JP2005077664A - Liquid crystal element and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To attain a liquid crystal element for suppressing thickness variation in the liquid crystal layer due to temperature increase, using a simple configuration. <P>SOLUTION: The liquid crystal element arranges a first transparent substrate 11A, a first transparent electrode 12A, the liquid crystal layer 13, a second transparent electrode 12B, and a second transparent substrate 11B, in this order. The liquid crystal layer 13 has 1×10<SP>-5</SP>/°C to 7×10<SP>-4</SP>/°C of the linear expansion coefficient. Herein, the liquid crystal layer 13 may be formed of a side-chain polymer liquid crystal. In addition, a reflecting mirror may be provided on a plane in between the first transparent substrate 11A which includes the surface and the liquid crystal layer 13 and a plane in between the second transparent substrate 11B which includes the surface and the liquid crystal layer 13. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a liquid crystal element capable of controlling emitted light by changing a substantial refractive index or retardation value of liquid crystal with respect to incident light according to the magnitude of an applied voltage, and a method for manufacturing the same.

Generally, a low molecular liquid crystal is used for a liquid crystal element, and this low molecular liquid crystal has a coefficient of thermal expansion of approximately 7 × 10 ⁻⁴ / ° C. to 8 × 10 ⁻⁴ / ° C., which is higher than that of a solid material. 10 times larger. As a result, it has been found that the thickness of the liquid crystal layer varies with changes in temperature in the conventional liquid crystal element. For example, a liquid crystal etalon structure in which the liquid crystal layer is sandwiched between a pair of reflecting mirrors that reflect most of the incident light and partially transmits it, and changes the substantial refractive index of the liquid crystal layer by applying a voltage to the liquid crystal layer. Thus, a wavelength tunable filter that makes the wavelength of transmitted light variable by changing the optical path length (resonator length) between reflecting mirrors has been proposed.

  Such a wavelength tunable filter is used in various external environments. When the ambient temperature rises, the liquid crystal is deformed by thermal expansion, and the resonator length between the pair of reflecting mirrors becomes long. As a result, there is a problem that the resonance wavelength, which is a transmission wavelength, changes according to the ambient temperature, and an optical signal having a desired wavelength corresponding to the applied voltage cannot be picked up.

  Therefore, in order to solve the above-described problem, a method is proposed in which a device including a wavelength tunable filter having a liquid crystal etalon structure is enclosed in an airtight chamber, and temperature control and pressure control are performed on the internal atmosphere (for example, Patent Document 1). Further, a countermeasure is disclosed in which a clamp member is connected to both ends of the liquid crystal element, and the variation in the distance between the reflecting mirrors is suppressed by suppressing the variation in the thickness of the liquid crystal layer with the clamp member (for example, Patent Documents). 2).

JP-A-1-287427 JP 2000-10080 A

  However, in the former technique, it is necessary to install a control device for maintaining a constant temperature and pressure in the hermetic chamber, which makes the apparatus large and complicated. In the latter technique, clamp materials other than liquid crystal elements are used. Since this is necessary, the apparatus becomes complicated, and in any case, the cost increases.

  Accordingly, the present invention has been made to solve the above-described problems, and provides a liquid crystal element capable of suppressing thermal expansion in the light transmission direction due to a temperature rise with a simple configuration and a method for manufacturing the same. Objective.

The liquid crystal element of the present invention is a liquid crystal formed by arranging a first transparent substrate, a first transparent electrode, a liquid crystal layer, a second transparent electrode, and a second transparent substrate in this order. An element,
The liquid crystal layer provides a liquid crystal element having a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or higher and 7 × 10 ⁻⁴ / ° C. or lower.

According to this configuration, by using a liquid crystal having a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or higher and 7 × 10 ⁻⁴ / ° C. or lower, it is possible to obtain a liquid crystal element in which the thickness variation of the liquid crystal layer is suppressed. it can.

  Moreover, the liquid crystal element of the present invention provides the above liquid crystal element in which the liquid crystal layer is made of a polymer liquid crystal.

  According to this configuration, it is possible to obtain a liquid crystal element in which the variation in the thickness of the liquid crystal layer is suppressed by using the polymer liquid crystal.

  In the liquid crystal element of the present invention, the reflection mirror is formed on the plane between the first transparent substrate including the surface and the liquid crystal layer and on the plane between the second transparent substrate including the surface and the liquid crystal layer. The liquid crystal device described above is provided.

According to this configuration, by using a liquid crystal having a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or more and 7 × 10 ⁻⁴ / ° C. or less in a wavelength tunable filter having a liquid crystal etalon structure, variation in the distance between the reflecting mirrors can be reduced. It is possible to suppress the fluctuation of the transmission peak wavelength with respect to the temperature change.

In the method for manufacturing a liquid crystal element of the present invention, the first transparent substrate, the first transparent electrode, the liquid crystal layer, the second transparent electrode, and the second transparent substrate are arranged in this order. A method for producing any one of the above-described liquid crystal elements,
Provided is a method for producing a liquid crystal element, wherein the liquid crystal layer is formed by photopolymerizing a photopolymerizable liquid crystalline monomer.

  According to this configuration, it is possible to easily manufacture a liquid crystal element in which the thickness variation of the liquid crystal layer is suppressed.

According to the present invention, by using a liquid crystal having a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or higher and 7 × 10 ⁻⁴ / ° C. or lower, it is possible to obtain a liquid crystal element in which the thickness variation of the liquid crystal layer is suppressed. it can.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
(First embodiment)
FIG. 1 is a side view showing a configuration example of a liquid crystal element according to the first embodiment of the present invention. In the liquid crystal element 10 of this embodiment, the first transparent substrate 11A, the first transparent electrode 12A, the liquid crystal layer 13, the second transparent electrode 12B, and the second transparent substrate 11B are arranged in this order. A liquid crystal layer 13 having a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or higher and 7 × 10 ⁻⁴ / ° C. or lower is used.

The first transparent substrate 11A and the second transparent substrate 11B form an antireflection film (not shown) on the surface opposite to the surface facing the liquid crystal layer 13 (surface facing the outside) as necessary. doing. As the transparent substrates 11A and 11B, for example, glass substrates, organic material substrates such as acrylic and polycarbonate, inorganic material substrates made of inorganic crystals such as crystal and LiNbO ₃ can be used.

As the transparent electrodes 12A and 12B, an oxide film such as ITO in which SnO ₂ is added to In ₂ O ₃ or a metal film such as Au or Al can be used. It is preferable to use an ITO film because it has higher permeability and excellent mechanical durability than a metal film.

By the way, according to various experiments and researches by the present inventors, the knowledge that the variation in the optical path length or retardation value in the liquid crystal layer is caused by the temperature variation (of two factors) between the thickness of the liquid crystal layer and the refractive index of the liquid crystal. Is obtained.
Among these, as for the refractive index of the liquid crystal, since the temperature fluctuation is about −5 × 10 ⁻⁴ / ° C., the temperature fluctuation of the refractive index can be canceled out by the change in the thickness due to the appropriate expansion of the liquid crystal layer. This knowledge is also obtained.
On the other hand, regarding the thickness of the liquid crystal layer, the linear expansion coefficient of the low molecular liquid crystal used in the conventional liquid crystal element is approximately 7 × 10 ⁻⁴ / ° C. to 8 × 10 ⁻⁴ / ° C. With a liquid crystal of 7 × 10 ⁻⁴ / ° C. or higher, the change in the optical path length or retardation value in the liquid crystal layer cannot be suppressed because of the relationship with the refractive index of the liquid crystal described above (see FIG. 2).
Further, even in a polymer liquid crystal having a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or less, the fluctuation of the optical path length or retardation value in the liquid crystal layer is suppressed from the relationship with the refractive index of the liquid crystal described above (see FIG. 2). I can't. In addition, the liquid crystal having a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or less is often a main chain polymer liquid crystal and has a substantially small change in refractive index with respect to the applied voltage. It is not suitable for use as a liquid crystal element having a function of controlling the retardation value.

Under such circumstances, when most of low-molecular liquid crystals and high-molecular liquid crystals are used, there is a possibility that proper use as a liquid crystal element cannot be performed due to temperature fluctuation.
Thus, in particular, the liquid crystal layer 13 of the present invention uses a liquid crystal having a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or higher and 7 × 10 ⁻⁴ / ° C. or lower as shown in FIG.

In the present invention, it is preferable to use a side chain polymer liquid crystal as a liquid crystal having a linear expansion coefficient of 7 × 10 ⁻⁴ / ° C. or less and a substantial change in refractive index with respect to an applied voltage. The liquid crystal is not limited as long as it is a liquid crystal that changes a substantial refractive index or retardation value with voltage application.

  In order to keep the liquid crystal layer 13 at a predetermined thickness, a known spacer (not shown) is mixed with the sealing materials 14A and 14B.

  Therefore, even if temperature fluctuation occurs in the thickness of the liquid crystal layer 13 and the refractive index of the liquid crystal, according to the liquid crystal element 10 of the present embodiment, by applying a voltage to the liquid crystal layer 13 using the AC power supply 15, The transmission wavelength in the liquid crystal element 10 can be variably controlled.

(Second Embodiment)
Next, a second embodiment of the present invention will be described with reference to FIG. In FIG. 3, the same parts as those in the first embodiment shown in FIG.

  FIG. 3 is a side view showing a configuration example of a liquid crystal etalon type wavelength tunable filter which is a liquid crystal element according to the second embodiment of the present invention. The liquid crystal element 20 of the present embodiment is shown in FIG. 1 except that reflection mirrors 21A and 21B are formed on the surfaces of the first transparent substrate 11A and the second transparent substrate 11B on the liquid crystal layer 13 side, respectively. The configuration is the same as that of the first embodiment.

Here, the reflecting mirrors 21A and 21B have a reflectance of 80% or more with respect to incident light composed of, for example, 1470 to 1630 nm (1.470 to 1.630 μm) which is a used wavelength band, and a part of light Has a non-zero transmittance so that it is transmitted. As the reflecting mirrors 21A and 21B, for example, a metal thin film or a dielectric multilayer film in which a high refractive index dielectric film and a low refractive index dielectric film are alternately laminated with an optical film thickness of the order of wavelengths can be used. In particular, a dielectric multilayer film is preferably used because the spectral reflectance can be controlled by the film configuration and light absorption is small. Ta ₂ O ₅ , TiO ₂ , Nb ₂ O ₅ , Si and the like are used as the high refractive index dielectric constituting the dielectric multilayer film, and SiO ₂ , MgF ₂ , Al ₂ are used as the low refractive index dielectric multilayer film. O ₃ or the like is used.

Note that, as the reflection mirrors 21A and 21B, for example, in the case of a dielectric multilayer film in which Si and SiO ₂ are alternately stacked, it functions as a transparent electrode by doping an impurity element and imparting conductivity to the Si film layer. Further, by using a metal such as Au or Ag in a thin film, the light absorption is large, but the function can be expressed in both the reflection mirror and the electrode. In this case, the first transparent electrode 12A and the second transparent electrode 12B need not be formed.

  Therefore, by configuring in this way, the variation in the distance between the reflecting mirrors 21A and 21B is suppressed by the same effect as the configuration example of FIG. 1, and even if the environmental temperature varies, it is caused by the thermal expansion of the liquid crystal. Since fluctuations in the transmission wavelength are suppressed, a highly reliable wavelength tunable filter can be realized.

(Third embodiment)
Next, a third embodiment of the present invention will be described with reference to FIG. In FIG. 4, the same parts as those in the first embodiment shown in FIG. 1 and the second embodiment shown in FIG.

  FIG. 4 is a side view showing a configuration example of a liquid crystal etalon type wavelength tunable filter which is a liquid crystal element according to a third embodiment of the present invention. The liquid crystal element 30 of the present embodiment is shown in FIG. 3 except that the solid transparent layer 31 is formed on the outer surface (upper surface in FIG. 4) opposite to the surface on which the transparent substrate 11B of the reflection mirror 21B is installed. The configuration is the same as that of the second embodiment.

  Therefore, according to this embodiment, since the solid transparent layer 31 is formed, an effect that the half-value width of the transmitted light peak can be reduced is obtained.

In addition, the liquid crystal element in this invention can be produced with the following manufacturing methods.
For example, in this liquid crystal element, a photopolymerizable liquid crystal monomer is applied on a transparent substrate having an alignment means, or a photopolymerizable liquid crystal monomer is provided between two transparent substrates, at least one of which has an alignment means. It can be obtained by polymerizing by light irradiation while interposing and in an oriented state.

Further, the orientation means can be achieved by using a transparent substrate surface or a polyimide film formed on the transparent substrate surface by rubbing with a cloth or the like, or a material obtained by obliquely depositing SiO ₂ on the transparent substrate surface. Further, instead of using a substrate subjected to such an alignment treatment, an electric field or a magnetic field is applied from the outside of the liquid crystal element, and the liquid crystal molecules are aligned using the dielectric anisotropy or magnetic anisotropy. Can be aligned. These orientation means may be used alone or in combination. Among them, a method using a substrate whose substrate surface is rubbed with a cloth or the like is preferable because of its simplicity.

  The ratio of change in the refractive index of the extraordinary light polarization is maximum at a tilt angle of 45 ° with respect to the change in tilt angle, which is the angle formed by the liquid crystal substrate surface and the orientation of the liquid crystal molecules. Therefore, by applying an electric field or a magnetic field, light irradiation is performed in a state where the initial alignment of the liquid crystalline monomer is aligned at a tilt angle of 45 °, and the polymer liquid crystal is solidified to fix the alignment of the polymer liquid crystal. A large substantial change in refractive index can be obtained with voltage. As a result, a wavelength tunable filter with a low driving voltage and a wide transmission wavelength tunable range can be obtained.

As described above, as the liquid crystal of the liquid crystal layer, it is preferable to use a side chain polymer liquid crystal having a linear expansion coefficient of 7 × 10 ⁻⁴ / ° C. or less and a substantial change in refractive index with respect to the applied voltage. However, the present invention is not particularly limited to this, and any liquid crystal that changes a substantial refractive index or retardation value with voltage application may be used.
By comprising in this way, the fluctuation | variation of the optical path length and retardation value of the liquid crystal layer 13 by the thermal expansion of a liquid crystal is suppressed.

  Next, a liquid crystal etalon type tunable filter (third embodiment) according to the first embodiment will be described with reference to a side view of FIG. 4 schematically showing the structure.

First, a manufacturing method of the liquid crystal etalon type tunable filter will be described.
(I) A dielectric multilayer film is formed as the first reflecting mirror 21A and the second reflecting mirror 21B on the quartz glass substrates 11A and 11B which are the first and second transparent substrates.
(Ii) Next, a quartz glass substrate having a thickness of 40 μm is bonded as a solid transparent layer 31 on the surface of the reflection mirror 21B.
(Iii) Next, the first transparent electrode 12A and the second transparent electrode 12B made of ITO are formed on the reflection mirror 21A surface and the solid transparent layer 31 surface, and the first transparent electrode 12A and the second transparent electrode are formed. An alignment film for liquid crystal (not shown) is formed on the electrode 12B, and an alignment process is performed so that the alignment directions of the liquid crystal molecules in the opposing surfaces are parallel to each other.
(Iv) Next, a spacer (not shown) is mixed with the sealing materials 14A and 14B on the solid transparent layer 31 provided with the alignment film for liquid crystal (not shown) and the second transparent electrode 12B of the ITO film. A seal pattern layer is formed with the combined adhesive, and a quartz glass substrate 11A provided with a liquid crystal alignment film (not shown) and an ITO film first transparent electrode 12A is bonded.
(V) Thereafter, a liquid crystal is filled between alignment films (not shown), and polymerized by light irradiation to form a polymer liquid crystal layer 13.

  In this embodiment, as the photopolymerizable liquid crystalline monomer constituting the polymer liquid crystal of the polymer liquid crystal layer 13, for example, 6- (4- (4-cyanophenyl) phenyloxy) hexyl acrylate, 3- (4 -(4-Cyanophenyl) phenyloxy) propyl acrylate, 4- (4- (2- (4-cyanophenyl) ethynyl) phenyloxy) butyl acrylate in a ratio of 0.6: 0.2: 0.2 did. These monomer compositions are converted into side-chain polymer liquid crystals by photopolymerization. However, since the alkyl chain connecting the mesogenic group and the polymer main chain is long, the responsiveness to electricity is good among the side-chain polymer liquid crystals.

Here, the linear expansion coefficient of the polymer liquid crystal was measured by producing the evaluation element 40 shown in FIG. 5 by the following method.
That is, the liquid crystalline monomer was interposed between two 25 × 25 mm glass substrates 11A and 11B bonded with a 50 μm-thick sealing material. At this time, the amount of the liquid crystalline monomer to be interposed was adjusted so that the air layer 41 was present in the center of the glass substrates 11A and 11B. The liquid crystalline monomer was polymerized by light irradiation to obtain a polymer liquid crystal layer 13 between the substrates. Next, the sealing material portion was cut so that only the polymer liquid crystal layer 13 and the air layer 41 existed between the glass substrates 11A and 11B. At this time, the air layer 41 between the glass substrates 11 </ b> A and 11 </ b> B was not sealed with the polymer liquid crystal layer 13 so as to be in free contact with the external space.

  Next, the light from the broadband light source having a broad emission spectrum in the 1550 nm wavelength band is applied to the evaluation element 40 of the present invention (using a liquid crystal polymer for the liquid crystal layer 13) thus produced. A preliminary experiment was conducted to examine the linear expansion coefficient by observing the emitted light with an optical spectrum analyzer. At this time, the temperature of the evaluation element 40 was changed from 30 ° C. to 40 ° C.

In this evaluation element 40, the emitted light appears as an etalon effect due to multiple reflection and interference on the glass surface, and its transmission wavelength depends on the optical path length. Here, in this evaluation element 40, it is the thickness of the liquid crystal layer 13 that determines the distance between the glass substrates 11A and 11B. Therefore, when the thickness of the liquid crystal layer 13 changes due to temperature changes, the distance between the glass substrates 11A and 11B changes, so the optical path length changes, and the transmission wavelength shifts accordingly. Thereby, the linear expansion coefficient of the liquid crystal can be calculated from the shift amount of the transmission wavelength.
As a result, the side-chain polymer liquid crystal having the composition of the evaluation element 40A of the present invention described above has a linear expansion coefficient of 4 × 10 ⁻⁴ / ° C., which is half that of the conventional low-molecular liquid crystal. found.

Therefore, based on the results of this experiment, a comparative experiment was conducted to investigate the amount of variation of the transmission wavelength with respect to temperature change using the conventional low-molecular liquid crystal and the polymer liquid crystal of the present invention in the configuration of FIG.
Then, in the configuration of FIG. 4, when a conventional low molecular liquid crystal was used, the amount of fluctuation with respect to the temperature change of the transmission wavelength was about 250 pm / ° C. Here, the fluctuation of the transmission wavelength with respect to the temperature change is caused by the fluctuation of the optical path length between the reflection mirrors 21A and 21B, that is, the temperature fluctuation of the thickness of the liquid crystal layer 13 and the refractive index of the liquid crystal. Among these, the variation amount of the transmission wavelength caused by the variation in the thickness of the liquid crystal layer 13 was 350 pm / ° C., and the variation amount of the transmission wavelength caused by the change in the refractive index of the liquid crystal was −100 pm / ° C.

On the other hand, when the polymer liquid crystal of the present invention is used in the configuration shown in FIG. 4, that is, when a polymer liquid crystal having a linear expansion coefficient of 4 × 10 ⁻⁴ / ° C. is used, the thickness of the liquid crystal layer 13 due to the thermal expansion of the liquid crystal. The contribution of the variation is considered to be 160 pm / ° C. Further, since the variation amount of the transmission wavelength due to the change in the refractive index of the liquid crystal is −100 pm / ° C., the variation amount with respect to the temperature change of the transmission wavelength is about 60 pm / ° C.

Therefore, in the liquid crystal element using the polymer liquid crystal of the present invention, the variation in the distance between the reflecting mirrors 21A and 21B due to the thermal expansion of the liquid crystal is larger than the fluctuation amount of 250 pm / ° C. when the conventional low molecular liquid crystal is used. It was confirmed that a good wavelength tunable characteristic that is not affected by temperature fluctuations can be obtained because it is greatly suppressed.
Thereby, a highly reliable wavelength tunable filter can be realized.

In addition, such a liquid crystal etalon only needs to use a polymer liquid crystal as the liquid crystal layer 13, and even when used for a wavelength tunable filter, the apparatus can be prevented from becoming large and complicated, and does not cause a large cost increase. .
In addition, this invention is not limited to embodiment mentioned above at all, In the range which does not deviate from the summary, it can implement with a various form.

  The liquid crystal element of the present invention has the effect of reducing the thermal expansion in the light transmission direction due to temperature rise with a simple configuration, and changes the substantial refractive index or retardation value of the liquid crystal with respect to incident light according to the magnitude of the applied voltage. This is useful for a liquid crystal element or the like that can control the emitted light.

The side view which shows the structural example of 1st Embodiment of the liquid crystal element which concerns on this invention. Explanatory drawing which shows the relative magnitude relationship of the refractive index and linear expansion coefficient of the liquid crystal in the liquid crystal element which concerns on this invention. The side view which shows the structural example of 2nd Embodiment of the liquid crystal element which concerns on this invention. The side view which shows the structural example of 3rd Embodiment and 1st Example of the liquid crystal element which concerns on this invention. The side view which shows the evaluation element for the preliminary experiments using the liquid crystal of this invention.

Explanation of symbols

10, 20, 30: Liquid crystal element (liquid crystal etalon type wavelength tunable filter)
11A, 11B: Transparent substrate 12A, 12B: Transparent electrode 13: Liquid crystal layer 14A, 14B: Sealing material 15: Rectangular wave AC power supply 21A, 21B: Reflection mirror 31: Solid transparent layer 40: Evaluation element 41: Air layer

Claims (4)

A liquid crystal element configured by arranging a first transparent substrate, a first transparent electrode, a liquid crystal layer, a second transparent electrode, and a second transparent substrate in this order,
The liquid crystal layer has a linear expansion coefficient of 1 × 10 ⁻⁵ / ° C. or higher and 7 × 10 ⁻⁴ / ° C. or lower.   The liquid crystal element according to claim 1, wherein the liquid crystal layer is made of a side chain polymer liquid crystal.   A reflection mirror is formed in a plane between the first transparent substrate including the surface and the liquid crystal layer, and a plane between the second transparent substrate including the surface and the liquid crystal layer. 3. The liquid crystal element according to 1 or 2. 4. The device according to claim 1, wherein the first transparent substrate, the first transparent electrode, the liquid crystal layer, the second transparent electrode, and the second transparent substrate are arranged in this order. A method for producing a liquid crystal element according to item 1, wherein
A method for producing a liquid crystal element, wherein the liquid crystal layer is formed by photopolymerizing a photopolymerizable liquid crystalline monomer.

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