JPS5952834A - Plasma vapor reactor - Google Patents

Abstract

PURPOSE:To improve productivity by setting up an introducing guide or an exhaust guide for a reactive gas in a cylindrical space, in which a substrate is arranged along the flow of the gas, in order to selectively orient the reactive gas and installing reaction vessels while mutually connecting them. CONSTITUTION:The substrates, one sides thereof have the surfaces to which the reactive gas is formed, are arranged in parallel in the cylindrical space at regular intervals of 3-4cm while their backs are fast stuck mutually by preventing dispersion to the whole sections in the reaction vessel of the reactive gas and utilizing the surfaces, to which the gas is formed, of the substrates, plasma discharge is executed only in the cylindrical space in which the substrates stand close together, and the reactive gas is introduced selectively, thus improving efficiency on the collection of the reactive gas. For prevent the discharge of the reactive gas by the guide 70 of a holder, a clearance 81 is brought to 1cm or less and the reactive gas is flowed in a stratiform shape. Side walls 96 are set up on the outsides of the grooves 95 while being separated by 10-20mm., and the generation of the turbulence of the reactive gas is prevented, thus improving the uniformity of film thickness at the end sections of the substrates 2.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for stacking and forming non-single crystal semiconductors having conductivity types of Km' type, 1 type and N type on a substrate in a layered manner. The present invention relates to a plasma vapor phase reactor that is formed using plasma vapor phase application reaction vessels, and by connecting the reaction vessels to each other, it is possible to form a semiconductor layer without exposing it to outside air (atmosphere).

The present invention is directed to a non-single crystal semiconductor layer doped with hydrogen or /
, 0 (means a general term for x<1), silicide Ge/L/i2: L--mu (day1XGe+-y (0<x(1) tin silicide (81XE1nI-40<X(1) Then, by filling this film with active hydrogen or a nitrogen element, a plurality of semiconductor layers having P-type and N-type conductivity types with a small recombination center density are formed, and at the layer boundary. For example, a PN junction, a P-type junction, an N-type junction, or a P-type-N junction is formed without impurities from other adjacent semiconductor layers being mixed into each semiconductor layer and deteriorating the bonding characteristics. In addition, between the steps of forming semiconductor layers on each layer, they are exposed to the atmosphere, especially oxygen.
The present invention relates to a plasma gas phase application manufacturing apparatus for continuous production in which glabellar insulators are not formed due to oxidation of a part of a semiconductor.

In the present invention, the semiconductor film to be formed is not sputtered (damaged), and even non-single-crystal semiconductors are grown polycrystalline (GROWTE) on the substrate. It is characterized by supplying an electric field for generating gas and plasma.

Furthermore, the present invention uses a multi-chamber type plasma reactor in which a large number of reaction vessels are connected, and uses a so-called mass production method in which a large number of substrates are simultaneously grown at a high film growth rate. By using the surface of the substrate to be formed, the substrates having the surface to be formed on one side are placed in a cylindrical space with their back surfaces close to each other at a certain distance, e.g. 6c
Typically, these substrates are arranged in parallel at a distance of 3 to 4 cm, and plasma discharge is performed only in the cylindrical space in which these substrates stand. Efficiency improved by 1-3% compared to conventional method Part 20-
It is characterized by being increased by 40 to 70%, which is 60 times higher.

Furthermore, when forming a film by repeating it many times,
At that time, in order to prevent the flakes (fine particles) attached to the upper part of the reaction vessel from causing Kltt-x pinholes on the surface of the substrate to be formed, the surface of the substrate to be formed was It is characterized by being oriented along the direction of gravity.

In order to prevent a large number of flakes from being generated on the reactive gas inlet side, the present invention uses an electrode provided in a mesh or multi-hole shape on the reactive gas inlet side as a negative electrode,
It is characterized by a positive electrode provided on the exhaust port side. That is, the present invention has experimentally found that many flakes tend to occur near the positive electrode, and is therefore characterized by arranging the negative electrode side at the top of the reactor or at the reactive gas inlet side.

In the present invention, the upper part of the substrate is arranged so that the surface to be formed is approximately parallel with a certain gap of 2 to 10 cm, preferably 3 to 5 cm;
In order to promote uniformity of film thickness and homogeneity of film quality in the lower and central parts: peripheral parts, infrared lamps are provided in the direction of the surface to be formed, and furthermore, rod-shaped infrared lamps are installed at least 90' from each other in the upper and lower directions. Bend it and place it, then heat it up. measured. i.e. 10 cm' or 10-20 cm in the electrode direction
Many of the medium 10 to 100 cm substrates with a temperature range of 100 to 400"C, for example 200±
It is characterized by being within 10°C, preferably within ±5'O.

The present invention is characterized in that a guide is provided to selectively cause plasma discharge primarily in the space and to selectively flow reactive gas primarily into the space. Furthermore, in the present invention, electrodes, reactive gas inlets, and exhaust ports are provided so as to satisfy these conditions and not cause any hindrance when the substrate moves between the multi-chambers that are laterally connected to each other. It is also characterized by the provision of heating infrared rays.

As described above, since the multi-chamber one-type system is the basic condition, in addition to improving the properties of the coating in each reaction vessel, it also prevents unnecessary reaction products from adhering to the inner wall of the chamber, and conversely, it also improves the supply. In order to increase the rate at which the reactive gas forms a film, that is, the fruit-like efficiency, the reactive gas is provided in a chimney shape in the cylindrical space where the substrate is placed.
The present invention relates to a plasma vapor phase reactor characterized in that the surface of the substrate to be formed substantially constitutes the inner wall of a chimney.

The present invention also relates to a plasma reaction manufacturing apparatus in which reaction vessels are successively arranged in equal numbers to the number of semiconductor layers to be laminated.

Conventionally, in the plasma vapor phase reaction of non-single crystal semiconductors such as amorphous silicon, the discharge method of the manufacturing equipment is 13.5
A high frequency such as 6 MHz is applied using a pair of planar flat plate electrodes as a parallel plate type electrode system, a substrate having a surface to be formed is placed on one of the electrodes, and a film is selectively grown only on one principal surface of the substrate. It was something that I did. Furthermore, in this method, regarding the introduction of the reactive gas, there is a method in which the reactive gas is blown out from the other side of the electrode in a direction perpendicular to the surface to be formed, and a method in which the reactive gas is simply introduced into the reaction container and the reaction occurs throughout the reaction container. It is known to fill the reactor with a reactive gas, in particular to supply a reactive gas without forming a unidirectional gas flow. However, in these conventionally known methods,
The growth rate of the film is as small as 0.1 to 2 seconds. In particular, in a method in which the entire reaction vessel is filled with reactive gas, '
O,1-(),4X,/sec, which is extremely small, and in addition, the reaction products adhere to the inner wall of the chamber in the form of flakes.
They fell onto the substrate and induced the generation of pinholes.Place the 〇ma7c substrate between the electrodes parallel to the electrodes,
A semiconductor layer is formed only on the main surface. For this reason, mass production is not sufficient at all, and when producing a solar cell, which is a typical application example, the manufacturing cost exceeds 5,000 yen for a substrate size of 10 cm', and 400
The current situation was completely insane, with equipment depreciation costs exceeding 0 yen.

For this reason, there has been a strong demand for a manufacturing apparatus that can produce substrates with a substrate size of 10 cm' and a productivity 10 to 30 times that size in a reaction vessel of the same size.

The present invention has been made to meet these objectives.

Semiconductor devices are not only made of intrinsic semiconductors, but also have P-type and N-type semiconductor layers that can be freely stacked and bonded according to their design, which expands their engineering applications.

For this reason, even if productivity is improved when semiconductor layers of different conductivity types are made in the same reaction vessel, impurities for each conductivity type will mix with each other within the semiconductor layer due to the sputtering effect. .

Therefore, when stacking multiple semiconductor layers having at least one PN%PI, Nx or FIN junction, when trying to form a sufficient junction at the interface, it is necessary to separate the reaction vessels for each conductivity type as described above. It is extremely important to separate them.

In addition to such a separate and independent method, the present invention aims to improve the bonding characteristics by eliminating the mixing of impurities. That is, for example, when trying to form one P-N junction by stacking a P-type semiconductor layer as the first semiconductor layer, the adsorption of impurities reacts at the same time as the semiconductor layer is formed. Occurs on the inner wall of the container or the surface of the substrate holder. In the present invention, impurities are prevented from being re-released from walls and surfaces other than the surface on which they are formed on the substrate, and reactive gases once adsorbed from the supply system and exhaust system are released when forming the second semiconductor layer. In order to prevent contamination, not only reaction vessels but also reactive gas supply systems and exhaust systems are provided independently for each reaction vessel. The substrate holder is also provided in such a way that the plasma-converted reactive gas is guided only to the wrinkle-forming surface of the substrate so that only the substrate is substantially coated with reaction products.

However, as a result of further investigation into the mixing of impurities, it became clear that this alone was not sufficient and that the formed first semiconductor layer itself could also be a source of impurity mixing.

Therefore, when trying to form a second semiconductor layer on the upper surface, the second semiconductor layer is grown on this base, and the reactive gas is supplied onto the surface to be formed so as to collide with the base semiconductor layer. It has been found that it is extremely important to avoid sputter effects as much as possible.

That is, when a high-frequency electric field is applied perpendicularly to the surface to be formed, the reactive gas that has been converted into a plasma by this electric field strongly collides with the substrate. For this reason, when the second semiconductor layers were being stacked, they mixed with each other at the interface. As a result, the surface to be formed is oriented parallel to the a-plane of one of the conventionally known parallel plate electrodes (i.e., 1
1 field is perpendicular to the substrate surface), and even if the mixing of impurities was eliminated using an independent reaction vessel system, it was found that it was not sufficient and the area where they were mixed with each other was approximately 1000-2000λ.

In order to avoid such drawbacks, the present invention employs an independently separated multi-chamber reaction method, and the direct current or high frequency electric field used for the plasma reaction is approximately parallel to the surface to be formed, and furthermore, the reactive gas is A laminar flow was configured and supplied so that it flowed along the surface, and reactive gases were prevented from creating turbulent flow within the chamber and mixing. In addition to these treatments, guides are provided at the reactive gas inlet and exhaust port, and the selective material X is diffused and spread only in the cylindrical space substantially created by the formation surface of the substrate between the guides. This prevents By using the plasma vapor phase reactor having the structure of the present invention, mixing of formed impurities from each semiconductor layer to another semiconductor layer is eliminated, and the mixing portion is reduced to about 1/1 of 200-600^. -115K, and an intrinsic or substantially intrinsic semiconductor layer having short range order crystallinity (order) can be grown continuously on a crystallographic KP type semiconductor layer. There is. Furthermore, even when a P1N type semiconductor layer was formed to provide a PN junction, it had the effect of providing not just ohmic resistance characteristics but also diode characteristics with reverse leakage of 1 μ8 or less at 5 μm.

By doing this, it was possible to sufficiently reduce the density of recombination centers concentrated at or near the junction. In other words, the recombination center does not become an acceptor or donor due to the mixing of impurities.I-valent impurities and V-valent impurities interact to create a deep trap level. 71 degrees can be reduced from the conventional 10 to 10 cm, /] , OO's 1
0 to 10 am K.

Embodiments of the present invention will be described below with reference to the drawings.O Example 1 An embodiment of the plasma vapor phase reactor of the present invention will be described with reference to FIG.

In this drawing, P-work joint, N-work joint, PN joint, P-work N joint, P-work N-work P joint, N-work P-work N joint, or P-work NP-work N
0-fist, PIN junction, etc. () Semiconductor layers of different conductivity types or the same conductivity type but with different main components or stoichiometric ratios of the semiconductors formed on the semiconductor on the substrate are connected to each semiconductor layer before it. In order to prevent the influence of the semiconductor layer formed in the process, the second semiconductor layer is entirely formed in another independent reaction vessel connected to the reaction vessel in which the previous semiconductor layer was formed, and the second semiconductor layer is completely formed. This is a device for automatically and continuously forming layers on top of each other to create a bond.

In the drawing, the three P's that make up the special KP N-joint,
1) An example of a multi-chamber (here, three reaction vessels) type plasma vapor phase reactor having first and second preliminary chambers formed by stacking and stacking N-type and N-type semiconductor layers is shown.

Systems I, n, I in the drawing represent each of the three reaction vessels (6)
, (7), and (8), each having independently reactive gas introduction means α, a, α, exhaust means (a),
e heart.

) to prevent reactive gases from flowing back from the supply system or exhaust system or from mixing with reactive gases from other systems.

This device has a first preliminary chamber (5) on the entrance side,
Door (42) and board holder (also called holder) ('
14) K substrates (4) and (4:) were inserted and placed in this preliminary chamber. The substrates having the surfaces to be coated are arranged in a row with their back surfaces on which no coating is to be formed in contact with each other with a gap of 2 to 100 m, preferably 5 cm. The length of this gap in the flow direction of the reactive gas of the substrate is 'loCm,
As the length increases to 15cm and 20cm, 3-4c
It was spread to m1-5cm5 torocnn. Furthermore, this first
The preparatory chamber (5) was evacuated with a vacuum pump 05)K by opening the valve (3).After this, the gates were inserted into the reaction vessels (6), ('7), and (8), which had been evacuated in advance. Valve←
4) was opened and the substrate and holder were transferred. For example, the container (6)K is moved from the preliminary chamber (5), and then the container (6)K is moved by closing the gate valve 04). At this time, the substrate held in the reaction container (6) (S is in the reaction container (8)
K, and the substrate (2) held in the reaction vessel (2).
) is the reaction vessel (8) K %Also, the substrate held in the reaction vessel (8)K is moved to the preliminary chamber (9)K on the second outlet side by opening the gate valves (45) (46) (47) at the same time. I let it happen.

2 After the gate valve 0''Q is closed, nitrogen is introduced into the substrate transferred to the second preliminary chamber (41) and the pressure is brought to atmospheric pressure.
3) The door was taken outside.

In other words, the movement of the gate valve is the door (42), and when the door (43) is opened at atmospheric pressure, the gate valve (44) and (45).
(46) (4'7) 22 chambers are closed, and a plasma gas phase reaction is carried out in each chamber. Conversely, when the four doors (43) are closed and the preliminary chambers (5), (9) are sufficiently evacuated, the gate valves (4, (45), (46),
(4'7) is opened and the substrate and holder of each chamber are moved to the adjacent chamber.

The case of forming a P-type semiconductor layer in the first reaction vessel (6) in system IK will be described below.

Reaction system I (including reaction container (6)) is -0 to 1ot
orr preferably 0.0 torr, for example 0.1 torr
It was set as rr.

The reactive gas is silane (S) for silicide gas (goods).
i n Htll, n≧1Special KSiH), dichlorosilane (S i H,9]?), trichlorosilane (S
iHO], ), silicon tetra7ide (SiF, ), etc.
Silane was used because it is easy to handle. Dichlorosilane is cheaper and may also be used.

In order to form BLxO(-A(0<xcl) in this example, O
Even if it is a carbide gas such as C4, carbon tetrachloride (
It may also be carbon chloride such as CIOη.

For silicon carbide (81XOz-a 0(X(1)
PM K-diluted diborane was supplied.

Also, T M G (G a (OHll))
J) Kyo #) 10 Supplementary XIOam may be added to the concentration.

As the carrier gas (39), hydrogen (H, ) was used during the reaction, but nitrogen (N) was used in the form of liquid nitrogen before and after the start of the reaction. These reactive gases are connected to their respective flow meters (33).
and through the pulp (32), the reactive gas inlet a-
Pass through the negative electrode of the high frequency power supply (6υ to the reaction vessel (6)
K was supplied. The reactive gas passes through the guide (70) and is introduced into the substrate (1) and holder ('/4) that constitute the cylindrical space, and generates electrical energy between the negative electrode (6]) and the positive electrode (51). For example, high frequency energy of 13.56 MH2 was applied to cause a reaction, and a reaction product was formed as a film on the substrate.

The substrate was heated to 10G-400°C (for example, using a 20Q'OK infrared heater).

This infrared heater is also called an infrared image furnace, and since it has a rod shape, the upper heater and the lower +7) heater are arranged in directions perpendicular to each other, so that the cylindrical space in the reaction vessel is preferably 200±10″a. The heater was installed within ±5'a. If the heater was installed only on the upper or lower side, it would cause non-uniformity between 200-120"0 and 80'O in the flow direction of the reactive gas, making it completely impractical. By making them orthogonal to each other, the temperature distribution between the substrates can also be ±10'O10.
After that, as described above, the reactive gas described above was introduced into this container, and high frequency energy α4 was further supplied to K1O-50W to cause a plasma reaction.

Thus, the P-type semiconductor layer is P''me81EL, 20. 5 chi.

A thin film having a thickness of about 100λ was formed in this reaction system (2) under the conditions of o V(s IB, -+O20.5).
10 (ncn9).

Conventional silicon carbide generally requires greater high frequency energy than silicon alone. Therefore, when the electric field is perpendicular to the surface to be formed, the transparent conductive film provided on the surface to be formed (TO
Or a tin oxide (600-40 OA electrode coating) is sputtered, and the tin oxide changes to metallic tin, making it cloudy instead of transparent. However, as shown in the embodiments of the present invention, the plasma electric field When parallel to the surface, the reaction products caused by this electric field move along the surface, so the clouding due to the sputtering effect is 30-50'! Compared to the vertical electric field, which had a limit of 2-5 W, the characteristic yield and manufacturing yield were improved.

The substrate can be a conductive substrate (stainless steel, titanium, titanium nitride, or other metal), a semiconductor (silicon, silicon carbide, germanium), an insulator (alumina, glass, organic material), or a composite substrate (tin oxide on a glass insulating substrate, ■A single layer conductive film such as To or a double layer film of 8nOz formed on ITo, a conductor electrode selectively formed on an insulating substrate, a KP or N type conductive film on an insulating substrate (on which a semiconductor was formed) was used. In this embodiment as well as in all of the present invention, these are collectively referred to as a substrate.Of course, this substrate may be flexible or may be a rigid plate.

In this manner, a plasma reaction was carried out for 4 minutes to produce a silicon carbide film doped with P-type impurities and -rim. Further, the substrate was transferred onto the first semiconductor layer to a second reaction vessel (7) according to the above-described operating sequence, and an intrinsic semiconductor layer was formed therein to a thickness of about 5000 nm. That is, as shown in FIG. In the reaction system H, cysine is supplied as a reactive gas for the semiconductor (C), and a carrier gas such as hydrogen is supplied as necessary to form a pair of electrodes (1H core). Similarly to system I), high frequency power source αI) supplied high frequency energy of 13.56 MH2. The substrate was heated by a heater θa (l).The reactive gas flows upward and downward along the surface of the substrate (2) to be formed, and reaches ζ to a vacuum pump (3η. A cross-sectional view of (43) viewed from the exit side is shown in FIG.

Figure 2 is outlined.

In Figure 2 1, the reaction vessel (1) has a peephole α8) a copper mesh for preventing radio wave leakage (49), and a quartz window (55) and waveguide (54) for microwave supply on the back side, and a microwave or It is equipped with a millimeter wave power source (56). The reactive gases (b), ni), and (c) and the electric field of high frequency 00 are arranged parallel to the surface of the substrate (2) to be formed.

Furthermore, in addition to high frequencies, frequencies of 1 GHz or higher, such as 2.
In Fig. 2, where a microwave of 45GH2 is being supplied, the reactive gas was introduced from (66) and led out through the quartz tube inlet and the mesh-like or porous electrode (6'Q). The relationship between the gas outlet 0→, the substrate (2), the holder 0, the exhaust port Q, and the pair of electrodes (6'7) (6B) is shown in Figure 3, which is a perspective view (the first half). (the minutes are cut off).

That is, in FIG. 3, the substrate (2) is placed in parallel with the holder (74) with its back surfaces aligned with each other with a fixed gap of, for example, 3 cm, in the vertical direction (vertical direction). It is made of quartz and has a disk-like disk on the upper side and a substrate groove (94) connected to the disk. The disk is held in space by four supporters (so) (sφ is the axis ('1
9) ('79) 2 revolutions, thereby rotating the disk at a speed of 3-'l O times/min to promote homogenization of the reactive gas.

The reactive gas is blown out downward from the outlet 0 → through the hole 03 (1-3 mm) through the mesh electrode (hole approximately 5-10 mm) (6'7:1).Holder guide e70
), the gap between (81) was set to 1 cm or less, preferably 2-5 mm, in order to prevent the reactive gas from being released in the (80) direction. The reactive gas is then flowed in a layered manner on the surface of the substrate (2) (2) to be formed and on the side wall of the quartz (9 grooves (95) ) is provided at a distance of 20 mm from the outer side of the substrate (96) to prevent the reactive gas from sagging on the side wall (96), thereby improving the uniformity of the film thickness at the edge of the substrate (2). I promoted it.

Regarding the exhaust system, the gap between the guide C/1 and the lower end of the substrate was set to ICm or less in order to reduce the inflow of reactive gas from the 8th stage and to selectively flush L and (85). That is, the conductance of the gas flow of (8s,
By setting xo o, reactive gas was selectively introduced into the cylindrical space. The distance between the positive electrode (6th day) and the lower end of the substrate was determined by adjusting the height of the guide.

Furthermore, the negative electrode (6)) and the upper end of the substrate, that is, the disk (74)
The distance to the guide (70) was adjusted in the same way.

As is clear from Figure 3, the outer peripheral side of the electrode is made of quartz (
7#i)"('i'o), upper f&(93), chi)"(
'71), the lower lid (94) was surrounded by the Ic to prevent parasitic growth between the electrode and the inner wall of the chamber (mostly stainless steel chamber). In addition, the reactive gas inlet (
The inner diameter of 68) and the negative electrode are approximately the same size, and the exhaust port? ! Since the inner diameter of (2) and the positive electrode are approximately the same size, when high-frequency discharge is performed, it flows along this cylindrical space, that is, the surface on which reactive gas is formed, causing a round-like plasma discharge in the space. There is. As a result, the rate of plasma conversion of the reactive gas is extremely low, which in turn prevents excessive reaction products from adhering to the inner wall of the reaction vessel (Pelger) in the form of flakes, which can cause pinholes. was completed.

In addition to the configuration shown in FIG. 3 as described above, in FIG. 2 with corresponding numbers, infrared lamps 0-- are provided in the upper and lower directions to promote homogenization of the substrate.

The structure shown in FIG. 3 is similar to the structure shown in FIG. 1 for the electrodes, substrates, holders, reactive gas outlets, and exhaust ports in the reaction vessels (6) and (8) in the 11K system.

Thus, in FIG. 3, the substrate and the substrate holder can be moved in the direction of the system ① of C77) without any hindrance.
It was possible to move it in the direction of the system (2) in the direction of Zf-, (78).

Regarding the effect of microwaves with a frequency of 1 GHz or more in FIG. 2, patent application 5'7- filed by the present inventor
126047 (S 5), filed 7.19) K details are shown.

In the drawing, the high frequency electric field is set to 2500 at 3~t2.
This could be obtained by setting the power to 0W and adding 30 cc/9 silane. a Compared to the current situation where the conventional parallel plate type electrode system has O01~1, when the same reaction vessel Urasuke is used, it is 6
It has become possible to produce a total of 48 times more volume. In addition, in the conventional space for manufacturing 50 cm, 20 cm x 5
0cm substrate with a gap of 5cm, 20 arrays can be arranged simultaneously, the area to be formed is 1tf (substantially the same as K 20X50X20-2XIOam).
The distance between the electrodes is now 25 to 27 cm (compared to the conventional 4 cm), which improves the ionization rate of the reactive gas and allows the film to be heated to 4t + s, resulting in a distance of 64 cm. It has been found that this is an extremely ideal mass production method that substantially doubles the growth rate.
Because t is long, the photoconductivity is also 2X10-7X10 (Ekun,
After forming a semiconductor layer having a conductivity of 3×10 to 1×10 (≈1×10) to a thickness of about 500 OA in the system 2, the substrate was heated in the system 2 according to the operations described above. The reaction vessel (8) was transferred to K, and an N-type semiconductor layer was formed.This N-type semiconductor layer was coated with Phosphin as shown in FIG.
s 1z, 1.0%31), also add silane (3
0) Okay, let's add hydrogen to the carrier gas! lls
1u4/a, 50, and 20 in the same manner as system I.
A polycrystalline semiconductor layer having a KN type microcrystalline or fiber structure with a thickness of 0λ is formed. The low-reaction device is the same as system ①.

After this process, an aluminum electrode is formed to a thickness of about 1 μm by vacuum evaporation on the substrate which is taken out of the second preparatory chamber (9) to form a P-N junction. On glass substrate
(ITO+SnO,) Surface electrode - (P-N semiconductor) (A
Its characteristics as a photoelectric conversion device are as follows: 7-9 chips, average 8 chips, AMx on a 1-00 m” substrate
(roomW/am)K has as an intrinsic efficiency characteristic,
Even on a 15 cm x 40 cm substrate made into a /S hybrid type, conkers could be obtained with intrinsic efficiency. This improvement in efficiency is achieved because the P-type semiconductor layer on the side where the light enters is extremely simple, and even in non-single-crystal semiconductors such as amorphous or semi-amorphous semiconductors, the P-type semiconductor layer is grown and laminated on the P-type semiconductor layer. This is due to the fact that
In addition, the open circuit voltage was 0.88-0°9■, but the short-circuit current was large at 2 o-22 m1y'cm', and the FF was also large at O, F) →, 78, and The density of recombination centers is much lower than that of the conventional method.
It is presumed that the increase in current caused by increasing the current to 50% led to a large improvement in characteristics.

As described above, the plasma reactor of the present invention is an extremely original device that improves the productivity of formed semiconductors by 30-J'IO times, and also improves the conversion efficiency by 30% compared to the conventional Toro conversion efficiency. It is something.

Embodiment 2 This embodiment is a modification of Embodiment 1, and the drawing corresponding to FIG. 2 is shown in FIG.
It is similar to the figure.

FIG. 4 is a vertical cross-sectional view of a reaction vessel '52-'7 in which a molded semiconductor layer is formed.
'j, n' are ejected laterally through the inlet (66) and the outlet α■]. In addition, the discharge port also goes through (c) c26
) Yoji rotary pump eη has been reached.

The board (2) is placed vertically in a forest, and the holder (74
) is held in space. The reactive gas is guided (
70) (71) K! It is designed to selectively flow into the horizontal cylindrical space. High frequency power supply 0υ is negative electrode (67)
There were seven positive electrodes, and infrared lamps were placed above and below θ, θ, to promote uniform heating.

This embodiment has the characteristic that it is easy to move the substrate (2) holder (74) to the system 1-1[. However, a large amount of reactive gas flows upward due to the rising air current, and the upper side of the substrate tends to be thick. This makes the substrate <10
It is necessary to arrange it in the -(c) direction, but this work has the disadvantage of being structurally difficult. In addition, since the flight distance of the reactive gas is long in the lateral direction of the substrate (2), variations occur in the electrical characteristics obtained on the reactive gas inlet side and the outlet side, which makes it difficult to mass produce. Although it was as excellent as Example 1, it had a drawback in terms of uniformly obtaining high quality characteristics over a large area ◇ Example 3 Figure 5 shows an example of the present invention. show.

FIG. 5(4) shows an outline of the drawing corresponding to FIG. 3 of the first embodiment. In FIG. 5(A), from the reactive gas inlet (66) to the θ-converting negative electrode (6'Q to the exhaust port), the positive electrode (68), and the exhaust system (74) K, The substrate (2) has a tapered shape, and is not narrow from the inlet side to the exhaust side of the substrate to further promote uniformity of the formed film.

In (4), the flakes tend to stick to the surface to be formed, so in (B), the outlet for the reactive gas is provided in the downward direction (it is also possible to provide one outlet in the upward direction).

In this way, flakes were not attached to the surface to be formed, that is, the manufacturing yield due to pinholes was improved, and in addition, the film quality of the film was homogeneous in the flow direction of the reactive gas. However, the productivity is about 1/1 compared to the manufacturing equipment shown in Figure 1.
It became 2.

In the embodiment of the present invention described above, one P-N junction is provided. However, for many applications such as P-type NIP type phototransistors, P-type NIP-type photovoltaic converters, P-type NIP-type photovoltaic conversion devices, etc., it is sufficient to further connect reaction vessels according to the number of semiconductor layers. It goes without saying that these are also included in the technical idea and design of an invention.

Regardless of whether the crystal structure in the non-single crystal semiconductor film formed in the present invention is amorphous or polycrystalline, there is no restriction on the structure. The present invention provides that the plurality of laminated semiconductor films formed are P-type, N-type, or type 1, at least P-P.
It is important that the semiconductor has one N or N junction. In addition, in order to reduce the leakage characteristics of the conductive properties of this semiconductor, a major feature is to mass-produce a high-quality coating that does not mix each other at the bonding surface.

Furthermore, instead of neutralizing the dangling bonds of silicon or carbon with hydrogen, i-H, hO-E K, 5i-01
,0-(31 and... It goes without saying that it may be carried out using chloride gas, especially ichloride gas, and this concentration is 10
Less than atomic atoms, for example 2-5 atoms, were preferred.

The types of semiconductors to be formed are shown in Example 1.
), 81 XG e t-((0<
J i X 8 n, -, 1 (0<
It goes without saying that a compound semiconductor such as P, Oas, etc. may be used. KP or N-type impurities are selectively mixed or diffused into the silicon carbide film formed by the present invention using a photo-etching technique. partially create a PN junction, and use this junction to create transistors, diodes, and brown-N-W (A from W
A visible light laser, a light emitting element, or a photoelectric conversion element of a P-N junction type having an LLO (more like Fi) structure may be manufactured. In particular, the so-called W-N (E to NAL
We believe that this technology is extremely important industrially, as it makes it possible to independently manufacture and laminate different conductivity types as well as different products in each reaction chamber.

[Brief explanation of drawings]

1 and 2 schematically show a manufacturing apparatus for forming a semiconductor film for carrying out the present invention. FIG. 3 shows a perspective view of a part of the apparatus shown in FIG. 2. 2 is another embodiment of the invention corresponding to the figure; FIG. 5 shows another embodiment corresponding to FIG. 3 of the present invention.

Claims (1)

[Claims] A semiconductor in which a junction is formed by laminating non-single crystal semiconductor layers of P type, 1 type and N type conductivity on a surface to be formed on a substrate in a reaction system maintained at a reduced pressure of 1.1 atmospheres or less. In order to form a P-type semiconductor layer, a reaction vessel for forming a P-type semiconductor layer, a reaction vessel for forming a processed semiconductor layer, and a reaction vessel for forming an N-type semiconductor layer are provided. The reaction vessel has a reactive gas introduction system and reaction generation! an exhaust system for evacuating the proboscis, the reaction vessels are connected to each other, and first and second preparatory chambers are connected to one side and the other side of the reaction vessel, In a plasma gas phase reactor, a gate valve is provided in a connecting part between a reaction chamber and a preliminary chamber to prevent reactive gases introduced into each of the reaction vessels from mixing with each other during a plasma gas phase reaction. A substrate having a formation surface has a reactive gas Y introduction guide or an exhaust guide in order to selectively orient the reactive gas in a cylindrical space arranged roughly along the flow of the reactive gas. A plasma gas phase reactor featuring: 2. The plasma vapor phase reaction device according to claim 1, wherein the surface of the substrate on which the substrate is formed is arranged along gravity in order to prevent flakes (microscopic pieces) from sticking to the surface.