JPS6122509A - Reduced transparent conductive film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a reducible transparent conductive film used as a transparent electrode, a transparent conductive layer, etc. in various devices.

BACKGROUND OF THE INVENTION In recent years, various devices such as optical sensors, solar cells, and thin film transistors have been actively developed. In this type of device, electrodes and conductive layers are often composed of transparent conductive films for purposes such as light transmission, light transmission, and display.

However, in the past, this transparent conductive film was
ITO (Indium Tin Oxide), 5nOz, 5nOz: S b, T iOz /A
Oxide semiconductors such as g/TiO2 are commonly used.

However, using this type of material has the following drawbacks. First, a glass substrate is usually used as a substrate, and alkali ions (Na, K, etc.) are emitted from this glass substrate.
etc.) easily diffuse into the film to form acceptor levels. As a result, the donor is captured and the conductivity of the transparent conductive film decreases.

The characteristics of the device will deteriorate. In addition, such a decrease in conductivity is local and causes uneven conductivity.
Characteristics will vary depending on location. In particular, when the area is increased, such non-uniformity becomes noticeable, resulting in a device with poor reliability and durability. Further, in the case of an oxide transparent conductive film, it is chemically unstable and is gradually decomposed by moisture in the atmosphere, resulting in a decrease in conductivity and deterioration of characteristics necessary for devices. Also, for example, a-8i:H
In a solar cell, when a film is formed in an SiH4 plasma decomposition atmosphere, an oxide type transparent electrode such as ITO is reduced because it is in a reducing atmosphere. As a result, reduced metallic indium diffuses into the a-5i:H film,
Detracts from the properties of solar cells. The same thing can happen with other devices.

the purpose The present invention was made in view of these points.

The purpose is to obtain a reducible transparent conductive film that can function as a transparent electrode, etc. without impairing the characteristics of the target device by reducing the decrease in conductivity due to the diffusion of alkali ions, etc. and the unevenness of the conductivity. .

composition In order to achieve the above-mentioned object, the present invention! lsn.

Element selected from lead Pb, indium In, and carbon C2
It is characterized by consisting of an element selected from nitrogen (N) and sulfur (S).

Embodiments of the present invention will be described below based on the drawings.

First Embodiment A first embodiment of the present invention is shown in FIGS. 1 to 3. This example is applied to an optical sensor. First, Fig. 1 shows an example of a photovoltaic type optical sensor, in which a glass substrate 1
A transparent conductive film 2 is formed thereon, and a photoconductive layer 3 is formed thereon in a predetermined pattern. Further, a back electrode 4 is formed on the transparent conductive film 2 and the photoconductive layer 3, and is fixed on the lead frame 5. Since the incident direction of light is on the glass substrate 1 side, the transparent conductive film 2 is used.

On the other hand, Figure 2 is an example of a sandwich type optical sensor.
Since the incident direction of light is different, the stacking order is different.

Here, as the photoconductive layer 3, an a-8i:H film using amorphous silicon, CdS, Cd55, or the like is used.

In an optical sensor having such a structure, a metal oxide transparent conductive film such as ITO has conventionally been used as the transparent conductive film. Here, for example, the photoconductive layer 3 is a-8i:H
If a film is to be formed, it will be formed by decomposing SiH4 gas using the plasma CVD method. At this time, the transparent conductive film on the glass substrate 1 is placed in a plasma atmosphere.

At this time, in the case of a metal oxide transparent conductive film, since a large number of hydrogen radicals are present in the plasma, oxygen in the conductive film reacts with hydrogen, resulting in a decrease in conductivity.

Furthermore, even if the photoconductive layer 3 is made of CdS, CdSe, etc., alkali ions (for example, Na +
, K''), the conductivity of the metal oxide transparent conductive film decreases.

Therefore, in this embodiment, the transparent conductive film 2 is configured as a reducible transparent conductive film that does not contain oxygen. Its constituent elements are tin n and lead Pb.

An element selected from indium In, carbon C1 nitrogen N,
It is composed of an element selected from sulfur S.

Therefore, 5nxC1-x, 5nxNx-x, 5nxSx-x.

PbxC:t-x, PbxNt-x, PbxSt-x.

InxCx-x+ InxNt-x, Inx5x
-x etc. are used as basic materials. In addition, both are 0
< x < 1. Then, if necessary, hydrogen H
These hydrides containing are used. That is, 5nxC
1-x:H, 5nxNx-x:H, 5nxSt-x:H
.

Pb xCt-x: H2Pb xN t-x: H, pb
x S t-x:H.

In xCt-x:H, In xN 1-X:H, In
x S x-x:H. Furthermore, for conductivity control.

If necessary, the range of 1 pp+m to 20 atomic % of Group IIIa of the atomic layer periodic table (B, AQ, Ga, In, TQ) or Group Va of the periodic table (N, P, As, Sb, Bi). Any element may be contained as an impurity.

According to such a transparent conductive film 2, as shown in FIG. 1, even if the photoconductive layer 3 is formed as an a-8i:H film by the plasma CVD method using silane gas, it has a reducing property that does not easily react with hydrogen radicals. Therefore, the conductivity of the transparent conductive film 2 decreases little. this is.

The same applies to alkali ions from the glass substrate 1, and since their diffusion is difficult to occur, there is no decrease in electrical conductivity.
It has good durability. Further, in FIG. 2, even when the photoconductive layer 3 is an a-8i:H film, since the transparent conductive film 2 does not contain oxygen, oxygen diffuses into the photoconductive layer 3 and deteriorates the characteristics. There is no such thing.

In the end, according to this embodiment, the conductivity of the transparent conductive film 2 does not decrease due to alkali ions or the like.

It has excellent durability and environmental resistance. As a result, even if the device has a large area, there is no unevenness in conductivity, and uniform characteristics can be obtained over the entire surface of the device as an optical sensor. Furthermore, the conductivity and light transmittance of the transparent conductive film 2 are improved, and the photoelectric conversion efficiency of the transparent conductive film 2 as a photosensor is improved.

By the way, the method for producing the transparent conductive film 2 in this example is a CVD method or a plasma CVD method.

Photo-CVD method, reactive sputtering method, etc. are effective.

In particular, it is effective to use a plasma CVD apparatus.

In this case, Sn(CH3)4.5n(Cz Ff)a
.

5n(C3H7)4.5nCC,s H9)4, Pb
(C2H5)4 , Pb(C4H9)4 , In(C
H3) 3゜I n(Cz Hs)3. I n(C3H7
)3, In(C4H9)3 and other organometallic compounds,
A suitable carrier gas He, Ar, H2, Nz, etc. is diluted and introduced, and at the same time carbon-containing gas (CH4, Cz He,
Hydrocarbon gases represented by 03IIIa, C2H4, C2H2, etc.), nitrogen-containing gases (NZ, NH3, etc.).

A plasma CVD method using one or more suitable gases selected from sulfur-containing gases (H2S, etc.) is used (here, a hydride such as 5nxCt-x:H is assumed). The thickness of the transparent conductive film 2 is 50 to 1000
0 angstroms is preferred.

FIG. 3 schematically shows a plasma CVD apparatus for carrying out this plasma CVD method.

Reference numeral 6 denotes a reaction vessel, in which counter electrodes 7 and 8 are provided above and below, and the glass substrate 1 is set on the electrodes 8. Then, an organometallic compound is introduced into the reaction vessel 6 into a novel blurr 9 along with a carrier gas from a gas cylinder 10, a carbon-containing gas from a gas cylinder 11, and the like. 12
is a flow meter, and 13 is a pressure gauge. At this time, electrodes 7, 8
During this time, a high frequency voltage is applied by the high frequency power supply 14, a high frequency glow discharge is generated, the raw material gas is decomposed in the plasma, and the transparent conductive film 2 is formed on the glass substrate 1. Note that during this film forming process, the inside of the first reaction vessel 6 is maintained at a predetermined pressure by being evacuated by the vacuum pump 15.

By the way, the optical sensor according to this embodiment can be applied to various fields such as facsimile reading devices, OCR, cameras, televisions, rotary encoders, and robots.

Second embodiment A second embodiment of the present invention will be explained with reference to FIG.

This example is applied to an electrophotographic photoreceptor. FIG. 4 is a cross-sectional view showing the structure of a belt-shaped photoreceptor, which is formed by laminating a photoconductive layer (PVK/TNF) 1B on a transparent support 16 made of a polyester film with a transparent conductive film 17 interposed therebetween. However.

The transparent conductive film 17 is an oxygen-free reducing transparent conductive film having the same composition and manufacturing method as the transparent conductive film 2 of the embodiment.

In the case of this type of photoreceptor, since exposure and charge removal are performed from the side of the transparent support 16, it is characterized by high cleaning performance and excellent durability.

Here, the photoreceptor requires a large area and is required to have uniform characteristics over the entire large area. In this regard, conventional metal oxide transparent conductive films are chemically unstable and tend to reduce their conductivity, resulting in uneven conductivity depending on location, making them unsuitable for large-area devices of this type. However, the characteristics were not uniform.

In the case of the transparent conductive film 17 made of 5nxNz:H or the like as in this embodiment, there is no decrease in conductivity and uniform characteristics can be obtained over the entire area. In addition, although the belt-shaped photoreceptor is subjected to mechanical stress (bending), it is better against this stress than conventional metal oxide transparent conductive films, and can improve durability. This is also what I found out.

By the way, as the photoconductive layer 18, copper phthalocyanine,
Pyrylium-based materials can also be used, and furthermore, an amorphous silicon a-8i film can be used. This a
In the case of the -5i film, if it were a conventional metal oxide transparent conductive film, the oxygen in this film would diffuse into the photoconductive layer and deteriorate its photoconductive properties, but in this example, For example, since the transparent conductive film 17 does not contain oxygen, there is no diffusion of oxygen into the photoconductive layer 18 and the characteristics are not deteriorated.

Note that a protective layer 19 may be provided on the surface as shown in FIG.

The electrophotographic photoreceptor structure shown in this embodiment can be applied not only to copying machines but also to laser printers, LED printers, liquid crystal printers, electrophotographic displays, and the like.

Third embodiment A third embodiment of the present invention will be explained with reference to FIG.

This example is applied to a solar cell. FIG. 6 shows the structure of an a-8i solar cell as an example, in which a transparent electrode 21 is placed on a glass substrate 20, and a p-type a-8i:
H layer 22, i-type a-Si:8 layer 23, n-type a-3i:H
The layer 24 and the AQ electrode 25 are sequentially laminated. Thus, the transparent electrode 21 is an oxygen-free reducing transparent conductive film having the same composition and manufacturing method as the transparent conductive film 2 of the first embodiment.

As a result, compared to a conventional metal oxide transparent conductive film using ITO or the like as a transparent electrode, the transparent electrode 21 of this example not only improved photoelectric conversion efficiency but also significantly improved durability. has been confirmed. By the way,
When the interface between the transparent electrode 21 and the a-3i layer 22 of the produced film was analyzed by Auger electron spectroscopy, it was found that the a-Si layer 2 is made of Sn, Pb, In, etc., which are the basic elements of the transparent electrode 21.
Diffusion into Nos. 2 to 24 was extremely small and did not cause any characteristic deterioration. Furthermore, there is almost no diffusion of alkali ions such as Na+ from the glass substrate 20 into the transparent electrode 21.
No decrease in conductivity occurred.

Note that, although the present embodiment has been described with respect to the a-8i solar cell, the present invention is not limited to this and can be applied to transparent electrodes of all solar cells.

Solar cells with this type of structure can also be applied to photoelectric interconversion devices, optical communication devices, etc.

Fourth Embodiment A fourth embodiment of the present invention will be explained with reference to FIGS. 7 and 8. This embodiment is applied to a plasma display. FIG. 7 shows an example of a DC type plasma display, and FIG. 8 shows an example of an AC type plasma display.

First, in the DC type shown in FIG. 7, a scan groove 27 is formed in the back glass 26 by cutting, and a thin wire-shaped scan anode 28 is disposed at the bottom of the groove. On the other hand, a transparent conductive film 30 is formed on the front glass 29 as a display anode, each of which serves as a display cell 31. In addition, a cell sheet 33 in which a discharge space 32 is formed by etching a photosensitive glass with a thickness of about 1 mm and a cathode 34 perpendicular to the 7 nodes are sandwiched between glasses 26 and 29, and the outer periphery is coated with a thin film such as pyroceram. It is sealed with melting point glass 35.

Next, in the AC type shown in FIG. 8, a transparent conductive film 37 is formed as an electrode on the front glass plate 36 and covered with a dielectric layer 38, and an electrode 40 is formed on the rear glass plate 39 to cover the dielectric layer 38. 41 and are placed facing each other with a spacer 42 interposed therebetween, and are sealed with a sealing body 43 such as powdered glass to seal a mixed gas 44. Note that, depending on the case, a protective film is further formed on the dielectric layer 38, 41. Here, the gap between the glass plates 36 and 39 is approximately 100 μm and 3
00 Torr of Ne or Ne + X e
A mixed gas such as the following is sealed.

Here, by applying a voltage from the outside, the dielectric layer 3
8.41 and the voltage is distributed across the discharge gap. By applying a voltage whose polarity changes to this cell, intermittent discharge is caused in response to the signal, and the intermittent light corresponding to each discharge can be used for display.

Therefore, in this embodiment, the transparent conductive film 30 forming the display anode in the case of the DC type shown in FIG. 7, and the transparent conductive film 37 forming the electrode in the case of the AC type shown in FIG. This is a reducible transparent conductive film containing no oxygen using the same composition as conductive film 2 and using the W method.

As a result, since the electrode (transparent conductive film 30) is exposed in the discharge space 32 in the DC type shown in FIG.
If the transparent conductive film is made of Oz or the like, its characteristics will deteriorate due to the influence of plasma, but the transparent conductive film 30 of this embodiment can suppress such deterioration of characteristics due to plasma. In addition, since there is no decrease in conductivity due to the diffusion of alkali ions from the glass substrate, the characteristics as a 5-electrode are maintained, and furthermore, the conductivity and light transmittance of the transparent conductive film 30 are improved, making it suitable for use as a display device. Luminous efficiency will be improved. These are A in Figure 8.
The same applies to the C type. In this Figure 8 method,
When a metal oxide transparent conductive film such as 5n02 was used, there was a problem of electrode deterioration due to plasma even when a dielectric layer or even a protective layer was provided, but this problem was resolved by this example. be.

The plasma display bracelet of this example is a television.

It can be applied to measuring instruments, display boards, PO8 terminals, in-vehicle displays, air traffic control, radar, machine tools, etc.

Fifth embodiment A fifth embodiment of the present invention will be explained with reference to FIG.

This example is applied to an electrophoretic display element.

FIG. 9 shows, as an example, the structure of a single particle electrophoretic display element, in which a transparent electrode film 46 is formed on a glass plate 45.
In addition, a plurality of electrodes 48a and 48b made of AQ or the like are provided on the substrate 47, and both are sealed and opposed to each other with a spacer 49 in between.

In this sealed space, for example, a black organic colored insulating solvent 50
At the same time, white electrophoretic particles 51 made of, for example, TiOz or ZnO are sealed. Therefore, a voltage is applied between the transparent electrode film 46 and the electrodes 48a and 48b, and depending on the polarity, the electrophoretic particles 51 migrate as shown in the figure, with the electrode 48a side displaying black color and the electrode 48b side displaying black color. In this case, the screen will be displayed in white.

Therefore, in this embodiment, the transparent electrode 46 is made into a reducible transparent conductive film that does not contain oxygen using the same composition and manufacturing method as the transparent conductive film 2 of the first embodiment.

As a result, compared to the case of conventional metal oxide transparent conductive films, uniform characteristics are ensured without a decrease in conductivity, and the conductivity and light transmittance are improved, resulting in improved display quality and responsiveness as a display device. This is an improvement.

In this embodiment, a single-particle system has been described, but the present invention is not limited to this and can be applied to all electrophoretic display elements such as a two-particle system.

The electrophoretic display element according to this embodiment can be applied to photoelectric interconversion devices, optical communication devices, and the like.

Sixth Embodiment A sixth embodiment of the present invention will be explained with reference to FIGS. 10 and 11. This embodiment is applied to an information recording medium. Figure 10 shows thermoplastic resin (thermoplastics)
This figure shows the structure of an information recording medium using a glass substrate 52, in which a transparent electrode 53, a photoconductive M54, and a thermoplastic resin layer 55 are sequentially laminated on a glass substrate 52. Here, the photoconductive layer 54 is made of polyvinyl carbazole/trinitrofluorein complex, copper phthalocyanine, hydrogenated amorphous silicon, selenium/
Tellurium, arsenic selenium, etc. are used. or.

The thermoplastic resin layer 55 is made of polyethylene, polypropylene,
Depends on the material such as polystyrene or polyvinyl chloride.

FIG. 11 shows a recording process b) using such an information recording medium. First, as shown in FIG. 4(a), the surface of the thermoplastic resin layer 55 is uniformly charged in a dark place using a corona charger 56. Next, image exposure is performed from either side of the medium. FIG. 8B shows exposure from the thermoplastic resin layer 55 side. Next, the surface of the thermoplastic resin layer 55 is charged again as shown in FIG. Finally, as shown in FIG. 4(d), by heating the medium by applying electricity to the transparent electrode 53, the thermoplastic resin layer 55 becomes thinner than the high charge density part number.

A frost statue is created. This frost image can then be reproduced using a Schlieren optical system.

Note that in order to erase the frost image once formed, the charge pattern disappears by heating the medium at a temperature slightly higher than that during development, so the thermoplastic resin layer 55 becomes flat due to its own surface tension. .

Therefore, in this embodiment, the transparent electrode 53 is an oxygen-free reducing transparent conductive film having the same composition and manufacturing method as the transparent conductive film 2 of the first embodiment.

As a result, compared to the case of a transparent electrode made of a conventional metal oxide transparent conductive film, the characteristics are stable, there is no decrease in conductivity due to diffusion of real alkali ions, etc., and the conductivity and light transmittance of the transparent electrode 53 are As a result, the recording SN ratio of the recording device is improved.

The information recording medium according to this embodiment can be applied to holographic memory, microphotography, etc.

Seventh Embodiment A seventh embodiment of the present invention will be explained with reference to FIG. This embodiment is applied to an optical modulator.

FIG. 12 shows the structure of a Pockels-type optical modulator using an electro-optic crystal, and 57 is an electro-optic crystal that causes a change in refractive index by applying an electric field. The materials include ferroelectric perovskite crystals such as LiNbO3゜L i Ta 03, potassium monophosphate (KDP), ammonium monophosphate (ADP), and KD2PO4 (where H in KDP is replaced with deuterium). DKDP) etc. are used. Transparent electrodes 58 and 59 are provided on both sides of this electro-optic crystal 57 and are connected to a driving power source 60.

In addition, a polarizer 61 and an analyzer 6 are installed before and after the electro-optic crystal 57.
2 are arranged. These three surfaces are arranged parallel to each other. Further, the orientation of the polarizer 61 is tilted at 45° with respect to the crystal principal axis X of the electro-optic crystal 57, and the orientation of the analyzer 62 is also tilted at 145' with respect to X.

Now, let Y be the axis perpendicular to the crystal principal axis X and included in the surface of the electro-optic crystal 57, and let 2 be the axis perpendicular to X and Y,
Consider the case where light is incident in the Z direction. First, when the electric field is 0, the transmitted light is 0 because the polarizer 61 and the analyzer 62 are orthogonal to each other. Therefore, the transparent electrode 58.59
When a voltage is applied between X and X in the electro-optic crystal 57,
The refractive index of the crystal in the Y direction n1. When n2 changes and the thickness of the crystal is Q, a phase difference of r=(2z/λ)·(nt−n2)·Q is generated. Therefore, the light transmitted through the electro-optic crystal 57 becomes elliptically polarized light, and the intensity of the light emitted from the analyzer 62 is
For the incident light intensity Io, I=I o gin”
(r'/2), which means that modulation has been performed.

Therefore, in this embodiment, the transparent electrodes 58 and 59 are oxygen-free reducing transparent conductive films having the same composition and manufacturing method as the transparent conductive film 2 of the first embodiment.

As a result, in the case of the conventional transparent electrode method using ITO, etc., the light transmittance is insufficient and the attenuation of the transmitted light cannot be ignored, resulting in S
The N ratio decreased, and furthermore, it was chemically unstable and was gradually decomposed by moisture in the atmosphere, resulting in a decrease in conductivity and unstable modulation characteristics. According to this, the characteristics are stable over a long period of time and there is no deterioration.

Stable modulation characteristics are obtained and the S/N ratio is improved. Further, there is little variation in characteristics between devices, and devices with large areas can be easily manufactured.

The optical modulator according to this embodiment includes an optical switch, an optical shutter,
It can be applied to display elements, etc.

A second embodiment of the present invention will be described with reference to FIGS. 13 and 14. This example uses a thin film transistor (TPT)
It was applied to First, a substrate 63 made of glass or the like
A transparent electrode 64 is formed on top and etched into a predetermined pattern. Next, a Cr (or AQ) gate electrode 65 is formed on the substrate 63 by vapor deposition and etching. Next, Si3N4,
5i02 etc. is formed, and further a-8i:
A semiconductor layer 67 made of an H film is formed and etched to leave only desired portions. Finally, the source electrode 68 and the drain electrode 69 are etched by vapor deposition and etching of AQ (or Cr).
It forms.

Since such a thin film transistor is used, for example, in a liquid crystal display panel, a transparent electrode 64 is provided and connected to a drain electrode 69.

Therefore, in this embodiment, the transparent electrode 64 is an oxygen-free reducing transparent conductive film having the same composition and manufacturing method as the transparent conductive film 2 of the first embodiment.

Here, since a metal oxide transparent conductive film is conventionally used, it is exposed to a reducing atmosphere during the formation of a semiconductor layer using an a-8i:H film, resulting in a decrease in conductivity and deterioration of electrical characteristics. do. Furthermore, since it is chemically unstable and has poor uniformity, the more integrated thin film transistors are, the more variation occurs in the characteristics of each element. Furthermore, the conductivity decreases due to alkali ions diffusing from the glass substrate 63.

Therefore, the characteristics of the thin film transistor depend on the insulating layer 66 and a
-3t:H It varies depending on the thickness of the single layer (semiconducting layer 67), material, and other geometric parameters, but when manufactured under almost the same conditions and compared with the conventional one, this example shows that The following effects were obtained. first,
The ON/OFF ratio of drain current 0 to gate voltage Va is high. Additionally, there is little difference in operating characteristics between each element.

This results in a device with uniform characteristics even when highly integrated. Furthermore, there is no deterioration in characteristics even after long-term operation, and it has excellent durability.

The thin film transistor of this example can be applied to image sensors and the like in addition to the liquid crystal display panel described above.

Ninth Embodiment A ninth embodiment of the present invention will be explained with reference to FIG. This example is applied to a thermoelectric conversion element. FIG. 15 shows the configuration of a thermoelectric conversion element equipped with a translucent heating element, in which a translucent heating layer 7 is placed on a translucent substrate 70 such as glass.
1 is provided and covered with a transparent protective layer 72. Here,
The material of the transparent protective layer 72 is 5iOz, TiOz
Heat-resistant polymeric materials such as polyimide, polyimide amide, and polydiphenyl ether are used, but polyester resins may also be used if the operating temperature is not so high.

In such a configuration, the light-transmitting heat generating layer 71 is heated by the power source.
When energized, it generates heat due to Joule heat, so by controlling the current value, it can be used as a heating element at a desired temperature.

Therefore, in this embodiment, the light-transmitting heat generating layer 71 is an oxygen-free reducing transparent conductive film having the same composition and manufacturing method as the transparent conductive film 2 in the first embodiment.

Conventionally, since a metal oxide transparent conductive film is used, the conductivity gradually decreases due to the diffusion of alkali ions and the like, resulting in a decrease in thermoelectric conversion efficiency. In particular, due to uneven conductivity depending on location, thermoelectric conversion characteristics become non-uniform when the area is increased.

However, according to the light-transmitting heat generating layer 71 of this embodiment, its electrical conductivity and light transmittance are stable over a long period of time, so the thermoelectric conversion characteristics are stable and visibility is good. Further, even if the area is increased, uniformity of characteristics can be ensured.

The thermoelectric conversion element according to this embodiment can be applied to anti-fog members such as mirrors and lenses used in various office automation equipment, anti-condensation members such as freezing cases, defroster of automobiles, etc. When used on the surfaces of mirrors, lenses, etc., the light-transmitting heat generating layer 71 may be directly formed on the surfaces of these substrates.

Embodiment of a Disciple An embodiment of a disciple of the present invention will be explained with reference to FIGS. 16 and 17. This embodiment is applied to a tablet-type information input device, particularly a translucent information input device that is stacked on top of a display device to form an integrated type.

FIG. 16 shows the detection principle of an information input device using electromagnetic induction. It is assumed that an indicator pen with a built-in permanent magnet or electromagnet at the tip is now at position B. A pulse current is sequentially supplied to the drive coils D1 to D3 every minute time, while the switches SW for the sense coils 81 to S3
SW1 to SW3 are sequentially closed for short periods of time. These timings are, for example, when the switch Sw1 is closed and a pulse current is sequentially applied to the drive coils D1 to D3.
Below, switch Sw1. The same process is repeated by closing sw3 in order. Therefore, in the illustrated state, only when a pulse current flows through the drive coil D2 with the switch SW2 closed, an electromotive force is generated in the sense coil S2 due to electromagnetic induction, and after being amplified by the amplifier circuit A, a signal (not shown) is generated. The signal is transferred to the processing circuit, and the position B is detected as the intersection of the drive coil D2 and the sense coil S2.

FIG. 17 shows the structure, in which transparent electrodes 75, 76 forming a drive coil and a sense coil are formed in a predetermined pattern on an insulating substrate 73, 74 made of glass or the like. The density of each coil is 0.5~5 loops/
It is about mm. A transparent protective layer 77 is provided on the transparent electrode 75.

Therefore, in this embodiment, the transparent electrodes 75 and 76 for the drive coil and the sense coil are made of oxygen-free reducing transparent conductive films having the same composition and manufacturing method as the transparent conductive film 2 in the first embodiment. be.

Conventionally, since the sensor is made of a metal oxide transparent conductive film, the accuracy of detecting the indicated position is reduced due to a reduction in conductivity. Furthermore, since the electrical conductivity tends to vary depending on the location, variations in input characteristics tend to occur when the information input surface is enlarged. Furthermore, the conductivity is at most 104Ω-1cm
-'', the detection accuracy will decrease when the area is increased.

However, according to the transparent electrodes 75 and 76 of this embodiment, the characteristics are stable over a long period of time and the conductivity does not decrease, so stable position detection can be performed and input performance can be stably improved. Further, even if the input screen is made large in area, there is no problem such as variations in input performance depending on the location.

In addition, in this example, an electromagnetic induction type device was explained.
Even if it is a capacitive method (the position of the indicator pen is detected by measuring the charging current flowing through a capacitor consisting of an indicator pen and a transparent electrode), the basic configuration of the input section remains the same, so the same applies. Applicable.

According to the information input device shown in FIG. 17, since all the constituent elements are translucent, it can be stacked on top of, for example, a cathode ray tube (CRT) display device, an electroluminescence (EL) display device, or a liquid crystal display device. By setting the body shape, it is possible to specify the display screen and display input information online on the screen.

Therefore, the information input device of this embodiment can also be applied to data input terminal devices for computers, word processors, etc.

Embodiment of a Disciple An embodiment of a disciple of the present invention will be explained with reference to FIGS. 18 and 19. This example is applied to a photoelectric conversion element that utilizes the photoconductive effect. FIG. 18 shows the principle, in which a signal electrode 79 is placed on a light-transmissive substrate 78 made of glass.
is formed in a pixel-like pattern, and a photoconductive layer 80 is further formed on the back surface. The signal electrode 79 is made of a transparent and conductive material. The photoconductive layer 80 is formed of antimony trisulfide (SbzS3), -lead oxide (pbo), cadmium selenide (CdSe), hydrogenated amorphous silicon (a-8i:H), or the like. 81 is an electron gun, 82 is a deflection coil, 83 is a control circuit, 84 is a power source, and 85 and 86 are switches.

Now, when the switch 86 is closed and the switch 85 is opened, and a voltage of about several +V is applied to the signal electrode 79, a light image is irradiated from the light-transmitting substrate 78 side. Electron-hole pairs are generated in the layer 80, the electrons move toward the signal electrode 79, and the holes move toward the back side (electron beam scanning surface) of the photoconductive layer 80. As a result, the photoconductive layer 80
Charges corresponding to the intensity of light are accumulated on the back surface of the device.

Next, when the switch 85 is closed and the switch 86 is opened to scan the back surface of the photoconductive layer 80 with an electron beam from the electron gun 81, the beam flows into the photoconductive surface according to its surface potential, and from the signal electrode 79. The signal is extracted for each pixel and transferred to the control circuit 83.

Therefore, in this embodiment, the signal electrode 79 is made of an oxygen-free reducing transparent conductive film having the same composition and manufacturing method as the transparent conductive film 2 of the first embodiment.

As a result, it is chemically stable compared to signal electrodes made of conventional metal oxide transparent conductive films, and there is no decrease in conductivity regardless of the type of substrate, resulting in stable photoelectric conversion characteristics over a long period of time. is obtained. Furthermore, even if the detection surface is made larger, there will be less unevenness in characteristics depending on location.

Figure 19 shows an image pickup tube (
(TV camera). 87 is a heater, 88
is a cathode, and 89 to 91 are grids.

92 is an alignment coil, 93 is a deflection coil, and 94 is a focusing coil. The operating principle is the same as that shown in FIG. 18, so the explanation will be omitted.

Embodiment of Disciple 2 An embodiment of Disciple 2 of the present invention will be explained with reference to FIGS. 20 and 21. This example is applied to a light transmission type switching element. Figure 20 shows the basic configuration.
Transparent conductive films 97 and 98 are formed on each of a light-transmitting substrate 95 such as glass and a flexible light-transmitting substrate 96,
They are arranged to face each other with a spacer 99 in between. The substrate 96 is formed of a resin film such as polyethylene or polyester.

In the light-transmissive switching element configured in this way, when the flexible substrate 96 side is pressed with a finger or the like, the transparent conductive films 97 and 98 come into contact and form the terminals T^.

There is conduction between Tn and the switch is turned on. On the other hand, when the finger is released, the flexible substrate 96 returns to its original state due to its own elasticity, and the transparent conductive films 97 and 98 are separated again, turning the switch OFF.

Therefore, in this embodiment, the transparent conductive films 97 and 98 are oxygen-free reducing transparent conductive films having the same composition and manufacturing method as the transparent conductive film 2 in the first embodiment.

As a result, it is chemically more stable than conventional metal oxide transparent conductive films, and therefore stable switching characteristics can be obtained over a long period of time, regardless of the type of substrate or usage environment. Furthermore, since the resistance of the transparent conductive films 97 and 98 is extremely low, it can also be applied to circuits with low load impedance.

Furthermore, since the conductivity of the transparent conductive films 97 and 98 is uniform, there is little variation in characteristics between elements, making it possible to handle larger areas and improving productivity.

The simplest application of the light-transmissive switching element of this example is to combine it with an electroluminescent EL element as shown in FIG.

In the figure, 100 is a transparent conductive film, which is a transparent conductive film 9
Same as 7.98. 101 and 102 are insulating layers, and a light emitting layer 103 is provided between them. This light emitting layer 10
3 is mainly composed of ZnS, in addition to which Mn, TbF3, and Sm
It is added with F3 etc. 104 is an AQ electrode which also serves as a reflection plate, and 105 is a substrate. Further, 106 is an EL drive power source. In such a configuration, when the flexible substrate 96 is pressed, the circuit is closed, and only while the flexible substrate 96 is pressed, the EL element, that is, the light emitting layer 103, emits light, and the light can be taken out to the outside. It is something.

Therefore, the light transmission type switching element according to this example is as follows:
It can be used as an input device by stacking it on a display or the like, or it can be used as an operation panel for various devices by stacking it on a light emitting body or various display marks.

Effects As described above, in the present invention, the transparent conductive film is made of tin, Sn, and button pb.
, an element selected from indium In and carbon C1 nitrogen N
, sulfur, and an element selected from sulfur and S, which does not contain oxygen and has a reducing property, it can be made into a chemically stable transparent conductive film, and the conductivity can be maintained without being affected by the substrate, environment, etc. It is possible to suppress the deterioration, and therefore, the characteristics can be exhibited well in the target device, and it is also possible to cope with an increase in area.

[Brief explanation of the drawing]

1 to 3 show a first embodiment of the present invention, in which FIG. 1 is a configuration diagram of a photovoltaic type optical sensor, FIG. 2 is a configuration diagram of a sandwich-inch type optical sensor, and FIG. 4 is a schematic block diagram of a plasma CVD apparatus, FIG. 4 is a block diagram of an electrophotographic photoreceptor showing a second embodiment of the present invention, and FIG. 5 is a block diagram showing a modification thereof. Fig. 6 is a block diagram of a solar cell showing a third embodiment of the present invention, Figs. 7 and 8 show a fourth embodiment of the invention, and Fig. 7 is a diagram of a DC type plasma display. A perspective view, FIG. 8 is a block diagram of an AC type plasma display, FIG. 9 is a block diagram of an electrophoretic display element showing a fifth embodiment of the present invention, and FIG. 10 is a block diagram of a sixth embodiment of the present invention. 11(a) to 11(d) are illustrations of the recording process. FIG. 12 is a perspective view of an optical modulator showing the seventh embodiment of the present invention. FIG. TP showing the first embodiment of the invention
Fig. 14 is a plan view thereof, Fig. 15 is a block diagram of a thermoelectric conversion element showing a ninth embodiment of the present invention, and Fig. 16 i is an information input device showing an embodiment of a disciple of the present invention. principle diagram,
Fig. 17 is a block diagram thereof, Fig. 18 is a block diagram of a photoelectric conversion element showing an embodiment of the present invention, Fig. 19 is a block diagram of an image pickup tube, and Fig. 20 is an implementation of the second embodiment of the present invention. FIG. 21 is a configuration diagram of a light transmission type switching element showing an example, and FIG. 21 is a configuration diagram showing a combination with an EL element. 2...Transparent conductive film, 17...Transparent conductive film, 21...
・Transparent electrode (transparent conductive film), 30...Transparent conductive film, 3
7...Transparent conductive film, 46...Transparent electrode (transparent conductive film), 53...Transparent electrode (transparent conductive film), 58-59...
・Transparent electrode (transparent conductive film), 64...Transparent electrode (transparent conductive film), 7]...Transparent heat generating layer (transparent conductive film), 7
5-76...Transparent electrode (transparent conductive film), 79...Signal electrode (transparent conductive film), 97-98...Transparent conductive film,
100...Transparent conductive film Applicant Rico Co., Ltd. - J, 10 countries 3'' Tsuyoshi, J3 J3 Fig. death

Claims (1)

[Claims] 1. An oxygen-free reducing transparent conductor characterized by comprising an element selected from tin Sn, lead Pb, and indium In and an element selected from carbon C, nitrogen N, and sulfur S. film. 2. Claim 1 characterized in that it contains hydrogen H.
The reducible transparent conductive film described in . 3. The reducible transparent conductive film according to claim 1 or 2, which contains an element selected from group IIIa or group Va of the periodic table.