the laser scribing method to form the second electrode according to the present invention, the N- or P-type semiconductor layer under the second electrode is not polycrystallized. , since only the electrode material was removed at the same time, the leakage current between these two electrodes (38>, <39) was less than 10-BmA/cm, and the P- or N-type semiconductor layer was made into an oxide insulator (15). 'A I was able to lower it to 7cm. Therefore, for general consumer use, it has become possible to omit the silicon nitride film coating (21) in FIG. 1(D).

Furthermore, regarding the connection part, since the first electrode is connected to the second electrode of the adjacent element on the side surface, the area required for this connection part (contact part) is sufficiently reduced to 1710 mm or less compared to the conventional method.・L・In turn, this could be useful for increasing the effective area of the panel.

The above is a case where the spot diameter of the YAG laser is used in Somet, but by further reducing the spot 1 yen based on the land 1/tt concept, this connection part can be made smaller, and the effectiveness as a photoelectric conversion device can be further reduced. It has the inventive step of being able to further improve the area.

FIG. 4 is an enlarged view of the external lead electrode section.

FIG. 4(A) corresponds to FIG. 1, but the external extraction electrode part (5) has a pad (48) that touches the external extraction electrode (47) by 1.8 (16), and this band (48) is connected to the second electrode (upper electrode) (4). At this time,
An opening groove (13'>) is provided to prevent a short circuit even if the pressure on the electrode (47) is too strong and the pad (48) penetrates the first electrode (2) and semiconductor (3) below. .Furthermore, in Fig. 4(B), the lower first electrode (2) (81)
Another pad (50) connected at (1B') is provided by a second electrode material. Furthermore, the pad (48) is in contact with the external extraction electrode (46),
Electrically connected to the outside. Open i (20'
) electrically isolates the pad (50) from the adjacent photoelectric conversion device.

Furthermore, by combining three or four panels in series, such as 40cm x 40cm or 60cm x 20cm, in an aluminum sash or carbon fiber frame, it is possible to create a 120cm x 40cm NEDO standard high power panel. be.

As is clear from the above description, in the photoelectric conversion device of the present invention, the substrate on the light incident side is a flexible OF.

(17) For this reason, it has become possible to generate electricity on the wall of a building or on the outside of a building made of concrete instead of the wall. Furthermore, base 4M + AI! Since 1 is inexpensive, it has become possible to manufacture it for 200 to 400 yen/W.

Furthermore, it is also possible to use the present invention as a NEDO standard panel and attach the back side to a translucent glass plate or the like using Seaflex to generate electricity while letting in sunlight.

The OF in the present invention can be made of other organic resin films instead of Sumilite. In particular, in Figures 1 to 2, if the light is incident from above rather than from the lower translucent organic resin, the light transmittance is (1) (Kapton, P
r3T (polyethylene terephtate) polyimide or polyamide resin can also be used. It can be applied in the same way as the present invention. However, in this case, the lower electrode was made of CTF and chromium layered thereon. That is, the second electrode material shown in FIG. 1 is used as the first electrode material,
It was necessary to form a contact between the oxide electrodes at the connecting portion by using the first electrode material as the second electrode material (18).

[Brief explanation of drawings]

FIG. 1 is a longitudinal sectional view showing the manufacturing process of the photoelectric conversion device of the present invention. FIG. 2 shows the characteristics when the transparent conductive film on the organic resin of the present invention is laser scribed. FIG. 3 shows the area where laser scribing is possible when the transparent conductive film on the organic resin of the present invention is laser scribed. FIG. 4 is a longitudinal sectional view showing an enlarged external lead electrode portion of another photoelectric conversion device of the present invention. Patent applicant (19) <')fLL ll3t15 (k) (z)! 20 If, 9 (ij:j

Claims (1)

[Claims] 1. An organic resin thin film having an insulating surface, a first electrode, and at least one PN or l''IN junction on the electrode.
A method for manufacturing a photoelectric conversion device in which a plurality of photoelectric conversion elements each having a non-single crystal semiconductor and a second electrode on the semiconductor are electrically connected in series and disposed on the insulating substrate. By irradiating the light-transmitting conductive film on the resin thin film with laser light to form an open groove on the conductive crotch without damaging the organic resin thin film, the first
1. A method for manufacturing a semiconductor device, comprising forming a first electrode of an element and a second element, and further laminating a non-rli crystal semiconductor on the opening and the electrode. 2. On the organic resin 1a having an insulating surface, connect the first electrode and the l'N or r'IN junction on the electrode with a small (1
) at least one non-single crystal semiconductor, and a second semiconductor on the semiconductor.
In the method for manufacturing a photoelectric conversion device in which a plurality of photoelectric conversion elements having electrodes are electrically connected in series and disposed on the insulating substrate, the non-single crystal semiconductor of the first and second elements and the irradiating the first electrode with a laser beam to form a second groove without damaging the organic resin film, and extending from the second electrode of the second element into the groove. A method for manufacturing a semiconductor device, characterized in that the conductor is brought into close contact with a side surface of the first electrode of the first element or an upper end surface of the side surface. 3. A semiconductor according to claims 1 and 2, characterized in that after being irradiated with a laser beam, the semiconductor is immersed in a liquid containing a halogen element or a cleaning liquid 1+ to remove any remaining open grooves. Method of manufacturing the device.