JPS5952835A - Plasma vapor reactor - Google Patents

Abstract

PURPOSE:To improve productivity by disposing substrates at regular intervals in mutually parallel while setting up a heat source in the direction of the surfaces, to which films are formed, of the substrates and installing reaction vessels while mutually connecting them. CONSTITUTION:To improve the uniformity of film thickness and the homogeneity of film quality in the upper sections, lower sections, and central sections ans peripheral sections of the substrates 4, 4', the surfaces thereof to which the films are formed are arranged in approximately parallel at regular intervals of 3- 5cm, infrared lamps 11, 11' are set up in the direction of the surfaces, to which the films are formed, and the substrates 4, 4' are heated by the infrared heaters 11, 11' at 100-400 deg.C such as 200 deg.C. Since the heaters 11, 11' have cylindrical parts, the heaters are arranged in the directions in which the upper heaters and the lower heaters cross mutually at right angles, and spaces, particularly, cylindrical spaces, in the reaction vessels are kept at 200+ or -10 deg.C, preferably, within + or -5 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION When forming non-single crystal semiconductors having conductivity types of KP type, 1 type and N type on a substrate in a layered manner,
By forming each semiconductor layer in a corresponding plasma gas phase application reaction vessel and by connecting the respective reaction vessels to each other, the semiconductor layer can be formed without exposure to outside air (atmosphere). It relates to a gas phase reactor.

The present invention is directed to a non-single crystal semiconductor layer doped with hydrogen or a halogen element, preferably silicon, germanium, silicon carbide (not only 810 but also BIXOt-
AO<Xζ1), germanium silicide (81xGe, -, 0<x<1) tin silicide (81X8n
I-2, O<x<1), and by filling this film with hydrogen or a halogen element in an active state, it has P-type and N-type conductivity types with a small number of recombination centers. A plurality of semiconductor layers are formed and bonded at the layer boundary, for example, P.
In addition to forming an N-junction, a P-junction, an N-junction, or a P-N junction, the formation is performed without impurities from other adjacent semiconductor layers being mixed into each semiconductor layer and deteriorating the junction characteristics; A method for continuous production in which interlayer insulators are not formed due to oxidation of part of the semiconductor by exposing it to air, particularly oxygen, between the steps of forming semiconductor layers on each semiconductor layer. Regarding plasma gas phase application manufacturing equipment.

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

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 back surfaces of the substrates having the surface to be formed on one side are brought into close contact with each other in a cylindrical space, and a certain distance, for example, 2 -y6
am is typically arranged in parallel at a distance of 3 to 4 cm, and performs psismal discharge only in the cylindrical space where these substrates stand, and in addition, selectively guides the reactive gas, resulting in the collection of the reactive gas. Efficiency improved by 1-3% compared to conventional method Part 20
It is characterized by increasing the temperature to 0 (~60 times 40~).

Furthermore, when forming a film by repeating it many times,
At that time, in order to prevent the flakes (fine particles) that were formed on the upper part of the reaction vessel from forming pinholes on the surface of the substrate to be formed, the surface of the substrate to be formed was The % sign is that the material is 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 upper part of the reactor or at the reactive gas inlet side.

According to the present invention, the constant length is 2 to 10 cm, preferably 3 to 5 cm.
, ' [The upper, lower and central parts of the substrate, where the surfaces to be formed are arranged approximately parallel to each other; The infrared lamps were provided in the direction of the surface to be formed, and furthermore, at least one rod-shaped infrared lamp was bent toward the other side and downward by 90 degrees to achieve uniform heating. i.e. 10 cm' or electrode direction K
Many substrates with a width of 10 to 1100 mm and a width of 10 to 20 cm have a temperature distribution of 100 to 400 mm.
°C, for example, within 200±10°C, preferably within ±5'0.

The present invention is characterized in that it is provided with a guide that primarily causes selective plasma discharge and selectively causes reactive gas to primarily flow into the space. Further misfire I
In JA, 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 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 collection 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 to 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 the whole surface side of the substrate. It was something like that. 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 vessel and the entire reaction vessel is A system is known in which the reactive gas is filled and the reactive gas is supplied without forming a unidirectional gas flow. However, in these conventionally known methods, the growth rate of the film is as low as 0.1-2 seconds.Especially in the method in which the entire reactor is filled with reactive gas,
The reaction time was extremely small, 0.1-0.45 seconds, and in addition, reaction products adhered to the inner wall of the chamber in the form of flakes, which fell onto the substrate and induced the generation of pinholes.

Further, the substrate is arranged parallel to the electrodes only once between the electrodes, and a semiconductor layer is formed only on the main surface thereof. However, when manufacturing a solar cell, which is a typical example of its application, the manufacturing cost exceeds 5,000 yen for a substrate size of 100:ff+'', and of that, 400
It was a completely absurd situation that more than 0 yen was equipment depreciation cost.For this reason, the size of 10cm0(7) board was
- There has been a strong demand for a manufacturing apparatus that can produce products with 30 times higher productivity in the same size reaction vessel.The present invention was made to meet this objective.

Semiconductor devices are not only intrinsic semiconductors, but also P-type 1. N
The fact that W semiconductor layers can be freely stacked and bonded according to their design expands its 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 ff4 semiconductor layers having at least one P-type, Nl'i, or P-N junction, when trying to form a sufficient junction at the interface, it is necessary to separate the reaction vessels for each conductivity type. It is extremely important to independently separate the '' as described above.

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 laminating a P-type semiconductor layer as the first semiconductor layer, this impurity is adsorbed at the same time as the semiconductor layer is formed. It occurs on the inner wall of the reaction vessel or on 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. In addition, regarding the substrate holder, the nucleation surface of the substrate is also 11°C so that only the substrate is substantially coated with reaction products.
However, as a result of further detailed study of the mixing of impurities, we found that this alone was not sufficient, and that the first It has become clear that the semiconductor layer itself can also be a source of impurity contamination.

Therefore, when trying to form a second semiconductor layer on the upper surface, the second semiconductor layer is grown on this base, and the base semiconductor rt=layer is grown on the base semiconductor rt= layer before being formed so that the reactive gas collides with the base semiconductor layer. It has been found that it is extremely important to avoid the spatter effect as much as possible when the nucleation surface is supplied. The gas strongly collides with the underlying layer.For this reason, when the 21st semiconductor layers were being laminated, they mixed with each other at the interface. As a result, the conventionally known parallel plate type
If the surface to be formed is oriented parallel to one electrode surface of the u-electrode (that is, the electric field is perpendicular to the substrate surface), even if the mixing of impurities is eliminated using the independent reaction vessel method, it will not be sufficient to eliminate the mixing of impurities with each other. It was found that there were about 1000-200 OA.

In order to avoid such drawbacks, the present invention employs an independently separated four-channel reaction system, and the direct current or high frequency electric field used for the plasma reaction is approximately parallel to the formation surface tζ, and the reactive gas is applied to the formation surface. A laminar flow was configured and supplied so as to flow along the surface, and reactive gases were prevented from creating turbulent flow within the tank and mixing. In addition to these processes, guides are provided at the reactive gas inlet and exhaust port, and a plasma reaction is selectively generated only in the cylindrical space substantially created by the surface of the substrate between these guides. This prevents the back from spreading and spreading, especially when the reaction takes place in the entire space inside the chamber (reaction vessel). By providing 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 200-300^ and approximately 1 /1o-115, and it was also possible to grow an intrinsic or substantially intrinsic semiconductor layer having short range order crystallinity (order) continuously on a crystallographic KP type semiconductor layer. It is a feature. Furthermore, even when a P1N type semiconductor layer was formed and a PM junction was provided, it had the effect of providing not just ohmic resistance characteristics but diode characteristics with reverse leakage of 5VK and less than IFA.

By doing so, 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, but such trap centers (recombination centers) are By tingling, it is possible to reduce the amount of light, and by growing crystallographically,
The concentration of dangling bonds in a semiconducting semiconductor is reduced from the conventional 10 to TL.
It is 17 in that it is about 10~'Cuno'No cm which is about V100 from Ocm.

Embodiments of the present invention will be described below with reference to the drawings.

Example 1 According to FIG. 1, an example of the plasma vapor phase reactor of the present invention will be explained.

This drawing shows P-joints, N-junctions, PN junctions, P-IT junctions, P-N-P junctions, N-PIN junctions, P-HP HP-N... Preventing semiconductor layers of different conductivity types or bundled conductivity types but with different main components or stoichiometric ratios from being influenced by semiconductor layers formed in the previous process. Therefore, a ninth semiconductor layer is formed in another independent reaction vessel connected to the reaction vessel in which the previous semiconductor layer was formed, and is laminated on top of the previous semiconductor layer to form a bond. It is also a device for continuous formation.

In the drawing, the three PIs constituting the special K PIN junction are shown.
A multi-channel amper (in this case, a 3-channel
An example of a plasma gas phase reactor using the two reaction vessels method is shown below.

Systems I, II, and M in the drawings represent three reaction vessels (6
), ('7), and (8), each having independently reactive gas introduction means 0*, 0→, α and exhaust means (
, 'J I H.

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

Jin's device has a first preliminary chamber (5) on the entrance side,
Door 0 board holder (also called holder X74) K
Boards (4) and (j) were inserted and placed in this preliminary chamber. The substrates having this surface to be formed are brought into contact with each other with their back surfaces on which no film is formed, and 2xlOC! m preferably 3-5 c
They are grown in a forest with a gap of m. The length of this gap in the flow direction of the reactive gas of the substrate is 10 cm, 15 cm,
As the length increases to 20 cm, 3-40 Tn, 4
-56 m, expanded to □ Qm. Further, this first preliminary chamber (5) was evacuated by using a vacuum pump (35)K and opening a valve (34). After this, the reaction vessels (6), (7), (8) K gate valves (4) which have been evacuated in advance
4) was opened and the substrate and holder were transferred. For example, the container (6)K is moved from the preliminary chamber (5), and the container is further moved by closing the gate valve 04). At this time, the substrate held in the reaction vessel (6) K (Me is in the reaction vessel cylinder, and the reaction vessel ()) The substrate (2) held in K is in the reaction vessel (8) K% Also, the reaction vessel (8) The substrate held in K is simultaneously placed in the preliminary chamber (9) on the second outlet side by the gate valve (4).
5) α6) Opened and moved.

) 2 Gate valve (4'i'l)
After the chamber was closed, nitrogen was introduced from 01) to bring it to atmospheric pressure, and it was let out through the door at (4, 3).

In other words, the movement of the gate valve is the door (42), and when (43) is opened at atmospheric pressure, the gate valve (44) 7 (45)
, (46), and (47) are closed, and a plasma gas phase reaction is performed in each chamber. Also, the doors (42) and (43) are closed and the preliminary room (5) is closed.
, When (9) is sufficiently evacuated, the gate valve (44)
(45) (46) (There are four chambers, and each chamber has a mechanism for moving the substrate and holder to the adjacent chamber.

The case of forming a P-type semiconductor layer in the first reaction vessel (6) in system (2) will be described below.

Reaction system ■ (including reaction container (6)) is 10 to 10 to
rr preferably O, 01xltorr for example 0.1tO
It was set as rr.

The reactive gas is silane (Sin) for silicide gas 09.
Hz-uz n2149K 811Q, dichlorosilane (Efi υ, trichlorsilane (ETiH[1
, ), silicon tetrafluoride (81F, ), etc., but silane, which is easy to handle, was used. Dichlorosilane is cheaper and may also be used.

B i X O/-X (0<X<1) of this example
For carbide gas f2), methane (c
It may also be a carbide gas such as OC using 9 or a carbon chloride such as carbon tetrachloride (001,).

For silicon carbide (sizCd, 0<x<1),
Boron as a P-type impurity with hydrogen at 2000I'FM
K-diluted diborane was supplied. Also, use TMG (()a COH;),) to F
) 10 A-9×10 am may be added.

Hydrogen (H, ) was used as the carrier gas (39) during the reaction, but nitrogen (Nj) was used instead of liquid nitrogen before and after the start of the reaction. These reactive gases are separated by their respective flow meters (3
stage and pulp (through the three, reactive gas inlet 07
) Connect the negative electrode (6) of the high frequency power supply to the reaction vessel (6).
) was supplied. The reactive gas passes through the guide (10) and is introduced into the substrate (1) and holder (14) that constitute a cylindrical space, and is transferred between the negative electrode (61) and the positive electrode (51) by applying electrical energy, for example, 13. A reaction was caused by applying high frequency energy of 56 MHz to form a film of the reaction product on the substrate.

Substrate 100-40060 was heated, for example, by a 200° a VC infrared heater (1ηθ4).

This infrared heater is also called an infrared image furnace, and since it has a rod shape, the upper heater and the lower heater are arranged in directions orthogonal to each other, and the cylindrical space in this reaction vessel is preferably within 200±XOa, preferably within ±60. It was installed in This heater caused non-uniformity of 200-120'O and so'a in the flow direction of the reactive gas when used only on the upper side or the lower side, so it was not practical at all. Furthermore, by making them perpendicular to each other, the temperature distribution between the substrates could be kept within ±xob. Thereafter, as described above, the above-mentioned reactive gas was introduced into this container, and high-frequency energy α◆ was further supplied to K 1O-50W to cause a plasma reaction.

Thus, the P-type semiconductor layer has B, F1a i HQ=0.
5%.

A thin film having a thickness of about 100 mm was formed using this reaction system (1) under the conditions of OH〆 (13i H4 + C) and 0.5.
0 ('L6Q' Tatsuta〇Conventional silicon carbide generally requires larger high-frequency energy than silicon alone. Therefore, when the electric field is perpendicular to the surface to be formed, transparent Conductive film (600% of tin oxide or tin oxide)
-800^ cypress film for electrode) is sputtered and oxidized with 2
The tin turns into metallic tin, making it cloudy instead of transparent.

However, as shown in the embodiments of the present invention, when the plasma electric field is made approximately parallel to the surface to be formed, the reaction products due to this electric field move along the surface, so that clouding due to the sputtering effect can be prevented even when 3O-5ffW is added. Compared to the vertical electric field case where the limit was 5W, the characteristic yield and manufacturing yield were improved.

Substrates are conductor substrates (stainless steel, titanium, titanium nitride, and other metals), semiconductors (silicon, silicon carbide, germanium), insulators (alumina, glass, organic materials), or composite substrates (tin oxide, engineered, etc. on glass insulating substrates). A single layer of conductive film such as To or K ElnOL formed on ITO2
A layer film was formed, a conductor electrode was selectively formed on an insulating substrate, and a KP or N type semiconductor was formed on an insulating substrate). These are collectively referred to as a substrate not only in this embodiment but also in all of the present invention. Of course, this substrate may be a flexible or rigid plate.

In this way, a gamma reaction was allowed to occur for 1-f5 minutes to produce a silicon carbide film doped with 70% Bohm as a P-type impurity.Furthermore, a substrate was placed on this first semiconductor layer according to the above-described operation sequence. A second reaction vessel (2) was moved, in which an intrinsic semiconductor layer was formed to a thickness of about 6000^.

That is, in the reaction system H in FIG. 1, silane is used as a reactive gas for the semiconductor (c) υ, and a carrier gas such as hydrogen is used as necessary ψ)f? 4 and supply a pair of electrodes (I) to the high frequency 1 similar to system ①:
High-frequency energy of 13.56 MHz was supplied from L lees (Ton). The substrate was heated to 250" O with a heater (1 wafer). Reactive gas Q was applied along the surface on which the group & (2) was formed. Figure 2 shows a cross-sectional view of the 0 system 11, which flows from the top to the bottom and reaches the vacuum pump (3'7)K, viewed from the outlet side.

Figure 2 is outlined.

In Fig. 2, the reaction vessel (1) has a peephole ←8) copper mesh 09) for preventing radio wave leakage, a quartz window (55) for supplying microwaves on the back side, and a waveguide ω9. Furthermore, it is equipped with Q power supplies for macrowaves or millimeter waves (H, Ti, reactive gas in parallel along the formed surface of the plate (2)), east, (C) and high frequency. It is provided so that an electric field of θ is distributed.

Furthermore, in addition to high frequencies, frequencies of 1 GHz or higher, such as 2.
In Figure 2, where a 45 GHz microwave is being supplied, the reactive gas is introduced through the quartz tube (66), and the reactive gas is led out through the quartz tube inlet through a mesh or porous electrode (6''Q). Outlet of silver body (I11 board (2), holder (
'74), exhaust port Q9, pair of electrodes (67) (68)
The correlation is further shown in a perspective view (cut away from the front) in FIG.

That is, in FIG. 3, the substrates (2) are placed in parallel with each other with a constant gap of 3 cm, for example, in the vertical direction (vertical direction) with their back surfaces aligned with each other. The holder is made of quartz and has a disk-shaped disk on the upper side and a substrate groove (94) connected to the disk.The disk is held in the space by four supports (so) (ad). , the supporter (so) (sd) rotates 2 according to the rotation of the axis ('79) ('7゜
2 rotations, thereby rotating the disk at a speed of 3-10 times per minute to promote homogenization of the reactive gases.

The reactive gas passes through the outlet port 01, a hole c73 with a diameter of 1 to 3 mm, and a reticular Ml electrode (with a hole diameter of approximately 10 mm).
It's blowing out downwards. To prevent the release of reactive gas in the (80) direction, the holder guide e10) is
81) The gap was 1 cm or less, preferably Sih-5 mm. The reactive gas is then flowed into the formation surface of the substrate (2) (2) and the side wall (96) of 0 quartz that holds the groove (95) for standing up the substrate (2).
95) The outer side K is placed 10-20 mm apart to prevent the reactive gas from sagging on the side wall (96), thereby improving the uniformity of the film thickness of the coating at the edge of the substrate (2). It has been promoted.

Regarding the exhaust system, the gap between the guide (7 m) and the bottom edge of the substrate was adjusted to 1 cm or less in order to reduce the inflow of reactive gas from the That is, by setting the conductance of the gas flow (82) and (84) to about 115 or less, preferably 0-17100, the reactive gas is selectively introduced into the cylindrical space. The distance between the positive electrode (68) and the lower end of the substrate was set by adjusting the height of the guide.

Furthermore, the negative electrode (6'/l) and the upper end of the substrate, that is, the disk (/4
) and the guide ('10) K was adjusted in the same way.

As is clear from Fig. 3, the electrode is surrounded on its outer periphery by a quartz guide ('yO), an upper lid (93), a guide (7υ), and a lower lid (94). This was done to prevent parasitic welding between the thread and the lever inside the stainless steel chain burner in the potato.Furthermore, the inner diameter of the reactive gas inlet (68) and the negative electrode are approximately the same size, and the exhaust Since the inner diameter of the opening 00 and the positive electrode have approximately the same size, when high-frequency discharge is performed, the reactive gas flows along this cylindrical space, that is, the surface on which reactive gas is formed, causing a cold plasma discharge in the space. As a result, the plasma conversion rate of the reactive gas is extremely high, and this prevents excessive reaction products from adhering to the inner wall of the reaction vessel (Pelger) in the form of flakes, which can cause pinholes. I was able to do that.

In addition to the structure of FIG. 3 as described above, infrared lamps d are provided in the upper and lower directions in FIG. 2, whose numbers correspond to each other, to promote homogenization of the substrate.

The configuration in Figure 3 is system 1 in Figure 1. The electrodes, substrates, holders, reactive analogue layer outlets, and exhaust ports in the reaction vessels (6) and (8) in the UK had similar configurations. Thus, in FIG. 3, the substrate and substrate holder can be moved in the direction of system I ('7'7) without any hindrance (L·I'),
It was possible to move the system in the direction of 't'l ('7E]) in the summer direction.

Regarding the effect of microwaves with a frequency higher than IGHz in Figure 2, patent application 5'/-1 filed by an unsuccessful student
2604 f e51.7.19 application).

In the drawing, 3 YA seconds at 2500 Hz is equivalent to 20 yA high frequency electric field.
It could be obtained by adding W and silane at s.o.c.c./9. Compared to the conventional parallel plate N-pole type N-pole method, which requires 0.1 to 1 ounces, using the same reaction container warehouse allows for 6 times as much production, making it possible to produce a total of 48 times as much. . In addition, in the conventional space where 50cm is made ('1),
With a 20cm x 50cm substrate with a gap of 5cm, 20 arrays can be arranged at the same time, and the V-formation area is 'LL''.
The distance between the electrodes can be doubled from the conventional 4cm to 92cm.
5 to 27 cm [As a result, the ionization rate of the reactive gas is also improved, and it is possible to apply 4 liters to the film in 74 seconds, resulting in an extremely ideal growth rate that is substantially 64 times faster. It turned out to be a mass production method.

The semiconductor layer thus formed is made of XEt in a plasma state.
Since * is long, the tip conductivity is also 2×1047×10 (how many 4″
, had a conduction #:, 3X10''~lXl0'(cc@-'.

After forming a semiconductor layer with a thickness of about 500 OA in System 1, the substrate was transferred to a reaction vessel (8)K in System 2 according to the above-described operations, and an N-type semiconductor layer was formed.

In this N-type semiconductor layer, phosphine is added to P as shown in FIG.
H/s i! (, 21, 0% 31), add silane (30), add carrier gas water (→
A single layer of a polycrystalline semiconductor having a KN-type microcrystalline or fibrous structure with a thickness of 200 Å was formed in the same manner as in system (2) by supplying yofi81) f, /H, and .5o.

Other reactor equipment is the same as for system ①.

After this step C, 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 + 5nOJ surface electrode - (P-N semiconductor) (Al
A back electrode) was constructed.

Its characteristics as a photoelectric conversion device are 8% lo
cm' substrate has AMPαoomw/am) K as an intrinsic efficiency characteristic, and is a hybrid type 15cm×4
Even on a 0 cm substrate, an intrinsic efficiency of 6-J7$i could be obtained. This efficiency improvement is due to the incident light (III
In non-single-crystal semiconductors such as amorphous or semi-amorphous semiconductors, this is due to the fact that a p-type semiconductor layer is grown and laminated on a p-type semiconductor layer, and the open-circuit voltage is 0.88
-0.9v, but the short circuit current was 2C□22mIy
It is large at 'cm' and the FF is 0. The density of recombination centers inside the PIN type semiconductor layer is /10-1150 K compared to the conventional method, which is considered to be the reason for the large improvement in characteristics.

The plasma reactor of the present invention is thus formed 4!
:This is a very unique method that improves the productivity of conductors by 30-70 times and also improves the characteristics by 30% compared to the conventional 5-896 conversion efficiency.Example 2 This example is This is a modification of Embodiment 1), and a drawing corresponding to FIG. 2 is shown in FIG. Other details are the same as in FIGS. 1 to 3.

Figure 4 shows a vertical cross section of a 1'5p-2 reaction vessel in which a semiconductor layer is formed.
p'I) PD is ejected laterally from the inlet (66) to the outlet θ tower. Also, the outlet? , ]) and then (/a) to the di-rotary pump (3'/).

Stand the board (2) vertically and place it in the holder ('7
4) is held in space by The reactive gas is made to flow selectively into the cylindrical space 4:/1jL:D by guides ('70) ('71). High frequency W, vP,
(Ii has a negative electrode (6η) and a positive electrode (c7), and infrared heating lamps are provided above and below (), θ) to promote heat uniformity.

In this embodiment, the substrate (2) holder (7 types of
It has Q, 'f Note that it is easy to move to ~■.

However, a large amount of the reactive gas flows upward due to the rising temperature, and the upper side of the substrate tends to float. For this reason, it is necessary to arrange the substrate in the direction (4 to e21), but this has the disadvantage of being structurally difficult. In addition, if the flying distance of the reactive gas is in the lateral direction of the substrate (2),
Because of the long length, there were variations in the electrical 11.1 characteristics obtained between the reactive gas inlet and outlet sides, and although it was excellent for mass production as in Example 1, it was not suitable for high quality. It has a drawback in that it cannot uniformly obtain the same characteristics over a large area.

Example 3 FIG. 5 shows another embodiment of the invention.

FIG. 5(4) shows an outline of the drawing corresponding to FIG. 3 of the first embodiment. In Figure 5 (4), the reactive gas inlet (66) leads to the negative electrode (6'Q to the exhaust port Q1), the positive electrode (6th), and the exhaust system (74) K. ,
The substrate (2) has a tapered shape, and does not become narrower from the inlet side to the sea outlet side of the substrate, thereby further promoting uniformity of the formed film.

In (A), the flakes tend to stick to the surface on which they are formed, so in (9), it is also possible to provide the 11 crystal opening from which the reactive gas is drawn out in the downward direction and the crystal opening in the upward direction.

In this way, flakes were not attached to the surface to be formed, that is, the production 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 V2 compared to the manufacturing equipment RK shown in Figure 1.
It has become.

In the embodiment of the present invention described above, one P-N junction is provided. However, for many applications such as P-type N-type phototransistors, P-type II'-N...@P-N tandem structure photoelectric conversion devices, 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 of the present invention.

Whether the crystal structure in the non-single-crystal conductive film formed in the present invention is amorphous or polycrystalline, there is no restriction on the structure. The present invention provides that the formed plurality of laminated semiconductor films are P type, N type or type 1, at least PI,
It is important that the semiconductor has one PM or N-type 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, this dangling bond of silicon or carbon is replaced with hydrogen)
It goes without saying that instead of neutralizing with 81-H% O-E K, it may be carried out using 5i-01, ($-01) and a halide, especially Y chloride gas. Less than 10 atoms, for example 2-5 atoms, were preferred.

Regarding the types of semiconductors to be formed, as shown in Example 1, 81, ()e, 81XO7-x(0(!(
1), El 1! G @ r-r+ (0'-X'
1) % 81X 8 n 7-4 (0(X (1)
Not only K, but also GaAs, ()aAIAg
It goes without saying that compound semiconductors such as , BP, Ods, etc. may also be used.

A selective KP or N-type impurity is mixed or diffused into the silicon carbide film formed by the present invention using photoetching technology to partially form a PM junction, and this junction can be used to create a transistor or a PXN. A junction-type visible light laser, light emitting device, or photoelectric conversion device may also be made. In particular, the so-called v-N (m from w
ovt) and in each reaction chamber, not only the conductivity type but also the product can be made independently and stacked, which I believe is extremely important industrially.

[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 portion of the apparatus of FIG. FIG. 4 shows another embodiment of the present invention corresponding to FIG. FIG. 5 shows another embodiment corresponding to FIG. 3 of the present invention. 45゛Applicant

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 an exhaust system for evacuating the reaction product, and the reaction vessels are connected to each other, and gas pipes are provided on one side and the other side of the reaction vessel. A first and a second preparatory chamber are arranged in series, and a gate is provided in the connection part of the reaction vessel and the preparatory chamber to prevent the reactive gases introduced into the respective reaction vessels from mixing with each other during the plasma gas phase reaction. In a plasma vapor phase reactor equipped with a valve, substrates having surfaces to be formed are arranged approximately parallel to each other with a predetermined gap, and a heating source is provided in the direction of the surface to be formed of the substrates. Characteristic plasma gas phase reactor. 2. A plasma vapor phase reactor according to claim 1, characterized in that the heating source is provided by an infrared lamp in the upper and lower directions of the reaction vessel, and the substrate is disposed in the direction of gravity.