JPH0436448B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION When forming non-single-crystal semiconductors having P-type, I-type, and N-type conductivity on a substrate, each semiconductor layer is exposed to a plasma corresponding to each layer. The present invention relates to a plasma vapor phase reaction apparatus that is formed of gas phase reaction vessels and that is capable of forming a semiconductor layer without being exposed to outside air (atmosphere) by connecting the reaction vessels to each other.

The present invention is directed to a non-single crystal semiconductor layer to which hydrogen or a halogen element is added, preferably silicon, germanium, or silicon carbide (not only SiC, but in the present invention means the general term SixC _1-x 0<x<1). , silicon germanium (SixGe _1-x 0<x<1) and tin silicide (SixSn _1-x 0<x<1), which can be recrystallized by filling this film with hydrogen or halogen elements in an active state. Forming a plurality of semiconductor layers having conductivity types of PI and N type with a small center density, forming a junction such as a PN junction, a PI junction, an NI junction, or a PIN junction at the lamination boundary, and
Each semiconductor layer is formed without contaminating impurities from other adjacent semiconductor layers and deteriorating the junction characteristics, and the semiconductor layer is exposed to air, particularly oxygen, between the steps of forming each semiconductor layer. The present invention relates to a plasma gas phase applied manufacturing apparatus for continuous production in which interlayer insulators are not formed due to partial oxidation.

Furthermore, the present invention relates to a so-called mass production system in which a large number of substrates are simultaneously grown at a high film growth rate in a multi-chamber type plasma reactor in which a large number of reaction vessels are connected.

For this reason, the reactive gas is prevented from being dispersed throughout the reaction vessel, and by using the formation surface of the substrate, the substrates having the formation surface on one side are placed in a cylindrical space with their back surfaces mutually placed. The substrates are arranged in parallel at a certain distance, for example, 2 to 6 cm, typically 3 to 4 cm, and plasma discharge is performed only in the cylindrical space in which the substrates are arranged. As a result, the collection efficiency of reactive gases has been increased from 1 to 3% in the conventional method to 40 to 70%, which is 20 to 60 times higher.

In this way, the present invention selectively introduces a reactive gas into the cylindrical space that stands in the cylindrical space in which the substrate is arranged, selectively discharges plasma primarily in that region, and at the same time, the reactive gas is selectively introduced into the cylindrical space where the substrate is arranged. It is characterized by the provision of a guide that allows the flow to flow mainly selectively 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.

Since the multi-chamber method is used as a basic condition, it not only improves the properties of the coating within each reaction vessel, but also prevents unnecessary reaction products from adhering to the inner walls of the chamber. In order to increase the rate at which the supplied reactive gas forms a film, that is, the collection efficiency, a chimney-shaped cylindrical space is provided in which the reactive gas is placed where the substrate is placed, so that the surface on which the substrate is formed is substantially the same as the chimney. The present invention relates to a plasma vapor phase reactor characterized in that it has an inner wall.

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 to provide a pair of planar flat plate electrodes as a parallel plate type electrode system to transmit a high frequency such as 13.56 MHz, A substrate having a surface to be formed was placed, and a film was selectively grown only on one principal surface of the substrate. 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 reactive gas is spread throughout the reaction container. It is known to fill with gas, in particular to supply reactive gases without forming a unidirectional gas flow. However, in these conventionally known methods, the film growth rate is 0.1~
It is as small as 2 Å/sec. In particular, in a method in which the entire reaction vessel is filled with reactive gas,
In addition, reaction products adhered to the inner wall of the chamber in the form of flakes, which fell onto the substrate and induced pinholes.

Further, the substrate is arranged parallel to the electrodes only once between the electrodes, and a semiconductor layer is formed only on one principal surface of the substrate.
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 10 cm square substrate, and within that amount, it costs more than 4,000 yen. The current situation was completely absurd, with equipment depreciation costs.

For this reason, there is a strong need for a manufacturing device that can produce substrates with a substrate size of 10 cm square with 10 to 30 times the productivity in a reaction vessel of the same size.

The present invention has been made to meet this objective.

Semiconductor devices are not just intrinsic semiconductors;
The fact that type and N type semiconductor layers can be freely stacked and bonded according to the design matters expands its engineering applications.

For this reason, even if the productivity is improved when semiconductor layers of different conductivity types are formed in the same reaction vessel, impurities for each conductivity type will mix with each other within the semiconductor layer due to the sputter effect. Therefore, at least one PN, PI, NI or PIN junction
When stacking a plurality of semiconductor layers, it is extremely important to separate the reaction vessels for each conductivity type independently, as described above, in order to form a sufficient junction at the interface.

In addition to such a separate and independent method, the present invention aims to improve bonding characteristics by eliminating the mixing of impurities. That is, for example, when trying to form one PIN junction by stacking a P-type semiconductor layer as the first semiconductor layer, the adsorption of impurities in the reaction vessel occurs at the same time as the semiconductor layer is formed. Occurs on the inner wall 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 surface of the substrate on which the reaction product is to be formed, so that only the substrate is substantially coated with reaction products.

In order to prevent such drawbacks, the present invention provides guides at the reactive gas inlet and outlet, and selectively generates a plasma reaction only in the cylindrical space substantially created by the formation surface of the substrate between the guides. This prevents the reaction product from diffusing and spreading throughout the entire space within the chamber (reaction vessel).
By providing a plasma vapor phase reactor having such a structure according to the present invention, mixing of formed impurities from each semiconductor layer to another semiconductor layer can be eliminated, and the mixing area can be reduced to 200 to 300 Å, approximately 1/10 to 1/10. In addition to reducing the size to 1/5, it was also possible to grow an intrinsic or substantially intrinsic semiconductor layer having crystallinity (order) in the short range order continuously on a crystallographically P-type semiconductor layer. It is characterized by Furthermore, even when P- and N-type semiconductor layers were formed to provide a PN junction, it had the effect of providing diode characteristics with reverse leakage of 1 μA or less at 5 V, rather than mere ohmic resistance characteristics.

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 is formed by mixing impurities, and the V-valent impurity interacts with the valent impurity that does not become an acceptor or donor, creating a deep trap level. By crystallographic growth, the concentration of dangling bonds in an intrinsic semiconductor can be reduced from 10 to ¹⁸
It is characterized by having a value of 10 ¹⁶ to ^{10 17} cm ^-3 , which is about 1/100 of 10 19 cm ^-3 .

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

Example 1 An example of the plasma vapor phase reactor of the present invention will be described with reference to FIG.

This drawing is PI junction, NI junction, PN junction, PIN junction, PINIP junction, NIPIN junction or PINPIN…
...Semiconductor layers of different conductivity types or the same conductivity type but with different main components or stoichiometric ratios are formed on a semiconductor on a substrate such as a PIN junction, and each semiconductor layer is formed in a previous process. In order to prevent the second semiconductor layer from being affected by the semiconductor layer, a second semiconductor layer was formed in another independent reaction vessel connected to the reaction vessel in which the previous semiconductor layer was formed, and was laminated on the previous semiconductor layer. This is a device that not only creates bonds but also automatically and continuously forms multiple layers.

In the drawings, a multi-chamber (here, three reaction vessels) type plasma is shown, which has first and second preliminary chambers formed by stacking three P, I, and N type semiconductor layers constituting a PIN junction. An example of a gas phase reactor is shown.

The system in the drawing has three reaction vessels 6, 7, 8, each independently equipped with reactive gas introduction means 17, 18, 19 and exhaust means 20, 2.
1 and 22 to prevent reactive gas from flowing back from the supply system or exhaust system or from mixing with reactive gas from other systems.

This device is provided with a first preliminary chamber 5 on the entrance side, and the substrates 4 and 4' are inserted into a substrate holder (also referred to as a holder or substrate support) 74 through a door 42.
I placed it in this spare room. The substrates having the surface to be formed have their back surfaces on which the film is not formed in contact with each other,
They are arranged in a forest with gaps of 2 to 10 cm, preferably 3 to 5 cm. This gap widened to 3-4 cm, 4-5 cm, and 5-6 cm as the length of the substrate in the flow direction of the reactive gas increased to 10 cm, 15 cm, and 20 cm. Furthermore, this first preliminary chamber 5 was evacuated using a vacuum pump 35 by opening a valve 34. After this, the gate valve 4 is inserted into the reaction vessels 6, 7, and 8, which have been evacuated in advance.
4 was opened and the substrate and holder were transferred. For example, the sample is transferred from the preliminary chamber 5 to the container 6, and further transferred by closing the gate valve 44. At this time, the substrate 2' held in the reaction vessel 6 is transferred to the reaction vessel 7, the substrate 2 held in the reaction vessel 7 is transferred to the reaction vessel 8, and the substrate held in the reaction vessel 8 is transferred to the second reaction vessel 7. The gate valves 45, 46, and 47 were simultaneously opened and moved to the preliminary chamber 9 on the exit side. The means for moving the substrate and the support may be appropriately selected from among various known means. After the gate valve 47 was closed, the substrate transferred to the second preliminary chamber was brought to atmospheric pressure by introducing nitrogen through 41, and was taken out through the door 43.

That is, the movement of the gate valves is as follows: when the doors 42, 43 are opened at atmospheric pressure, the gate valves 44, 45, 46,
47 is closed, and a plasma gas phase reaction takes place in each chamber. On the other hand, door 42,
43 is closed and the preliminary chambers 5, 9 are sufficiently evacuated, the gate valves 44, 45, 46, 47 are opened, and the substrates and holders of each chamber are moved to the adjacent chamber. There is.

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

The reaction system (including reaction vessel 6) is 10 ^-3 to 10 torr
Preferably it is 0.01 to 1 torr, for example 0.1 torr.

For the silicide gas 24, reactive gases include silane (SinH _2o+2 n1, especially SiH), dichlorosilane (SiH ₂ Cl ₂ ), trichlorosilane (SiHCl ₂ ), silicon tetrafluoride (SiF ₄ ), etc. However, we used silane, which is easy to handle. Dichlorosilane is cheaper and may be used.

Methane (CH ₄ ) was used for the carbide gas 23 to form SixC _1-x (0<x<1) in this example. It may be a carbide gas such as CF ₄ or a carbon chloride such as carbon tetrachloride (CCl ₄ ).

For silicon carbide (SixC _1-x 0<x<1),
2000PPM of boron with hydrogen as a P-type impurity
diborane diluted to 25%. In addition, galiyum was treated with TMG (Ga(CH ₃ ) ₃ ) at 10 ¹⁹ ~
It may be added to a concentration of 9×10 ²¹ cm ⁻³ .

As the carrier gas 39, hydrogen (H ₂ ) was used during the reaction, but nitrogen (N ₂ ) was used in the form of liquid nitrogen before and after the start of the reaction. These reactive gases passed through the respective flowmeters 33 and valves 32, and were supplied to the reaction vessel 6 through the reactive gas inlet 17 and the negative electrode 61 of the high frequency power source. Reactive gas is 70
The negative electrode 61 and the positive electrode 5 are introduced into the substrate 1 and the holder 74 forming a cylindrical space.
Electrical energy, such as high frequency energy of 13.56 MHz, was applied between 1 and 1 to cause a reaction, and a reaction product was formed as a film on the substrate.

The substrate was heated to 100-400°C, for example 200°C, by infrared heaters 11, 11'.

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 perpendicularly to each other, so that the cylindrical space in the reaction vessel can be heated to 200±10°C, preferably ±5°C. It was installed within ℃. This heater only has a 200~200°
Temperatures of 120°C and 80°C also caused non-uniformity and were not practical at all. Furthermore, by making the substrates orthogonal to each other, the temperature distribution between the substrates could be kept within ±10°C. Thereafter, as described above, the above-described reactive gas was introduced into the container, and high-frequency energy 14 of 10 to 50 W was further supplied to cause a plasma reaction.

Thus, the P-type semiconductor layer has B ₂ H ₆ /SiH ₄ =0.5%,
A thin film having a thickness of about 100 Å was formed using this reaction system under the conditions of CH ₄ /(SiH ₄ +CH ₄ )=0.5. Eg=2.0eV, σ=1×10 ^-4 ~3×10 ^-3 (Ω
em) It was ^-1 .

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, a transparent conductive film (ITO or tin oxide with a thickness of 600 to 800 Å
(electrode coatings) are sputtered, and the tin oxide turns into metallic tin, making them less transparent and more likely to become cloudy.

To achieve this, it is best to make the plasma electric field approximately parallel to the surface to be formed, and since the reaction products caused by this electric field move along the surface, clouding due to the spaght effect is not seen even when 30 to 50 W is applied, and the vertical electric field Compared to the case where the limit was 2 to 5 W, the characteristic yield and manufacturing yield were improved.

Substrates include conductor substrates (stainless steel, titanium, titanium nitride, and other metals), semiconductors (silicon, silicon carbide,
germanium), insulators (alumina, glass,
Organic materials) or composite substrates (conductive films such as tin oxide or ITO on a glass insulating substrate or a single layer on ITO)
One in which a two-layer film with SnO ₂ is formed, one in which conductive electrodes are selectively formed on an insulating substrate,
A P- or N-type semiconductor formed on an insulating substrate was used. 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 flexible or a rigid plate.

In this manner, a plasma reaction was performed for 1 to 5 minutes to produce a silicon carbide film doped with boron or gallium as a P-type impurity. Further, the substrate on this first semiconductor layer is moved to the second reaction vessel 7 according to the above-described operation sequence, and here the intrinsic semiconductor layer is deposited about
It was formed to a thickness of 5000 Å.

In other words, in the reaction system shown in FIG.
Similarly to the system, high frequency energy of 13.56 MHz was supplied from the high frequency power supply 15 to the electrodes 18 and 21 forming the pair. The substrate was heated to 250° C. by heaters 12, 12. The reactive gas flows from above to below along the surface of the substrate 2 to be formed, and reaches the vacuum pump 37 . A sectional view of the system viewed from the outlet side of 43 is shown in FIG.

Figure 2 is outlined.

In FIG. 2, the reaction vessel 7 is equipped with a viewing window 48, a copper mesh 49 for preventing leakage of radio waves, a quartz window 55 for supplying microwaves on the back side, a waveguide 54, and a power supply 56 for microwaves or millimeter waves. Reactive gases 26, 27, 2 are applied parallel to the formation surface of the substrate 2.
8 and a high frequency electric field 15 are arranged.

Furthermore, in addition to high frequencies, microwaves with a frequency of 1 GHz or higher, for example 2.45 GHz, are supplied.

In FIG. 2, the reactive gas is introduced from the quartz tube inlet into the mesh or porous electrode 6.
7 and derived it. reactive gas outlet 18;
Substrate 2, holder (substrate support) 74, exhaust port 2
1. The correlation between the pair of electrodes 67 and 68 is further shown in a perspective view (with the front half cut away) in FIG.

To show a more preferable example, in FIG. 3, it is preferable that the substrates 2 are placed parallel to each other with a fixed gap of, for example, 3 cm, in a vertical direction (vertical direction) in a holder 74 which is an insertion type with their back sides aligned with each other. . The holder is made of quartz and has a disk-shaped disk on the upper side and a substrate groove 95 connected to the disk. The disk is held in space by four supports 80, 80', which are connected to the shaft 7.
9,79' rotations, thereby rotating the disk at a rate of 3 to 10 times per minute to promote homogenization of the reactive gases.

The reactive gas is blown out downward from the outlet 18 through a hole 73 of 1 to 3 mm, then to a mesh electrode (hole of about 5 to 10 mm) 67. The guide 70 of the holder prevents the release of reactive gas in the 82 direction.
1, the gap was 1 cm or less, preferably 2 to 5 mm.
The reactive gas is formed into a cylindrical shape by the formation surfaces of the substrates 2, 2 and the wall 96 for holding the groove 95 for raising the substrate 2, that is, a chimney-shaped hollow. It is preferable to flow it in layers in the directions of 83 and 85. That is, a substrate support is placed between a hood made up of the upper lid 93 and the guide 70 and a hood made of the lower lid 94 and the guide 71, using a substrate holder, to create a closed space that confines the plasma. The quartz sidewall 96 is placed 10 to 20 mm away from the groove 95 to prevent reactive gas from sagging on the sidewall 96, thereby improving the uniformity of the coating thickness at the edge of the substrate 2. promoted.

Regarding the exhaust system, in order to reduce the inflow of reactive gas from 84 and selectively give priority to 85, the gap between guide 71 and the bottom end of the substrate was set to 1 cm or less. In other words, the conductance of the gas flow of 82, 84 should be about 1/5 or less, preferably 1/3 of that of 83, 85.
By setting the ratio to 0 to 1/100, reactive gas was selectively introduced into the cylindrical space. The distance between the positive electrode 68 and the lower end of the substrate was determined by adjusting the height of the guide.

Furthermore, the negative electrode 67 and the upper end of the substrate, that is, the disk 74
Similarly, the distance between the guide 70 and the guide 70 was adjusted.

As is clear from FIG. 3, the electrode has a quartz guide 70, an upper lid 93, a guide 71,
It is surrounded by a lower lid 94, which serves to prevent parasitic discharge between the electrode and the inner wall of the chamber (particularly the stainless steel chamber). Furthermore, since the inner diameter of the reactive gas inlet 18 and the negative electrode have approximately the same size, and the inner diameter of the exhaust port 21 and the positive electrode have approximately the same size, when high-frequency discharge is performed,
It flows along this cylindrical space, that is, the surface on which the reactive gas is formed, preferentially causing plasma discharge in the space.
As a result, the plasma conversion rate of the reactive gas becomes extremely high, and it is possible to prevent excessive reaction products from adhering to the inner wall of the reaction vessel (belgear) in the form of flakes, which can cause pinholes. Ta.

In addition to the configuration of FIG. 3 as described above, in FIG. 2 with corresponding numbers, infrared lamps 12,
12' are preferably provided in the upper and lower directions to promote homogenization of the substrate.

The structure shown in FIG. 3 is similar to that of the electrodes, substrates, holders, reactive gas outlets, and exhaust ports in the reaction vessels 6 and 8 in the system shown in FIG. Thus, in FIG. 3, the substrate and substrate holder were able to arrive from the system direction 77 and move in the system direction 78 without any problem.

In the drawing, a growth rate of 3 Å/sec at 250°C could be obtained by using a high frequency electric field of 20 W and adding silane at 30 c.c./min. As a result, compared to 0.1 to 1 Å/sec in the conventional parallel plate type electrode system, the film growth rate in the same reaction vessel is 10 cm □ 8 Å/sec compared to 10 cm □ 1 Å/sec in the former case. If it is 0.5 Å/sec, it will be 6 times, totaling 48
It has become possible to produce double the amount. Furthermore, in the conventional space for fabricating 50 cm substrates, 20 cm x 50 cm substrates can be arranged at the same time with a gap of 5 cm, making it possible to arrange 20 at the same time, and the area to be formed is essentially 8 times as large as 20 x 50 x 20 = 2 x 10 ⁴ cm ² . The distance between the electrodes is shorter than the conventional 4 cm.
Since the length is 25 to 27 cm, the ionization rate of the reactive gas is improved, and the film growth rate is 4 Å/sec. As a result, it is an extremely ideal mass production method that effectively has a growth rate 64 times faster. It turns out that it is.

Since the semiconductor layer thus formed has a long plasma state distance, its photoconductivity also ranges from 2×10 ^-4 to 7×
10 ^-3 (Ωcm) ^-1 , dark conductivity 3×10 ^-7 to 1×10 ^-9 (Ω
cm) ^-1 .

In this way, the type semiconductor layer is approximately 5000 Å thick in the system.
After forming the substrate to a thickness of , the substrate was transferred to the reaction vessel 8 of the system according to the operations described above, and an N-type semiconductor layer was formed. To this N-type semiconductor layer, as shown in FIG. 1, phosphin was supplied from 31 at PH ₃ /SiH ₄ =1.0%, silane was supplied from 30, and carrier gas hydrogen was supplied from 29 at SiH ₄ /H ₂ =50 to form a system. Similarly, an N-type microcrystalline or polycrystalline semiconductor layer having a fiber structure was formed to a thickness of 200 Å. Other reaction equipment is the same as the system.

After this process, enter the PIN from the second preliminary room 9.
An aluminum electrode with a thickness of about 1 μm was made by vacuum evaporation on the substrate that had been formed by forming the bond, and an (ITO + SnO ₂ ) surface electrode - (PIN semiconductor) (Al back electrode) was formed on the glass substrate. .

Its properties as a photoelectric conversion device are 7 to 9%, with an average of 8% as an intrinsic efficiency characteristic at AM1 (100mW/cm ² ) on a 10cm□ substrate, making it a hybrid type.
Even on a 15 cm x 40 cm substrate, we were able to obtain an intrinsic efficiency of 6 to 7%. This improvement in efficiency is due to the extremely planar structure of the PI junction on the side where light enters.
Also, in non-single crystal semiconductors such as amorphous semiconductors or semi-amorphous semiconductors, an I-type semiconductor layer is grown and laminated on a P-type semiconductor layer, and the open circuit voltage is 0.88 to 0.9V. The short circuit current is large at 20-22mA/ ^cm2 , and
FF is also large at 0.70 to 0.78, and the density of recombination centers inside the PIN type semiconductor layer is 1/1 compared to the conventional method.
It is estimated that the increase in current due to the reduction in current by 10 to 1/50 has led to a significant improvement in characteristics.

As described above, the plasma reactor of the present invention improves the productivity of semiconductors formed by 30 to 70 times, and also has improved characteristics compared to the conventional conversion efficiency of 5 to 7%.
This is an extremely original product that improves performance by 30%.

Reference Example 1 This example is a modification of Example 1, and a drawing corresponding to FIG. 2 is shown in FIG. 4. Other details are the same as in FIGS. 1 to 3.

FIG. 4 is a vertical sectional view of a plasma reaction vessel in which an I-type semiconductor layer is formed.
It is ejected laterally from 8. Further, the discharge port also passes through 21 and reaches the rotary pump 37 from 76. The substrates 2 are arranged vertically in a row and are held in space by a holder 74. Guides 70 and 71 allow the reactive gas to flow selectively into the horizontal cylindrical space. The high frequency power source 15 has a negative electrode 67 and a positive electrode 72, and the infrared lamp has one
2 and 12' were installed above and below to promote uniform heating.

This embodiment has the characteristic that the substrate 2 holder 74 can be easily moved to the system. However, a large amount of reactive gas flows upward due to the rising temperature, and the upper side of the substrate tends to become thicker. For this reason, it is necessary to arrange the substrate in the direction of 18 to 21, but this has the drawback 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 outlet side. 1
However, it had a drawback in that it could not uniformly obtain high-quality characteristics over a large area.

Reference example 2 FIG. 5 shows another reference example.

FIG. 5A shows an outline of the drawing corresponding to FIG. 3 of the first embodiment. In FIG. 5A, the reactive gas flows from the inlet 66 through the negative electrode 67 to the exhaust port 21, the positive electrode 68, and the exhaust system 74.
The substrate 2 has a tapered shape and becomes narrower from the inlet side to the exhaust port side of the substrate, further promoting uniformity of the formed film.

In case A, the flakes tend to adhere slightly to the surface on which they are formed, so in case B, it is also possible to provide the outlet for the reactive gas upward rather than the outlet downward.

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 was about half that of the manufacturing equipment shown in Figure 1.

In the embodiments of the present invention described above, one PIN junction is provided. However, for many applications such as PINIP type phototransistors, PINPIN......PIN tandem structure photoelectric conversion devices, it is sufficient to further connect reaction vessels according to the number of semiconductor layers, and the technical idea of the present invention also covers these applications. Needless to say, it is included.

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. In the present invention, it is important that the plurality of stacked semiconductor films formed are P-type, N-type or I-type semiconductors having at least one PI, PN or NI 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 by Si-H or C-H,
It goes without saying that -Cl, C-Cl and a halide gas, particularly a chloride gas, may be used, but the concentration is preferably 10 atomic % or less, for example 2 to 5 atomic %.

Regarding the type of semiconductor to be formed, see Example 1.
However, in the group Si, Ge, SixC _1-x (0<x<
1), SixGe _1-x (0<x<1), SixSn _1-x (0<x
<1) In addition to this, GaAs,
It goes without saying that it may be a compound semiconductor such as GaAlAs, BP, or Cds.

P- or N-type impurities are selectively mixed or diffused into the silicon carbide film formed according to the present invention using photo-etch technology to partially form PN junctions, and this junction can be used to create transistors, diodes, W A PIN junction type visible light laser, light emitting element, or photoelectric conversion element having a -N-W (WIDE-NALLOW-WIDE) structure may be made. The so-called W-N (WIDE TO NALLOW) has a heterojunction structure with a particularly large energy band width on the incident light side.
This makes it possible to independently manufacture and stack products of different conductivity types in each reaction chamber, which we 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. Figure 3 is the second
Figure 2 shows a perspective view of a portion of the illustrated apparatus; FIG. 4 is a reference example corresponding to FIG. 2. FIG. 5 shows the third embodiment of the present invention.
This is another reference example corresponding to the figure.

Claims (1)

[Scope of Claims] 1. A plurality of substrates are placed between a pair of electrodes fixed in a reaction container, a hood outside the reaction container, and the pair of electrodes, with the distances between opposing surfaces to be formed kept at equal intervals. By providing a movable substrate support that surrounds the plurality of substrates and having holding means, the pair of hoods and the substrate support form a closed space that confines plasma, and a reactive gas is introduced into the closed space. An apparatus for laminating a film on a substrate, the apparatus comprising a plurality of reaction vessels connected via gate valves for opening and closing the reaction vessels, each of which is equipped with a supply system for a reaction vessel and a discharge system for a reactive gas from the closed space, the apparatus comprising: means for arranging the substrate support in a plasma region between a pair of electrodes in the reaction vessel so as to confine the plasma and prevent formation of a film on the inner wall of the reaction vessel, and then the closed space; and means for generating plasma by introducing a reactive gas into the substrate to form a first film on the surface to be formed, and holding the substrate after the film has been formed in the first reaction vessel. means for moving the support and the substrate to an adjacent second reaction vessel using a jig for holding the support and means for opening the gate valve; means for closing the gate valve; and a pair of electrodes in the second reaction vessel. and means for forming a second coating on the first coating by arranging the substrate support between a pair of hoods on the outside thereof in the same manner as in the first reaction vessel. Plasma gas phase reactor. 2. The reaction vessel in claim 1,
a reaction vessel for forming a P-type semiconductor layer;
A reaction vessel for forming an N-type semiconductor layer and a reaction vessel for forming an N-type semiconductor layer are connected, and the reactive gas introduced into each reaction vessel is connected to the connected part of each reaction vessel as a plasma gas. A plasma gas phase reactor equipped with a gate valve to prevent the gas from entering other reaction vessels during the phase reaction.