The present invention relates to a method for manufacturing an optical element having a polarization-reversed structure which is formed by the application of an electric field. Specifically, the present invention relates to a method for forming an optical element having polarization-reversed regions which is used for wavelength conversion elements, deflector elements, optical switches, phase modulators, and so on constituting coherent sources used in the fields of processing, optical information processing, optical measurement control, and so on.
A polarization reversal phenomenon that forcibly reverses the polarization of a ferroelectric is used to form periodic polarization-reversed regions (a polarization-reversed structure) in the ferroelectric. The polarization-reversed regions formed thus are used for optical frequency modulators using surface acoustic waves, wavelength conversion elements using the reversal of nonlinear polarization, optical deflectors using a reversed structure in prismatic or lens shape, and so on. Particularly, by using this technique, it is possible to fabricate a wavelength conversion element having remarkably high conversion efficiency when the fundamental wave of input is converted into wavelength-converted light. Further, the wavelength conversion element is used to perform wavelength conversion on light of semiconductor laser, fiber laser, solid-state laser, and so on, so that high-power laser light sources can be applied in the fields of processing, printing, optical information processing, optical measurement control, and so on.
Methods for forming a periodic polarization-reversed region include a method for forming a periodic polarization-reversed region using the reversal of spontaneous polarization of a ferroelectric due to an electric field. Specifically, the minus z face of a substrate cut out along the z-axis direction is irradiated with an electron beam, or the plus z face thereof is irradiated with positive ions. In either case, polarization-reversed regions with a depth of several hundreds of μm are formed by an electric field which is formed by irradiated charged particles. Further, another method has been known in which a periodic electrode is formed on the plus z face, a flat electrode is formed on the minus z face, and a direct current or pulsed electric field is applied to form deep polarization-reversed regions having a high aspect ratio.
Moreover, various supplemental methods have been proposed for improving the characteristics of wavelength conversion elements. For example, in order that a wide polarization-reversed structure having a short period is formed deeply and uniformly, a method has been known in which polarization-reversed regions are formed, heating is then performed on a ferroelectric substrate at 200° C. or higher, and the front and back surfaces of the substrate are electrically short-circuited (e.g., see Patent Literature 1). This method can prevent the polarization-reversed regions from being eliminated and increase transparency in the substrate to reduce optical loss. Moreover, a method has been known in which heat is applied to a substrate with a surface thereof entirely covered by a conductive substance in order to remove an undesired polarization-reversed structure remaining after the formation of polarization reversal (e.g., see Patent Literature 2). Alternatively, a method has been known in which high temperature annealing is performed to fabricate a low-loss optical waveguide in order to achieve uniform refractive-index distribution after the formation of polarization reversal (e.g., see Patent Literature 3). As described above, high temperature heating is essential in manufacturing a polarization-reversed structure used for practical wavelength conversion elements, and the like.
Patent Literature 1: Japanese Patent Application Laid-Open Publication No. 2004-246332
Patent Literature 2: Japanese Patent Application Laid-Open Publication No. 2004-020876
Patent Literature 3: Japanese Patent Application Laid-Open Publication No. 8-220578
However, for example, in wavelength conversion elements manufactured by the above-described methods including heating processes according to the related art, the heating processes cause small strains in the wavelength conversion elements. These strains increase the input power of the fundamental wave as well as the amounts of the fundamental wave and the wavelength-converted light thereof absorbed into the wavelength conversion elements, thereby reducing the output power of the wavelength-converted light.
Thus, even if the fundamental wave power is increased to obtain high-power wavelength-converted light exceeding 1 W, the conversion efficiency of the wavelength conversion element is reduced. Hence, it is difficult to obtain high-power wavelength-converted light.
The present invention has been devised to solve the problem. An object of the present invention is to provide a method for manufacturing an optical element whose conversion efficiency is not lowered, even when the high-output fundamental wave is inputted to the optical element having a polarization-reversed structure subjected to heating.
In order to solve the problem, a method for manufacturing an optical element includes: an electrode forming step of forming metal films on the plus z face and minus z face of a ferroelectric substrate to fabricate electrodes; a periodic electrode forming step of forming the metal film formed on the plus z face into a periodic electrode; a polarization reversal forming step of applying a voltage between the periodic electrode and the electrode on the minus z face to form polarization-reversed regions in the ferroelectric substrate; a surface treating step of removing the electrode, the periodic electrode, and surface layers on the plus z face and minus z face of the ferroelectric substrate; and an annealing step of applying predetermined heat to the ferroelectric substrate having the surface layers removed therefrom.
The method for manufacturing an optical element of the present invention suppresses an increase in spontaneous polarization which causes strains in an optical element having a polarization-reversed structure manufactured by annealing. Thus, the strains are reduced in the optical element, and the fundamental wave and the wavelength-converted light thereof absorbed into the optical element are suppressed even when the input power of the fundamental wave is increased. Hence, it is possible to obtain an optical element whose conversion efficiency is not lowered.
Before describing embodiments of the present invention, first, the polarization reversals of ferroelectrics will be described. The ferroelectric has uneven charge distribution due to spontaneous polarization in the crystal thereof. An electric field can be applied to change the direction of such spontaneous polarization in the ferroelectric.
The direction of the spontaneous polarization varies depending on the type of crystal (material). The crystals of substrates of LiTaO3, LiNbO3, and LiTa (1−x) NbxO3 (0≦x≦1), which is the mixed crystal of LiTaO3 and LiNbO3, have spontaneous polarization only in the z-axis direction. Thus, these crystals have only two types of polarization in a plus direction along the z-axis direction or a minus direction opposite to the plus direction. An electric field is applied to turn the polarization of the crystals 180 degrees in a direction opposite to the initial direction. This phenomenon is called polarization reversal. The electric field required for causing the polarization reversal is referred to as a polarization reversal threshold electric field. The crystals of LiNbO3, LiTaO3, and the like require an electric field of about 20 kV/mm at room temperature, and MgO:LiNbO3 requires an electric field of about 5 kV/mm.
The following will specifically describe embodiments of a method for manufacturing an optical element according to the present invention with reference to the accompanying drawings.
The present embodiment will describe a method for manufacturing a wavelength conversion element as an optical element having a periodic polarization-reversed structure in a ferroelectric substrate.
a) shows the electrode forming step. A ferroelectric substrate 1 in the drawing is, in the present embodiment, a Z-cut MgO:LiNbO3 substrate with a thickness of 1 mm. Electrodes 2 are formed on the plus z face and minus z face of the ferroelectric substrate 1 of the MgO:LiNbO3 substrate. The electrodes 2 are made of metal films for polarization reversal formation. In the present embodiment, the electrodes 2 having a thickness of 100 nm are deposited by sputtering tantalum films.
b) shows the periodic electrode forming step. The right drawing in
c) shows the polarization reversal forming step. A pulsed electric field equal to or larger than the polarization reversal threshold electric field is applied between the electrodes on the plus z face and the minus z face by a pulsed voltage application system 4 to form polarization reversal 5. At this point, when the temperature of the substrate is increased during the application of the electric field, the polarization reversal threshold electric field can be reduced to 5 kV/mm or less. For this reason, in the present embodiment, the ferroelectric substrate 1 is put in an insulating liquid, the temperature of the insulating liquid is set to 100° C., and the electric field is applied. The substrate is heated, so that the polarization reversal threshold electric field is reduced to 5 kV/mm or less. In this case, however, margins are allowed to set the pulsed electric field at 6 kV/mm and the pulse width at 1 msec. The pulsed electric field is applied, so that the reversal 5 is formed from the plus z face toward the minus z face of the substrate.
d) shows the surface treating step. The left drawing in
In the present embodiment, the electrodes and the surface of the substrate are removed by polishing, but the process for removing is not limited to polishing. The same effect can be produced even by performing drying etching or wet etching to remove the electrodes and the surface of the substrate. Any dry etching may be used as long as both of the electrodes and the substrate can be etched. In wet etching, any acid or alkali solution may be used as long as the electrodes and the substrate can be etched.
e) shows the annealing step. In the annealing step of the present embodiment, an oven 7 (manufactured by Kusumoto Chemicals, Ltd.) capable of heating at high temperature is used to anneal the wavelength conversion element 6 in an environment of 400° C. for one hour.
However, as shown in
b) shows changes in spontaneous polarization during the high temperature annealing step in the wavelength conversion element fabricated by the manufacturing method of the present invention. The upper drawing in
The depth of polishing from the substrate surface (crystal substrate surface excluding electrodes) is also important. Considerable effects can be obtained only by removing the surface electrodes but more remarkable effects can be obtained by increasing the depth of polishing to larger than 10 nm.
The following will describe the mechanism of an optical absorption-reducing effect depending on the depths of polishing.
The adjustment of the surface resistivity when completing the surface treating step is also important. This is because the reduction of the surface resistivity accelerates the movement of pyroelectric charges made by the high temperature annealing step. In this case, the surface resistivity indicates the resistance per unit area of the plus z face and minus z face of the ferroelectric substrate, and the unit of the resistance is represented by Ω/□. In order that the movement of ferroelectric charges is suppressed to suppress substrate strains, the annealing step has to be performed with the surface resistivity set at 105 Ω/□ or higher. A SiO2 film is formed on the surface of the ferroelectric substrate and the film formation conditions are changed to adjust the contents of Si and O2, so that the surface resistivity can be adjusted. As shown in
Desirably, the conductive properties of the substrate surface are taken into consideration and contact with low-resistance materials is avoided. This is because the pyroelectric charges generated by the high temperature annealing step move through the low-resistance materials.
Thus, desirably, the annealing step is performed on the substrate which is provided on an insulator. This makes it possible to suppress an increase in spontaneous polarization according to the movement of pyroelectric charges through materials contacted by the substrate, thereby suppressing a reduction in the conversion efficiency of the wavelength conversion element.
The heating temperature of the annealing step is also important. The annealing step has to be performed at 300° C. or higher to reduce the optical absorption and prevent the reduction of the conversion efficiency. The Mg-doped LiNbO3 substrate of the present embodiment is subjected to the annealing step.
As described above, desirably, the annealing step is performed at an annealing temperature predetermined by the material of the substrate.
The wavelength conversion element used in the present embodiment has a polarization-reversed structure in which the period is 7 μm and the polarization reversal width is 3.5 μm in the periodic direction. It was confirmed that fabricated polarization-reversed regions were not eliminated although they were subjected to annealing at 400° C. Thereafter, even when heat cycling was performed on the polarization-reversed regions at −20° C. to 100° C., the polarization-reversed structure was not eliminated and the conversion efficiency was not lowered. However, with the polarization reversal width set to 1 μm in the periodic direction, the polarization-reversed regions were partially eliminated even when the annealing step was performed at 100° C. As a result of performing experiments by gradually increasing the polarization reversal width, with the polarization reversal width of 2 μm or larger in the periodic direction, the polarization-reversed structure was not eliminated even when the annealing step was performed at 400° C. Even when the subsequent heat cycling was performed on the polarization-reversed structure at −20° C. to 100° C., the polarization-reversed structure was not eliminated and the conversion efficiency was not lowered. Thus, the present invention is remarkably useful as a method for manufacturing an optical element which effectively stabilizes a polarization-reversed structure with a polarization reversal width of 2 μm or larger and removes crystal strains at the interface of the polarization-reversed structure.
In the first embodiment, the surface treating step is performed by means of mechanical polishing. However, the present embodiment is different from the first embodiment in that anisotropic wet etching is performed in the z-axis direction of a substrate as the surface treating step. The method makes it possible to prevent a reduction in conversion efficiency at the time of high output.
In the present embodiment, wet etching is performed using a fluoronitric acid solution to form steps on the substrate, but chemical mechanical polishing may be performed to form the same steps. In particular, an acid or alkali chemical mechanical polishing solution having a large difference in etching rate in the z-axis direction can easily and effectively form steps.
In the first and second embodiments, the z-cut MgO-doped LiNbO3 substrate is used as a ferroelectric substrate, but the ferroelectric substrate is not limited to the z-cut MgO-doped LiNbO3 substrate. The ferroelectric substrate may be similar substrates having a stoichiometric composition including MgO-doped LiTaO3 substrates, Nd-doped LiNbO3 substrates, KTP substrates, KNbO3 substrates, Nd:MgO-doped LiNbO3 substrates or Nd:MgO-doped LiTaO3 substrates, and Mg-doped LiTa (1−x) NbxO3 (0≦x≦1).
The present invention is preferable for the fabrication of an optical element having a highly transparent polarization-reversed structure without crystal strains, since the present invention can stably produce a pyroelectric effect in annealing. Further, since the altered layers, impurities, or electrodes on the substrate surface are completely removed, the insulation of the substrate can be secured, thereby achieving an optical element with high output and stability.
The method for manufacturing an optical element according to the present invention can be used as a method for manufacturing a wavelength conversion element and the like with high efficiency and stability having a periodic polarization-reversed structure in, for example, a Mg-doped crystal. Moreover, the method for manufacturing an optical element according to the present invention makes it possible to provide a highly transparent optical element without crystal strains by stably forming and retaining a polarization-reversed region. The method can also provide a highly reliable optical element having polarization-reversed regions with stable optical output at the time of high output.
In the first and second embodiments, the optical element having a polarization-reversed structure is a wavelength conversion element. However, an optical element having a polarization-reversed structure formed in prismatic or grating shape may be applied to fabricate a deflector, in addition to the wavelength conversion element. The deflector may be applied to, for example, the phase shift, optical modulators, lenses, and so on. Moreover, a voltage is applied to a polarization-reversed region, so that a change in refractive index can be caused by an electro-optical effect. Thus, an optical element can be achieved using the change in refractive index. For example, since the change in refractive index can be controlled by an electric field, the optical element having the change in refractive index may be applied to switches, deflectors, modulators, phase shifters, beam forming, and so on. The method for manufacturing an optical element according to the present invention enables the formation of a polarization-reversed structure with stability and high transparency, thereby enhancing the performance of optical elements.
The method for manufacturing an optical element according to the present invention is useful in fields in which an optical element having a polarization-reversed structure is required. In particular, the method for manufacturing an optical element according to the present invention makes it possible to stably form and retain polarization-reversed regions, and provide an optical element having the polarization-reversed regions with high reliability and stable optical output at the time of high output. Thus, the optical element is useful as an optical element having polarization-reversed regions which is applied to wavelength conversion elements, deflector elements, optical switches, phase modulators, and so on constituting coherent sources used in the fields of processing, optical information processing, and optical measurement control.
Number | Date | Country | Kind |
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2009-239040 | Oct 2009 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP2010/005615 | 9/15/2010 | WO | 00 | 2/28/2012 |