JPS63177475A - Manufacture of photoelectric semiconductor device - Google Patents

Abstract

PURPOSE:To prevent the reliability from lowering due to the absorption of moisture of the like and to enhance the mechanical strength for a semiconductor device by a method wherein, after a semiconductor layer and an electrode layer have been formed on a substrate, a film of an organic substance is formed in such a way that it can cover these layers and adheres closely to the substrate. CONSTITUTION:A photoelectric semiconductor device is made by forming a semiconductor layer 22 on a substrate 21 having the conductive surface and by forming an electrode layer 25 on the semiconductor layer 22. During this process, hydrogen or a hydrogen element as a key neutralizer for recombination is introduced into the semiconductor layer 22; the semiconductor layer 22 is formed in such a way that its size is enough to expose the substrate 21 at the outer circumference of the semiconductor layer 22 as viewed fro[m the side of the electrode layer 25. Then, after the electrode layer 25 has been formed on the semiconductor layer 22, a film 26 of an organic substance is formed in such a way that the film 26 covers said semiconductor layer 22, the side faces of the semiconductor layer 22 and the electrode layer 25 and adheres closely to the substrate 21. Said film 26 of the organic substance is to be composed of, e.g., an acrylic resin or a polyimide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a non-single crystal semiconductor having the same type, different type, Schottky junction, or multiple junctions thereof, which can generate photovoltaic force when irradiated with light, and a pair of electrodes sandwiching the semiconductor. The present invention relates to a method for manufacturing a photoelectric conversion device in which a protective film made of an organic or inorganic material is provided to cover the photoelectric conversion device.

The present invention aims to cover the side and periphery of a non-single-crystal semiconductor with such a protective film to prevent deterioration in reliability due to adsorption of moisture and the like and to improve mechanical strength as a semiconductor device.

The present invention provides a semiconductor in which light irradiation is performed by simultaneously adding an additive that can increase the energy band width (forbidden band width, or Eg) in a semiconductor in a photoelectric conversion device in proportion to the time when the semiconductor is formed. The object is to gradually reduce or substantially gradually reduce the EQ from the surface toward the depth direction. Furthermore, the present invention has one or more bonding surfaces approximately parallel to the semiconductor surface to which light is irradiated in the semiconductor, and the entire system includes PIN junction, NIP junction, P
ll 12N junction (intrinsic semiconductor ■ , ■2...
..., its Eg is Eq1>E Q2>...
) MIN junction or Mll 12N
It relates to providing a junction (M means providing a Schottky junction between a metal and a semiconductor).

That is, the present invention provides a method in which a non-single crystal semiconductor is provided in a layer on a substrate in which a metal or a transparent conductive film is partially or entirely coated on a conductor substrate, an insulator substrate, or an insulator carrier. , improvement of reliability as a device for photoelectric conversion semiconductor devices, especially solar cells and photocells, in which this semiconductor and other electrodes are provided on the upper surface thereof, and in particular, the formation of conductive parasitic chianels on the semiconductor surface due to light irradiation. The present invention relates to a structure of a photoelectric conversion device that prevents deterioration in reliability such as a decrease in output characteristics due to deterioration of diode characteristics due to deterioration of diode characteristics, and further improves mechanical strength and makes it easier to handle.

The present invention makes it possible to industrially mass-produce this type of semiconductor device, which has hitherto been made with a single crystal, but by making it a non-single crystal semiconductor, and the cost is 1/10th of that of the previous one.
The purpose is to have a diameter of 0 to 1/1000/10 cm.

Conventionally, as a photoelectric conversion semiconductor device, a solar cell using a homojunction for a silicon single crystal semiconductor has been used for artificial satellites, unmanned lighthouses, and other special purposes. In addition, CdS,
The main type thereof is a photocell having a heterojunction structure using a compound semiconductor such as GaA JAS or GaAs.

However, in both cases, the semiconductor material used was a single crystal material, so the manufacturing cost was so high that it was said to be a lump of electrical energy, and a large amount of ordinary thermal power and
There was no position to compete with hydroelectric power generation in terms of price. In addition, when compound semiconductors are used, the material itself is rare (expensive), and since it is a single crystal material, the energy band width changes discontinuously at the PN junction or other junctions. I had left it behind. That is, in a heterojunction using such a compound semiconductor, the interface of the PN junction and the interface of the semiconductor having different EQ are the same. Therefore, a large number of interface units (hereinafter referred to as NS) caused by the difference in Eg, that is, the difference in lattice constant, are generated in large numbers and intensively at the electrically very sensitive junction interface. Due to this crystal lattice misalignment, local levels due to dangling bonds and lattice defects (referred to as interface levels NS) have become recombination centers for excited carriers. For this reason, since the photo-excited charges are also recombined via the NS, the so-called absorption efficiency, in which the excited charges are taken out from the electrode as electrical energy, is reduced, making it impossible to put it into practical use.

FIG. 1 shows an energy band diagram in a conventional embodiment. That is, <A) is GaO, 3△I As
(N-type) and GaAs (P-type) using a Po,7N junction. In this case, the W-N structure (W
It has an IDE-to-NALLOW structure), and is designed so that short-wavelength light of light energy is absorbed quickly, so it is excited in a semiconductor region with a large Eg near the surface, and long-wavelength light is excited internally. ing. However, GaAIAs(1
) The excited electrons move to the substrate electrode 11 as shown in 7,
The holes move to the counter electrode 12 as shown in 8. G at the same time
The electrons excited in aAs (2) are like 10 at electrode 1.
However, the holes move toward the counter electrode 12 as shown in 6 because they are blocked by spikes 5 in the band etching that create an interface as shown in 13, and cannot diffuse and move to the counter electrode 12 as shown in 6. In addition, many of the holes 13 recombine with the electrons 7 via N5 (9), thereby erasing the electrons 7. This is an extremely serious drawback, and is the biggest drawback when attempting to produce photoelectric conversion semiconductor devices having these WN structures. In (B), 5n02, which is a conductive semiconductor, is formed with silicon 14 to form a Schottky junction (heterojunction). This structure has spikes 15,
There is a jump 20, but it also has a W-NII construction.

There is a drawback that the electrons in SnO2 (19) and the electrons in the hole pair 17 are recombined with holes excited in the silicon 14 via NS<16). Therefore, in both of Fig. 1 (A) and (B), even though we know that the energy band width of the most efficient conversion element is the W-N structure by light irradiation with a continuous light spectrum, this interface unit NS Due to the existence and distortion of the energy band width at the interface, that is, discontinuities due to jump spikes, etc.
In reality, it was completely impossible to create a practical device.

The present invention eliminates such drawbacks, and the energy band width (EQ) is continuous at or near the same or different junctions (continuous EGI in the present invention means its conduction band (EC), valence band ( (This means that Evl changes continuously and local discontinuous factors such as spikes and jumps cannot exist in reality or in theory regarding the structure.) and W in the same semiconductor.
-N band structure.

In addition, since the present invention has an optimal bandwidth under sunlight (AMI conditions), the semiconductor on the W side has a width of 1.5 to 3.
OeV, and the N side has 2.0 to 0.7 eV. The production of the present invention uses a reactive gas of a hydride or a halide such as chlorine, for example, a silicide gas such as silane, dichlorosilane, trichlorosilane, silicon tetrachloride, etc., and the film formation is also performed by a reduced pressure method. CVD
(vapor phase method) or glow discharge method.

For this reason, these reactive gases are stoichiometrically controlled to a controlled extent according to the amount of other additive reactive gases introduced, such as methane for carbon, ammonia for nitrogen, and water vapor for oxygen. It has the characteristic that it can be simultaneously mixed into the silicide gas described above. Therefore, semiconductors with different Eg can be continuously formed into multiple structures using the same reactor, and as a result, Eg
can be changed continuously. In addition, since the present invention is a non-single crystal, lattice mismatches or dangling bonds do not exist locally at lattice junctions, but lattice mismatches or dangling bonds exist equally everywhere. Furthermore, dangling bonds and the like generated due to this asymmetry are neutralized by hydrogen or a halide such as chlorine. That is, S
s r -H instead of l.

It is neutralized as 5i-CI binding. Of course, it is structurally irregular in addition to this, but it has a 3i-8: bond and s;-c-st, s for the addition of C, N, and O.
;-N-st, 5t-O-8i bonds.

Therefore, since the additive and 3i can be combined without any restrictions, the energy band width can be continuously and arbitrarily controlled due to the combination. That is, by simply changing the amount of additive between one semiconductor and the other, the result is 5i-c-st, 5t-N- per unit volume.
The density of the bonds of s + , s + -o-s t or their modified bonds changes, and as a result, <EQ can be changed based on the energy band theory attributed to such bonds. And the transition region is also continuous because the seedlings and types of additives are added in a continuous and homogeneous mixture (two semiconductors with a specific thickness have a specific EQ, and only the transition region is continuous). It can be industrially manufactured into a structure that has a continuous structure) or a substantially continuous structure (the two semiconductors have no thickness and the entire semiconductor is a smooth continuous structure).

The present invention will be described in detail below with reference to the drawings.

FIG. 2 shows the manufacturing process of a semiconductor device having the structure of the present invention. In FIG. 2(A), the substrate 21 is
An insulating carrier such as alumina, magnesia, beryllia, ferrite, or glass having a thickness of 100 to 1000μ or a metal film such as tungsten, molybdenum, titanium, or a translucent conductive film such as 5N02 on the upper surface thereof.
．． It is formed to have a thickness of 0.5 to 5 μm. Further, as the substrate, a metal substrate electrode made of titanium, stainless steel, iron or a base metal alloy, chromium, nickel, etc. may be used with a thickness of 100 to 1000 μm. Furthermore, a semiconductor layer was formed on this upper surface by a low pressure vapor phase method or a glow discharge method. This reduced pressure vapor phase method (hereinafter simply referred to as CVD)
The above-described substrate is sealed in the furnace at a pressure of ~0.01 torr, particularly 0.1 to 10 torr, and electrical or thermal energy is applied thereto. Furthermore, a reactive gas is decomposed or reacted in this reactor using electric or thermal energy, and the reaction product is formed into a film and deposited on the substrate.

In addition, in this CVD, the pressure is particularly 0.1 to 5 torr.
If only high-frequency energy is applied from the outside through a high-frequency induction coil spirally wound around the outside of the reactor, the reactive gas and carriers are turned into plasma, which is essentially the same as glow discharge. Generally, the glow discharge method is called a glow discharge method because glow discharge occurs in a reactor by applying such high frequency energy. In this method, it goes without saying that the substrate described above may be used as one of the electrodes for causing discharge. However, in this case, parallel planes must be formed between the electrodes forming another pair, which is not necessarily preferable in terms of mass production.

As the reactive gas, in the case of a single material, a semiconductor and an inexpensive material, ie, silicon or germanium, particularly silicon, was mainly used. That is, silane, dichlorosilane, trichlorosilane, and silicon tetrachloride, which are reactive gases of silicon, were used as the first reactive gas. In addition, boron (produced by decomposing diborane) is used as an impurity added to a semiconductor to form a P- or N-type conductive film, and for arsenic or phosphorus, arsine or phosphin is added to hydrogen or hydrogen chloride. Bombo diluted to .01-1% was used. Aluminum, gallium, or indium may be used as the P-type impurity.

In addition, silicon whose Eo is variable (hereinafter simply referred to as 3i),
Carbon (hereinafter simply referred to as C), Nitrogen (hereinafter simply referred to as N)
, oxygen (hereinafter simply referred to as O), tin, antimony,
For oxide semiconductors and conductors such as indium, the above-mentioned silicide gases, methane (CH4) or carbon chloride (CCI), ammonia (NH3) or hydrazine (N2 H4), water vapor (H20) or oxygen (02 ) or chlorides and hydrocarbons such as tin, indium, and antimony were used as the second gas. Of course, a composite reactive gas of two or more of N201No2, Co2, CH30H, etc. may also be used.

In this example, a horizontal furnace capable of mass production was used as the reaction furnace. In this, 20 to 100 boards 21 with a 100m opening are placed.
The sheets were arranged in parallel on the susceptor. A rotary pump was used for evacuation, and its displacement was 15001/min.

For heating, a high-frequency heating furnace of 1 to 10 MHz was used, and an induction heating coil connected to this heating furnace was installed in a helical manner around the outside of the reaction furnace, and its output was 50 to 500 KH. In this embodiment, high frequency energy is further added to the outer cylinder 2, and the structure is designed to absorb and reflect the high frequency energy emitted to the outside. Furthermore, an electrostatic shield is placed on the outside, and in addition, a heater is installed in a direction perpendicular to the induced current, that is, perpendicular to the coil surface, to prevent the dielectric current from flowing into the heating heater, so that the board can be heated by radiation using a resistance heating furnace. did. In this way, it is possible to apply both high frequency energy and radiant energy to the substrate. At the same time, in order to reduce the total energy consumption of this device, the high-frequency current from the high-frequency heating furnace was kept as low as possible, while the high-frequency voltage was applied as much as possible.

By doing this, this high frequency energy creates a discharge state of reactive gas in the reactor under reduced pressure,
turned into plasma and chemically excited or decomposed. On the other hand, with radiation heating, the temperature of the substrate can be controlled arbitrarily from room temperature to 1000℃.
The reaction product formed a film at a temperature of .

In the embodiments of the present invention as described above, heating is carried out to promote the formation of a film on the substrate, and reactive gas is turned into plasma.
The discharge that promotes excitation can now be controlled independently. Therefore, this device has many features such as saving energy for the entire device, improving the accuracy of temperature control of the substrate, and making it possible to arbitrarily control the excited state of the device depending on the additives and the reactive gas used. As a result, it was found that this is extremely important in industrially manufacturing the device of the present invention. In addition, by this method, the thickness of the coating is 10 to 1
Even 00A can be manufactured with high precision, and the accuracy of contamination and addition of impurities and additives is ±5°0% between lots.
I was able to do it within.

In the present invention, by employing such a method, in addition to already decomposed silicon, hydrogen, or chlorine, an additive of 01N or O is added to the substrate.

In addition to coating additives such as Sn and Sb, S
i-H, S i -CI, C-H, 0-CI, N
-81N-CI, O-H, 'O-CI and other reaction products that neutralize dangling bonds are 0.1 to 200%, especially 10
It was possible to mix in a concentration of ~50% using radio frequency energy. In particular, in order to neutralize these dangling bonds, after forming a semiconductor film in which additives are appropriately added as necessary, these dangling bonds are added in an atmosphere containing only halides such as hydrogen or chlorine. Holding the substrate and semiconductor, exciting these I2, HCl, and C12 with radio frequency energy, injecting some of the atoms into the film, and further chemically exciting H1H2, C1, C12, and HCl in this film. However, it was found experimentally that it is possible to bond with unneutralized dangling bonds naturally occurring in semiconductor films. By doing so, the occurrence of NS due to lattice misalignment can be sufficiently reduced even in a non-single crystal semiconductor. Therefore, if a non-monocrystalline film is simply made by vacuum evaporation or sputtering, 1
Concentrations of Ns from 0 to 1022 cm-3 were present as per the MOTT theory, but instead of covalently bonding each dangling bond to each other, they were bonded to the aforementioned dangling bonds as hydrogen or a halide such as silicon. By summing, this can be reduced to a concentration of 10 to 10 cm, i.e. 109
It has become possible to reduce the amount to ~1/104th. Furthermore, 10 to 50% of silane was added to form this film.
At the same time as introducing 0cc/min, B2H6 or PH, A3
10 to 10 to make this semiconductor H3 P or N type.
It was added to a concentration of 22 cm-3. In order to create an intrinsic semiconductor, this addition of impurities was discontinued, and the impurities adhering to the inner wall of the reactor were sufficiently purged. Industrially, it is of the P-1 or N-type, and the concentration of impurities present as a packing ground was 1014 to 1016 cm-3.

Further, C was added at a concentration of 10 18 cm -3 or more, for example, 0.1 to 100 atomic %.

Then, depending on the concentration of C and 3i, 3°5eV (S
An arbitrary EQ between i C) and 1,1 eV (Si) could be made. Of course, due to hydrogen such as H or halides such as 01, this Eq is apparently 0.2 to 0.6.
8V can be modified.

Similarly, in the case of N, 6. OeV and 1.18! In the case of O, it was between 8 eV and 1.18 V.

For solar cells, the EQ of the semiconductor surface is particularly 1.5 to 3.
．． The voltage was limited to a range of OeV, and the voltage at or near the substrate surface was set to 1.0 to 2 degrees OeV, particularly about 1.1 eV. Of course, germanium, GeH4, G
It may be further adjusted to a range of 0.7 to 1.1 eV using eCl4 or the like. Thus, PN junction, PIN junction, NIP
junction, PI3 I2N junction (EQll>E(JI2),
NII I2P junction, P1N1P2N2 junction, N1P
1N2P2 junction, MIN junction (Schottky junction), Ml
l One or multiple homogeneous, heterogeneous, or Schottky junctions such as I2N junctions were provided. Of course, if a specific junction is to be selectively formed in the semiconductor layer, a photoetching process, selective oxidation process, selective diffusion, or implantation method known in the IC manufacturing technology may be applied. In this way, semiconductor devices having special functions using various non-single crystal semiconductors can be manufactured. Furthermore, regarding the setting of the substrate, is it amorphous in the temperature range from room temperature to 500°C? (pure amorphous or polycrystalline with a crystal structure on the order of 10-100A(1) short range) is generally formed, and in the temperature range of 300-1000℃, the crystal grain size is 100A-1ooμ. Polycrystals of the order of magnitude could be formed by the flow of reactive gases in the reactor, film formation rate, and heat treatment (annealing) described above.

In the present invention, non-single crystal is a general term for both amorphous and polycrystalline structures, and basically, rather than seeking a more perfect crystal structure, it is possible to create a semiconductor by energetically neutralizing dangling bonds. The idea is to use a semiconductor with a structure in which grain boundaries do not become a problem, that is, a non-single crystal semiconductor.

In this example, when the thickness of one semiconductor layer is made by low-pressure CVD or glow discharge using plasma and the vacuum pressure in the reactor is 0.05 to 5 torr, a film with no pinholes can be obtained even if the thickness is 5 to 100 A. It has the great feature of being able to be formed with good controllability. The semiconductor layer is P, I,
The thickness of each N layer is variable within the range of 20A to 40μ. If the layer thickness is greater than this, cracks are likely to occur in this reactor, so 40 μm is the industrial limit.

As described above, the semiconductor 2 in this example and in FIG. 2(A) was provided. An example of the energy band structure is shown in Figure 3.
This is shown in FIG.

Further, since FIG. 2 shows an example of a photoelectric conversion semiconductor device, such as a solar cell, lower silicon oxide or lower silicon nitride was formed on the upper surface of the device as an antireflection film. These are shown in Figure 2 (A).
In this case, it is sufficient to simply increase the date of addition of 01N. Further, when the additives are 0, it is preferable to add Sn and In1Sb to an extent constituting 5n02 or the like. When the semiconductor and the barrier film are changed continuously, electrically one is a semiconductor and the other is an insulator or a conductor. However, since there is virtually no boundary between the two, a non-reflective coating could be obtained. In particular, silicon nitride (hereinafter abbreviated as SiN)
That's what it means. This is S j N −S i 3 N 4
-x) serves as a barrier layer against H and CI, and also serves as an anti-reflection film that is virtually non-reflective against light, making it extremely desirable for the stability and reliability of semiconductor devices. .

As described above, the semiconductor 22 was formed to a thickness of 1 to 10 .mu.m, and then an antireflection film was formed to a thickness of 0.05 to 0.5 .mu.m. What is important in such a case is that Eg does not change discontinuously at the interface between the SIN and the semiconductor. Also, the refractive index does not change discontinuously.

Therefore, it is not necessary to design the thickness of the coating 23 so as to cancel out the reflection on the coating 23, the reflection from the interface between the semiconductor 22 and the coating 23, and the wavelength.

In other words, a major feature is that there is little or virtually no reflection from the interface.

In order to provide a counter electrode to this film (protective film) 23,
．． Holes with a thickness of 10 to 100 μm were punched in a comb shape or a mesh shape at intervals of 1 to 10 mm. In this case, the wavelength of this light was 23 and 22 depths. Also 0 in 22
．． Overetching may be performed to a depth of 1 to 0.5 microns.

Of course, in such a case, the conductivity type on the side surface of the counter electrode is limited to the same depth as that on the bottom surface. Furthermore, a metal such as titanium, aluminum, nickel, or chromium is formed on this upper surface by vacuum deposition, chemical vapor deposition (CVD), or sputtering to a thickness of 0.1 to 2 μm, and is further selectively formed into a comb or mesh shape. A counter electrode 25 was formed by photo-etching. Of course, in this case, the counter electrode 25 may be formed only in the etched hole by electroless plating. In this case, one step can be omitted and the cost can be reduced. Furthermore, in the present invention, after this, the upper surface is covered with acrylic, P.
Organic film such as IQ (polyimide resin) or SiO
This was done to prevent deterioration of reliability such as deterioration of output characteristics due to the formation of parasitic chianels on the semiconductor surface due to the adsorption of water etc. from the outside. In particular, as shown in the drawings, covering the exposed sides of the non-single crystal semiconductor with organic resin or inorganic material was extremely effective in preventing deterioration.

Furthermore, it is extremely important to prevent corrosion of metal electrodes and to prevent decrease in conductivity due to invasion of alkali sulfur into transparent conductive films. This protective film is also effective as a so-called mechanical shock protective film to facilitate handling in general use, and was formed to cover the photoelectric conversion device as shown in No. 26.

As described above, a second vertical cross-sectional view of the photoelectric conversion semiconductor device was obtained. In this case, light was irradiated from 27 on the upper side. If the substrate is glass, it is also possible from below. The conversion efficiency could be obtained in the range of 5-20%.

FIG. 3 is an energy band diagram of a semiconductor formed according to an embodiment of the present invention.

FIG. 3(A) shows a PN junction, and Ea has a W-N structure. The semiconductor 31 is provided on the electrode (substrate) 31 and is connected to a continuous junction (C0NTINUOUSJUNCTIO).
N) 33, 33' and reaches the P-type semiconductor 32.

A counter electrode 34 is provided at 32, and charges excited by light incident from the 34 side are transferred to 30 for electrons and 34 for holes.
It diffuses into the air, generating photovoltaic power. When 31 is silicon, the semiconductor 32 is a semiconductor doped with 01N or O, and in order to receive sunlight, 32 is 1.5~
2.5 eV, and 31 is preferably 1.0 to 1.5 eV. However, in order to further promote charge excitation and prevent a decrease in the diffusion distance due to impurity scattering of B or P, we
) is used.

This has a PIN junction, and the N-type semiconductor 31 and P-type semiconductor 35 each have a thickness of 50 to 5000A, typically 1
00OA, and the ■-type semiconductor 32 has a thickness of 0.5 to 10μ, typically 2μ. 31.35 is 102
It has an impurity concentration of 0 to 1022 cm-3, and the semiconductor 32
．． In No. 35, the amount of C added is 1 to 10% and 10 to 50%, respectively, and EQ>1.5 to 2. OeV, 1°8~2.
5 eV.

FIG. 3(C) shows a two-layer structure of ■-type semiconductor. Of the excited charges, electrons diffuse to the electrode 30 and holes diffuse to the counter electrode 34, generating photovoltaic force. 11
36 and I237 each have Eq=1.5 to 2.0.1.
It has 0 to 1.5ev. The thicknesses of I and I are 0°05 to 5μ, respectively. In these, the photoelectric conversion efficiency was 2.5 to 4% for (A), 5 to 7% for (B), and 5 to 13% for (C).

Of course, the substrate electrode, counter electrode, antireflection coating, etc. are in accordance with the embodiment shown in FIG. However, in FIG. 3, the conversion efficiency decreased significantly at high temperatures; for example, at 100° C., the conversion efficiency decreased by 50 to 70% compared to room temperature. Therefore, in order to improve efficiency at high temperatures, we created the structure shown in Figure 4.

FIG. 4(A) shows a PNPN structure. Between the electrode 40 and the counter electrode 45 is a semiconductor 41 (N
type) and 44 (P type). Further, semiconductors 42 (P type) and 43 (N type) with a concentration of 1015 to 1018 cm-3 are provided between them, and their thickness is 100 to 5000 A, which is sufficiently smaller than the diffusion distance of excited electron holes.
have. Also, Fig. 4 (B) shows PllNI PI3.
It had an N structure and was made in the same manner as (A). In (A), the efficiency was obtained at room temperature from 13 to 18%,
At 100°C, it was possible to obtain 10 to 15% under AM conditions. Of course, this counter electrode may be of a Schottky type, or a light-transmissive conductive film such as SnO2 may be formed instead of the counter electrode.

FIG. 5 shows an example of this, and FIG. 5(A) shows a MIN structure, in which a semiconductor 52 is placed on a substrate 51, and a light-transmissive platinum or titanium film with a thickness of 50 to 500 A is placed on top of the semiconductor 52 on top of the substrate 51. A film of gold mlI having a Schottky junction such as tungsten was deposited. A counter electrode 56 for extraction is provided around it.

The antireflection film was formed as 53. Furthermore, (B) is Sn
○2 A heterojunction according to (56) is provided. An extraction electrode 55, a substrate 51, and a semiconductor 52 are provided. In these (A) and (B), the semiconductor itself must be an IN junction or an 11 I2N junction in which the P-type semiconductor 35 is removed in FIGS. 3(B) and (C).

In this manner, a Schottky junction, a so-called MINSM1112N junction, was provided in FIGS. 5A and 5B.

As is clear from the above explanation, the present invention uses a non-single crystal semiconductor, continuously changes the EQ, and includes NS.
is uniformly dispersed in the semiconductor itself without localizing it to the interface or other specific parts, and the concentration is 10 to 10 cm.
-3 points. Of course, it is essentially preferable that the concentration be 1013 or less. For this reason, the dangling bonds in semiconductors are neutralized by mutually bonding with hydrogen (including deuterium) or halides such as chlorine, and the energy band width is limited to that of expensive materials such as compound single crystal semiconductors. carbon, nitrogen,
It is based on a method of uniformly dispersing an inexpensive material such as oxygen into a semiconductor film by using low pressure CVD or a plasma discharge method (glow discharge method) in combination to form a semiconductor film. Therefore, both impurity concentration and EQ are determined in proportion to the flow rate ratio of reactive gas introduced into the reactor.
It is extremely industrially superior in that it is easy to mass produce and is inexpensive.

It goes without saying that the same technique can also be performed using Si and Ge stoichiometrically. However, it should be noted that the concept is largely different from simply mixing in a single crystal semiconductor in that it is mixed in the form of a film at the same time as the film is formed and has a non-single crystal structure.

As mentioned above, silicon is mainly used as the material in the present invention. However, germanium, Cd51GaAs, GaP
The same applies to use as a compound semiconductor base semiconductor such as , BP, etc. Additionally, additives are not limited to sr, c, N, and o;
, Sb, ■n, Ge, Cd, S, Ga, etc. can also be used. However, it is well stated in the conventional explanation based on FIG. 1 that the concept of the present invention can only be developed in a non-single crystal semiconductor structure.

The present invention mainly describes photocells, solar cells, etc. Needless to say, the present invention can be applied to all photoelectric conversion semiconductor devices or light emitting semiconductor devices.

In the present invention, covering the photoelectric conversion semiconductor device provided on the substrate with an organic resin or the like is extremely effective in reducing or eliminating the so-called Stebleronski effect, in which the optical conductivity decreases due to light irradiation. This is one of the most important requirements when putting such a device into practical use using such a non-single crystal semiconductor. The device of the present invention has 10
Even when irradiated with light for a time of AM I (100 mW/cm2), the deterioration was reduced from 60% or more when there was no protective film to 5 to 20%.

As is clear from the above description, the present invention is based on reducing the number of recombination centers in order to extend the lifetime of carriers in a non-single crystal semiconductor. And as a result,
Even if Eg is changed as claimed by the present invention, it will jump to the changed region and no discontinuities such as spikes will occur, making it possible to manufacture a very convenient semiconductor device. As a result, the price of the finished product is 1/30 to 1/1000 compared to conventionally known single crystal semiconductor devices (solar cells).
Moreover, the mass productivity could be increased 10 to 1000 times.

[Brief explanation of the drawing]

FIG. 1 shows an energy band diagram of a conventional semiconductor device. FIG. 2 shows the manufacturing process of a semiconductor device having the structure of the present invention. FIGS. 3 and 4 are typical energy band diagrams of the semiconductor device of the present invention. FIG. 5 shows another embodiment of the invention. Figure 1 Figure 2 Figure 3

Claims (1)

[Claims] 1. A method for manufacturing a photoelectric conversion semiconductor device comprising: forming a semiconductor layer on a substrate having a conductive surface; and forming an electrode layer on the semiconductor layer. introducing hydrogen or a halogen element into the semiconductor layer as a recombination center neutralizing agent, and forming the semiconductor layer in a size that exposes the substrate around the outer surface of the semiconductor layer when viewed from the electrode side; Furthermore, after forming an electrode layer on the semiconductor body, an organic film is formed so that the film covers the semiconductor layer, the side surface of the semiconductor 1, and the electrode layer, and is in close contact with the substrate. A method for manufacturing a photoelectric conversion semiconductor device. 2. A method for manufacturing a photoelectric conversion semiconductor device according to claim 1, wherein the organic substance is made of acrylic or polyimide resin.