Phase difference element having birefringent film containing titanium oxide tantalum oxide

Abstract

A phase difference element has a transparent substrate and a birefringent film with tantalum oxide and titanium oxide obliquely deposited on one surface of the transparent substrate. The birefringent film has a first photorefractive film and a second photorefractive film laminated to each other and having different oblique deposition directions. The ratio of titanium atoms to the total of titanium atoms and tantalum atoms in the birefringent film is 4.0 atomic % or higher to 30 atomic % or lower.

Claims

1. A phase difference element, comprising a transparent substrate and a birefringent film in which tantalum oxide and titanium oxide are obliquely deposited on one surface of the transparent substrate, wherein: the birefringent film comprises a plurality of first photorefractive films and second photorefractive films that are directly and alternately laminated to each other and have different oblique deposition directions, a ratio of titanium atoms to a total of titanium atoms and tantalum atoms in the birefringent film is 4.0 atomic % or higher and 30 atomic % or lower, each of the first photorefractive films and each of the second photorefractive films comprises crystal grains oriented along the oblique deposition direction, and each of the first photorefractive films and each of the second photorefractive films comprise tantalum oxide and titanium oxide, and each of the first photorefractive films is a single layer and each of the second photorefractive films is a single layer.

2. The phase difference element according to claim 1, wherein the ratio of titanium atoms to the total of titanium atoms and tantalum atoms in the birefringent film is 10 atomic % or higher and 20 atomic % or lower.

3. The phase difference element according to claim 1, wherein the transparent substrate is a quartz glass substrate.

4. The phase difference element according to claim 1, wherein a component parallel to a front surface of the transparent substrate in the first oblique direction and a component parallel to the front surface of the transparent substrate in the second oblique direction are directed to respective directions opposite to each other.

5. A display device comprising: the phase difference element according to claim 1; and a liquid crystal display, wherein light passing through the liquid crystal display and the phase difference element is emitted from the display device.

6. A phase difference element, comprising a transparent substrate and a birefringent film, the birefringent film including a plurality of first photorefractive films and second photorefractive films that are directly and alternately laminated to each other, each of the first photorefractive films being grown on the transparent substrate or one of the second photorefractive films along a first oblique direction from which a material vapor enters, the material vapor being emitted from a deposition material containing Ta.sub.2O.sub.5 and TiO.sub.2 and going straight ahead, and each of the second photorefractive films being grown on one of the first photorefractive films along a second oblique direction from which the material vapor enters, the second oblique direction being different from the first oblique direction, wherein: a ratio of Ti to a total of Ta and Ti, (Ti/(Ta+Ti)), of the first and the second photorefractive films is 4.0 atomic % or higher and 30 atomic % or lower, each of the first photorefractive films comprises crystal grains oriented along the first oblique direction and each of the second photorefractive films comprises crystal grains oriented along the second oblique direction, and each of the first photorefractive films and each of the second photorefractive films comprise tantalum oxide and titanium oxide, and each of the first photorefractive films is a single layer and each of the second photorefractive films is a single layer.

7. The phase difference element according to claim 6, wherein the ratio of Ti to the total of Ta and Ti, (Ti/(Ta+Ti)), of the first and the second photorefractive films is 10 atomic % or higher and 20 atomic % or lower.

8. A method for producing a phase difference element, comprising: obliquely depositing Ta.sub.2O.sub.5 and TiO.sub.2 on a transparent substrate in a first oblique direction to form a first photorefractive film, and obliquely depositing Ta.sub.2O.sub.5 and TiO.sub.2 on the first photorefractive film in a second oblique direction to form a second photorefractive film, the second oblique direction being different from the first oblique direction, and forming a birefringent film having a plurality of first photorefractive films and second photorefractive films that are directly and alternately laminated to each other, wherein Ta.sub.2O.sub.5 and TiO.sub.2 are obliquely deposited such that a ratio of titanium atoms to a total of titanium atoms and tantalum atoms in the birefringent film is 4.0 atomic % or higher to 30 atomic % or lower, each of the first photorefractive films comprises crystal grains oriented along the first oblique direction and each of the second photorefractive films comprises crystal grains oriented along the second oblique direction, and each of the first photorefractive films and each of the second photorefractive films comprise tantalum oxide and titanium oxide, and each of the first photorefractive films is a single layer and each of the second photorefractive films is a single layer.

9. The method for producing a phase difference element according to claim 8, comprising, after forming the birefringent film, performing an annealing treatment.

Description

BRIEF DESCRIPTION OF THE DRAWING(S)

(1) FIG. 1 is a schematic diagram illustrating an example of the deposition apparatus used for the present invention;

(2) FIGS. 2A to 2E are schematic diagrams illustrating the process for producing the phase difference element of the present invention;

(3) FIG. 3 is a schematic diagram illustrating the structure of the thin film formed by oblique deposition;

(4) FIG. 4 is a schematic diagram illustrating the transparent substrate having elongated ridges on the front surface thereof;

(5) FIG. 5 is a schematic diagram illustrating the birefringent film formed on the transparent substrate;

(6) FIG. 6 is a graph showing the relationship between the value of Ti/(Ti+Ta) and transmittance; and

(7) FIG. 7 is a graph showing the relationship between wavelength and birefringence n when the birefringent film is formed on the transparent substrate having elongated ridges and on the flat transparent substrate.

DETAILED DESCRIPTION OF THE INVENTION

(8) The phase difference element of the present invention will be described according to the production process thereof.

(9) As shown in FIG. 1, a deposition material 14 containing Ta.sub.2O.sub.5 and TiO.sub.2 is disposed beforehand in a vacuum chamber 6 of a deposition apparatus 5, and a transparent substrate 1 of FIG. 2A is installed into the vacuum chamber 6. The transparent substrate 1 is disposed at the position above the deposition material 14 with the front surface of the transparent substrate 1 being oblique to the deposition material 14. As the transparent substrate 1 disposed at an oblique angle in the vacuum chamber 6, the substrate made of quartz glass can be preferably used, but any types of transparent materials can be used as long as they can withstand deposition conditions.

(10) The deposition material 14 is then heated in the vacuum chamber 6 under vacuum atmosphere, and a material vapor containing a mixture of Ta.sub.2O.sub.5 vapor and TiO.sub.2 vapor is emitted into the vacuum chamber 6 and allowed to enter (deposited on) the front surface of the transparent substrate 1 from a first oblique direction to form a first refractive film 21 on the transparent substrate 1 as shown in FIG. 2B.

(11) A crystal grain 19 constituting the first refractive film 21 is grown along the first oblique direction 18 from which the material vapor enters as shown FIG. 3.

(12) The first refractive film 21 is formed to have a predetermined thickness, and subsequently the transparent substrate 1 is rotated 180 about a center line 11 that is perpendicular to the front surface thereof and passes through the center of the front surface.

(13) Accordingly, as viewed from the transparent substrate 1, the material vapor enters the front surface of the first refractive film 21 from a second oblique direction, which is different from the first oblique direction, to form a second refractive film 23 on the front surface of the first refractive film 21 as shown in FIG. 2C.

(14) The arrow designated by reference numeral 10 in FIG. 1 represents the traveling direction of the material vapor, and reference numeral 11 represents the normal perpendicular to the front surface of transparent substrate 1 on which the thin film is formed. The first oblique direction and the normal 11 of the transparent substrate 1 are set to form a first angle of preferably 60 or larger and 80 or smaller. The second oblique direction and the normal 11 are also set to form a second angle of preferably 60 or larger and 80 or smaller.

(15) Here, the first angle and the second angle have the same value, but they have different incident direction to the transparent substrate 1. In particular, since the transparent substrate 1 is rotated 180 about the center line, a component parallel to the front surface of the transparent substrate 1 in the first oblique direction and a component parallel to the front surface of the transparent substrate 1 in the second oblique direction are directed to respective directions opposite to each other. In short, the angle formed by the component parallel to the transparent substrate 1 in the first oblique direction and the component parallel to the transparent substrate 1 in the second oblique direction is 180.

(16) After the second refractive film 23 is formed to have a predetermined thickness, the transparent substrate 1 is rotated 180 about the center line, and the material vapor is allowed to enter the front surface of the second refractive film 23 from the first oblique direction to form another first refractive film 21 on the front surface of the second refractive film 23.

(17) In this manner, with the material vapor having the same composition, rotation of the transparent substrate 1 by 180 allows switchover between the first refractive film 21 and the second refractive film 23 to be formed.

(18) When the first refractive films 21 and the second refractive films 23 are alternately laminated in a plurality of layers, as shown in FIG. 2D, a birefringent film 20 including a plurality of the first refractive films 21 and the second refractive films 23 alternately laminated is formed on the front surface of the transparent substrate 1. A plurality of layers of the first refractive films 21 and a plurality of layers of the second refractive films 23 are present. The total thickness of the birefringent film 20 may be 6 m in this case, but is not limited to thereto.

(19) The first angle may have different value from the second angle . Also, the rotation angle is not limited to 180 and may be, for example, 30, 45, 60, or 90.

(20) The first and the second refractive films 21 and 23 preferably have the same composition. The birefringent film 20 is an oxide thin film adjusted to have the value of Ti/(Ti+Ta) (wherein, Ti and Ta represent the number of titanium atoms and the number of tantalum atoms, respectively.) of 4.0 atomic % or larger and 30 atomic % or lower, thereby obtaining significantly increased light transmittance of linear polarization with respect to visible light.

(21) The value of Ti/(Ti+Ta) in the birefringent film 20 can be adjusted by controlling the ratio of Ta.sub.2O.sub.5 and TiO.sub.2 in the deposition material and the temperature of deposition, etc. Therefore, the compositions of the first and the second refractive films 21 and 23 can be different from each other.

(22) When water is attached between columnar constitutions of the first and the second refractive films 21 and 23 constituting the birefringent film 20, the refractive index of the first and the second refractive films 21 and 23 is changed thereby to cause characteristics of the birefringent film 20 to largely vary. Therefore, it is preferable to perform an annealing treatment on the formed birefringent film 20, for example, heating at 200 C. to decolor the birefringent film 20 and remove water adsorbed between columnar constitutions of the birefringent film 20 by evaporation.

(23) Preferred examples of the annealing treatment include the treatment of increasing the temperature of the birefringent film 20 to the temperature at which water is actively evaporated (for example, the temperature of 100 C. or higher). However, when the temperature is too high, the columnar constitutions are grown with each other to form columns and thereby to cause decreased birefringence and decreased transmittance, etc. Thus, the temperature of the annealing treatment is preferably set to 300 C. or less.

(24) After the annealing treatment, a protective film 26 is formed on the birefringent film 20, if necessary, to obtain a phase difference element 7 of the present invention, as shown in FIG. 2E.

(25) The amount of birefringence of the birefringent film 20 can be changed by controlling the first and the second angles and in forming the first and the second refractive films 21 and 23.

(26) As the protective film 26, a thin film known as a protective film for a phase difference element and having relatively low moisture permeability can be applied. In addition, it is preferable that such a protective film 26 be provided with a function of an antireflective film (an AR film) to increase light transmittance. In this case, the AR film may be a multilayer thin film including a commonly used high refractive film and low refractive film. After the AR film is formed, the film can be cut into a desired size with a cutting apparatus such as a glass scriber.

(27) In the above phase difference element 7, the birefringent film 20 is formed on the flat front surface of the transparent substrate 1 by oblique deposition. As illustrated by reference numeral 2 in FIG. 4, the phase difference element can be also formed by the following steps. The steps include: forming parallel grooves 31 on the front surface of a glass substrate (a quartz substrate) 33 by an etching method to make a transparent substrate 2 having linear elongated ridges 32 spaced from one another in parallel on the front surface of the glass substrate 33; and subsequently allowing the material vapor to arrive at the front surface of the elongated ridges 32 to grow the birefringent film on the front surface of the elongated ridges 32.

(28) As an example, a phase difference element 8 can be obtained by the following steps (FIG. 5). The steps include: forming the grooves 31 having a depth D of 50 nm with a fixed width and a fixed space in parallel on the glass substrate 33 to obtain the elongated ridges 32 with a distance P between adjacent center lines of a constant value of 150 nm; disposing the glass substrate 33 such that the first and the second angles and are set to, for example, 70 with respect to the deposition material containing Ta.sub.2O.sub.5 and TiO.sub.2, as shown in FIG. 1; and allowing the material vapor to arrive at the glass substrate 33 to alternately laminate a plurality of the first and the second refractive films 22 and 24 on the front surface of the elongated ridges 32, thereby forming a birefringent film 30. In this case, in switching over formation of the first and the second refractive films, the transparent substrate can be rotated 180 to change the orientation of the transparent substrate with respect to the incident direction of the material vapor several times. The phase difference element 8 will have the birefringent film 30 having the first and the second refractive films 22 and 24 alternately laminated in a plurality of layers.

(29) The distance P between adjacent center lines of the elongated ridges 32 is a pitch of the elongated ridges 32 wherein a plurality of columns of the elongated ridges 32 are disposed in parallel to one another. When the distance P between adjacent center lines is set to be shorter than the value of the shortest wavelength, large amount of birefringence is obtained for light having the shortest wavelength or more among light subjected to birefringence.

(30) Further, when the birefringent films are formed on the elongated ridges 32 disposed in parallel to one another, the value of birefringence is increased. This is considered to be based on that influence of form birefringence is additionally exerted since the birefringent films formed on the adjacent elongated ridges 32 are spaced from one another thereby producing a gap therebetween, and an air space having lower refractive index than the first and the second refractive films is present between the birefringent films.

(31) This grooves 31 and the elongated ridges 32 form so-called one dimensional lattice, and in the case of the wavelength or less, they can be obtained by random patterning or a pattern forming method with the block copolymer described in the literature (The Toshiba Review, vol. 60, No. 10, p. 32 (2005)), that is, the method including forming a film of SiO.sub.2 on the glass substrate as in the method described above, pattering with the block copolymer, and transferring the pattern of the block copolymer on SiO.sub.2.

(32) Here, without forming a film of SiO.sub.2, a pattern may be directly formed on the glass. In the wave plate produced in this manner, the phase difference element having excellent transmittance can be provided by use of the deposition material having the content of Ta.sub.2O.sub.5+TiO.sub.2 such that the value of Ti/(Ti+Ta) ranges from 4.0 atomic % or higher and 30 atomic % or lower.

(33) In the above description, it is assumed that the material vapor is emitted by increasing the temperature of the deposition material in which Ta.sub.2O.sub.5 and TiO.sub.2 are mixed. However, the material vapor can also be obtained by disposing Ta.sub.2O.sub.5 and TiO.sub.2 in different containers in the vacuum chamber, respectively, and increasing the temperature thereof individually to generate a vapor of Ta.sub.2O.sub.5 and a vapor of TiO.sub.2 separately. In this case, the vapor of Ta.sub.2O.sub.5 and the vapor of TiO.sub.2 arrive at the same transparent substrate simultaneously, and therefore they can be emitted from Ta.sub.2O.sub.5 and TiO.sub.2 disposed separately so as to form the birefringent film in which the ratio of Ti to the total of Ta and Ti, (Ti/(Ta+Ti)), is 4.0 atomic % or higher and 30 atomic % or lower.

EXAMPLES

Examples 1 to 3, Comparative Examples 1 to 3

(34) A deposition material to which Ta.sub.2O.sub.5 and TiO.sub.2 were added was disposed in a vacuum chamber, and deposition was carried out at a first incident angle of 70 between the normal direction of a glass substrate (a quartz substrate) and the traveling direction of a material vapor incident on the glass substrate. Subsequently, the glass substrate was rotated 180 and then deposition was carried out at a second angle of 70 to form the birefringent film, thereby producing a phase difference element.

(35) In this case, the deposition materials having different ratios of Ta.sub.2O.sub.5 and TiO.sub.2 were disposed to form six types of birefringent films having different compositions, each of which was then subjected to the annealing treatment at 200 C. The values of Ti/(Ti+Ta) of the formed birefringent films were determined by the measuring instrument of EDX (energy dispersive X-ray spectroscopy), and the values of 0, 3.0, 5.0, 10, 19, 33 atomic % were obtained. The thickness of each birefringent film was set to 6.0 m which was required for a broadband half-wave plate. The antireflective film was formed on the back surface of the glass substrate to decrease the reflectance of the incident light.

(36) The values of Ti/(Ti+Ta) of the birefringent films were 0 atomic % for the phase difference element of Comparative Example 1, 3.0 atomic % for the phase difference element of Comparative Example 2, 5.0 atomic % for the phase difference element of Example 1, 10 atomic % for the phase difference element of Example 2, 19 atomic % for phase difference element of Example 3, and 33 atomic % for the phase difference element of Comparative Example 3.

(37) To the birefringent film of phase difference element of each of Examples and Comparative Examples, three types of measuring lights having respective wavelengths of 680 to 600 nm, 590 to 520 nm, and 510 to 430 nm were irradiated, and the transmittance of measuring light having each wavelength (the mean value in each wavelength range) was determined.

(38) In the graph of FIG. 6, the horizontal axis represents the value of Ti/(Ti+Ta), and the vertical axis represents the value of the transmittance. Based on the measurements for each birefringent film, it is found that the transmittance is increased in 4.0 atomic % or higher, and in particular, the transmittance is significantly increased in the wavelength range of blue light ranging from 510 to 430 nm. It is considered that the factors to increase the transmittance are that Ti serves as a getter of impurities and TiO.sub.2 is activated to supply oxygen to the oxygen-deficient sites of Ta.sub.2O.sub.5.

(39) On the other hand, it is found that the value of Ti/(Ti+Ta) exceeding 30 atomic % results in decreased transmittance, and lager content of TiO.sub.2 results in decreased transmittance. The reason is considered that larger content of TiO.sub.2 in the birefringent film increases the amount of light absorbed by TiO.sub.2 since the optical absorption edge of TiO.sub.2 is on the side of longer wavelength than Ta.sub.2O.sub.5 and TiO.sub.2 readily absorbs visible light.

(40) As a result, in particular, in the phase difference element having a thick birefringent film such as a broadband half-wave plate, the deposition material was disposed in the vacuum chamber to generate the material vapor, wherein the deposition material had the content ratio of Ta.sub.2O.sub.5 and TiO.sub.2 such that the value of Ti/(Ti+Ta) of the birefringent film to be formed becomes 4.0 atomic % or higher and 30 atomic % or lower, and preferably 10 atomic % or higher and 20 atomic % or lower. In this manner, the phase difference element having excellent transmittance could be provided.

Example 4

(41) In this Example, a phase difference element of the aspect shown in FIG. 4 and FIG. 5 was produced. More specifically, grooves having a depth of 50 nm with a fixed width and a fixed space in parallel were formed on a glass substrate to obtain elongated ridges with a distance between adjacent center lines of a constant value of 150 nm. The transparent substrate was disposed such that first and second angles and are set to 70 with respect to a deposition material containing Ta.sub.2O.sub.5 and TiO.sub.2 as shown in FIG. 1. While the transparent substrate was rotated 180, the material vapor was allowed to arrive at the transparent substrate to obtain the phase difference element of Example 4 having the birefringent film having a plurality of first and second refractive films alternately laminated on the front surface of the elongated ridges. In this case, the value of Ti/(Ti+Ta) was adjusted to 10 atomic %.

(42) Birefringent films having the same composition and the same thickness were formed on the front surface of a flat transparent substrate (see FIG. 1) to produce a phase difference element. For this phase difference element and the phase difference element of Example 4, the birefringences n{n=n.sub.en.sub.o (n.sub.e: the refractive index of the extraordinary ray, n.sub.o: the refractive index of the ordinary ray)} were determined, respectively.

(43) In the graph of FIG. 7, the horizontal axis represents the wavelength of the light, and the vertical axis represents the birefringence n. In this graph, the curve L.sub.1 represents the measurements of the birefringent film of the phase difference element of Example 4 formed on the elongated ridges, and the curve L.sub.2 represents the measurements of the birefringent film formed on the front surface of the flat transparent substrate. In FIG. 7, the amount of birefringence of the birefringent film formed on the elongated ridges was 2.8 times that of the birefringent film formed on the front surface of the flat transparent substrate. Thus, in the case of the phase difference element of Example 4, the thickness of the birefringent film required to obtain a desired amount of birefringence can be thinner than the transparent substrate with flat front surface in order to realize advantages such as increased speed and efficiency of manufacturing processes and low material cost used for forming a film.

INDUSTRIAL APPLICABILITY

(44) The phase difference element of the present invention has high light transmittance and high birefringence properties. Accordingly, the phase difference element of the invention is useful for, for example, a viewing angle compensating film and a /4 plate for a liquid crystal display element such as a TFT-LCD and a reflective TFT-LCD.

DESCRIPTION OF REFERENCE NUMERALS

(45) 1, 2 . . . transparent substrate 14 . . . deposition material 18 . . . first oblique direction 21, 22 . . . first refractive film 23, 24 . . . second refractive film 20, 30 . . . birefringent film