JPH0499609A - Method of forming polymer film - Google Patents

Abstract

PURPOSE:To allow the titled film to be a good quality medium for propagating pulse lights having a width of the order of femto-seconds by uniformly dispersing a soluble compound in a solvent polymer compound on a substrate for forming a film, and thereafter subjecting the film to a hot rolling process while adding one directional shearing stresses. CONSTITUTION:A soluble compound and solvent polymer compound are added into a solvent, and the solution obtained is dropped on a glass substrate, and then the glass substrate is mounted on a high-speed rotating disk for forming a film sample. It is quietly left under room temperatures for three days for conducting preliminary drying, and then subjected to a treatment for two hours at 100 deg.C under vacuum conditions. Voids in the sample generated during the drying process are treated by a vacuum hot rolling device in the form of being held by another substrate with the same quality. The film sample 6 is charged within a vacuum vessel 1 for carrying out vacuum air discharging to it by a vacuum air discharging device 5 under room temperature for 30mins., and then it is heated by a heating device 2 at the rate of 50 deg.C/mins., and at the time when it reaches 100 deg.C, vacuum air discharging is stopped and the vacuum condition is maintained herein so as to perform further heating, and at the time when it reaches 150 deg.C, hydrostatic pressure of 50kg/cm<2> is applied thereto by means of a hydraulic press main body, and after it is held for 10mins. cooling is effected at the rate of 100 deg.C/hr.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is responsive to the incidence of pulsed light having a duration of, for example, picoseconds, femtoseconds or shorter, and which is different from the incident light. 6 (Prior Art) Regarding Improvement of Method for Forming Thin Polymer Films Accompanied by Release of Polymers 6 (Prior Art) A method of forming a thin film by dissolving inorganic and organic compounds having various optical functions in a polymer compound.

This method has been widely used in the past as a method for manufacturing thin polymer films with various optical functions.

In this method, as shown in FIG. 3, both the solvent polymer compound 7 and the solute compound 8 are dissolved and uniformly dispersed in one or more organic or inorganic solvents 9, and then
This is dropped onto a glass or other transparent substrate 1O, and only the solvent is evaporated to hold the solute compound 1 in the polymer compound 2 to form a thin film.

(Problems to be Solved by the Invention) However, since the method shown in FIG. 3 uses a solvent, the thin film sample is removed from the solvent by drying, etc.
Even if such an operation is performed, the solvent remains in the sample, or bubbles are generated after the solvent is removed, resulting in a cloudy sample. In addition, attempts have been made to make the drying speed uniform in order to avoid this clouding phenomenon, but even with this, air bubbles or pores of several microns are generated within the sample, and solvent remains within the sample. At present, this significantly deteriorates the optical properties of the sample.

Furthermore, a light pulse propagates only 300 nanometers in one femtosecond, and propagation of pulsed light with a width of about femtoseconds requires optical path adjustment and sample uniformity on the order of micrometers. Therefore, it is necessary to suppress the non-uniformity within the thin film sample to less than the propagation distance of the pulse duration.

Therefore, the first object of the present invention is to reduce the size of inhomogeneous parts such as pores existing in the thin film sample and the unevenness of the sample surface to below micrometers, thereby producing pulsed light with a width of approximately femtoseconds. An object of the present invention is to provide a method for forming a thin polymer film that serves as a high-quality medium for the propagation of.

On the other hand, in order to increase the mechanical strength of the thin film sample formed as described above, by applying tensile stress in one direction within the film surface, the polymer compound itself, which is the holding material,
Alternatively, a method of controlling the arrangement of organic compounds dissolved in solid solution is widely known as a thin film stretching method, but this method has the following drawbacks.

In other words, as mentioned above, it is known that a single molecule of an organic compound held in a polymer compound exhibits a wide variety of properties, but when applying tensile stress to a thin film sample as described above, the organic compound The orientation is greatly restricted by the polymer compound itself that is the holding material or the physical properties of the compound itself, and even if tensile stress is applied, the number of organic compound molecules that can be stretched and oriented is limited accordingly.

+= Then, mechanically or optically by thin film stretching method,
For this reason, it is generally known that the properties of the crystal or thin film as a whole are smaller than the amount shown per molecule of the organic compound.

Therefore, the second purpose of this invention is to bring out the properties of a single molecule of an organic compound as properties that extend over the entire thin film, and to form a thin polymer film that becomes a high-quality medium for the propagation of pulsed light with a width of approximately femtoseconds. It is about providing law.

c) In order to solve the above problems, this invention involves the formation of a thin polymer film in which solute compounds having various optical functions are uniformly dispersed in a solvent polymer compound to form an N4 film. The present invention provides a method in which a thin film is formed on a substrate by a uniform fraction of the solute compound in the solvent polymer compound, and then the thin film is hot-rolled.

Furthermore, the present invention provides a method of hot rolling while applying unidirectional shear stress to the thin film in the hot rolling step.

Here, as the solvent polymer compound, polymethylmethacrylate-1-(PMMA) or the like can be used.

Furthermore, as the solute compound, organic or inorganic compounds having various optical functions can be used. Specifically, the organic compound is 2-methyl-4-nitroaniline (MNA).
), etc., and conventional methods can be used to form the thin film on the substrate.

For example, as shown in Fig. 3, a solute compound and a solvent polymer compound are added to a purifying agent, and the resulting wet liquid is dropped onto a substrate.
Furthermore, the substrate is mounted on a disk that is rotated at high speed, the diaphragm is centrifuged, and the solvent is left to stand still for preliminary drying at room temperature.The remaining solvent is removed by heating and vacuum treatment to form a thin film on the substrate. can be formed.

Of these, the step of forming a thin film on a substrate mounted on a high-speed rotating disk may be omitted, and the thin film may be formed on a stationary substrate. A thin film may be formed by omitting or changing the order.

Alternatively, a solute compound and a solvent polymer compound may be mixed at a fixed ratio, sufficiently pulverized and mixed, and then sandwiched between substrates to form a thin film.

On the other hand, hot rolling of a thin film is performed by heating the thin film sample to, for example, about 150° C. and applying a hydrostatic pressure of 50 kg/cm2 to the thin film sample for about 10 minutes.

Note that it is preferable to use vacuum hot rolling treatment for these hot rolling treatments.

(Function) As described above, according to the present invention, by hot rolling a thin film obtained by a conventional method, pores and the like in the thin film can be removed and the surface of the thin film can be made smooth.

Therefore, according to the present invention, by reducing the size of the inhomogeneous portion existing in the thin film and the unevenness of the thin film surface to less than micrometers, it is possible to prevent the incidence of pulsed light having a duration of picoseconds, femtoseconds, or shorter. It is possible to provide a material that is responsive to light and emits light that is different from the incident light.

In addition, according to the present invention, solute compounds can be uniformly dispersed in various polymer thin films, so that they can be dispersed in ultraviolet, visible, and
It is possible to provide a material that is optically transparent in the infrared light region and has low scattering loss.

Furthermore, according to the present invention, by applying unidirectional sliding stress to the thin film during the hot rolling process, the molecular orientation of the organic compound dispersed in the polymer thin film is promoted, so that one molecule of the organic compound is This property can be extracted as a property that covers the entire thin film.

(Example) Examples of the present invention will be shown below, but the combination of solute organic compound and solvent polymer compound, mixing ratio, formation temperature, etc. explained in this example are examples for explanation, and the invention does not limit the scope of application.

Example 1 A solute compound and a solvent polymer compound are added to a solvent, the resulting solution is dropped onto a glass substrate, and the glass substrate is placed on a disk that is rotated at high speed to form a thin film sample.

The formed thin film sample was pre-dried by standing at room temperature for 3 days, and was further treated under vacuum at 100° C. for 2 hours to remove residual solvent in the sample. The pores in the sample generated during this drying process are sandwiched between another substrate of the same quality as above, and processed by a vacuum hot rolling apparatus shown in FIG.

As shown in the figure, the vacuum hot rolling equipment has a vacuum container 1 inside.
The vacuum container 1 is heated by heating devices 2.2 provided above and below.

It is constructed so that it can be pressurized by the hydraulic press main body 4 from above and below via the heat insulating material 3.3. Further, the vacuum container 1 is connected to a vacuum exhaust device 5 via a valve.

The thin film sample 6 is loaded into a vacuum container l as shown,
After evacuation at room temperature for 30 minutes, it was heated at a rate of 50°C/min, and when it reached 100°C, evacuation was stopped and the vacuum state was maintained and further heated, and when it reached 150°C, it was heated at a rate of 50 kg/sq. Add a hydrostatic pressure of 1 and in this state
After holding for 0 minutes, it was cooled at a rate of 100°C/hour.

Through this treatment, the pores in the sample were removed, and the size of the heterogeneous portions present in the sample and the unevenness of the sample surface were controlled to below micrometers.

The formed thin film sample was sandwiched between two glass substrates each having a thickness of about 150 μm, and the thickness of the sample was about 30 μm.

Example 2 MNA and P sufficiently purified by conventional chemical methods
MMA, MNA/152mg, PMMA/100m
g, thoroughly pulverized with a mortar, mixed, sandwiched between two glass substrates with a thickness of about 150 LLm, and loaded into a vacuum hot rolling machine, as in Example 1. A thin film sample was formed. The thickness of the thin film sample formed was approximately 30 LLm.

Example 3 The thin film samples prepared in Examples 1 and 2 were placed in the resonator of a CPM laser so as to be confocal with each other.
It was placed at the confocal point of two concave mirrors.

The diameter of the laser beam at the confocal point is about 10 μm. When the time width of the optical pulse output from the oscillated laser resonator is measured using an SHG autocorrelator, an optical pulse with a time width of 50 fm seconds shown in Fig. 2 is obtained, and as shown in Fig. 2. It was observed that the time width of the obtained light pulse was shorter than 73 fmsec, which is the light pulse width when no thin film sample was installed, as shown in FIG. It was found that the sample exhibited excellent femtosecond optical pulse responsiveness.

(Effects of the Invention) In summary, according to the present invention, a high-quality medium can be provided for the propagation of pulsed light having a width of approximately femtoseconds.

Further, according to the present invention, since the molecules of the organic compound can be oriented, the properties of one molecule of the organic compound can be brought out as the properties of the entire thin film.

Furthermore, the thin film forming method according to the present invention uses an organic compound as f! It is suitable for dense formation, and is particularly suitable for forming a medium for advanced applications that requires homogeneity down to the wavelength of the incident light.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a vacuum hot rolling apparatus used in an embodiment of the present invention, and FIG. Light pulse with time width of milliseconds, Fig. 2 fb
Figure 3 is an explanatory diagram of a conventional method for forming a thin film of a polymer compound using a solvent. In the figure, 1 is a vacuum container, 2 is a heating device, 3 is a heat insulator, 4 is a hydraulic press body, and 5 is a vacuum exhaust device. Figure 1 Figure 2 TimeDplay (fsec) Procedural amendment (daytime) October 3Q, 1991

Claims (2)

[Claims] (1) In a method for forming a thin polymer film in which solute compounds having various optical functions are uniformly dispersed in a solvent polymer compound to form a thin film, the solute compounds are dispersed in the form of a substrate into the solvent polymer compound. A method for forming a thin polymer film, which comprises forming a thin film by uniformly dispersing it, and then subjecting the thin film to a hot rolling treatment. (2) The method for forming a thin polymer film according to claim 1, wherein the hot rolling treatment is performed while applying shear stress in one direction.