JP5387626B2 - Fluorescent lamp - Google Patents

Description

  The present invention relates to a fluorescent lamp that emits light in the ultraviolet region, and more particularly to a fluorescent lamp that obtains light emission in the vicinity of a wavelength of 200 to 250 nm.

Ultraviolet rays are used in the production of substances by modification of various objects to be treated or treatments using photochemical reactions. For example, ultraviolet light having a wavelength of about 200 nm is used in the curing process of a resin such as an adhesive with ultraviolet rays or the exposure process of a printed circuit board.
In recent years, ultraviolet light having the same wavelength band is also used in a process for improving the mechanical strength of a low dielectric constant film (low-k film) in a semiconductor manufacturing process.

In the manufacturing of low dielectric constant films (low-k films) for semiconductors, the demand for fine wiring and multilayer wiring structures has increased in recent years due to the high integration of devices, increasing the processing speed of devices while reducing power consumption. In order to reduce the interlayer capacitance, a low-k film material has been used.
For this reason, a decrease in the mechanical strength (elastic modulus or EM) of the material due to a decrease in the dielectric constant of the material is not negligible. From the conventional heat (annealing) curing process, ultraviolet rays are used for the purpose of increasing the mechanical strength. A method of improving strength reduction by irradiating and curing is being adopted.
As ultraviolet light used for improving the strength of such a low-k film, as shown in Patent Document 1 (Japanese Patent Laid-Open No. 2009-289996), ultraviolet light including light having a wavelength of about 200 nm is effective. In particular, it is said that light having a wavelength of 200 to 260 nm, more preferably 220 to 250 nm is required.

JP 2009-289996 A

Conventionally, a long arc type high-pressure mercury lamp in which mercury is sealed inside an arc tube is known as a lamp that emits ultraviolet light in a wavelength range of 200 nm.
However, such an ultraviolet radiation lamp is one in which mercury is sealed in the arc tube, and naturally its characteristics depend on the state of mercury evaporation. Therefore, there is a problem that the rise is slow and the light emission characteristics are not stable.
The high-pressure mercury lamp mainly emits light in the range of 250 to 320 nm, which is a typical resonance line of mercury, and is 200 to 260 nm, preferably 220 to 250 nm, necessary for improving the strength of the low-k film. There is a problem that the light output is not sufficient.
Furthermore, since the high-pressure mercury lamp has an electrode inside the arc tube, the life of the electrode is determined by the depleted state of the emitter contained in the electrode. Therefore, the life is usually as short as 10,000 hours and the running cost is high. There is a problem of becoming.
For this reason, there is a demand for the development of a long-life light source that has a large light output at a wavelength of 200 to 260 nm, desirably 220 to 250 nm, and does not use mercury.

  In view of the circumstances as described above, the present invention is to provide a fluorescent lamp having a high ultraviolet light emission intensity with a wavelength of 200 to 260 nm, in other words, high conversion efficiency, without using mercury as a discharge gas.

In order to solve the above-described problems, a fluorescent lamp according to the present invention is made of quartz glass, an arc tube in which a discharge gas containing xenon is enclosed, and a pair of electrodes disposed outside the arc tube. In the fluorescent lamp comprising a phosphor layer formed on the inner surface of the arc tube, the phosphor layer is represented by a general formula (Y _1-X , Pr _X ) Al ₃ B ₄ O _12. It is characterized by comprising a phosphor.

  The phosphor is characterized in that x is in the range of 0.05 to 0.07.

  Further, a glass layer made of soft glass or hard glass is formed between the arc tube and the phosphor layer.

  Further, an ultraviolet reflecting film is formed on the inner surface of the arc tube.

Moreover, the ultraviolet reflection film, calcium pyrophosphate _{(Ca 2 P 2 O 7)} , calcium phosphate _{(Ca 3 (PO 4) 2} ), magnesium pyrophosphate _{(Mg 2 P 2 O 7)} , or, Ba-Na-Si- Any one of O is included.

According to the fluorescent lamp of the present invention, the emission spectrum of the 200 nm range is efficiently emitted, and there is an effect that deterioration due to long-time lighting is small.
Further, since the glass layer is formed between the arc tube and the phosphor layer, the phosphor layer is firmly bonded to the arc tube, and does not peel off or fall off.

Sectional drawing of the fluorescent lamp which concerns on this invention. The expanded sectional view of the P section of FIG. Sectional drawing of the other Example of this invention. The emission spectrum graph of the fluorescent lamp of this invention. The luminous efficiency (relative value) graph of the fluorescent lamp of this invention.

FIG. 1 is a cross-sectional view of a fluorescent lamp according to an embodiment of the present invention, in which (A) is an axial cross-sectional view and (B) is a radial cross-sectional view. FIG. 2 is an enlarged cross-sectional view of FIG.
As shown in FIG. 1, a pair of external electrodes 3 and 4 are disposed oppositely on the outer peripheral surface of an arc tube 2 made of quartz glass, and the external electrodes 3 and 4 have a substantially band-like shape extending in the tube axis direction. For example, it is formed of a conductive film such as a silver paste mixed with silver (Ag) and frit glass, or a gold paste mixed with gold (Au) and frit glass.
Lead wires W1 and W2 are connected to the external electrodes 3 and 4, respectively, and these are connected to a power source 8 that generates a high-frequency voltage.

The arc tube 2 is made of quartz glass that is highly transmissive to ultraviolet rays having a wavelength of 200 nm, and any of fused quartz glass, synthetic quartz glass, and ozone-less quartz glass can be used. In this case, however, it is desirable to use quartz glass having an OH group concentration of 100 ppm or more in order to reduce deterioration due to ultraviolet rays.
The arc tube 2 is filled with a rare gas as a discharge gas. The rare gas may be either xenon alone or a mixed gas of xenon and another rare gas.

As shown in detail in FIG. 2, a glass layer 5 is formed on the inner surface of the arc tube 2 so as to spread almost entirely. A phosphor layer 6 is formed so as to be laminated on the inner surface of the glass layer 5.
The glass layer 5 is for adhering the phosphor layer 6 to the quartz glass constituting the arc tube 2, and preferably has a softening point as the firing temperature of the phosphor (400 to 900 ° C.). ) And is specifically soft glass or hard glass. Particularly preferred is a hard glass with good thermal shock resistance.

By interposing such a glass layer 5 between the phosphor layer 6 and the arc tube 2, the following effects are exhibited.
When the phosphor layer 6 is directly attached to the arc tube 2, the phosphor is applied to the inner surface of the arc tube 2, and then the firing temperature is raised to near the temperature of the glass constituting the arc tube 2. It goes through the process to do. However, when quartz glass is used as the arc tube material, the softening point is about 1600 ° C., and when the phosphor is heated to such a high temperature range, the phosphor is deteriorated and predetermined light is emitted. It can no longer be obtained. On the other hand, when the firing temperature of the phosphor is lowered to a temperature range that does not cause a problem in the light emission characteristics, for example, 900 ° C. or less, the quartz glass cannot be softened, and the phosphor layer 6 is removed from the tube wall. It causes the problem of peeling off and falling. As a result, there arises a problem that a predetermined light distribution cannot be obtained.

  According to the fluorescent lamp according to the present embodiment, the glass layer 5 made of soft glass or hard glass having a softening point lower than that of quartz glass is formed on the inner surface of the arc tube 2, so that the firing temperature of the phosphor is set low. The phosphor layer 6 can be stably held. Furthermore, if the thickness of the glass layer 5 itself is set to about 3 to 30 μm, the phosphor layer 6 can be held. Therefore, the glass layer 5 does not significantly reduce the transmittance.

  Specific materials for the glass layer 5 include borosilicate glass (Si—B—O glass, softening point: about 800 ° C.), aluminosilicate glass (Si—Al—O glass, softening) in the case of hard glass. Point: about 900 ° C.) or a glass added with an alkaline earth oxide, alkali oxide, or metal oxide based on any of these compositions is preferable, and such a hard glass may be used alone. And you may mix and use it in a suitable ratio. In addition, it is preferable that it is a powder form as a form of glass.

Since the glass layer 5 is formed on the inner surface of the arc tube 2, as described above, the phosphor layer 6 laminated on the glass layer 5 is firmly held by the arc tube 2, and the phosphor layer Thus, it is possible to provide a highly reliable fluorescent lamp that does not peel off or fall off.
Moreover, since quartz glass having a high ultraviolet transmittance is used as the material of the arc tube 2, the transmittance of ultraviolet light with a wavelength range of 200 nm (200 to 260 nm, desirably 220 to 250 nm) is good and the radiation efficiency of ultraviolet light. The fluorescent lamp can be made high.

  The phosphor constituting the phosphor layer 6 is irradiated with vacuum ultraviolet light such as 146 nm and 172 nm emitted by the excimer emission of xenon gas, and excited by this to be in the wavelength range of 200 nm, specifically, the wavelength of 200 to 260 nm. Desirably, the phosphor has good light emission characteristics of 220 to 250 nm, and is represented by the following general formula.

(Y _1-X , Pr _X ) Al ₃ B ₄ O ₁₂
Preferably, x = 0.05 to 0.07

  By using the above phosphor, it is possible to provide a fluorescent lamp that maximizes light emission characteristics at a wavelength of 200 to 260 nm, desirably 220 to 250 nm, and has extremely good efficiency.

In the present invention, various changes can be made to the structure of the lamp, some of which are illustrated in FIG.
In FIG. 3A, a part of the circumference of the phosphor layer 6 is removed, and this part is an aperture 10 for light extraction. With such a configuration, the 200 to 260 nm ultraviolet light generated inside the arc tube 2 is guided to the aperture portion by reflection on the surface of the phosphor layer 6 so that the ultraviolet light is efficiently emitted from the aperture 10. become.

Further, in FIG. 3B, an ultraviolet reflecting film 7 is formed on the inner surface of the arc tube 2, and an aperture 10 is formed by cutting out a part of the circumference thereof. A glass layer 5 and a phosphor layer 6 are laminated.
The ultraviolet reflective film 7 includes calcium pyrophosphate (Ca ₂ P ₂ O ₇ ), calcium phosphate (Ca ₃ (PO ₄ ) ₂ ), magnesium pyrophosphate (Mg ₂ P ₂ O ₇ ), and Ba—Na—Si—O. It is desirable that the total amount of these be included in the film in a range exceeding 50%.
According to this, the ultraviolet rays generated in the arc tube 2 are reflected by the ultraviolet reflecting film 7 in the arc tube, and pass through the phosphor layer 6 and the glass layer 5 in the aperture 10 portion in this order, and the arc tube 2. Radiated with directivity to the outside.

  FIG. 3C shows an example in which the aperture 10 is also formed on the phosphor layer 6 in the case of FIG. 3B, and ultraviolet rays are transmitted only through the glass layer 5 at the aperture 10 portion. And efficiently radiated to the outside of the arc tube 2.

Hereinafter, an example of the production procedure of the present invention will be described.
1. As the arc tube material, a cylindrical quartz tube made of fused silica glass is used.
2. A glass powder slurry is applied to the inner surface of the arc tube.
First, a glass powder slurry in which glass powder is dispersed is prepared by mixing a glass powder having a softening point in a low temperature range compared with quartz glass, nitrocellulose, and butyl acetate liquid at a predetermined ratio to prepare a suspension. Make it.
Glass used for the glass layer is borosilicate glass (Si—B—O-based glass) and aluminosilicate glass (Si—Al—O-based glass), or an alkaline earth oxide or alkali based on any of these compositions. It can select from the glass which added the oxide and the metal oxide, for example, Nippon Electric Glass Co., Ltd. glass, model BFK, BS, and PS-94.
The glass powder slurry is applied to the inner surface of a quartz glass arc tube by a pouring method or a suction method.

3. Dry the layer of glass powder.
After the slurry is fixed, dry nitrogen gas (or dry air) may be passed through one opening of the arc tube to evaporate butyl acetate contained in the glass slurry. As a result, a layer made of glass powder having a thickness of 3 to 10 μm is obtained on the inner surface of the glass tube.
In addition, as a distribution state of the glass layer after drying, it is preferable that it is uniformly disperse | distributing by 30 to 90% of area ratio. Moreover, the thickness of a glass layer becomes like this. Preferably it is 3-10 micrometers, Most preferably, it is 3-6 micrometers.
When the concentration of the glass layer is low, when the fluorescent lamp is finally constructed, the exposed surface of the quartz glass becomes too wide and it becomes difficult to hold the phosphor. On the other hand, when this is larger than 90%, the glass powder constituting the glass layer is formed in a continuous state, and the heat generated due to the temperature change during lamp manufacturing and the repeated lighting / extinguishing of the lamp. Due to the expansion, a gap may be formed at the interface between the arc tube and the glass layer, and the glass layer may be peeled off.

4). Firing the layer of glass powder.
The dried glass powder layer is fired at 800 ° C. for 1 hour in the air. In addition, as an optimal baking temperature, when using the borosilicate glass mentioned above and an aluminosilicate glass, it is preferable to carry out at 600-900 degreeC. Moreover, when using the glass which added any of an alkaline-earth oxide, an alkali oxide, and a metal oxide with respect to these glass, it is preferable to carry out at 500-800 degreeC.
The glass powder is partially bonded to each other by this baking process, and is fused to a glass tube made of quartz glass, so that the glass layer is strongly bonded to the substrate.

5. A phosphor slurry is prepared.
The phosphor is a phosphor made of a praseodymium-activated aluminoborate compound, which is expressed as follows in general formula.
(Y _1-X , Pr _X ) Al ₃ B ₄ O ₁₂
Preferably, x = 0.05 to 0.07
6). A phosphor slurry is applied to the inner surface of the arc tube.
A phosphor slurry is applied in the arc tube 2. The application method is appropriate, such as a suction method or a pouring method.
7). Dry the phosphor.
Dry nitrogen gas (may be dry air) is allowed to flow inside the glass tube to evaporate butyl acetate contained in the phosphor slurry.

8). The phosphor is fired.
A glass tube for the arc tube is placed in a furnace and fired. Firing conditions are about 500 to 800 ° C. in the atmosphere, and heating is performed for 0.2 to 1 hour as a holding time at the maximum temperature. In this firing step, softening of the glass occurs at the interface between the phosphor layer 6 and the glass powder layer 5, and the phosphor is bound to the glass powder layer 5. As a result, a strong bonded state is obtained.

  Finally, after firing, the arc tube is cooled, the inside of the arc tube is evacuated, discharge gas is sealed and hermetically sealed (chip off), and an external electrode is formed.

In the fluorescent lamp configured in this manner, when a high frequency voltage is applied to the pair of outer electrodes 3 and 4 from the power source 8 in FIG. 1, a dielectric (upper and lower walls of the arc tube 2) is interposed between the electrodes 3 and 4. Discharge is formed, and ultraviolet light having a wavelength of 172 nm is generated by light emission of a discharge gas such as xenon (Xe) gas.
The ultraviolet light obtained here is light emission for exciting the phosphor, and the phosphor is excited by irradiating the phosphor layer 6 with this ultraviolet light having a wavelength of 172 nm, and the wavelength is 200 to 260 nm, preferably 220 to 250 nm. In this way, a fluorescent lamp with good emission characteristics can be obtained. Furthermore, by using quartz glass as the material of the arc tube, it is possible to obtain a fluorescent lamp having good ultraviolet light transmission characteristics in the 200 nm range.

<Experimental example>
Subsequently, a fluorescent lamp was constructed by changing the composition of the phosphor in the same manner as in the above example, and the emission spectrum was measured with a spectral distribution meter (USR40 manufactured by USHIO INC.).
Specifically, the phosphor is a praseodymium-activated yttrium aluminoborate phosphor ((Y _1-X , Pr _X ) Al ₃ B ₄ O ₁₂ ), and the value of x is set to 0, 0.005. , 0.01, 0.03, 0.05, and 0.07.
In all the fluorescent lamps, the sealed gas was xenon gas, and the sealed pressure was 21 kPa (160 Torr). Measurement was performed by applying a rectangular wave voltage of V _0-p = 1700 V to the lamp and lighting the lamp.

And the example of the emission spectrum of wavelength ((lambda)) 200-350 nm area | region of each said fluorescent lamp is shown in FIG.
In FIG. 4, in order to eliminate the overlapping of the emission spectrum graphs of the fluorescent lamps, the emission intensity on the vertical axis is sequentially increased as the value of X increases with reference to the emission spectrum of the fluorescent lamp when x = 0. The value of is added by “1”, and the emission spectrum is shifted to express the overlap.
As is clear from the figure, all of the fluorescent lamps can obtain a good light emission state at a wavelength of 200 to 300 nm, but the light emission intensity varies greatly depending on the composition of the phosphor (ratio of Y and Pr).

Furthermore, the dependence of the luminous efficiency on the ratio of x was examined by dividing the integrated light quantity of all the lamps in the wavelength range of 200 to 300 nm by the lamp power. The result is shown in FIG.
The spectroscope uses USR-40D manufactured by Ushio Electric Co., Ltd., and performs spectroscopic measurement at a distance of 25 mm from the center of the arc tube. At this time, the input to the lamp lighting power supply 8 is 10 W / m per 1 m of the lamp length.
According to the figure, the highest luminous efficiency is obtained when x is 0.05. When the luminous efficiency when x is 0.05 is 100%, it can be seen that when x is 0.05 to 0.07, the luminous efficiency is 98% or more and a good fluorescent lamp is obtained.

As described above, in the fluorescent lamp of the present invention, the fluorescent lamp having the general formula (Y _1-X , Pr _X ) Al ₃ B ₄ O ₁₂ is provided on the inner surface of the arc tube made of quartz glass. Therefore, ultraviolet light having a wavelength of 200 to 260 nm, more preferably 220 to 250 nm can be efficiently emitted, and a glass layer made of soft glass or hard glass is provided between the arc tube and the phosphor layer. By forming and interposing, the phosphor layer is firmly held by the arc tube, and a highly reliable fluorescent lamp can be provided in which the phosphor layer does not peel off or fall off. This is an excellent effect.

1 fluorescent lamp 2 arc tube (quartz glass)
3, 4 External electrode 5 Glass layer 6 Phosphor layer 7 Ultraviolet reflective film 10 Aperture

Claims (5)

An arc tube made of quartz glass, in which a discharge gas containing xenon is enclosed, a pair of electrodes disposed outside the arc tube, and a phosphor layer formed on the inner surface of the arc tube In the fluorescent lamp
The phosphor layer is generally formula _{(Y 1-X, Pr X} ) Al 3 B 4 fluorescent lamps, characterized in that represented by _{O 12} in which comprises a phosphor.   2. The fluorescent lamp according to claim 1, wherein x is in the range of 0.05 to 0.07.   The fluorescent lamp according to claim 1, wherein a glass layer made of soft glass or hard glass is formed between the arc tube and the phosphor layer.   The fluorescent lamp according to claim 1, wherein an ultraviolet reflecting film is formed on an inner surface of the arc tube. The ultraviolet reflective film is made of calcium pyrophosphate (Ca ₂ P ₂ O ₇ ), calcium phosphate (Ca ₃ (PO ₄ ) ₂ ), magnesium pyrophosphate (Mg ₂ P ₂ O ₇ ), or Ba—Na—Si—O. The fluorescent lamp according to claim 4, comprising any one of them.

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