JPH02220395A - Light emitting member - Google Patents

Abstract

PURPOSE:To obtain a light emitting member which is free from dispersion of luminous strength and made up of a fine grain film with high luminance by specifying the composition of an oxide in case of a light emitting member whose light emitting layer is made up of fine grain containing oxidized Group IV element. CONSTITUTION:A light emitting layer which is a fine grain film containing oxidized Group IV element whose composition formula where the value of X of AOX (A contains any one of Group IV elements) is within a range of 1.5<=1.98 is laid on an arbitrary substrate of quartz glass, silicon wafer, etc. This oxidizability can be controlled by accelerately leaving the fine grain film under a high temperature hard environment as it is and selecting temperature, humidity and time of treatment. Thereby, a light emitting member which is free from dispersion of luminous strength and made up of fine grain film with high luminance can be obtained.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention absorbs excitation energy such as electric fields, electron beams, X-rays, ultraviolet rays, visible light, and infrared rays, and emits light such as fluorescence and phosphorescence. The present invention relates to a light emitting member having:

(Prior Art) Various materials have been known as light-emitting members that emit fluorescence or phosphorescence. For example, crystals of m-v group compounds such as semiconductor GaAs and InP, and I
Those using crystals of I-rV group compounds as luminescent materials are direct transition type, and 5iC1K(:I:Te”
, Y, 02S:Eu", ZnS:Ag+, etc. as luminescent materials are typical examples of the indirect transition type. These luminescent members emit light when the luminescent layer is irradiated with electromagnetic waves or electron beams. In addition, as a light-emitting member that emits light (electroluminescence: EL) by applying an electric field, ZnS:
It is well known that Mn%ZnS:CuC1 or the like is used as a light emitting material.

In addition, the present inventors have developed a new light-emitting material, a light-emitting layer made of fine particles having a particle size comparable to or smaller than the emission wavelength, particularly fine particles containing group (I) elements such as carbon, silicon, and germanium. I have found that what I have is useful.

When these fine particles have a structure in which the constituent elements are oxidized, they are more effective and the actual luminous intensity is also increased, and they are usually used as a luminescent layer in the form of a layered deposited film or a binder-dispersed film. .

(The problem that the invention is trying to solve) However,
A light-emitting member whose light-emitting layer is a fine particle film mainly composed of the above-mentioned Group Ⅰ elements has a problem in that the luminescence intensity varies due to differences in oxidation state.

Therefore, it is an object of the present invention to provide a light-emitting member that overcomes the drawbacks of the prior art described above, that is, a light-emitting member that has a stable oxidation state and has a high-brightness fine particle film with no variation in emission intensity as a light-emitting layer. The goal is to provide parts.

(Means for solving problems) The above object is achieved by the present invention as described below.

That is, the present invention provides a light-emitting member having a light-emitting layer that emits light upon application of excitation energy, in which the light-emitting layer is made of fine particles containing an oxidized group Ⅰ element and whose oxide composition formula is ^0X (A is a group Ⅰ element). The light-emitting member is characterized in that the X value of the element (including any one of the elements) is in the range of 1.50≦x≦1.98.

(Function) In a light-emitting member whose light-emitting layer is made of fine particles containing an oxidized group ■ element, the oxide composition formula is 〇, and the X value of (A contains any of the group ■ elements) is 1.50≦x. By controlling it within the range of ≦1.98, it is possible to provide a light-emitting member having a high-brightness fine particle film as a light-emitting layer with no variation in emission intensity.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

The light-emitting member of the present invention is provided with a light-emitting layer made of a fine particle film containing Group 2 elements, representative examples of which are carbon, silicon, and germanium, either singly or as a composite, on any substrate such as quartz glass or silicon wafer. Furthermore, the fine particles have a structure in which the constituent elements thereof are oxidized.

The above-mentioned fine particles may have a size comparable to or smaller than the emission wavelength, and when emitting visible light, the particle size should be 1 μm or less, preferably 0.1 μm or less, and more preferably 500 Å or less. It is something. The lower limit of particle size is unknown, but transmission electron microscopy 1! (TEM) and field emission scanning electron microscope (FE-5EM), this effect has been recognized even in ultrafine particles having an average particle size of 100 to several tens of particles.

Although the shape of the fine particles is not particularly limited, it is desirable to use particles that are relatively spherical and of uniform size.

As a result of extensive research, the inventors discovered that in order to obtain good luminescent properties with no variation in luminescent intensity, the degree of oxidation of the fine particles needs to satisfy the following conditions.

In other words, by controlling the X value of the oxide composition formula of the fine particles in the range of 1.50≦x≦1.98 (where ＾ includes either one of the group II elements), it is possible to eliminate variations in the luminescence intensity. A high-luminance light-emitting member can be obtained.

In the light-emitting member of the present invention, the light-emitting layer made of the above-mentioned fine particles is formed by depositing fine particles containing group Ⅰ elements, of which carbon, silicon, and germanium are typical examples, singly or as a composite, on a substrate in the form of a deposited film or a binder-dispersed film. After the formation, it is created through an oxidation process. There are various methods for producing a particulate film, and as one example, an apparatus using a microwave plasma CVD method and equipped with a nozzle for turning particulates into a beam is shown in FIG.

For example, when creating a silicon-based fine particle film using the above-mentioned apparatus, first, a carrier gas such as Sin gas and hydrogen gas is fed as raw materials from the gas inlet 10, and microwave This generates plasma, causing a gas decomposition reaction and forming fine particles.

These fine particles, together with some unreacted gaseous active species, are ejected from a contraction/expansion nozzle 2 equipped with a magnetic coil 3 into a downstream chamber 4 in the shape of a heavy beam, and the spray is fixed onto a substrate 7 supported by a holder 6. .

At this time, the inside of the downstream chamber 4 is normally at a low pressure of about 10-'Torr or less, and the pressure ratio with the upstream side of the nozzle is preferably about several tens to a hundred.

Regarding the raw material gas, not only 5iHa but also silane derivatives normally used for silicon film formation, such as Si, )1.
, SiF, etc. can also be used. Furthermore, an amorphous carbon film can be formed by using other group Ⅰ gases, such as methane, methanol, ethane, and other hydrocarbon gases.
Furthermore, a germanium film made of GeHa or the like can be formed into a light-emitting layer having a fine particle structure using exactly the same apparatus. It is also possible to use a mixture of two or three gases, such as a silicon-based gas and a carbon-based gas, or a silicon-based gas and a germanium-based gas.

The fine particle film thus prepared is subsequently subjected to oxidation treatment. Such processing is performed by leaving the room in a high temperature and high humidity environment at an accelerated rate, and increasing the temperature (
50 to 100°C), humidity (50 to 100%R) I)
The degree of oxidation can be controlled by selecting the treatment time. Furthermore, since the series of processes described above does not include any high temperature treatment of 100° C. or higher, various substrates with low heat resistance can also be used.

(Example) Next, the present invention will be explained in more detail based on Examples.

Example 1 After a silicon-based fine particle deposition film was formed on a silicon substrate using a SiH4 mixed gas diluted with 3% hydrogen as a raw material, the oxidation treatment conditions were controlled and the relationship between the degree of oxidation and the luminescence intensity was investigated.

The silicon-based fine particle deposited film was prepared using the apparatus shown in FIG. The ultimate vacuum degree is 2 x 10-' Torr, the above raw material gas is flowed at 1005 CCM, and a microwave of 2.456) Iz is input with a power of 150 W to generate discharge plasma.
The generated fine particles are passed through a nozzle onto a silicon substrate to a thickness of 3.
A thickness of 0 μm was deposited. The pressures in the upstream and downstream chambers at this time were 4×10 −' and 4,5×10 −′ Torr, respectively, and the substrate temperature was room temperature.

The obtained silicon-based fine particle deposited film was observed with a field emission scanning electron microscope 11 (FE-5EM) and had a uniform spherical shape with an average diameter of 10
It was made up of fine particles, about 0 people. Infrared absorption spectrum (FT-In)? From the 1lII constant, it had a structure mainly composed of silicon-hydrogen bonds.

Subsequently, the above membrane was heated to a constant temperature and humidity chamber at a set temperature (40°C).
The degree of oxidation was controlled by processing under various conditions (from 15% to 80°C), humidity (15% to 85%R11), and standing time (1 to 48 hours), and the luminescence intensity (emission wavelength λem=600 nm). The results are summarized in FIG. 2 using the emission intensities of a-5io, aco, and a (λex=430 nm, λem=600 nm) as reference values.

In oxide composition formula Si low, 1.50≦x≦1.98
It was found that good luminescent properties were exhibited within the range of . The degree of oxidation at this time was calculated by thermogravimetric analysis.

Example 2 When forming a silicon-based fine particle deposited film on a silicon substrate by a method similar to Example 1, Si diluted with 5% hydrogen was used as a raw material gas.
H, the flow rate was 100 SCCM, and the microwave input power was 100 W. The thickness of the obtained film is approximately 3μ
m, and approximately 150 fine particles were observed by SEM observation. FT-IR measurements revealed that the structure consisted mainly of silicon-hydrogen bonds.

Subsequently, using a constant temperature and humidity chamber, the above film was treated under various conditions similar to those in Example 1 to control the degree of oxidation, and the luminescence intensity (λem = 6
00nm) and found that! , 50≦x≦1
．． 96 with a 5inX composition showed good luminescent properties.

Example 3 When forming a silicon-based fine particle deposited film on a silicon substrate by a method similar to Example 1, (argon + hydrogen) was used as a raw material gas.
A 5% dilution of SiH4 was used. The carrier gas here (
The mixing ratio of argon + hydrogen was 1:9. The thickness of the obtained film was approximately 3 μm, and approximately 80 fine particles were observed by SEM observation. FT-IR measurement is silicon-
The structure consisted mainly of hydrogen bonds.

Subsequently, using a constant temperature and humidity chamber, the above film was treated under various conditions similar to those in Example 1 to control the degree of oxidation, and the luminescence intensity (λem = 6
00nm) and found that 1.50≦x≦1
．． Good luminescent properties were exhibited for those having a composition of 98 Sin.

(Effects) As explained above, according to the present invention, in a light-emitting member in which the light-emitting layer is made of fine particles containing an oxidized group Ⅰ element, the oxide composition formula ^0ba^ corresponds to one of the group Ⅰ elements. By controlling the X value of (including) within the range of 1.50≦x≦1.98, it is possible to provide a light-emitting member having a high-brightness fine particle film as a light-emitting layer with no variation in emission intensity.

Further, in the present invention, since high temperature treatment is not required for oxidation treatment, any substrate material can be used.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an example of an apparatus used to create a fine particle film that is a light emitting layer of a light emitting member of the present invention, and FIG. 2 is a diagram showing an example 1 of the present invention.
Oxidation degree and luminescence intensity of the luminescent layer (xenon lamp 430n
FIG. 4 is a diagram showing the relationship between the emission intensity at a wavelength of 600 nm and the emission intensity of 600 nm by excitation light irradiation. 1... Reduction/expansion nozzle 2... Nozzle throat 3... Magnetic coil 4-Downstream chamber 5...Cavity resonator 6...Substrate holder 7--Base 8-Microwave input window 9 ...Microwave waveguide 10...Gas inlet 11-...Exhaust pump

Claims (1)

[Claims] (1) In a light-emitting member having a light-emitting layer that emits light upon application of excitation energy, the light-emitting layer is oxidized I
Consisting of fine particles containing group V elements, and its oxide composition formula A
The X value of O_x (A includes any of group IV elements) is 1.
A light emitting member characterized in that the light emitting member is in the range of 50≦x≦1.98.