JPS61195585A - Manufacture of electroluminescence panel - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method for manufacturing an electroluminescent panel having a yellow-orange luminescent layer.

[Background of the invention]

Conventional AC thin film electroluminescent panel (AC
TFEL) comprises a thin film device, for example ZnS:Mn, sandwiched between a pair of insulated electrode-bearing glass substrates. Traditionally used ZnS:M
Thin film deposition methods are sputtering or e-beam evaporation, in both cases a subsequent heat treatment of 450'C is usually required to impart acceptable quality to the luminescent film. Current state of the art devices are approximately 20 f when excited at peak intensities in excess of 220 volts.
The average luminance of t is generated. By making the film even thinner, the above drive voltage can be increased.
If you try to lower the brightness
s) decreases and therefore does not reach an acceptable state.

On the other hand, in the presence of the vapor of cyclopentadienylmanganese, the vapor of alkylzinc and the gaseous hydride of either sulfur or selenium, which are chalcogen elements, are applied to the heated substrate. , a method for producing a light-emitting film made of manganese-doped zinc chalcogenide,
It is disclosed in Japanese Patent Application Laid-Open No. 58-176897. Using this method, chalcogenides are chemically vapor grown (C
VD)L, and manganese dopant ions are said to diffuse accordingly. ” According to the two-pass CVD method, (1
) By adjusting the vapor pressure of the growth atmosphere, a light emitting film with controlled stoichiometry can be formed. (2) Excellent features such as the ability to simultaneously grow uniform layers on multiple large wafers are expected.

However, at present, the luminous efficiency of ZnS:M,n fluorescent films formed by the above method is inferior to that of films formed by conventional sputtering or electron beam evaporation methods. This is because the organic manganese vapor is thermally stable and requires a high temperature of 5500C or higher to fully decompose.

Generally, as the crystallinity of the ZnS matrix improves, the brightness of the electroluminescent panel increases.

The optimum crystallization temperature of ZnS thin film by the above method is 350℃
Since the temperature is in the range of ~450°C, if the film is formed at this temperature, the organic manganese vapor will not be completely thermally decomposed and will be incorporated into the ZnS matrix.
nS: Mn cannot be obtained, and therefore no improvement in brightness is achieved. Therefore, it is necessary to study a method for adjusting the substrate temperature to the optimum crystallization temperature of ZnS and efficiently decomposing the organic manganese vapor.

[Purpose of the invention]

The present invention aims to obtain a method for producing electroluminescent panels with a high degree of luminance efficiency.

[Summary of the invention]

The method for manufacturing an electroluminescent panel according to the present invention includes:
In the presence of organic manganese vapor, alkylzinc vapor and alkylated vapor or gaseous hydride of either sulfur or selenium, which are chalcogen elements, are made to act on a heating substrate for film formation placed under light irradiation. By this,
This is a fluorescent film made of zinc chalcogenide doped with manganese. According to the above method, chalcogenide is chemically grown in a vapor phase, manganese dopant ions are diffused and introduced uniformly, and organic manganese vapor is decomposed because the substrate is heated to the optimum crystallization temperature. This is because, in addition to this, the decomposition is sufficiently promoted by light irradiation.

Tricarbonylmethylcyclopentadienylmanganese compound, which is a typical example of the organic manganese vapor, has the following chemical structure.

H3 The wavelength of the irradiation light is 320 nm to 340 nm, which corresponds to the absorption band near the peak of the charge transfer absorption band from manganese to the methylcyclopentadienyl ring, and the absorption band near the peak of the absorption band from manganese to the excited π orbital of carbonyl. 230 nm to 270 nm corresponding to the band are preferred, but 280 nm to 405 nm and 220 nm to 2
The effect appears even in the 80 nm range. Alternatively, the effect appears even with only light having a wavelength in the range of 280 nm to 405 nm, or only with light having a wavelength in the range of 220 nm to 280 nm.

In addition, tricarbonylalkylcyclopentagenylmanganese, biscyclopentagenylmanganese, triluponylcyclopentagenylmanganese, manganese acetyl acetate, manganese mesotetraphenylporphyrin acetate-1, etc. other than the above-mentioned methyl can be used. Even in such cases, wavelength-selective light irradiation is effective.

Next, the state of minute i due to light irradiation will be explained with reference to the drawings. The excitation wavelength is 253 nm in Figures 1 and 2, respectively.
Absorption spectrum 1 of tricarbonylmethylcyclopentagenylmanganese when irradiated with and 332 nm light separately
Indicates a change in Hell. When the absorption band corresponding to the transition from manganese to the excited state orbit of the carbonyl group in Figure 1 is irradiated with light, the bond between the manganese and carbonyl group is efficiently broken, but a peak is observed around 330 nm. It can be seen that the bond between the manganese and cyclopentagenyl rings is relatively difficult to break. On the other hand, when the charge transfer absorption band from manganese to the cyclopentagenyl ring in Figure 2 is irradiated with light, the manganese-cyclopentagenyl ring is efficiently cleaved, but the carbonyl group is difficult to separate. I understand. In the figure, a, b, c, d, e, f indicate the increasing order of irradiation energy. In order to quantitatively understand the photolysis efficiency, FIG. 3 shows the dependence of the 340 nm manganese-cyclopentagenyl ring absorption band intensity on irradiation energy. 1 shown on the horizontal axis is light irradiation at 253 nm, 2 is light irradiation at 332 nm, and 3 is the result when irradiated with light at 253 nm and 332 nm. This result shows the remarkable effect of photolysis on 1-helicarbonylmethylcyclopentadienylmanganese by irradiation with two-wavelength light.

Next, the structure of an apparatus used for depositing a manganese-doped zinc sulfide thin film on a substrate will be explained with reference to FIG. This device is designed to introduce gases containing zinc, sulfur, and manganese, heated by a ceramic heater 104, and mix and react near the surface of a substrate 103 supported by a substrate holder 105. A quartz window 110 for light irradiation is provided. Reference numerals 1 and 02 in the figure indicate irradiation light emitted from the light source 100. The support plate 111 of the Pelger 109 includes:
Three inlets 106, 107, 108 for introducing gases containing zinc, sulfur and manganese, respectively, a thermocouple 113 and an exhaust pipe 112 are installed.

[Embodiments of the invention]

Next, the present invention will be explained in detail.

Example 1 Using the reaction apparatus shown in Figure 4, diethylzinc, H2S diluted with He (partial pressure 2%) and tricarbonylmethylcyclopentadienylmanganese were used as raw material sources, and a thick layer was deposited on Nesa glass (ITO glass). Af1 with a diameter of 0.27zm
A manganese-doped zinc sulfide light-emitting layer was formed using the substrate to which 203 was attached. The flow rate is 5 per minute for diethylzinc.
cc (2,OX 10-'mol), I-(e dilution H
2S was supplied at 1400 cc (], 3311033 mol per minute) and +helicarbonylmethylcyclopentagenyl manganese was supplied at a vapor pressure maintained at 110°C.

The pressure during the reaction was 2 Torr. During film growth, KrF excimer laser light with a wavelength of 248 nm is continuously applied for an average of 5 times.
W/cn? It was irradiated with an energy density of The thickness of the grown emissive layer was approximately 0.47 zm. On top of this, Y2O3 with a thickness of 0.217 In was deposited by electron beam evaporation, and an An electrode was further placed to create an electroluminescent panel. For comparison, a light emitting layer was formed without irradiating the above light. The thickness of the light emitting layer of this electroluminescent panel was also about 0.4 mm, and the thickness of the Y2O3 layer was about 0.2 mm. After aging, an AC rectangular wave voltage of 170V501 (z, duty 1/10) was applied to each of these panels, and relative brightness was measured.

Separately from the above panel, for the purpose of evaluating the light emitting layer, a manganese-doped zinc sulfide thin film was formed without depositing anything on top. The average crystal grain size of the thin film was determined by X-ray diffraction, and the Mn in the film was
The concentration was measured by X-ray microanalysis and chemical analysis (solution emission spectroscopy), and the residual carbon was measured by photoelectron spectroscopy, and a comparison was made between cases where light was irradiated and cases where no light was irradiated.

These results are summarized in Table 1 along with the examples below, and it was found that the brightness was improved by light irradiation, and the Mn concentration and crystal grain size were increased.

Example 2 Under the same conditions as in Example 1 above, wavelength 3 was used when forming the light emitting layer.
37 nm N2 gas laser light with an average energy density of 0.
Continuous irradiation was performed at 5 W/d. The thickness of the grown emissive layer was approximately 0.41 tm. Thereafter, an electroluminescent +- panel was created through the same steps as in Example 1, and the luminance was measured, and a sample for evaluation of the light-emitting layer was also created separately. The results of these measurements are shown in Table 1. An improvement in brightness, an increase in Mn concentration, and an increase in particle size were observed by light irradiation.

Example 3 ``1'' Under the same conditions as in Example 1, KrF excimer laser light with a wavelength of 248 nm and a KrF excimer laser beam with a wavelength of 337 nm were used to form a light emitting layer.
The N2 gas laser beam was superimposed on the irradiation. The average energy density of each is 5W/d and 0.5W/C, respectively.
I (. Thereafter, an electroluminescent 1-panel was created through the same process as in Example 1, and the luminance was measured. Separately, a sample for evaluating the luminescent layer was created. These measurement results are as follows. As shown in Table 1, by light irradiation, an even greater improvement in brightness and an increase in Mn concentration were observed, as well as an increase in particle size.Furthermore, studies using photoelectron spectroscopy revealed that residual carbon was significantly reduced in this case.

Example 4 Under the same conditions as in Example 1 above, 200
Light from a W deuterium discharge lamp was irradiated onto the substrate.

The light was focused by a lens and illuminated the 1-inch square substrate with almost uniform intensity. ” - The spectral distribution of the 200W deuterium discharge lamp has a peak at 220nm and a peak at 180nm.
It extends from the visible part to the visible part. After forming the light emitting layer, an electroluminescent panel was created through the same steps as in Example 1, and after aging, the panel was heated at 170 V, 50 Hz,
Relative brightness was measured by applying an AC rectangular wave voltage of duty 1/10. In addition, a separate sample for evaluation of the light-emitting layer was prepared. The results of these measurements are shown in Table 1.

Upon light irradiation, an increase in brightness, Mn concentration, and particle size was observed.

Table 1 [Effects of the Invention] As described above, the method for producing an electroluminescent panel according to the present invention is to combine alkylzinc vapor and an alkylated vapor of either sulfur or selenium, which are chalcogen elements, in the presence of organic manganese vapor. By applying a gaseous hydride or a gaseous hydride to a heating substrate for film formation placed under light irradiation, chalcogenide is chemically grown in a vapor phase, and manganese dopant ions are diffused and uniformly grown. As a result, it is possible to create high-brightness, high-efficiency light-emitting films for electroluminescent panels.

[Brief explanation of drawings]

Figures 1 and 2 are absorption spectra showing the effect of light irradiation on tricarbonylmethylcyclopentadienylmanganese. Figure 1 shows the case where the excitation wavelength is 253 nm, and Figure 2 shows the case where the light is irradiated with the excitation wavelength of 332 nm. FIG. 3 is a diagram showing the light irradiation effect of tricarbonylmethylcyclopentadienylmanganese, and FIG. 4 is an explanatory diagram of a luminescent film manufacturing apparatus for an electroluminescent panel.

Claims (5)

[Claims] (1) In the presence of organic manganese vapor, alkylzinc vapor and alkylated vapor or gaseous hydride of either sulfur or selenium, which are chalcogen elements, are applied to a heating substrate for film formation placed under light irradiation. A manufacturing method for electroluminescent panels formed by interaction. (2) The above-mentioned light irradiation is applied to manganese-organic manganese compound.
Claim 1, characterized in that at least one type of ultraviolet/visible light having a wavelength included in the ultraviolet/visible absorption band wavelength range involved in carbon bonds is irradiated in a wavelength-selective manner. Manufacturing method for electroluminescent panels. (3) The method for producing an electroluminescent panel according to claim 1 or 2, wherein the organic manganese vapor is tricarbonylalkylcyclopentadienylmanganese vapor. (4) The method for manufacturing an electroluminescent panel according to claim 3, wherein the organic manganese vapor is a vapor of tricarbonylmethylcyclopentadienylmanganese. (5) A patent characterized in that the organic manganese vapor is any one of biscyclopentagenylmanganese, tricarbonylcyclopentagenylmanganese, manganese acetylacetonate, and manganese mesotetraphenylporphyrin acetate. A method for producing an electroluminescent panel according to claim 1 or 2.