JPS6391910A - Manufacture of transparent conductive film - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a transparent conductive film that is transparent in the visible light range and has electrical conductivity, and is used in various displays, solar cells, and the like.

Conventional technology In recent years, transparent conductive films have been developed with the development of various displays.
The demand is on the rise. Types of transparent conductive films include indium oxide and zinc oxide.

Among these, indium oxide (ITo) containing tin as an impurity is currently mainstream due to its tetraelectricity. However, tin oxide is gaining attention for its low cost and long life.

Traditionally, tin oxide films have been produced by heating the base material itself or by heating the entire reaction chamber containing the base material to thermally decompose the reactive gas around the base material to generate thermal decomposition products. A common method has been to form a certain tin oxide on a substrate.

Problems to be Solved by the Invention However, in the conventional manufacturing method of tin oxide film, the entire space around the base material is at high temperature, so thermal decomposition products of reactive gases are Thirdly, there is a problem in that bits are generated in the formed thin film due to thermal decomposition or reaction of thermal decomposition products with undecomposed reaction gas. In addition, since the base material is strongly heated, distortion of the base material 1
Many damages occur to both the formed thin film and the base material, such as warping, shrinkage, etc., loss of dimensional accuracy due to heating, deterioration of the structure of the base material itself, and changes in the film-like structure already formed on the base material. There was a problem with that.

On the other hand, there is also the problem that tin oxide films generally have high resistance and cannot obtain sufficient characteristics as a conductive film.

Means for Solving the Problems In order to solve the above problems, the present invention provides a method for producing a transparent conductive film of the present invention, in which a gas is By sending a gaseous airflow whose main components are a tin compound gas containing a phosphorous compound and oxygen gas, and heating the substrate surface with a laser beam, the gaseous airflow is thermally decomposed, and the gaseous airflow is thermally decomposed onto the substrate surface. The structure is such that a tin oxide film containing phosphorus is formed.

According to the present invention, only the surface of the base material irradiated with the laser beam is instantaneously heated by the above-described configuration, and only the heated surface is heated with a reactive gas consisting of a tin compound gas containing a phosphorus compound and oxygen gas. can induce thermal decomposition of That is, a film forming reaction can be caused only on the surface of the substrate without involving an external process of reactive gas existing in a space close to the substrate.

EXAMPLE Hereinafter, an example of the method for manufacturing a transparent conductive film of the present invention will be described with reference to the drawings.

FIG. 1 shows the configuration of an apparatus for manufacturing a transparent conductive film in the atmosphere used in one embodiment of the present invention. The carbon dioxide laser beam 14 emitted horizontally from the laser transmitter 1 is deflected downward by the reflecting mirror 2, and then
It is swept in two directions of XY by the rotating mirror 3 of the school. That is, the surface of the glass substrate 5, which is a base material placed on the sample stage 8, is swept and irradiated in the X and Y directions. At this time, the laser irradiation part on the substrate is instantaneously heated.

Now, the reaction gas system that is the tin oxide material is dimethyltin chloride lO, which is a tin compound in a liquefied state, and phosphorus oxychloride, which is a phosphorus compound, respectively, and Ar gas 11.12
By bubbling, the reactive gas 4 containing tin and phosphorus is ejected from the reactive gas supply nozzle 6 together with the oxygen gas 13 onto the plate 75. Note that the ejected gas is recovered from the reactive gas υ air lower.

FIG. 2 shows the mechanism of the reaction part, and the reactive gas supply nozzle 6 has blowholes provided at regular intervals in the injection groove and the groove bottom.

A r: 31/min, O,: 31/m
in, A r containing dimethyltin chloride gas: 0.
31. 'min.

Ar containing pocx3 gas: 0. 01~0. 3
When the reactive gas composition is 1/min, the shape of the reactive gas 4 ejected from the reactive gas supply nozzle 6 has a width of 100 mm.
mm, thickness approximately 10. , which passes horizontally over the surface of the glass substrate 5 on the sample stage at a speed of about 3 m/sec.

When a laser beam 14 emitted from a laser transmitter 1 and whose direction is changed by a reflection mirror 2 is swept over a glass substrate 5 in the Y direction by a rotating mirror 3, a tin oxide film is formed on the substrate surface as the laser beam sweeps. Deposition occurs. Furthermore, if the laser is continuously swept over the substrate in two directions, X and Y, using a rotating mirror, a tin oxide film will be deposited over a large two-dimensional area. The deposition rate of the tin oxide film depends on the laser output and the laser travel speed. That is, the deposition rate increases as the laser output increases, and rapidly decreases as the laser sweep rate increases. This is because both greatly depend on the substrate surface temperature of the laser irradiation part. For example, when the laser output is 50W, the laser beam diameter is 5++++, and the laser sweep speed on the substrate is 3 am/sec,
The irradiated area is locally heated to 400-600'C. Although this sufficiently satisfies the substrate temperature required to form a high-quality tin oxide film, the high-temperature heating section is limited to only the surface layer of the substrate, and moreover, only at the moment of laser beam irradiation. Therefore, the tin oxide film was produced in a substantially low temperature process without raising the temperature of the substrate itself. Accordingly, many damage to both the formed thin film support and the substrate, which occur due to conventional high IA processes, are avoided, and homogeneous and reliable thin films can be produced.

Further, in this embodiment, the flow rate of the phosphorus compound gas as an impurity in the tin oxide film can be adjusted independently.

Adding phosphorus to a tin oxide film is the most effective method for lowering the resistance of the film. FIG. 3 is a graph showing the relationship between the flow rate of phosphorus compound gas and the electrical characteristics of the membrane. From this result, the specific resistance of the thin film can be lowered by 2t13 by doping with phosphorus.

Further, the transmittance of the tin oxide film produced at this time was as good as 90 to 95% in the visible range. In the above embodiments, a carbon dioxide laser is used as the laser source and glass is used as the substrate, but the present invention is not limited to these. Any laser may be used as long as it has a large heat generation effect when irradiated onto the substrate. In other words, it is desirable that the substrate absorb the laser efficiently. Therefore, an optimal combination exists between the substrate and the laser. That is, in addition to the combination of a carbon dioxide laser and a glass substrate as an example, Ar was used for the Si substrate.

Kr and ruby lasers can be used, and YAG and HF/DF chemical lasers can be used for ceramic and oxide substrates.

In addition, dimethyltin chloride is used as the tin compound 10, but in addition to this, it is also possible to form a liquid at room temperature or when heated.
Or it is a gas, and by using a carrier gas such as an inert gas to the reaction zone, it can be used as a gaseous stream of tin compounds.
It is sufficient as long as it can be supplied to the reaction zone, and in addition to the examples, 5n
C14゜(CH3), Sn, (C4H,)SnH3
゜(C4H0)Sn(13,(C,H,)2SnC12
゜(C,Hg) 2 SnO,(C,Hg
) 4 Sn.

(CB H,)25nC12, (C8H,)2 SnO
.

(C,l H,), Sn, (C,H9)2 Sn(○C
H3).

(C, HlO), Sn.

Examples include (C,Hg)2Sn(OCCH3)2. The same can be said for phosphorus compounds, 8
3PO,,PH3,P (CH3)3゜P (C2H5
) 3. Examples include P2.

In this example, the film forming reaction of the tin oxide film is carried out in the atmosphere, but it can also be carried out in a sealed atmosphere using a chamber or the like or under reduced pressure.

As described above, according to this embodiment, only the surface of the substrate irradiated with the carbon dioxide laser beam is instantaneously heated, inducing a thermal decomposition reaction limited to the heated surface, and forming a tin oxide film doped with phosphorus. can be created by a substantially low-temperature reaction.

Effects of the Invention As described above, the present invention allows a gaseous air flow mainly composed of a tin compound gas containing a gaseous phosphorus compound and oxygen gas to be brought into contact with the surface of a desired base material in the atmosphere or under reduced pressure. By irradiating and heating the base material surface with a laser beam, the gaseous air flow is thermally decomposed and a tin oxide film containing phosphorus is formed on the base material surface, thereby producing a high-quality product with low resistance and no damage to the substrate. A transparent conductive film can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a configuration diagram of an apparatus for manufacturing a transparent electrode in the atmosphere according to an embodiment of the present invention, FIG. 2 is an explanatory diagram of the mechanism of the reaction part of the apparatus for manufacturing a transparent conductive film in FIG. 1, and FIG. Transparent conductive 11! was created in one embodiment of the present invention! It is an N electrical characteristic diagram. DESCRIPTION OF SYMBOLS 1... Laser transmitter, 4... Reactive gas, 5... Substrate, 6... Reactive gas supply nozzle, 9......・Phosphorus compound, 10...
・Tin compounds. Name of agent: Patent attorney Toshio Nakao 1 person 1-1-ft, 5?5r. 2-12 company mirror 3--mouth tz... 4--tomo + ID 5--r Umata Shufutsu 6--'; 6) 6 units - D η IO - Division 16 Isu H, + 9 - - 71 and Hun D"s 13 - Quiet and Su 14 - Roof Be 4 3 - 13 Autumn, 7 Now ° - Anti-flame! 12r Also 5-m-car, e1(, ga6--Ste person I tsu pass,'l Tami Rei λ pass 5j +4
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Claims (1)

[Claims] A transparent method characterized by sending a gaseous air flow mainly composed of a tin compound containing a gaseous phosphorus compound and oxygen gas in contact with the surface of a predetermined base material, and heating the base material surface by irradiation with a laser beam. Method for manufacturing a conductive film.