JPS6057679A - Semiconductor device - Google Patents

Abstract

PURPOSE:To drive electronic machines by a method wherein a non-single crystal semiconductor layer element, in which hydrogen or halogen element is added, is formed on an arbitrarily shaped semiconductor substrate, and a photoelectric conversion is performed. CONSTITUTION:An irradiation light 43 is supplied to the semiconductor layer having the roughened surface of 1mm., for example, in height difference 44 on one main surface of a substrate 41. Glass is used for the substrate 41, for example. An ITO is formed on the upper surface of said substrate 41 by performing a sputtering method, and then a hydrogen-added single crystal semiconductor having a P-I-N junction is formed using a plasmic vapor-phase reactor. Then, a P type non-single crystal semiconductor is formed using silicon carbide, and an I type silicon semiconductor is formed on the upper surface of said P type non- single crystal semiconductor using silane. Besides, an N type non-single crystal semiconductor is formed in specific thickness, and Al is used for a back side electrode.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides at least one PN junction, PIN junction, and job 1-main junction in a semiconductor layer provided in a layered manner on a substrate, and utilizes such junction to convert photoelectric conversion devices ( 1- cells, solar cells, also fluorescent lamp cells).

The present invention is applicable to containers such as plates, cups, and cups, electric light umbrellas,
A part of a roof having a glass window or an uneven surface,
By forming it on a substrate having an arbitrary shape, it is intended to be used as part of power generation equipment for consumer use or general home use.

In particular, the present invention can reduce the degree of such unevenness with a height difference of 10 μm.
In particular, it may have a thickness of 1 mm or more.

Conventionally, it has been thought that it is impossible to provide a semiconductor surface layer with a uniform thickness due to the irregularities on the surface, especially the recessed portions of the concave surface. However, it has been found that this impossibility is largely attributable to the manufacturing method of the semiconductor film. That is, conventionally, when forming and completing by a gas phase method at normal pressure, the amount of carrier gas was flowed in an amount 100 to 10,000 times that of the reactive gas.

For this reason, the carrier gas, which is an inert gas, actually prevents the reaction products from adhering to the recesses.

Based on this fact, we do not use carrier waste at all.
In addition, a reaction system that is virtually unused is utilized.

A typical example of this is the reduced pressure gas phase method. However, the reduced pressure gas phase method is characterized only by the fact that the inside of the reaction tube is kept under reduced pressure. For this reason, if the degree of pressure reduction is set to about strong<1 m+nHg, the formation of a film on the substrate by the reaction product will be significantly reduced. In the present invention, the pressure inside the reaction vessel is 0.01 to 10 to
rr, and in addition, the container is characterized by containing substantially only reactive gas or only reactive gas and additives. In addition, to further strengthen the semiconductor properties of the semiconductor film.
0.1 to 200 mol (atomic)% of hydrogen or halogen elements
The second feature is that it is added to the semiconductor film.

In the present invention, the substrate having an uneven surface is 1μ or less, especially 0.1μ or less, which is found in so-called integrated circuit electronics.
~0.5μ height difference, i.e. at least 10
It means irregularities of μ or more, preferably l mmo. This substrate can have any shape, such as a container such as a plate, a pot, a cup, an electric light umbrella, a glass window, or even a part of a roof with an uneven surface. The present invention provides such irregularities of such a size that they are sufficiently visible to the naked eye, and a semiconductor layer is provided on the inner or outer surface of such a hard or elastic flexible substrate. According to the present invention, it is possible to fabricate a photoelectric conversion element using a non-single crystal semiconductor, and even if such a non-single crystal semiconductor is subjected to some local stress, there is an abnormal decrease in reliability or stress sensitivity. This is based on the experimental fact that the method of the present invention is not necessarily flat, and the fact that the substrate having the surface to be formed does not necessarily have to be flat, at least as long as the method of the present invention is used.

Examples thereof will be described below with reference to the drawings.

FIG. 1 shows the principle of operation when used in a photocell or solar cell.

That is, in FIG. 1(A), a conductive film (2) such as tin oxide (SnOL) or ITO is formed on a transparent substrate (3) of a semiconductor layer (1) such as glass or sapphire, and a semiconductor layer is further formed on top of this. Layer (1) was formed. This semiconductor layer may be a MIN (metal-intrinsic semiconductor-N-type semiconductor) Schottky junction structure, a PIN <P-type semiconductor-intrinsic semiconductor-N-type semiconductor) junction structure, or a PN junction structure, or It may be possible to connect these in multiple ways. It fulfills the purpose of the invention and has high light-
It may be determined based on the electrical conversion efficiency (η) obtained and the ease of manufacturing.

Furthermore, in Figure 1, an electrode (4) is placed on the upper side of this semiconductor layer (1).
has been established. Light is incident from the left side in (5).

Although this drawing uses a light-transmitting substrate, the present invention is capable of converting artificial light such as a photocell, solar cell, or fluorescent light battery (such as a white fluorescent light) into electricity to produce radios, electronic clocks, etc. It may also be a battery that operates other electronic devices.

・For such cells or batteries, especially fluorescent lamp batteries, a flat battery is not necessarily a preferable form, and the structure of the present invention using the structure of FIG. 1(A), that is, FIG. 3(A) When you consider its shape, you can see that it is extremely efficient.

After making the external case for radios, electronic watches, etc.
This is because the substrate, which is a case, protects against mechanical stress, and for photo-electrical conversion, part or all of the surface of the container can be used as a light-receiving surface.

In FIG. 1(B), a lower electrode (2), a semiconductor layer (1), and an upper electrode (4) are provided on a substrate (3). The upper electrode is shaped like a comb or a fish bone to improve light absorption and electrical conductivity.

The structure shown in FIG. 1 (B, ) can be used, for example, as an umbrella for an electric light. An example thereof is shown in FIG. 3(B). This is a case in which a photoelectric conversion battery is installed in the -813 protective case for an electric light or fluorescent lamp, for example, inside the upper case of the electric light. In such cases, it is necessary to make a hole in the medium heat part. Also, by using this method, it is possible to easily draw out a voltage different from 100V. Therefore, a low voltage can be generated without using a transformer etc. It can also be used as a charger for , radios, curriculum lakes, etc.
In addition, such electricity can be used to produce light different from continuous light, such as red,
It may be electrically connected to a light emitting element that emits light of a specific wavelength such as green.

The structure of the semiconductor layer in FIGS. 1(A) and 1(B) is disclosed in Japanese Patent Application No. 53-086867 filed by a fudo disciple.
-086868 (filed on July 17, 1978), "Photoelectric Conversion Semiconductor Device and Method for Manufacturing the Same".

FIG. 2 shows an apparatus for carrying out the method of manufacturing a semiconductor device according to the present invention, in which a semiconductor layer is provided on a substrate having a partially uneven shape. The molded substrate (21) is attached to the holder (22).
) J:, and unnecessary parts are shielded by (23). This substrate was placed in a reactor (24). The reactive gases are (28) a silicide gas such as silane, (28) a silicide gas such as silane;
9) introduces a carbide gas such as methane, (30) introduces an impurity capable of exhibiting P type conductivity such as diborane, and (31) introduces an impurity exhibiting N type conductivity such as phosphine or arsine. (35) is an inert gas that is used to purge the inside of the reactor before and after the reaction. These are introduced into the reactor (24) from the entrance (27) through an excitation system (exciter) <26) using microwaves. Microwave is 1~10G
For example, a frequency of 2.46 GIIz is used to chemically activate, decompose, or react a reactive gas, resulting in a plasma state. Carbon is mixed into silicon, resulting in silicon carbide 5ix
When C1-x (0≦X<1) is formed, the energy gap is larger than 1.5 eV and is 1.7 to 3.5 eV.
Any value between can be obtained by changing the value of X. It has been experimentally found that the surface on which reactive gases are formed does not necessarily have to be flat in a reactor because only reactive gases are excited, decomposed, or reacted in an exciter. Furthermore, this exciter (26) and reactor (24) are 0.01~
The pressure is reduced to 10 torr, and the reaction product in the active state is 1 to
It is further activated by high frequency energy (25) with a frequency of 10 MIIz, adheres to the uneven substrate surface, and becomes II. The degree of pressure reduction can be set to a constant pressure using a vacuum pump (34) and a needle valve (33) in the preceding stage.

Silane was used as the silicide for the reactive gas, but dichlorosilane (SiH, CI), trichlorosilane (S
iHCll>, silicon tetrachloride (SiC1,) may be used, and the carbide may be not only methane (C11,) but also other hydrocarbons such as propane (CIH,).

Moreover, even if this carbide is not used, ammonia (Nl+, ), hydrazine (NLll,
) may be used. Nitrogen, which is generally inexpensive, is used as an inert gas for purging, but after the semiconductor layer has been formed on the substrate, active hydrogen can be added to the semiconductor to eliminate unpaired atoms in the semiconductor layer. Hydrogen (II) may be introduced from this (35) in order to neutralize and remove the bond. By such induction annealing of hydrogen, 10 to 50 atomic % of hydrogen could be added into the semiconductor layer. Adding a halogen element instead of hydrogen was effective in neutralizing and removing dangling bonds. The temperature of this induction aryl is below 250°C for silicon and 350°C for silicon carbide.
It is preferable that the temperature is below .degree. C.; above these temperatures, added hydrogen tends to be re-released and 5i-H bonds and C-H bonds are broken.

The substrate temperature in the reactor was room temperature to 350°C.

Of course, the temperature may be from room temperature to 500°C. However, since temperature control for the substrate brings about material limitations,
0°C was practically preferred.

The reaction products are determined in relation to the pressure inside the reactor, but
The film could be formed evenly thicker than that. The growth rate of the semiconductor film is 10 people/min to 1
μ/min, which can be carried out by changing the pressure from 0.01 to 1 Qtorr and by adjusting the microwave energy of the exciter or the high frequency energy of the reactor.

The semiconductor device of the present invention was achieved because the following major process characteristics were discovered.

Firstly, because the reactor is under reduced pressure, the mean freedom of the reactive gas or reaction product is about 20% thick (therefore, it is possible to sufficiently fly into the interior of the recess, and there is Because an exciter is installed at the same time, the reactive gases mix completely with each other, resulting in stoichiometrically homogeneous reaction products.

Secondly, because the reactive gas or energy is extremely excited, the height difference between the unevenness of the substrate is 0.
Not only fine roughness such as 1 to 1μ, but also 10μ or more, especially even if the surface is shaped like a container, can be coated uniformly on the surface of all parts.

Thirdly, since the substrate itself is heated by resistance heating etc., the coating temperature is insensitive to the temperature of the substrate surface.
And the temperature of the board is room/l! ! ~200℃ or 350″
C, the temperature of the surface of each part of the substrate is unlikely to become non-uniform, and as a result, non-uniformity in the film thickness of the film is not promoted.

Fourth, although Fig. 2 shows a horizontal reactor, it is also possible to create a vertical reactor or a movable continuous reactor in which the substrate can be moved.In other words, reactive gas It is possible to form a large amount of film on the inlet side, and not to form any film on the back side.

The semiconductor device of the present invention was invented because many of these features were experimentally obtained. Of course, uniformity as used in the present invention means that the variation in film thickness is generally within ±5%, and that the electrical characteristics are such that it is not necessary to take into account the non-uniformity of the film.

As described above, the reduced pressure vapor phase method or the plasma vapor phase method can also be called a glow discharge method in which glow discharge occurs in the reactor due to the pressure in the reactor.

FIG. 3 shows an embodiment of the semiconductor device of the present invention.

(A) and (B) are as shown in (A> and (13>) in FIG. 1, and are irradiated with light from (43).

FIG. 3 () 3) shows that 1 (J height difference < 44) of the − main surface of the substrate (41) is 1 μ or more, for example, 1. mm or more.

A semiconductor 1m (42) was formed on this uneven surface.

FIG. 3(D) shows a container-like structure with a hole partially formed. An example is an indoor table clock.

Specific examples of the semiconductor device of the present invention will be shown below to supplement the content of the present invention.

Specific Example 1 Glass (thickness 1.1 mm) is used as a substrate, and its upper surface has a height difference of 1 mm, and there are four convex rfl (inside is 1 mm). Its vertical cross-sectional view is shown in Fig. 3<B. ) is shown in
An enlarged view is shown in FIG.

ITO was formed on the upper surface by sputtering, and a hydrogen-doped non-single crystal semiconductor having a PIN junction was formed using the plasma vapor phase reactor shown in FIG.

That is, a P-type non-single-crystal semiconductor was formed of silicon carbide (thickness: 150 mm), and an I-type silicon semiconductor was formed on the upper surface thereof using 100% silane without using any carrier gas. The average film thickness was 0.7μ.

Furthermore, N-type non-single crystal semiconductor has a pH of 7/Sil+4.
= 1% and laminated to an average thickness of 500. The back electrode was made of aluminum. The reaction conditions for forming a non-single crystal semiconductor are a substrate temperature of 210°C and a high frequency output of 3.0°C.
50MHz, pressure 0.1torr, film growth rate 9
0 people/minute. f'f characteristic is open circuit voltage 0.6
V, short circuit current 20μ8, fill factor 0.48, conversion efficiency 3
,7%.

Concrete Example 2 In FIG. 4, a semiconductor film was formed under the process conditions of Concrete Example 1 on a monitor substrate j& (41) for investigating the uniformity of a film formed on the uneven surface of the structure of the present invention.

The height difference (14) of the unevenness of the substrate was 1 mm, and the concave portions and convex portions were all 1 mm. The above-mentioned non-single crystal silicon was formed on such a substrate, and the uniformity of the film was examined. The results are as follows.

Surface of convex part (11) 0.8μ Surface of concave part (13) O', 7μ Side surface of concavo-convex part (12) 0.6μ This value is the surface of convex part in the conventional method using a large amount of carrier gas. 0 to 1.1 μ Surface of four parts 0.6 to 0.7 μ Side surface of unevenness 0.1 to 0.5 μ Therefore, the characteristics of the photoelectric conversion device as shown in Example 1 could be obtained for the first time.

In the present invention, a typical example of the substrate is a hard material such as glass, ceramic ζnox, or a metal plate. However, it goes without saying that a flexible substrate such as polyimide resin may also be used. Alternatively, the substrate may have elasticity.

Note that the non-single-crystal semiconductor material meant in the present invention simply refers to silicon,
Not only silicon carbide but also other compound semiconductors may be used.

The feature of the present invention is that a layer of a non-single crystal semiconductor is provided on a part or all of the uneven substrate surface, and a photoelectric conversion element or a light emitting element is provided using this layer. A predetermined low voltage of 5 to 6 V could be generated without using a lance. Furthermore, the battery is used to charge the radio or calculator, and a photoelectric conversion element is provided on the surface of the radio or calculator on which the user rests or in close contact with the inside of a concave case, for example.

It is believed that the provision of a photocell, solar cell, or fluorescent lamp battery in close contact with such an uneven container according to the present invention will have extremely large industrial applications.

[Brief explanation of the drawing]

FIG. 1 shows an embodiment of a photoelectric conversion device for carrying out the present invention. FIG. 2 shows a method for manufacturing a semiconductor device of the present invention. (A) (8-inch rack 1■ y2 (2)

Claims (1)

[Claims] 1. Hydrogen or halogen elements are added onto a substrate of any shape, which is a container such as a plate, a pot, or a cup, an electric light umbrella, a glass window, or a part of a roof having an uneven surface. A semiconductor device characterized in that it performs photoelectric conversion by forming a non-single crystal semiconductor layer. 2. In claim 1, the substrate is hard or elastic, and a non-single crystal semiconductor layer having a PN junction, an I''IN junction, or a Schottky junction is provided on the inside or outside of the substrate. 3. A semiconductor device according to claim 1, characterized in that the degree of unevenness is at least 10 μm or more.