JP3457288B2 - Plasma display panel and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high luminance and high picture quality of a plasma display panel by enabling the formation of phosphor layer having excellent luminance and emission intensity. SOLUTION: In the phosphor material expressed by BaMgAly Oz : Eu<2+> the amount of the Eu<2+> ion substitution is set to 8% or less, preferably 1 to 6% in atomic ratio to the Ba element in the mother material BaMgAly Oz . This phosphor material is used as the blue phosphor for forming phosphor layer of the plasma display panel.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a plasma display panel and a method for manufacturing the same.

[0002]

2. Description of the Related Art Plasma display panels (hereinafter referred to as P
(Hereinafter referred to as DP) has attracted attention as a display capable of realizing a large screen with a small depth, and is roughly classified into a direct current type (DC type) and an alternating current type (AC type). Mold is the mainstream.

FIG. 4 is a schematic sectional view showing an example of a general AC type PDP. In the figure, reference numeral 41 denotes a front glass substrate (front cover plate) on which a display electrode 42 is formed, and a dielectric glass layer 43 and a magnesium oxide (MgO) dielectric film are formed on the display electrode 42. A body protection layer 44 is coated.

Further, 45 is a rear glass substrate (back plate), and on the surface of this rear glass substrate 45, address electrodes 46, partition walls 47, and phosphor layers 50 to 50 are formed.
52 is provided. The phosphor layers 50 to 52 have three color phosphor layers of red 50, green 51, and blue 52 sequentially arranged for color display. The front glass substrate 41 and the rear glass substrate 45 are arranged and sealed so that the electrodes 42 and 46 face each other, and a discharge gas is sealed between the partition walls 47 to form a discharge space 49. .

In each discharge space 49, ultraviolet rays with a short wavelength (wavelength 147 nm) are generated by the discharge between the display electrodes 42, and each of the phosphor layers 50 to 52 is excited to emit light, whereby each color of red, green, and blue is emitted. It emits light. In such a PDP, the phosphor layer is formed by arranging an ink or a sheet containing phosphor particles that are excited and emitted by ultraviolet rays on a panel substrate, and then firing the ink or sheet at about 500 ° C. It is formed through a process of burning out the binder component. As the phosphor particles of each color, those having a structure in which the metal element constituting the base material is partially replaced with an activator such as Eu or Mn are often used.

[0006]

By the way, it is known that in such a firing process, the phosphor particles forming the phosphor layer undergo a thermal change, and the brightness and chromaticity of the phosphor layer deteriorate. . In particular, a blue phosphor containing Eu ²⁺ ions as an activator is significantly deteriorated in brightness and emission chromaticity due to firing.

[0007] With respect to such a problem, measures have been taken to improve the thermal deterioration of the phosphor. For example, optical technology contact Vol. 34 No. 1 (1996) P.I. 23-2
4 was conventionally known as BaMgAl14O23: Eu ²⁺ as an excellent blue phosphor, but deterioration and chromaticity change during panel operation became a problem, and BaMgAl was used to improve this point. ₁₀ O ₁₇ : Eu ²⁺ was developed,
It is described that the luminance deterioration due to the firing during the panel manufacturing was also improved.

However, as the demand for higher quality of displays increases, even in PDPs, in order to improve the brightness and image quality, the deterioration of the brightness and chromaticity of the phosphor layer is further suppressed, and the emission intensity (brightness) is improved. Is desired to be improved). The present invention has been made based on such a background, and it is possible to form a phosphor layer having excellent brightness and emission intensity, and to realize high brightness and high image quality of PDP and the like. To aim.

[0009]

[Means for Solving the Problems]
Therefore, the present invention relates to a replacement target in a base material in a PDP.
Element is Eu²⁺Phosphor materials substituted with ions, especially pairs
Formula is BaMgAl_TenO ₁₇: Eu²⁺Or BaMgAl
₁₄O_{twenty three}: Eu²⁺Using the phosphor represented by
Eu for elementary (Ba)²⁺Ion replacement amount is 8 at% or less
It was set lower (preferably 1 to 6 at%).

Blue fluorescence having a structure in which the element to be replaced in the base material is replaced with Eu ²⁺ ion as an activator, including the phosphor whose composition formula is represented by BaMgAl ₁₀ O ₁₇ : Eu ²⁺ Conventionally, a body material having a substitution amount of Eu ²⁺ ions with respect to an element to be replaced of 10 to 15 at% has been used, but a phosphor layer is formed by using the phosphor material of the present invention. Thus, it is possible to improve the brightness and the light emission intensity as compared with the conventional case. When such a phosphor material is used as a blue phosphor material, PDP
It is possible to improve the image quality and brightness of the.

This is because when a PDP is manufactured, a phosphor material is applied and then fired to burn off the binder to form a phosphor layer, but the firing is also performed in the step of sealing the panel thereafter. However, the phosphor material is exposed to firing twice or more, and under such a condition, it is better to set the substitution amount of Eu ²⁺ ions in a range smaller than the conventional range as described above to obtain high brightness and This is because high emission intensity can be obtained.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the outline of the present invention will be described.
As described above, in the phosphor layer of PDP, a phosphor material having a structure in which the metal element constituting the base material is partially replaced with an activator is often used. For example, BaMgAl
_{In the} blue phosphor material represented by ₁₀ O ₁₇ : Eu ²⁺ ,
It has a structure in which the Ba element constituting the base material BaMgAl ₁₀ O ₁₇ is replaced with Eu ²⁺ ions.

Conventionally, in such a type of blue phosphor material, as described above, the substitution amount of Eu ²⁺ ions for the element (Ba) to be substituted is set to about 10 to 15 at%. Is considered as follows. The phosphor layer is basically formed by a process in which particles made of a phosphor material are mixed with a binder and applied, and thereafter, the binder is burned off by firing at about 500 ° C.

Here, in a phosphor material such as BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , the larger the substitution amount of Eu ²⁺ ions, the higher the initial brightness of the phosphor material, but the heat resistance. Since there is a tendency for the brightness and the emission intensity of the phosphor to decrease due to the firing, it is necessary to take into consideration this point so that the brightness and the emission intensity of the phosphor layer after firing take excellent values. In addition, it is considered that the substitution amount of Eu ²⁺ ions was set in the above range (10 to 15 at%).

When actually manufacturing a PDP, after the phosphor layer is formed, firing is usually performed at a temperature of about 400 ° C. to seal the front panel and the back panel. That is, the phosphor in the phosphor layer is exposed to firing twice. Conventionally, since the baking at the time of sealing is performed at a temperature considerably lower than the baking temperature (about 500 ° C.) at the time of forming the phosphor layer, it was considered that the phosphor is not so affected. However, the present inventors have found that the second firing also considerably affects the emission intensity of the phosphor layer.

When the phosphor material is exposed to firing twice as described above, the Eu.
It is better to use the one in which the substitution amount of ²⁺ ions is set to 8at% or less, which is lower than the conventional one, because the luminance and the emission intensity of the phosphor layer are excellent. Especially, the substitution amount of Eu ²⁺ ions is set in the range of 1 to 6at%. It turned out that it is preferable to do. Hereinafter, embodiments of the present invention will be described.

FIG. 1 is a sectional view showing an outline of an AC surface discharge type PDP according to an embodiment of the present invention. Although only one cell is shown in FIG. 1, a PDP is configured by arranging a large number of cells that emit red, green and blue colors. This PDP has a front panel in which a display electrode 12, a dielectric glass layer 13 and a protective layer 14 are arranged on a front glass substrate (front cover plate) 11, an address electrode 16 on a rear glass substrate (back plate) 15, The visible light reflection layer 17, the partition wall 18, and the rear panel on which the phosphor layer 19 is arranged are bonded together, and the discharge gas is enclosed in the discharge space formed between the front panel and the rear panel. And is produced as shown below.

(Production of Front Panel) In the front panel, a display electrode 12 is formed on a front glass substrate 11, a display glass 12 is covered with a lead-based dielectric glass layer 13, and further the dielectric glass layer 1 is formed.
3 is formed by forming the protective layer 14 on the surface. In the present embodiment, the display electrode 12 is a silver electrode and is formed by a method of applying a silver electrode paste by screen printing and then baking the paste.

The dielectric glass layer 13 is formed by applying a paste containing a lead-based glass material by a screen printing method and baking it. The composition of the glass material is, for example, 70% by weight of lead oxide [PbO] and boron oxide [B ₂ O ₃ ].
15 wt% and silicon oxide [SiO ₂ ] 15 wt%. Next, a protective layer 14 of magnesium oxide (MgO) is formed on the dielectric glass layer 13 by the CVD method (chemical vapor deposition method).

(Preparation of Back Panel) Back glass substrate 15
The address electrode 16 is formed by a method of screen-printing a silver electrode paste on the screen and then baking the paste, and a paste containing TiO ₂ particles and dielectric glass particles is applied thereon by a screen-printing method and baked. Thus, the visible light reflection layer 17 is formed, and a paste containing glass particles is also repeatedly applied at a predetermined pitch by a screen printing method, and then fired to form the partition wall 18.

Then, in each space sandwiched by the partition walls 18,
A phosphor obtained by arranging one of a red phosphor, a green phosphor, and a blue phosphor together with a binder, and baking the binder in the air to burn off the binder, whereby phosphor particles are bound in a film shape. Form layer 19. The method of forming the phosphor layer 19 and the phosphor material used will be described in detail later. In addition, in this embodiment, the film thickness of the dielectric glass layer 13 is about 20 μm in accordance with the 40-inch class high-definition television.
The thickness of the protective layer 14 is about 1.0 μm. Also,
The height of the partition 18 is 0.1 to 0.15 mm, the partition pitch is 0.15 to 0.3 mm, and the thickness of the phosphor layer 19 is 5 to 50.
μm.

(Production of PDP by panel bonding)
Next, the front panel and the back panel thus produced are stacked so that the display electrodes of the front panel and the address electrodes of the back panel are orthogonal to each other, and a sealing glass is inserted, and the temperature is about 10 ° C. at 450 ° C. Bake for ~ 20 minutes to seal. And once to remove the gas inside the panel,
The panel is baked while evacuating the inside of the panel to a high vacuum (8 × 10 −7 Torr) (for example, at 350 ° C. for 1 hour). Then, by enclosing the discharge gas, the PDP
Is created.

The discharge gas used in this embodiment is
In the Ne-Xe system, the content of Xe is 5% by volume, and the filling pressure is set in the range of 500 to 800 Torr. (Regarding Method of Forming Phosphor Layer and Phosphor Used) FIG. 2
Is an ink application device 2 used when forming the phosphor layer 19
It is a schematic block diagram of 0. As shown in FIG. 2, in the ink application device 20, the phosphor ink is stored in the server 21, and the pressure pump 22 pressurizes this ink and supplies it to the header 23. The header 23 is provided with an ink chamber 23a and a nozzle 24, and the ink pressurized and supplied to the ink chamber 23a is continuously ejected from the nozzle 24.

Further, the header 23 is a rear glass substrate 15
It is designed to be scanned over. The header 23 is scanned by a header scanning mechanism (not shown) that linearly drives the header 23 in the present embodiment.
May be fixed and the rear glass substrate 15 may be linearly driven.
While scanning the header 23, ink is ejected from the nozzles 24 so as to form a continuous ink flow 25 (jet line), so that the phosphor ink is formed between the partition walls 18 on the rear glass substrate 15. Is evenly applied.

The phosphor ink used here is one prepared by mixing phosphor particles of each color, an organic binder and a solvent so as to have an appropriate viscosity (10 to 1000 centipoise at 25 ° C.), and if necessary. Further, a surfactant, silica, etc. may be added and mixed. Examples of the red phosphor include YBO ₃ : Eu ³⁺ and (YaGd1-a) B.
O ₃ : Eu ³⁺ can be mentioned.

YBO3: Eu³⁺Is the base material YB
O₃The Y element that makes up Eu is Eu³⁺With the structure replaced by
, (Y_aGd_1-a) BO₃: Eu³⁺Is the matrix material
(Y_aGd _1-a) BO₃The Y element and the Gd element that constitute
Eu³⁺The structure is replaced with. As a green phosphor,
For example, Zn₂SiO_Four: Mn²⁺And BaAl₁₂O₁₉: Mn
²⁺Can be mentioned.

Zn ₂ SiO ₄ : Mn ²⁺ has a structure in which the Zn element constituting the base material Zn ₂ SiO ₄ is replaced with Mn ²⁺ ions, and BaAl ₁₂ O ₁₉ : Mn ²⁺ is a base material. It has a structure in which the Ba element constituting the material BaAl ₁₂ O ₁₉ is replaced with Mn ²⁺ . These red and green phosphors are
What is generally used in PDP is used as it is.

On the other hand, as the blue phosphor, BaMgAl
_The one represented by ₁₀ O ₁₇ : Eu ²⁺ is used. E for the Ba element constituting the base material BaMgAl ₁₀ O ₁₇
Although the substitution amount of u ²⁺ of about 10 to 15% has already been used in the PDP, in the present embodiment, the substitution amount of Eu ²⁺ with respect to the Ba element is 8 at% which is lower than the conventional one.
The one set below is used.

The red, green, and blue color phosphors are in the form of particles having an average particle size of 1 to 7 μm. It is preferable to use ethyl cellulose or acrylic resin as the binder (0.1 to 10% by weight of the ink) and terpineol (C ₁₀ H ₁₈ O) as the solvent. Other than this, a polymer such as PMMA or polyvinyl alcohol can be used as the binder, and an organic solvent such as diethylene glycol methyl ether or water can be used as the solvent.

After arranging the red, blue, and green phosphors in this way, the rear glass substrate 15 is placed in a firing furnace,
Baking is performed at a temperature of about 500 ° C. for 10 to 20 minutes. By this firing, the organic binder contained in the phosphor ink or paste or the resin of the sheet is burned off, and a phosphor layer 19 formed by binding phosphor particles in a film shape is formed.

In this case, the phosphor is arranged by the method of scanning while ejecting the phosphor ink from the nozzle.
Other than this, the phosphor can be arranged by a method of applying the phosphor paste by a screen printing method. In addition to this, a sheet of a photosensitive resin containing phosphor materials of each color is prepared, and the sheet is attached to the surface of the rear glass substrate 15 on the side where the partition wall 18 is arranged, patterned by photolithography, and developed. The fluorescent substance can also be provided by a method of removing an unnecessary portion.

(Regarding Manufacturing Method of Phosphor Material) The above-mentioned phosphors of respective colors can be manufactured, for example, by the following method. Manufacturing method of BaMgAl ₁₀ O ₁₇ : Eu ²⁺ which is a blue phosphor:
As raw materials, barium carbonate (BaCO ₃ ), magnesium carbonate (MgCO ₃ ), aluminum oxide (α-Al ₂ O)
₃ ) and europium oxide (Eu ₂ O ₃ ) are mixed so that the ratio of (the sum of the number of moles of Ba and the number of moles of Eu), the number of moles of Mg and the number of moles of Al is 1: 1: 10. To do.

Here, the ratio between the number of moles of Ba and the number of moles of Eu is set based on the substitution amount of Eu ²⁺ ions for the Ba element of the target phosphor. For example, when the substitution amount of Eu ²⁺ ions with respect to Ba element is set to 8 at%, the ratio between the number of moles of Ba and the number of moles of Eu is 92: 8.
Is. Therefore, the molar ratio of barium carbonate, europium oxide, magnesium carbonate and aluminum oxide to be blended is set to 92: 4: 100: 500.

Then, an appropriate amount of flux (AlF ₂ , BaCl ₂ ) is added to the above mixture and mixed by a ball mill. Then, under a weakly reducing atmosphere (in H ₂ and N ₂ ), 1
At a temperature of 400 ° C to 1650 ° C for a predetermined time (for example, 0.5
By firing for a time, particles of BaMgAl ₁₀ O ₁₇ : Eu ²⁺ having a predetermined substitution amount of Eu ²⁺ ions are obtained.

Manufacturing method of YBO ₃ : Eu ³⁺ which is a red phosphor: Yttrium hydroxide Y ₂ (OH) ₃ and boric acid (H ₃ BO ₃ ) and europium oxide (Eu ₂ O ₃ ) are used as raw materials (Y
(The sum of the number of moles of Eu and the number of moles of Eu) and the number of moles of B
Blend so that it becomes 1: 1. Here, the number of moles of Y and E
The ratio of u to the number of moles is set based on the substitution amount of Eu ³⁺ ions for the Y element of the target phosphor.

Then, an appropriate amount of flux is added to the above mixture and mixed by a ball mill. And in the air,
By firing at a temperature of 1200 ° C. to 1450 ° C. for a predetermined time (for example, 1 hour), YBO ₃ : Eu ³⁺ particles having a predetermined Eu ³⁺ ion substitution amount can be obtained. Production method of Zn ₂ SiO ₄ : Mn ²⁺ which is a green phosphor: zinc oxide (ZnO), silicon oxide (Si 0 ₂ ) and manganese oxide (Mn ₂ O ₃ ) are used as raw materials (the number of moles of Zn and Mn The ratio of the sum of the number of moles) and the number of moles of Si is 2: 1.

Here, the ratio between the number of moles of Zn and the number of moles of Mn is Mn ^{2+ with} respect to the Zn element of the target phosphor.
Determined based on the replacement amount of. Then mix with a ball mill. Then, by firing in air at a temperature of 1200 ° C to 1350 ° C for a predetermined time (for example, 0.5 hour),
Particles of Zn ₂ SiO ₄ : Mn ²⁺ having a predetermined Mn ²⁺ substitution amount are obtained.

[0038]

EXAMPLE A PDP of an example based on the above embodiment
Was produced. The green phosphor is Zn ₂ SiO ₄ : Mn ²⁺ (M
The content of n is 2.3% by weight), the red phosphor is YB
O ₃ : Eu ³⁺ (the substitution amount of Eu ³⁺ for the Y element is 0.
1) was used.

The blue phosphor is BaMgAl ₁₀ O ₁₇ : Eu.
The substitution amount of Eu ²⁺ ions for the Ba element of the host material, which is ²⁺ , is No. 2 in Table 1. As shown in 1-4, 0.5
, 2.0, 5.0, and 8.0 at% were used. In Table 1, the composition of the blue phosphor, Ba1-xMgAl ₁₀ O _17: are expressed as EuX. This represents the same phosphor as BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , but the x value showing the substitution amount of Eu ²⁺ ions for the Ba element of the base material is described in the formula.

[0040]

[Table 1]

The average particle size of each color phosphor was about 3 μm, the baking after the phosphor layer was prepared was carried out at 520 ° C. for 10 minutes, and the baking at the time of panel bonding was carried out at 460 ° C. for 10 minutes. The thickness of the phosphor layer was set to 20 μm and the discharge gas pressure was set to 500 Torr. In addition, the panel No. 5 is the PD of the comparative example
This PDP relates to P and was manufactured in the same manner as in the example except that the substitution amount of Eu ²⁺ ions for Ba element was set to 0.100 at%.

<Experiment 1> With respect to each of the PDPs of Examples and Comparative Examples thus produced, the color temperature non-adjusted luminance and the color temperature adjusted luminance were measured. What is color temperature unadjusted brightness?
It is the brightness when the same signal is input to the three colors (that is, the equivalent ultraviolet rays are generated in the discharge spaces of the three colors) and white display is performed. The color temperature adjustment brightness is the color temperature adjusted by adjusting the signal of each color. It is the luminance when displaying white at 9500 degrees.

The luminance was measured by measuring the discharge sustaining voltage 15
The discharge was performed at 0 V and a frequency of 30 kHz. And
The measurement results are shown in Table 1 above. Looking at the measurement results in Table 1, regarding the non-adjusted brightness of color temperature, No. 1 to
No. 4 (x = 0.005 to 0.080). 5
(X = 0.100) shows a higher value, but regarding the color temperature adjustment luminance, No. No. 5 compared with 5 (x = 0.100). 1 to 4 (x = 0.005 to 0.080) show a higher value.

The results show that in the PDP, the panel brightness can be improved as compared with the conventional case by setting the x value of the blue phosphor to be 0.08 or less, which is smaller than the conventional value. Especially No. 2 (x = 0.020) and No.
The color temperature adjustment luminance of 3 (x = 0.050) shows a high value.

This color temperature adjustment luminance is measured by using an actual PD.
In order to improve the image quality in P, the white balance needs to be taken into consideration, and the higher the color temperature adjustment brightness, the higher the brightness while maintaining the image quality. And, it is considered that the emission intensity of the blue phosphor becomes high, which makes it possible to obtain high panel brightness by setting the x value of the blue phosphor to 0.08 or less as described above.

That is, in order to obtain a good image quality in a PDP, it is necessary to set the color temperature to 9000 degrees or more in white balance, but the blue phosphor is usually brighter than the phosphors of other colors. Therefore, when all the colors are turned on with the same signal, the color temperature becomes around 6000 degrees, and good image quality cannot be obtained. In order to set the color temperature to 9000 degrees or higher, it is necessary to perform signal adjustment to reduce the brightness of green and red as compared to blue. However, the higher the emission intensity of the blue phosphor, the higher the brightness of green and red. Is lessened, and a high value can be obtained for the color temperature adjustment brightness.

No. 1 (x = 0.005),
No. The color temperature adjustment luminance is lower than that of 2 (x = 0.020), which is considered to be because the amount of Eu ²⁺ ions in the blue phosphor is too small and the ultraviolet ray excitation probability is low. <Experiment 2> BaMgAl ₁₀ O ₁₇ which is a blue phosphor material:
Regarding Eu ²⁺ , the relationship between the substitution amount of Eu ²⁺ ions and heat resistance was examined as follows.

BaMgAl ₁₀ O ₁₇ : Eu was produced by the above-mentioned manufacturing method.
^When making ²⁺ , europium oxide (Eu ₂ O ₃ )
Various x values (Eu
Ba _1-x MgAl ₁₀ O ₁₇ : E having ²⁺ ion substitution amount)
ux was made. Then, a phosphor paste was prepared using each of the prepared phosphor materials, applied on a substrate, and baked in air at 520 ° C. for 10 minutes to form a phosphor layer. Then, the formed phosphor layer was further baked in air at 460 ° C. for 10 minutes.

Here, before firing at 520 ° C. (when not fired), after firing at 520 ° C. (after firing once), 460 ° C.
After baking in (after baking twice), UV is added to the phosphor layer.
The brightness and the emission intensity of the phosphor layer were examined while irradiating the lamp with ultraviolet rays. The brightness was measured using a brightness meter. The emission intensity was obtained by measuring the emission spectrum from the phosphor layer using a spectrophotometer, calculating the y value of chromaticity from this measurement value, and determining the y value of this chromaticity and the measurement value of luminance ( Luminance / chromaticity y value).

FIG. 3 shows the results of this measurement. FIG. 3A is a characteristic diagram showing the relationship between x value and relative luminance, and FIG. 3B is a characteristic diagram showing x value and relative emission intensity. In each figure, the solid line shows the characteristics when not fired, the broken line shows the characteristics after firing once, and the chain line shows the characteristics after firing twice. Further, the values of the relative luminance and the relative emission intensity in FIGS. 3A and 3B are x =
The value is shown as an index when the value of the phosphor of 0.1 and the value when not fired is 100.

From the characteristic diagrams of FIGS. 3A and 3B, the following can be understood. * In the unbaked state, the higher the x value, the higher the brightness, but the emission intensity is highest around the x value of 0.1. * After firing once, the brightness is highest when the x value is slightly larger than 0.1, and the emission intensity is 0.1 when the x value is 0.1.
The value is almost constant in the following range, but when the x value exceeds 0.1, it decreases as the x value increases.

From this, when the judgment is made based on the measurement result after one-time firing, the x value is 0.1 to 0.
It can be understood that setting to about 15 is suitable for obtaining a high-performance phosphor layer. * After firing twice, the brightness shows the highest value when the x value is slightly smaller than 0.1, and the x value is considerably small 0.01
It keeps a high value to some extent. The emission intensity is x = 0.0
It is the highest around 3 to 0.06, and drops considerably in the range exceeding x = 0.08.

From this, the x value is 0.0 after firing twice.
8 or less, particularly 0.01 to 0.06, and 0.03 among them
It turns out that the range of 0.06 is preferable. * Particularly noteworthy is that the influence of firing on the emission intensity shows the opposite tendency in the range where the x value is larger than 0.08 and in the range where it is 0.08 or less. That is, x
When the value is greater than 0.08, the emission intensity after firing is lower than when unfired, whereas when the value x is 0.08 or less, the firing intensity is rather higher than when unfired. The light emission intensity is higher after the firing, and the brightness and the light emission intensity are higher after firing twice than after firing once.

The difference in such a tendency is that, as the phosphor is baked, the Eu ²⁺ ions are oxidized, impurities such as water are removed and the crystallinity is improved, which improves the emission intensity. In the range where the x value is larger than 0.08, the former influence is larger, whereas when the x value is 0.08 or less, the latter influence is larger.

In this experiment, the case of firing at 460 ° C. after firing at 520 ° C. was investigated.
When firing at about 350 ° C. after firing at about the same temperature or performing firing twice at the same temperature (for example, 460 ° C.), almost the same result is obtained. Further, in FIG. 3, the firing at 520 ° C. is followed by the firing at 460 ° C. 2
Although the measurement results up to the second firing are shown, the same tendency as the result after the second firing is obtained even when the third firing is performed at a temperature of 460 ° C. or lower and the measurement is performed thereafter. was gotten.

That is, 2 as shown by the one-dot chain line in FIG.
The tendency of brightness and luminescence intensity after repeated firing is
However, it turned out that it did not change much. (Other matters) In the above embodiment, Eu²⁺Ion
As an example of a blue phosphor contained as an activator, BaMg
Al_TenO₁₇: Eu²⁺The phosphor represented by
Brightness is not limited to this, but BaMgAl₁₄O_{twenty three}: Eu²⁺And B
a_aSr_1-aMgAl_TenO₁₇: Eu ²⁺Such as blue phosphor
It is also applicable when using.

That is, in BaMgAl ₁₄ O ₂₃ : Eu ²⁺ ,
The substitution amount of Eu ²⁺ ions for Ba element is calculated as Ba _a Sr.
_{In 1-a} MgAl ₁₀ O ₁₇ : Eu ²⁺ , by setting the substitution amount of Eu ²⁺ ions with respect to the sum of Ba element and Sr element to 8 at% or less (preferably 1 to 6 at%),
The same effect can be obtained. Further, in the above embodiment, the AC type PDP has been described as an example, but the same can be said for the DC type PDP.

The blue phosphor described in the above embodiment is not necessarily used only for PDP,
For example, it can be used for a fluorescent lamp. And in that case, the same effect can be obtained.

[0059]

INDUSTRIAL APPLICABILITY As described above, the present invention can be applied to the PDP.
And the element to be replaced in the base material is Eu ²⁺Replace with ion
Phosphor material, especially the composition formula BaMgAl_TenO₁₇:
Eu²⁺Or BaMgAl₁₄O_{twenty three}: Eu²⁺Fluorescence represented by
Eu for the element to be replaced (Ba) using the body²⁺Io
The amount of substitution of hydrogen at 8 at% or less, preferably 1 to 6 at%
Depending on the setting, phosphors with higher heat resistance than before
A film is formed to improve the brightness and emission intensity of the phosphor layer.
Made it possible.

When such a phosphor material is used as a blue phosphor material, thermal deterioration of the phosphor layer in the firing process during PDP production can be suppressed, and the image quality and brightness of the PDP can be improved.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a configuration of an AC surface discharge type PDP according to an embodiment.

FIG. 2 is a schematic configuration diagram of an ink application device used when forming a phosphor layer in the embodiment.

FIG. 3 is a characteristic diagram showing an experimental result using the phosphor material of the example.

FIG. 4 is a schematic sectional view showing an example of a conventional AC surface discharge PDP.

[Explanation of symbols]

11 Front glass substrate 12 Display electrode 13 Dielectric glass layer 14 Protective layer 15 Rear glass substrate 16 address electrodes 17 Visible light reflective layer 18 partitions 19 Phosphor layer 20 Ink coating device

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References Keiji Ichinomiya et al., Phosphors for plasma displays, 263rd Lectures of the Society of Phosphors, Japan, September 13, 1996, pp. 9-13 (58) Fields investigated (Int.Cl. ⁷ , DB name) H01J 11/02 C09K 11/64 CPM H01J 9/227

Claims (8)

(57) [Claims] 1. A plasma display panel in which ultraviolet rays are radiated in a discharge cell formed between a front panel and a back panel and converted into visible light by a phosphor layer, wherein at least one color in the phosphor layer is used. Is represented by BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , and is BaMgA
The substitution amount of Eu ²⁺ ion for Ba element of l ₁₄ O ₂₃ is 8
A plasma display panel formed of a phosphor material having at% or less. Wherein said the front panel and the rear panel, a plasma display panel of claim 1, wherein which is sealed by glass. 3. The substitution amount of Eu ²⁺ ions with respect to Ba element of BaMgAl ₁₄ O ₂₃ is 1 to 6 at%.
The plasma display panel according to 1 or 2 . 4. A BaMgAl ₁₀ film is formed on the first panel substrate.
O ₁₇ : Represented by Eu ²⁺ and Ba of BaMgAl ₁₀ O ₁₇
Phosphor disposing step of disposing a phosphor material having a substitution amount of Eu ²⁺ ions for the element of 8 at% or less together with a binder, and calcining step of calcining the first panel substrate on which the phosphor material is disposed. And a sealing step of sealing the second panel substrate by stacking the second panel substrate on the first panel substrate after the firing step with a sealing agent and firing the substrate. 5. The substitution amount of Eu ²⁺ ions for Ba element of BaMgAl ₁₀ O ₁₇ is 1 to 6 at%.
4. The method for manufacturing a plasma display panel according to 4 . 6. A BaMgAl ₁₄ film is formed on the first panel substrate.
O ₂₃ : represented by Eu ²⁺ and Ba of BaMgAl ₁₄ O ₂₃
Phosphor disposing step of disposing a phosphor material having a substitution amount of Eu ²⁺ ions for the element of 8 at% or less together with a binder, and calcining step of calcining the first panel substrate on which the phosphor material is disposed. And a sealing step of sealing the second panel substrate by stacking the second panel substrate on the first panel substrate after the firing step with a sealing agent and firing the substrate. 7. The substitution amount of Eu ²⁺ ions for Ba element of BaMgAl ₁₄ O ₂₃ is 1 to 6 at%.
6. The method for manufacturing a plasma display panel according to item 6 . The method according to claim 8 wherein said phosphor disposed step, the ink or sheet obtained by mixing the particles and a binder made of a phosphor material, to any one of claims 4 to 7 disposed on said first substrate A method for manufacturing the plasma display panel described.