JPS6057678A - Fluorescent lamp battery - Google Patents

Abstract

PURPOSE:To drive the electronic machines such as a radio and the like by a method wherein a non-single crystal semiconductor layer in which hydrogen is added is provided on the surface of a substrate, and the light of a fluorescent lamp and the like projected on the semiconductor layer is converted into photoelectricity. CONSTITUTION:A semiconductor layer 42 having the roughened surface with the unevenness of 1mm. or more, for example, of the difference in height is formed on the main surface of a substrate 41. At this time, tin oxide is formed on the upper surface of said substrate 41 using glass, for example, and a hydrogen- added non-single crystal semiconductor having a P-I-N junction is formed using a plasmic vapor-phase device. In this case, the P type non-single crystal semiconductor consists of silicon carbide, and an I type semiconductor is formed using silane. Besides, an N type non-single crystal semiconductor is formed in the prescribed thickness, and a back side electrode is formed using aluminum. As a result, the irradiating light emitted from a fluorescent lamp is converted into photoelectricity, and the power source with which an electronic clock and the like will be driven can be obtained.

Description

Detailed Description of the Invention The present invention provides at least one PN junction, IIIN junction, or Schottky junction in a single crystal semiconductor layer doped with hydrogen or a halogen element, and the junction is illuminated by artificial light such as a white fluorescent lamp. This invention relates to fluorescent lamp batteries that irradiate radios, clocks, and other electronic equipment.

The present invention particularly relates to such a fluorescent lamp battery, in which a non-single crystal semiconductor is provided on tin oxide or ITO on a transparent substrate, and furthermore, such a transparent mt& may have an uneven surface formed on its surface. 4. +I sign.

Conventionally, as is clear from the fact that photoelectric conversion devices are generally referred to as solar cells, their purpose has been to irradiate sunlight and convert it into electrical energy. In addition, the semiconductor used for power generation is a single crystal semiconductor,
The present invention claims that the non-i11 crystalline semiconductor to which hydrogen or halogen elements are added (its crystal structure is also +1.
) Gender was also different.

The present invention uses a non-single-crystal semiconductor instead of a single-crystal semiconductor, so that the thickness of the semiconductor layer that performs charge conversion is not 200 to 400 μm thick as that of a single-crystal semiconductor.
The thickness was 1μ or less. Furthermore, since hydrogen or halogen elements are added, the optical energy band is wider than 1.1 eV of single crystal semiconductor (silicon), and is 1.5 to 1.5 eV.
It has 2,5eν. For this reason, it is particularly good for short wavelength light, rather than strong red light like the sun. As a result, it was found that the light emitting lamp battery using artificial light such as a white fluorescent lamp according to the present invention is extremely effective.

Further, in order to form a semiconductor having a thickness of 1 μm or less on a substrate, particularly preferably a substrate having an uneven surface, the present invention provides a reaction system that does not use carrier gas at all or substantially does not use carrier gas. is used. A typical example of this is the reduced pressure gas phase method.

However, the reduced pressure gas phase method is characterized only by keeping the inside of the reaction vessel under reduced pressure. For this reason, the degree of depressurization should be increased to < 1
If it is about mm1+g, the rate of film growth of the reaction product on the substrate will be significantly reduced. The present invention is characterized in that the pressure inside the reaction vessel is set to 0.01 to 10 torr, and in addition, the inside of the vessel is substantially filled only with reactive gas or reactive gas and additives. In addition, in order to further strengthen the semiconductor properties of the semiconductor film, 0.1% of hydrogen or halogen element is added.
-200 Tnyl% was added into the semiconductor coating.
It is a characteristic of ζ.

The present invention is characterized in that the photoelectric conversion element is fabricated from a non-single crystal semiconductor, and such a non-single crystal semiconductor exhibits unreliability or stress sensitivity even if some local stress is applied. This is based on the experimental fact that there is no such thing, and the fact that, at least as long as the method of the present invention is used, the substrate having the surface to be formed does not necessarily have to be a 5I/water surface.

The embodiment will be described below with reference to the drawings.

FIG. 1 shows the principle of 193 operation when used in the light emitting lamp battery of the present invention.

That is, in FIG. 1 (8), a conductive film (2) such as tin oxide (Sn(1)) or ITO is formed on a transparent substrate (3) of a semiconductor layer (1) such as glass or sapphire, and then this film is further coated. A semiconductor layer (1) doped with hydrogen or an element is formed on the upper side. This semiconductor layer is
Whether it is a MIN (metal-intrinsic semiconductor-N-type semiconductor) Schottky junction structure, f) IN (P-type semiconductor-intrinsic semiconductor-N-type semiconductor) junction structure or a PN junction structure, Multiple junctions may also be used. It satisfies the purpose of the present invention, that is, it has the highest light-to-electrical conversion efficiency (η), and may be determined based on the ease of manufacturing.

In FIG. 1, an electrode (4) is provided on the upper side of this semiconductor layer (1). Light is incident from the left side in (5). Although this drawing uses a light-transmitting substrate, the present invention relates to such a light-emitting lamp battery (a battery that operates radios, electronic clocks, and other electronic devices by converting artificial light such as white fluorescent lamps into electricity). ).

For such cells or batteries, particularly for luminescent lamp batteries, a flat battery is not necessarily of a preferred form, as shown in Figure 1 (
Considering the shape of the structure of the present invention that utilizes the structure of A), that is, the structure of FIG. 3(A), it is expected that the commercial value is extremely high. After creating the outer case of a radio, 7Ii child watch, etc., the R-core stress is protected by the board that is the case.
This is because a part or all of the container can be used as a light-receiving surface in photo-electrical conversion.

FIG. 1(B) shows a lower electrode (2) on a substrate (3).

A semiconductor layer (1) and an upper electrode (4) are provided. The upper electrode was 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 a lampshade. An example thereof is shown in FIG. 3(B). This is a device in which a photoelectric conversion cell is provided as part of the protective case of an electric light or fluorescent lamp, for example, provided inside the upper case of the electric light. In this case, it is necessary to make a hole in the center.

Also, due to this usage, a voltage different from 100ν can be applied to f.
f? You can pull it out to your i-car. For this reason, low voltage can be generated without using a transformer etc. Some radios, potash etc.
It can also be used as a charger for a toyulator, etc., and it can also be used as an electric light source to emit light of a specific wavelength, such as red or green, using such electricity. May be connected.

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-pupil.
-086868 (1 horse released on July 17, 1978)
This is the same as that described in "Photoelectric Conversion Semiconductor Device and Method for Manufacturing the Same".

FIG. 2 shows an apparatus for manufacturing a fluorescent lamp battery according to the present invention in which a semiconductor layer is provided on a substrate at least partially having an uneven shape. The embodiment will be explained according to the drawings. In the drawing, a substrate (21) having an uneven shape is placed on a holder (22), and unnecessary parts are shielded by (23). This substrate was placed in a reactor (24). Reactive gas foil 2
8) is a silicide gas such as silane, (29) is a carbide gas such as methane, (30) is an impurity that can exhibit P-type conductivity such as diborane, and (31) is N-type conductivity such as Humeshin and Arson. Introducing impurities that exhibit properties. (
35) is an inert gas that purges the inside of the reactor before and after the reaction. From the entrance (27), they pass through an excitation system (exciter) using microwaves (26) and then into a reactor (24).
) will be introduced. Microwaves use a frequency of 1 to 10 GIlz, for example 2.46 GHz, to chemically activate, decompose or react a reactive gas, resulting in a plasma state. Carbon is mixed into silicon, and silicon carbide 5ixC+-×(
When 0≦x<1) is formed, the Konifurugi gasop can be obtained by changing the value of X to any value greater than 1.5 eV and between 1.7 and 3.5 eV.

Since the reactive gas is excited, decomposed, or reacted in such an exciter, it has been experimentally found that the surface to be formed does not necessarily have to be flat in the reactor. Furthermore, this exciter (26) and the reactor (24) are 0.01 to 1 OtOr.
The reaction product in the active state is reduced to 1-10 M
It is further activated by high frequency energy (25) at a frequency of It z and adheres to the uneven substrate surface to form a film. The degree of pressure reduction can be set to a constant pressure using the vacuum pump (34) and the two-door valve (33) in front of it.
It is Noh.

Although silane was used as the silicide, the reactive gas may also be dichlorosilane (S iHLc It), trichlorosilane (SillCI7), silicon tetrachloride (StCI), or methane (C11, ) as the carbide. Other hydrocarbons such as pronoman (C, )l, ) may be used instead of mercury.

Moreover, even if this carbide is not used, ammonia (NH3) or hydrazine (Nzl14) may be used as a nitride instead. Nitrogen is generally used as the inert gas (35) for purging, which is cheaper than nitrogen, but after the semiconductor layer has been formed on the substrate, by adding active hydrogen in the semiconductor, Hydrogen (llz) may be introduced from this (35) in order to neutralize and remove the dangling bond. By such hydrogen induction annealing, 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. This induction annealing is performed at a temperature of 250°C or less for silicon and 35°C for silicon carbide.
The temperature is preferably below 0°C; above these temperatures, the added hydrogen is re-released, forming SiH bonds, (, -H
There was a tendency for the bond to come undone.

The temperature in the reactor was from chamber aL to 350°C. Of course, the temperature may be from room temperature to 500°C. However, since controlling the temperature of the substrate brings about material limitations, a temperature of room temperature to 300° C. is 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 could be performed by varying 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 by Jli1.

The important features of the method of the present invention are, firstly, because the reactor is under reduced pressure, the mean free path of the reactive gas or reaction product is large, so that it can sufficiently fly even into the interior of the recess;
In addition, because the exciter was installed in front of the reactor, the reactive gases were completely mixed with each other, resulting in a stoichiometrically homogeneous reaction product. Because it is in an excited state, the surface of the substrate can be coated uniformly on all parts of the surface, even if the substrate has a fine roughness of 0.1 to 1μ, usually 10μ or more, especially if it is shaped like a container. Thirdly, since the substrate itself is heated by resistance heating etc., the coating temperature is insensitive to the temperature of the surface of the substrate, and since the temperature of the substrate is between room temperature and 200℃ or 350℃, each part of the substrate The temperature of the surface is less likely to become non-uniform, and as a result, non-uniformity of the film thickness 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, it is possible to form a large amount of film on the inlet side of the reactive gas, but not at all on the back side.

The semiconductor device of the present invention was invented by experimentally obtaining many of these features.Of course, the uniformity in the present invention means that the variation in film thickness is generally within ±5%, and the electrical This means that the optical characteristics are such that it is not necessary to consider the non-uniformity of the coating.

As mentioned 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>, (B) are as shown in (A), <B) of FIG. 1, and light is irradiated from (43).

Figure 3 (B) shows the height difference (44) between the -top surface of the substrate (41).
has a diameter of 1 μ or more, for example, 1 ntm or more.

A semiconductor layer (42) is formed on such an uneven surface.

The container shown in FIG. 3 (C) and <D) is shaped like a container and has a hole in a part thereof. An example is 111 when placed indoors.

Specific examples of the fluorescent lamp battery of the present invention will be shown below to supplement the present invention.

Concrete Example 1 A glass substrate (thickness 1.1 mm) was used, and tin oxide was formed on the upper surface of the glass substrate, and a hydrogen-doped non-monomer with a PIN junction was formed using a plasma vapor phase apparatus as shown in FIG. A crystalline semiconductor was formed. At this time, the P-type non-single crystal semiconductor was silicon carbide (jV 150). Furthermore, the I-type semiconductor was made to have a thickness of 0.7 μm using silane at a concentration of 100% without using any gear gas. Further N
The non-single crystal semiconductors were stacked to a thickness of 500 nm with PH3/SiH, = 1%. The back electrode was made of aluminum. The reaction conditions for forming a non-single crystal semiconductor are:
Substrate temperature 210℃, high frequency output 3.5M)lz, pressure Q
, 1 torr, and a film growth rate of 90 people/min. The obtained characteristics are: open circuit voltage 0.6 V, short circuit current 20 μ8, 15 fill factor 0.4 when irradiated with 300 Lx of white fluorescent light.
8. Conversion efficiency was 3.7%.

In the present invention, the substrate is typically made of a hard material such as glass, ceramics, 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 is provided using such a layer.
A predetermined low voltage of v! - It could be generated without using a lance. Furthermore, it is characterized in that a photoelectric conversion element is provided in close contact with the inside of a concave case on its usage surface, for example.

[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 using a -J reaction system. FIG. 3 shows an embodiment of the fluorescent lamp cell of the present invention.

Claims (1)

[Claims] 1. A non-single-crystal semiconductor layer doped with hydrogen or a halogen element is provided on the formation surface of the substrate, and the semiconductor layer is irradiated with artificial light such as a white fluorescent lamp. 1. A fluorescent lamp battery, which converts it into electricity and operates it by connecting an electrode provided on the semiconductor layer to a radio, a heavy-duty watch, or other electronic equipment. 2. In claim 1, the non-single crystal semiconductor layer is provided with a conductive film such as tin oxide or ITO on a transparent substrate, and a Schottky junction, PIN junction,
A fluorescent lamp battery characterized by having a PN junction or a multiplexed junction.