JPH02133402A - Apparatus for polymerization of thin organic film - Google Patents

Abstract

PURPOSE:To improve the crystallinity, orientation, etc., of a thin organic film by providing a light radiating apparatus wherein glass fibers for introducing light and a condenser lens are integrated above a watery layer so as to make it possible to irradiate only a restricted part with light. CONSTITUTION:A water-insoluble organic material (e.g., heptacosa-10,12-diynoic acid is spread on the water surface in a water tank 1 and a bar is moved to adjust the surface tension. Then ultraviolet light is radiated in the vicinity of a substrate 9 through lens-integrated optical fibers 5 which is a light radiating apparatus wherein glass fibers for introducing light and a condenser lens are integrated, thereby polymerizing the organic material to obtain a thin organic film.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an organic thin film polymerization apparatus for polymerizing organic materials spread on the surface of water.

BACKGROUND OF THE INVENTION In recent years, various electronic devices using water surface-deployable films and Langmuir and Projet films for transferring these onto substrates have been actively researched. Among these, when organic thin films are used as insulating films, protective films, etc.

It is generally known to impart polymerizability to an organic material, and then irradiate it with light during development on the water surface or after accumulation to turn it into a polymer.

Polymerization of water surface membranes is usually carried out by installing a lamp on the top of the water tank.
It is performed by irradiating light over the entire water surface (for example, D, D
ay et al, Makuromol, Chew
, 180 (+979) +059) , L. In this polymerization method, the organic material expands thermally under the influence of radiant heat from the light source, and the irradiation of the entire surface of the aquarium with light creates a barrier that compresses the organic material. The vicinity of the plate that detects surface tension also polymerizes, and pinholes occur due to changes in surface tension due to changes in plate position during substrate accumulation and decrease in fluidity of the organic material, resulting in changes in the crystallinity, orientation, and backing density of the organic thin film. It's very problematic in that respect.

In order to avoid this problem, there is a method of introducing light from a distance and irradiating it by reflecting it with a mirror on the water surface, but this method requires increasing the size of the device and adjusting the optical axis by introducing multiple mirrors and their driving bag Problems such as operability arise.

Problems to be Solved by the Invention The present invention aims to improve the crystallinity, orientation, and backing density of organic thin films by irradiating light onto a limited area without being affected by heat.
The purpose of the present invention is to provide a thin film manufacturing device that is compact and has excellent operability.

Means for Solving the Problems The present invention is an organic thin film manufacturing apparatus in which a polymerizable organic material insoluble in wood (e.g., diacetylene, dienoic acid, etc.) is spread on a water surface and a polymerized thin film is formed by light irradiation. This is an organic thin film manufacturing apparatus that has a light irradiation device integrated with a glass fiber for introducing light and a condensing lens at the top of the water tank in order to photopolymerize the peripheral portion of the substrate.

A lens-integrated optical fiber uses a lens to focus and project light, since light spreads out in a normal fiber, and a cartridge-type holder containing multiple lenses is attached to the fiber end.

Part of the holder can be replaced depending on the irradiation area.

According to the present invention, it is possible to separate the light source from the irradiation area, thereby avoiding thermal expansion of the organic material due to the influence of radiant heat from the light source, and irradiating only the necessary areas. , there is no polymerization near the barrier that compresses the organic material or the plate that detects surface tension, which occurs when the entire surface of the aquarium is irradiated with light, and as a result, the surface tension detection plate is attracted to the substrate when the substrate is accumulated, and the surface tension value fluctuates. This also solves the problem of pinhole formation due to decreased fluidity of the organic material.

In addition, the single method does not require the enlargement of equipment (introducing equipment such as drive systems and mirrors) or complicated optical axis adjustment that would occur when using a light introduction method that uses mirror reflection on the water surface.
The light source can be made smaller compared to full-surface irradiation.

Furthermore, since it is polymerized only in the necessary parts in a compressed state,
The crystallinity, orientation, and backing density of the cumulative film can be improved.

This will be explained in more detail below. The glass fiber has good transmittance for the light used, and in the case of ultraviolet rays, it is best to use quartz glass.Furthermore, the fiber opening can be determined according to the irradiation area, and can be rectangular, square, circular, etc. It is.

The lens connected to the fiber opening is explained in Figure 2.
If the fiber opening is rectangular, a cylindrical lens and a spherical lens are used, and if it is circular, a combination of several spherical lenses is used depending on the irradiation area.

A lens with a focal length suitable for the equipment environment can be selected. In addition, slits are placed in front of and between the lenses to limit the area. These are housed in one holder and can be replaced depending on the required irradiation area.

The light irradiation method may be by using one fiber as shown in Fig. 3, or by using multiple fibers as shown in Fig. 4, or by applying light to the meniscus part during substrate accumulation as shown in Fig. 5. It may also be irradiated.

In this case, if the area around the barrier plate that compresses the organic material polymerizes, the fluidity of the organic material will decrease, so it is better to install an aluminum coating plate in the tank to reduce the influence of reflected light from the bottom of the tank. (3rd
Fig. 4).

In addition, the light irradiation to the meniscus part is focused linearly by a lens, but in order to avoid polymerization of the peripheral part due to light reflected from the substrate, an aluminum coated reflector is used in the water tank (Figure 5). Furthermore, the reflection angle φ is preferably in the range of 10 to 80 degrees to facilitate the installation of the reflector. Among these devices, it is better to keep the light source part away from the aquarium in order to prevent changes in the temperature of the environment.

Example 1 Hereinafter, the present invention will be described in detail with reference to the drawings.

Figure 1 shows the entire rice bag, where ■ is a width of 10 cm, length is 80 cm, and depth is lc ■ A water tank coated with polytetrafluoroethylene, and 2 is a surface compression bar coated with polytetrafluoroethylene. . This is moved by motor 7.

3 is a plate for measuring changes in surface pressure, and the surface pressure is detected using an electronic balance 4 that measures the weight of the plate.
This is done using the llhe1mt type.

5 is a quartz glass fiber equipped in the organic thin film manufacturing apparatus of the present invention, which has a core diameter of 220 μm, is made of 4200 mm wood with an exit area IXZc, and has a slit and a cylindrical lens (focal length 38 m) at the tip. be.

The fiber length is 2 m, and the ultra-high pressure mercury lamp (25°W)
) 6 and installed in a separate room from the aquarium 21. This is to prevent ambient temperature changes from occurring.

Reference numeral 8 denotes an aluminum coated reflector that prevents polymerization of the surrounding area due to reflection from the bottom of the tank.

An example of manufacturing an organic thin film using one apparatus will be described below.

First, Heptacosa 10. +2 diyic acid was dissolved in chloroform to prepare a developing solvent with a concentration of 1.0 g/ml.

A small amount of this solution was dropped onto a 500d aqueous solution containing 2.5XIO-4M CdCl2 at 18°C, and after evaporating the chloroform, the bar 2 was moved to lower the surface tension by 20dyn.
/am.

While keeping the surface tension constant, ultraviolet rays are passed through the fiber and lens to the approximately 8c layer 2 near the substrate at 30 W/c112.
．． It was irradiated for 1 hour.

While maintaining the surface tension at about 20 dyn/c, this film was lowered onto a Si substrate provided with a gold electrode at a substrate speed of [■/■in] to transfer three layers. A gold electrode was deposited on top of this film (area 1c weight 2), and the resistance was measured to be 1016Ω.
・It was effi.

Example 2 Heptacosa 10,12 diynoic acid was dissolved in chloroform to prepare a developing solvent with a concentration of 1.0 g/41, and this solution was
8℃Te2, 5 x 10-' M (F) CdC'
500d containing l2 (7) Drop a small amount onto the aqueous solution,
After chloroform was evaporated, the bar 2 was moved to adjust the surface tension to 20 dyn/c.

While keeping the surface tension constant, ultraviolet rays were passed through the fiber and lens to irradiate the meniscus near the substrate from 45@ with a width of 1 aps and a length of 2 C. In this state, the 31 substrate with gold electrodes was exposed to 1+ Three layers were transferred by moving the substrate up and down at a substrate speed of m/m/in. A gold electrode is placed on top of this film.
Area IC112)L, resistance measured 1016Ω
Comparative Example: Heptacosa+0, 12 diyic acid was dissolved in chloroform, a developing solvent with a concentration of 1.0 g/l was prepared, and this solution was heated to 18° C. (J
After the chloroform was evaporated, the bar 2 was moved to adjust the surface tension by 20 db.

While keeping the surface tension constant, the entire surface was irradiated with ultraviolet rays of 30111I/c112 for 1 hour from an ultra-high pressure mercury lamp above the water surface. At this time, an increase in membrane area due to temperature rise (2° C.) was observed.

While maintaining the surface tension at 20 dyn/cm, three layers of this film were transferred onto a Si substrate provided with a gold electrode by moving it up and down at a substrate speed of 1 inch/inch.

At this time, the plate on which the surface tension was being measured was drawn toward the cumulative substrate, the surface tension value changed by ±5 dman/c, and a striped pattern was observed on the cumulative film. A gold electrode was deposited on this film (area: 1 cm x 2), and when the resistance was measured, there was a variation in the range of 10 8 to 10 14 Ω/0 layer.

Effects of the Invention According to the present invention, photopolymerization is performed only in the necessary areas without being affected by heat, improving the crystallinity, orientation, and backing density of the IafiJ film, and producing an organic thin film that is compact and has excellent operability. We can provide manufacturing equipment.

[Brief explanation of the drawing]

The drawings all show embodiments of the present invention; Fig. 1 is a perspective view of the entire device, the fiZ drawing schematically shows the fiber tip, and Figs. 3 and 4 show wooden tablet irradiation. figure(
(d) is an elevation view, (b) is a top view), and FIG. 5 is an explanatory view showing irradiation to the meniscus portion. l... Water M, 2... ψ bar, 3... Plate, No. 4... Electronic balance, 5. Life - Optical fiber with integrated condensing lens,
6...Ultra high pressure mercury lamp, 7...Motor, 8...Aluminum coach ink reflector, 9...ψ substrate, lO.
・Reference up and down motor, 11・Ichiban Huai/<, 121+
$6 slit, 13-...lens, 14...φ irradiation area, 15...bottom of the aquarium.

Claims (1)

[Claims] An organic thin film production device that spreads an organic material on a water surface and forms a polymerized thin film by irradiating it with light.This organic thin film polymerization device enables light irradiation of a portion of the water surface using a lens-integrated optical fiber.