JP2006282890A - Luminant, manufacturing method and manufacturing apparatus for the same, and light emitting element or apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminant which is always formed in desired composition by co-sputter using a stable target material, a manufacturing method and a manufacturing apparatus for the same, and a light emitting element or apparatus. <P>SOLUTION: The EuxSiyOz luminant layer comprises a crystal of a europium silicate compound expressed by the chemical formula: EuxSiyOz (wherein, x is 10-40%, y is 20-72% and z is 12-60%). A sputtering apparatus using a complex target of a silicon target 2 and an Eu<SB>2</SB>O<SB>3</SB>sintering member 1 in order to deposit this luminant by co-sputtering is provided. The light emitting element or apparatus using this luminant is provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a light-emitting body suitable for, for example, optical communication, a light-emitting display device, an optical integrated circuit, and a light-emitting source, a manufacturing method and manufacturing device, and a light-emitting element or device.

  Conventionally, phosphorescent phosphors or phosphors that emit afterglow over a relatively long time when irradiated with light such as sunlight are known. For example, they can be used in display devices by being mixed in plastic or the like. There are uses.

  In order to produce the EuxSiyOz compound reported so far as such a light emitter, for example, treatment at a high temperature of 1400 ° C. under HCl gas (reducing atmosphere) is required (see Non-Patent Document 1 described later). . Further, a higher temperature such as 1800 ° C. is required for crystallization (see Non-Patent Document 2 described later).

On the other hand, in the method using sputtering capable of forming a film at a low temperature, for example, a method of co-sputtering using a target made of Eu metal powder and Si powder or a target in which EuSi ₂ powder is dispersed on Si is used. (See Patent Document 1 described later).

Kaldis E, Etreit P and Wachter P, 1971 J. Phys. Chem. Solids, 32, 159 Machida K, Adachi G, Shiokawa J, Shimada M, Koizumi M, Suito K and Onoera A, 1982, Inorg. Chem. 21, 1512 JP 2000-306664 A (page 4, left column, line 10 to page 5, left column, line 19)

However, the above-described film formation method at a high temperature is difficult to control the film formation including temperature control. In addition, the above sputtering method requires a target using Eu (europium) metal powder that is difficult to handle in the atmosphere, or requires co-sputtering using an uncommon EuSi ₂ powder. There is a disadvantage that the productivity of the membrane is poor.

In particular, Eu metal powder, which is a high-luminance luminescent material, is easy to oxidize. In addition, when this is used, oxidation of the target surface is likely to occur, which may cause fluctuations in sputtering conditions and changes in the composition of the film forming material. EuSi ₂ powder is not commercially available and is very difficult to obtain.

  Therefore, when using a material having such unstable characteristics, it becomes difficult to reproducibly form a film, and it is difficult to obtain a stable target material, and accordingly, quantitative and stable sputtering is likely to be difficult.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a light-emitting body that is always formed into a desired composition by co-sputtering using a stable target material, a manufacturing method thereof, and a manufacturing apparatus thereof. And providing a light-emitting element or device.

That is, the present invention
Chemical formula:
EuxSiyOz
(However, x = 10-40%
y = 20-72%
z = 12-60%)
The present invention relates to a light emitter made of a crystal of a europium silicate compound represented by the formula:

  The present invention also includes a step of disposing a target made of a composite of silicon and europium oxide so as to face a substrate, and a step of co-sputtering the silicon and the europium oxide, to thereby form the europium silicate compound. The present invention also relates to a method for manufacturing a light emitting body, in which a light emitting body made of crystals is formed on the substrate.

  The present invention also includes a light emitting device manufacturing apparatus comprising: a target made of a composite of silicon and europium oxide; an electric field generating unit that applies an electric field to the target; and a magnetic field generating unit that applies a magnetic field to the target. Is to provide.

  The present invention further provides a light-emitting element or device constituted by a light-emitting body made of a crystal of the europium silicate compound.

  According to the present invention, since a composite of silicon and stable europium oxide, which is easily available and can be formed at a low temperature, is used as a co-sputtering target, a stable target material that does not cause surface oxidation is produced. By using it, it is possible to prevent a change in sputtering conditions and a composition change of a film forming material, and to easily and reproducibly produce a light-emitting body made of a crystal of a europium silicate compound having a quantitative and stable composition.

  In the present invention, in order to increase luminous efficiency, the europium composition x is preferably 20 to 30%.

  Further, in order to improve the sputtering efficiency, the co-sputtering is performed by simultaneously applying an electric field and a magnetic field to the target, and at this time, the electric field and the magnetic field intersect with each other, and the magnetic field lines are concentrated (especially an erosion region) It is desirable to dispose the europium oxide.

  The amorphous europium silicate compound formed by co-sputtering is preferably crystallized by annealing in a vacuum atmosphere.

  In addition, the manufactured light emitter can be configured as a light emitting element or device that is excited by incident light or voltage application and emits light of a predetermined wavelength.

  In this case, a light-emitting element or a device in which the light-emitting body is sandwiched between counter electrodes to form a display pixel may be configured.

  Next, a preferred embodiment of the present invention will be described in detail with reference to the drawings.

  FIG. 1 schematically shows a magnetron discharge type high-speed and low-temperature sputtering (DC magnetron sputtering) method and apparatus using a region where a DC electric field and a magnetic field are orthogonal to each other.

On a silicon target 2 made of a disk-shaped silicon substrate, Eu ₂ O ₃ sintered body 1 (europium oxide) is disposed in an erosion region 3 where an electric field E and a magnetic field B are orthogonal and magnetic flux concentrates. The composite target of the silicon target 2 and the Eu ₂ O ₃ sintered body 1 is disposed on a substantially cylindrical permanent magnet 5. On the opposite side of the composite target from the permanent magnet 5, there is a fixed target. A substrate 12 for film formation is disposed oppositely at a distance.

  Further, by using the substrate 12 and the silicon target 2 as electrodes and applying a DC voltage V therebetween, an electric field E can be applied to the target. Further, the permanent magnet 5 generates a continuous magnetic field B from the central part to the outer peripheral part, and the erosion region 3 where the electric field E and the magnetic field B intersect (especially orthogonal) on the surface of the target is formed in a ring shape. Can be generated.

If the Eu ₂ O ₃ sintered body 1 is disposed in the erosion region 3 where the magnetic field lines are concentrated, sputtering can be performed efficiently.

FIG. 2 shows a state where a plurality of Eu ₂ O ₃ sintered bodies 1 are annularly arranged in the erosion region 3 on the silicon target 2. Here, for example, the diameter of the silicon target 2 is 6 inches, and the size of one Eu ₂ O ₃ sintered body 1 is φ10 mm × 5 t. In addition, the number of Eu ₂ O ₃ sintered bodies 1 is 49, and they are arranged in duplicate, with 22 on the inner side (φ70 mm) and 27 on the outer side (φ90 mm). Note that the Eu ₂ O ₃ sintered body 1 only needs to be placed on the silicon target 2.

  Next, the co-sputtering conditions are, for example, performed in an atmosphere having a power of 400 W to 500 W (RF) (for example, 400 W (RF)), an Ar flow rate of 20 sccm, and 0.5 Pa. The substrate 12 used for forming the EuxSiyOz luminescent material can be any material that can withstand a subsequent vacuum annealing atmosphere, such as Si or quartz.

  As a result of co-sputtering, the composition of EuxSiyOz formed on the substrate 12 is, for example, x: y: z = 23: 41: 36. In this state, it is amorphous (amorphous) and does not emit light.

Next, this amorphous EuxSiyOz is formed at 700 to 1200 ° C. (for example, 1000 ° C.) for 30 to 60 minutes in a vacuum atmosphere of about 10 ⁻⁴ Pa or an Ar, O ₂ or N ₂ atmosphere of 0.133 Pa ( For example, annealing is performed for 40 minutes. As a result, crystallization of EuxSiyOz proceeds, and for example, a europium silicate compound (light emitter) having a light emission characteristic having a peak wavelength of yellow 603 nm can be formed.

  FIG. 3 shows the principle of light emission characteristics of the EuxSiyOz light-emitting layer 11 formed on the substrate 12: a low temperature photoluminescence method (LT-PL).

That is, for example, the EuxSiyOz light emitting layer 11 is irradiated with 325 nm He—Cd laser light L1 in liquid N ₂ at −196 ° C. (77 K), the excitation wavelength light L2 generated at that time is observed, and its emission spectrum is observed. Ask for.

  FIG. 4 shows the relationship between the wavelength (nm) and the relative intensity of light emission. For example, a yellow emission spectrum of a europium silicate compound having an intensity peak near 603 nm is shown.

Note that this structure can be applied to, for example, a self-luminous electroluminescent element (for yellow) by applying a voltage or a cathodoluminescent element. Further, by controlling the number of the Eu ₂ O ₃ sintered bodies 1 arranged on the silicon target 2, it is possible to change the emission wavelength and the emission intensity as shown in FIG. For example, if the number is increased, light emission characteristics of a shorter wavelength color can be generated, and the light emission intensity can be improved after once decreasing.

  FIG. 6 shows the correlation between the emission peak wavelength (nm), the Eu composition ratio (%), and the emission intensity (relative value).

  For example, in the EuxSiyOz light emitting layer 11 with x = 10 to 40% and y + z = 90 to 60%, the emission peak wavelength changes as the ratio of x increases, as shown by the broken line.

  Further, as indicated by the solid line, the emission intensity changes as the ratio of x increases. In particular, when x is less than 20%, the light emission is weakened, and when x is over 30%, the light emission efficiency is lowered due to concentration quenching. Therefore, in order to keep the luminous efficiency good, it is preferable that x = 10 to 40%, particularly 20 to 30%.

  In the conventionally known europium silicate, the Eu content ratio is several to 0.00. Although it is a few percent and is small, this is because concentration quenching occurs when it is several percent or more. On the other hand, since europium silicate based on the present invention is crystallized, even if Eu is increased to 10 to 40%, particularly 20 to 30%, the light emission characteristics can be maintained well.

  Next, in FIGS. 7A and 7B, the above-described EuxSiyOz light emitting layer 11 is used, for example, on a rectangular substrate 12, a striped electrode 16 and a striped EuxSiyOz light emitting layer 11 and an electrode 7 are used. Are arranged so as to intersect with each other in a matrix form, and a display element or device in which each pixel is configured is shown. By selectively applying a voltage between both the electrodes 16-7, the light emitting layer 11 of the pixel is excited, and an element or device that emits light of a predetermined wavelength can be configured.

  According to the present embodiment, since a composite of silicon 2 and stable europium oxide 1 that can be easily obtained and can be formed at a low temperature is used as a co-sputtering target, surface oxidation does not occur. By using the target material, it is possible to prevent the fluctuation of the sputtering conditions and the composition change of the film forming material, and to easily and easily produce the light emitter 11 made of the europium silicate compound crystal having a quantitative and stable composition. It becomes possible.

  Further, for example, it is possible to easily form a yellow-emitting EuxSiyOz light emitting layer 11 having an emission peak wavelength of 603 nm by co-sputtering using a general material.

  As mentioned above, although this invention was demonstrated based on embodiment, it cannot be overemphasized that this invention is not limited to these examples at all, and can be suitably changed in the range which does not deviate from the main point of invention.

For example, the composition ratio, placement position, arrangement number and size, co-sputtering conditions, annealing conditions, etc. of the Eu ₂ O ₃ sintered body 1 can be variously changed according to the target film performance of the EuxSiyOz light emitting layer 11. It's okay.

It is sectional drawing (sectional drawing which follows the II line | wire of FIG. 2) of the magnetron sputtering by embodiment of this invention. FIG. 3 is a plan view of the silicon target. It is sectional drawing of an EuxSiyOz light emitting layer similarly. It is a graph which shows the relationship between a light emission wavelength and light emission intensity similarly. 4 is a graph showing the correlation between the emission peak wavelength and emission intensity and the number of Eu sintered bodies. It is a graph which shows the correlation with the light emission peak wavelength and light emission intensity, and the composition ratio of Eu. It is the top view (A) of the display element or apparatus, and the VIIB-VIIB sectional view (B).

Explanation of symbols

1 ... Eu ₂ O ₃ sintered body, 2 ... silicon target, 3 ... erosion region,
5 ... Permanent magnet, 7, 16 ... Electrode, 11 ... EuxSiyOz light emitting layer, 12 ... Substrate,
E ... Electric field, B ... Magnetic field

Claims (11)

Chemical formula:
EuxSiyOz
(However, x = 10-40%
y = 20-72%
z = 12-60%)
A luminescent material comprising a crystal of a europium silicate compound represented by:   The luminous body according to claim 1, wherein the composition x of the europium is 20 to 30%. Through a step of disposing a target made of a composite of silicon and europium oxide so as to face the substrate, and a step of co-sputtering the silicon and the europium oxide,
Chemical formula:
EuxSiyOz
(However, x = 10-40%
y = 20-72%
z = 12-60%)
A method for producing a light emitter, wherein a light emitter comprising a crystal of a europium silicate compound represented by the formula is formed on the substrate.   4. The light emission according to claim 3, wherein the co-sputtering is performed by applying an electric field and a magnetic field to the target, and the europium oxide is disposed in a region where the electric field and the magnetic field intersect to concentrate magnetic lines of force. Body manufacturing method.   The method for manufacturing a light emitter according to claim 3, wherein the amorphous europium silicate compound formed by co-sputtering is crystallized by annealing in a vacuum atmosphere.   An illuminant manufacturing apparatus, comprising: a target composed of a composite of silicon and europium oxide; an electric field generating unit that applies an electric field to the target; and a magnetic field generating unit that applies a magnetic field to the target.   The said europium oxide is arrange | positioned in the area | region where the said electric field and the said magnetic field cross | intersect and a line of magnetic force concentrates, The manufacturing apparatus of the light-emitting body of Claim 6. Chemical formula:
EuxSiyOz
(However, x = 10-40%
y = 20-72%
z = 12-60%)
A light-emitting element or a device constituted by a light emitter made of a crystal of a europium silicate compound represented by the formula:   The light-emitting element or device according to claim 8, wherein the composition x of the europium is 20 to 30%.   The light emitting element or device according to claim 8, wherein the light emitting element or device is excited by incident light or voltage application to emit light having a predetermined wavelength.   The light emitting element or device according to claim 10, wherein the light emitter is sandwiched between counter electrodes to constitute a display pixel.

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