JPS5971206A - Light transmissive conductive film and method of producing same - 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] This invention is based on the addition of a light-transmitting conductive film (hereinafter abbreviated as conductive film) mainly composed of tin oxide on a substrate, which increases the transmittance of visible light to 8 or more. It also relates to an OTF that has further improved electrical conductivity.

The present invention relates to a transparent insulating substrate (hereinafter simply referred to as a transparent insulating substrate, or TIS).
In other words, boron is contained in a proportion of 0.01 to 3.0% by weight on a first light-transmitting conductive film whose main component is indium oxide (hereinafter referred to as mono-K ITO) in which tin oxide is added to soil at a concentration of 10.0% by weight or less. The main component is tin oxide (hereinafter referred to as simply KS).
A second transparent conductive film (referred to as nO) (second CTF) is provided, and a P-type conductive film whose main component is silicon or silicon carbide doped with hydrogen or a halogen element is provided on this second CTF. The present invention relates to a method for producing a transparent conductive film characterized by providing a P-type semiconductor layer made of a non-single-crystal film or a P-type single-crystal semiconductor layer.

When forming a transparent conductive film containing tin oxide as a main component by electron beam evaporation, the present invention uses tin oxide doped with 0001-X% of boron oxide or a boron compound as the evaporation source. By irradiating this with an electron beam, a highly conductive tin oxide film doped with boron is formed on the substrate or the substrate on which the TIS1 J: has been formed, and the overcast film is oxidized. Boron is released by heat treatment in an atmosphere. . 01-3
The present invention relates to a method for producing cTF containing tin dioxide as a main component.

Regarding conventional CTF K, 5no2 film or TO is well known. However, sno, , is an oxygen-rich acceptor type OTF, and TO is an oxygen-deficient donor type OTF. However, especially regarding this acceptor type OTF K, even though it has excellent heat resistance and resistance to oxidizing agents against hydrochloric acid, the electrical conductivity is 500 to 100.
It was not possible to obtain Z of 100 or less at a thickness of 0λ.

The present invention uses such boron in a weight ratio of 0.01 to 3, preferably 0.05-(). By adding 5 g, 500 ym
The object is to have a sheet resistance of 1004% or less that has a transmittance of 80% or more with reference to '.

That is, although FIG. 1 shows a vertical sectional view of the present invention, FIG.
), the transparent insulating substrate (1) was made of 0TF (2
). This formation method is as follows: -Tin oxide (actually, tablets with sulfur dioxide added thereto)
By creating an evaporation source] and irradiating this tablet with an electron beam, a tin monoxide film doped with boron (2) is created.
was formed on the substrate (1). Further, this film is subjected to heat treatment in an oxidizing atmosphere, preferably at a temperature of 300 to 6 o'o'c, to transform the tin oxide into tin dioxide and convert the boron into an acceptor type. When used as an impurity, its electrical resistance (sheet resistance) is preferably 10% or less, preferably 0.01 to 3 fVF.
It is characterized by having a D.

Furthermore, in FIG. 1(B), a transparent insulating film such as a glass substrate is coated with phosphor-doped To or phosphorous-doped To as a base for the boron-doped tin oxide film. The boron-doped OTF of the present invention is formed on this donor-type CTF.
The invention relates to a two-layer structure in which

This two-layer structure C1TFK was deposited on a glass substrate in the same vacuum system using the electron beam evaporation method.
In an oxygen atmosphere at a temperature of °C,
A TO film of a predetermined thickness was formed by irradiating the substrate with a K electron beam, and then the above-mentioned boron-doped tin monoxide was evaporated while lowering the temperature of the substrate. has a yellow color and is not translucent, so all of these are further oxidized at 200 to 600' OK, and -
By converting tin oxide to tin dioxide, the sheet resistance is 10 Jt/or less, and special KO001 to IC4 is achieved. This is extremely effective when the amount of boron added is 0.01.

Furthermore, Fig. 1 (0) shows the glass substrate (1) and the soil (To(3)
) and boron-doped tin oxide (2) by low-pressure OVD (chemical vapor deposition) or plasma OVD method, silicon oxide or silicon carbide doped with hydrogen or halogen elements is deposited. In this drawing, a semiconductor (8) having a P-type semiconductor layer (4) as a component is formed.
), a ■-type semiconductor layer (5), and an N-type semiconductor layer (6) are laminated. Further, metal such as aluminum or silver is formed as an electrode ('7) on the upper surface of the TO or TO1 to which phosphorus is added by vacuum evaporation.

Further, the content of the present invention will be explained below according to its embodiments.

Example 1 This embodiment is shown in FIG. 1(A), which is a vertical sectional view.

The vacuum evaporation apparatus used is an electron beam evaporation apparatus manufactured by Shinku Kikai B, Teoo (1 m vacuum chamber, inner diameter 800 mm). The evaporation source (tablet) is SnO (actually about 20% 5
A 15J having a thickness of 8 mm and containing 1.0 weight or less of boron dioxide (Bto3) in a so-called main component containing nO1 is tin monoxide was used.

Vacuum deposition shows a damage profile including temperature distribution according to curve 2 in FIG. The area 0υ is the degree of vacuum lX
A vacuum atmosphere of 10 torr or less, in which a substrate having a surface to be formed, for example, IOXIOcm', 20X20c
Bake the glass substrate of (a) for about 15 minutes, g s,
Water vapor was removed. Furthermore, in the region 0 → vacuum degree lX
In a vacuum atmosphere of 10 torr or less, the SnO containing boron of the present invention was deposited at a deposition rate of 1 to 5'A/sec. In addition, the area (1 point 2) was 420° in the electric furnace.
C! is heated in air for 3 hours to produce C! whose main component is tin dioxide. TF K metamorphosed.

As a result, when the thickness of the conductive film was 100 OA, (9) a sheet resistance of 3 Ω% was obtained, and the transmittance was 50 Ω%.
It had a coefficient of 90 at the wavelength of o'im. In this detail, we theoretically eliminate 4-5 reflections at other surfaces where 0CTF is not formed.

Example 2 This example shows that in Example I, the boron additive in the tablets was 0.01%, 0.1%...
This is the case when the . The rest is the same as in Example 1. As a result, P had a sheet resistance value of curve αa shown in Figure 3, and a transmittance of curve α]).The 100% (RT) hydrochloric acid immersion test showed that the sheet had acid resistance for more than 60 minutes. Was.

Example 3 This embodiment shows a vertical sectional view of FIG. 1(B).

In the vacuum evaporation apparatus of Example 1, the Qrl+(10
) The glofill is shown by the curve (tr) K in FIG.

That is, after placing the substrate in the vapor deposition apparatus, the degree of vacuum is set to lXl0.
torr or less, add a substrate in area (b) and make a tablet (15 mm x 8 m → 1 ~
The first C was deposited on the ITO film at a vacuum deposition rate of 3/sec.
TF was formed to a thickness of 500 mm.

Further, in region (c), the vacuum level is reduced to 1X10 torr or less, and the deposited TO film is crystallized to form a donor-type CT.
It was set as F. As it is, the sheet resistance is 10 or more. Furthermore, after this, when lowering the temperature in region (A), SnO doped with 0.3T of sulfur was simultaneously deposited to a thickness of 500λ at a rate of 1 to 3A/sec.

A film constituting two layers on the substrate was vacuum evaporated (formed at 14K) with a temperature of %', and then heated and oxidized in an oxidizing atmosphere in the same manner as in Example 1 in an area (1 inch (-1>f&z+)). I did this.

In this way, sheet resistances of 1 to 1 were obtained.

Example 4 In this example, the amount of boron impurity added to SnO was varied in Example 3.

In this way, we were able to obtain the curve α→ in FIG.

Example 5 ■By adding phosphorus to TO, the sheet resistance can be reduced to less than 1% at a thickness of 500^, for example. , 05% was obtained. As a result, by varying the amount of boron in EInO, the curve α→ shown in FIG. 3 could be obtained.

Embodiment 1 shows an embodiment of a photoelectric conversion device shown in the vertical sectional view of FIG. 1(0).

In the drawing, the first 0TF (3) is placed on the glass substrate (1).
and a second CTF (2) was formed according to Example 4. At this time, 0% phosphorus is added to the first CTF. Furthermore, 0.3 g of boron is added to the second CTF.

After that, these substrates are activated and decomposed by high frequency or microwave to reduce the reaction products to 0% Si using the so-called plasma OVD method.
H4,1:1, B, T(,/S IH,=1%, thick single crystal semiconductor (5) is SiHz or SiL
H/+1: Further, the KN type semiconductor layer (6) is set to PHJ/SiH,=1 inch to a thickness of 0.5μ, and the upper surface K
A non-single crystal semiconductor (8) with a thickness of 100λ and doped with hydrogen or a halogen element was formed in close contact with the P-type semiconductor layer (4). Thereafter, by forming a back electrode (7) and irradiating it with light of AMI- (100 mW/c clause 00), 11 chips (area 1 cA) could be obtained.

[Brief explanation of the drawing]

FIG. 1 shows a vertical cross-sectional view of a transparent conductive film of the present invention provided on a substrate. FIG. 2 shows an operation profile for forming the transparent conductive film of the present invention. FIG. 3 shows the sheet resistance and transmittance of the transparent conductive film of the present invention.

Claims (1)

[Scope of Claims] (1) A translucent conductive film on a substrate, characterized in that the translucent 1L conductive film containing tin oxide as a main component contains 0.01 to 3% fluorine by weight or less. 2. Second light-transmitting conductive film mainly composed of indium oxide to which 10% by weight or less of tin oxide is added on a light-transmitting insulating substrate, lKM P
21i! ! (7) A light-transmitting conductive film characterized in that a semiconductor layer is provided. A translucent conductive film characterized in that antimony oxide is added in an amount of 2.5 to 10% by weight. 4. A method for forming a translucent conductive film containing tin oxide as a main component by electron beam evaporation. By irradiating an evaporation source mainly composed of tin monoxide to which 0.01 to 3% by weight of boron oxide or a boron compound is added with an electron beam, tin oxide is deposited on the substrate or the transparent insulating substrate. A process of forming a coating mainly composed of tin oxide doped with boron on a transparent conductive film mainly composed of indium oxide added in an amount of 10M or less, and a step of forming a film mainly composed of tin oxide doped with boron, and a step of forming a film mainly composed of tin oxide added with boron. A method for producing a translucent conductive film, which comprises producing a translucent conductive film as a main component. 5. In claim 4, the heat treatment in an oxidizing atmosphere contains oxygen or nitrogen oxide. 30 in atmosphere
A method for producing a translucent conductive film, characterized in that it is carried out at a temperature of 0 to 6 o♂C.