JPH03197584A - Luminescent element - Google Patents

Abstract

PURPOSE:To obtain a luminescent element which shows high luminous intensity in a visible region and suffers little deterioration of luminous efficiency with time by forming a luminescent layer from a specified substance in a luminescent element having a first conductive layer, a first dielectric layer, a luminescent layer, a second dielectric layer, and a second conductive layer on a supporting base material. CONSTITUTION:A luminescent element having a first conductive layer, a first dielectric layer, a luminescent layer, a second dielectric layer, and a second conductive layer on a supporting base material, wherein the luminescent layer is formed from an arylated polysilane (e.g. a compound of the formula) doped with a semiconductor impurity (e. g. AsF5).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a light emitting element such as El-. In particular, the present invention relates to a light emitting device using a silicon-based material for a light emitting layer.

[Conventional technology]

Conventionally, light-emitting devices using silicon-based materials for their light-emitting layers have been made using silicon carbide films (hereinafter referred to as "a-3iC") deposited by decomposing trimethylsilane (TMS) using a plasma CVD method.
”) is used as a luminescent material (Appl,
Phys, Lett, 42(5) I Marc
h 1 9 83 ” Electrolumin
essence inhydrogenated a
morphous 5ilicon-carbon
alloyH, Munekata et al), and those using an a-3iC film as a luminescent material, which was decomposed and deposited by ECR plasma CVD using a mixed gas of silancus (SiH4) and methane gas (CH4) (J, Non-C).
rystalline Solids, 97 & 9 B,
(1987), P. 293296 “Improv.
element of carrier 1njectio
efficiency in a-S i Cpi
n LED using1+ig old y-conduct
ive video-gapP, N Type
aS i Cprepared by ECRCVD
”) etc.

[Problems with conventional technology]

In devices using the a-3iC film produced by the plasma CVD method as a light-emitting material, the luminous efficiency deteriorates over time due to structural changes over time due to the non-equilibrium structure of the a-3iC film. There was a problem.

In addition, when depositing an a-3iC film by the plasma CVD method, in order to obtain a uniform deposited film, the method of introducing the raw material gas,
It is necessary to consider the exhaust method, the relationship between the substrate point electrodes, etc. in a complicated manner, which increases the equipment cost and reduces the amount of deposited a-
The cost of the 5iC film was also high.

Furthermore, the a-3iC film has a large number of localized levels within the forbidden band and tends to function as a non-emissive center.
There was a problem in that the efficiency of light emission was low.

In addition, there is another problem in that the light emitting device generates heat due to recombination of electrons and holes via non-luminous centers in the a-3iC film, accelerating deterioration of the light emitting device.

[Purpose of the invention]

The present invention aims to solve the problems of the prior art.

In other words, it solves characteristic problems such as aging deterioration of luminous efficiency, low luminous efficiency, and heat generation of light emitting devices using conventional a-3iC films as light emitting materials, and manufacturing problems such as high device manufacturing costs. An object of the present invention is to provide a silicon-based luminescent material that can be used as a light-emitting material.

Furthermore, the present invention aims to provide a large-area light emitting device.

[Means for solving problems]

The present invention was completed as a result of repeated research on a new silicon-based light emitting material that can solve the problems in the conventional technology. a second dielectric layer and a second conductive layer, characterized in that the light emitting layer is made of polysilane containing an aryl group and doped with a semiconductor impurity.

[Structure of the invention]

FIG. 1 shows the layer structure of the light emitting device of the present invention.

As shown in FIG. 1, the light emitting device 100 of the present invention includes, from the bottom, a support 101, a first conductive layer 102, a first dielectric layer 103, doped with an impurity, and containing an aryol group. A light-emitting layer 104 made of polysilane, a second dielectric layer 105, and a second conductive layer 106 are arranged in this order, and further,
Contact electrodes 107, 109 and lead wire 108 are removed.

Hereinafter, the light emitting device of the present invention having the above configuration will be specifically explained in order for each component.

The support used in the present invention may be either electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel AA, Cr, Mo, and Au.
, Nb, Ta, V, Ti.

Examples include metals such as pt and pb, and alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, and the like.

The shape of the support can be a plate, an endless heald, a cylinder, etc. with a smooth surface or an uneven surface, and its thickness is determined as appropriate so as to form a desired light emitting element.
When flexibility as a light emitting element is required, it can be made as thin as possible within a range that allows the function as a support to be fully exhibited. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

First Conductive Layer The first conductive layer used in the present invention includes, for example, NiCr, stainless steel, AR, and Cr.

Mo, Au, Nb Ta, V, Ti, Pt, Pb.

Examples include metals such as Ag and alloys thereof.

In addition, if the support is a transparent support such as glass or polyester film and you do not want the light from the light-emitting element to pass through to the support side, a semitransparent layer of the metal is vacuum-deposited on the support and electron beam is applied. It may be deposited by vapor deposition, sputtering, or the like. Furthermore, I n03. on the support. ITO(Inz)
A transparent conductive film such as O3-1-5n) may be deposited by vacuum evaporation, electron beam evaporation, sputtering, spraying, or the like.

When the support is conductive, the first conductive layer may also serve as the support, but in order to improve the adhesion between the upper layer and the support, the same type of conductive material or different type of conductive material may be deposited. 1st
It is even better to use a conductive layer of

First dielectric layer and second dielectric layer As shown in FIG.
are stacked, and a light emitting layer 104 and a second conductive layer 106
A second dielectric layer 105 is laminated between.

In the present invention, the first and second dielectric layers 103°105
has a function of uniformly applying an electric field to the light emitting layer 104 and a function of preventing dielectric breakdown of the light emitting layer 104 due to a high electric field.

Materials that achieve the purpose of the present invention and have the above functions include:
Y2O2, Sin, 5i02. SiN.

An insulating material such as A6203 is suitable.

Further, as a material that can uniformly apply a high electric field to the light emitting layer 104 and lower the voltage (driving voltage) applied to the entire light emitting element, P b T i O3゜B a T i
03. KTN (KTa+-xNbxo3).

Ferroelectric materials such as P ZT (P b Z x-XT 1XC)+ are effective materials.

In the present invention, in order to fully achieve the purpose of the present invention,
The layer thickness of the first dielectric layer and the second dielectric layer is an important factor, and the layer thickness is preferably 100 to 1 μm.
1 Optimally 0.1 μm to 0.5 μm.

The method of depositing the first dielectric layer and the second dielectric layer of the present invention to the preferable layer thickness using the above-mentioned materials includes:
Examples include electron beam vacuum evaporation, sputtering, and CVD. In particular, when deposited by sputtering, the most dense film can be obtained.

As shown in FIG. 1, the light emitting layer of the present invention is sandwiched between a first dielectric layer 103 and a second dielectric layer 105. The light emitting layer 104 is formed from an aggregate of polysilane containing an aryl group doped with impurities.

The light-emitting layer of the present invention was developed as a result of extensive research into new silicon-based light-emitting materials that can solve the problems of the prior art.

That is, a polysilane containing an alcoholic group and doped with a semiconductor impurity is used as a material for the light emitting layer.

The luminescent material of the present invention is effective because by attaching an aryl group to polysilane, a transition occurs between the 5i-3i Oj bond of polysilane and the π bond of the aryl group, and this transition is in the visible range. It is thought that it can be used as a light-emitting material.

It is also possible to change the emission wavelength by changing the aryl group.

Furthermore, since the aryl group is larger than other substituents, the polysilane containing the aryl group tends to become solid. That is, the structure is stable at normal usage temperatures.

In the present invention, preferred aryl groups include phenyl group, tolyl group, xylyl group, naphthyl group, and the like.

Furthermore, by toping polysilane containing an aryl group with a semiconductor impurity, the aryl content in the polysilane can be increased, and the emission intensity can be increased.

Impurities suitable for the present invention include A s F 5SbF
Examples include oxidizing agents such as No. 3. These impurities serve to increase the hole concentration in polysilane.

It is thought that when a high electric field is applied to polysilane by increasing the concentration of holes in polysilane, excited carrier pairs are likely to be formed, resulting in an increase in emission intensity.

The amount of semiconductor impurity added to the polysilane of the present invention is suitably from t ppm to 1%.

In the present invention, the average molecular weight of the polysilane doped with a semiconductor impurity and containing an aryol group used as a material for the light emitting layer is preferably 6,000 to 200,000. If the molecular weight is less than 6000, the thermal stability of the structure will be poor, resulting in a drawback that the luminous efficiency will tend to deteriorate over time. Moreover, when the molecular weight is greater than 200,000, it becomes difficult to synthesize polysilane.

Furthermore, the layer thickness of the light-emitting layer of the present invention is an important factor related to the emission intensity of the light-emitting element, and is preferably 0.1 μm to 0.1 μm.
It is 1 μm, more preferably 0.2 to 0.6 μm. If the thickness of the light-emitting layer is less than 0, ] μm, the light-emitting layer will be thin and the luminescence intensity will be low. Furthermore, if the thickness of the light-emitting layer exceeds 1 μm, the absorption of emitted light by the light-emitting layer itself increases, resulting in a drawback that the intensity of light emitted that can be substantially extracted to the outside is reduced.

An aryl group-containing polysilane suitable for the light-emitting layer of the present invention is synthesized as follows.

That is, as shown in the following formula (0) or (11), it is synthesized by the Urtufinotenohi reaction in which organic dichlorosilane or organic trichlorosilane is desalted using an alkali metal such as Na and condensed.

1 Hydrocarbon solvent 2 1 (n> Furthermore, hydrocarbons such as alkyl groups, allyl groups, and aryl groups are suitable for the terminal groups (A, A') of the polysilane compounds represented by formulas (1) and (II). .

Details of the synthesis of the above-mentioned polysilane compounds used in the present invention are given in J et al. below.

That is, in a high-purity inert atmosphere free of oxygen and moisture, dichlorosilane τ no-TeJ! Condensation catalyst consisting of potash metal, 1,000 to 1,000.・＼I″+6″: i tax separation) degeneracy i) recanning Intermediate, j, Il □7-芥;in F5J1, (11qμml2) Separate the intermediate polymer from unreacted 1,000 ml, It is synthesized by reacting a predetermined halogenated organic reagent with the intermediate polymer in the presence of a condensation catalyst made of an alkali metal to condense an organic group at the end of the polymer.

In the above synthesis operation, the dichlorosilane monomer as the starting material, the intermediate polymer, the halogenated organic reagent, and the alkali metal condensation catalyst all have high reactivity with oxygen and moisture, so these oxygen and moisture are present. Under such an atmosphere, the desired polysilane compound described above cannot be obtained.

Therefore, the above-mentioned operation for obtaining the above-mentioned polysilane compound used in the present invention needs to be carried out in an atmosphere in which neither oxygen nor moisture is present. Therefore, care must be taken regarding the reaction container and all reagents used so that neither oxygen nor moisture is present in the reaction system. For example, regarding the reaction vessel, vacuum suction and argon gas replacement are performed in a blow box to prevent adsorption of moisture and oxygen within the system. In any case, the argon gas to be used must be
Transfer to a licagel column and dehydrate 7, then add 100% copper powder.
It is used after being deoxidized by passing it through a column heated to (°).

The dichlorosilane monomer as a starting material is introduced into the reaction system after being distilled under reduced pressure using the above-mentioned argon gas which has been deoxygenated immediately before introduction into the reaction system.

The halogenated organic reagent and the solvent used for introducing a specific organic group are also deoxidized in the same manner as the dichlorosilane monomer before being introduced into the reaction system.

The solvent is deoxidized by distilling it under reduced pressure using the deoxygenated argon gas described above, and then further dehydrating it with metals 1 to 3.

The above condensation catalyst is used in the form of wires or chips, and the wires or chips are formed in an oxygen-free paraffinic solvent to prevent oxidation.

The dichlorosilane monomer as a starting material used in producing the polysilane compound represented by the above-mentioned general formulas (I) and (II) used in the present invention has the following formula: R,
A silane compound represented by R25iC42 or -
Formula: R:+R45iCI! A silane compound represented by 2 is selectively used.

As the above-mentioned condensation catalyst, an alkali metal capable of causing a condensation reaction by eliminating halogen is preferably used, and specific examples of the alkali metal include lithium, sodium, and potassium, with lithium and sodium being preferred.

The above-mentioned halogenated organic reagents are for introducing substituents represented by A and A', and include halogenated alkyl compounds, halogenated cycloalkyl compounds, halogenated teryl compounds, and halogenated aralkyl compounds. A suitable compound selected from the group consisting of compounds, i.e. -i of formula: A
-X and/or -Formula: A' -X (However, X is C7
! or Br), and appropriate compounds from the specific examples described below are selectively used.

The dichlorosilane monomer represented by the general formula: R, R2SiCβ2 or this and general 2: 5 1; When introduced, a paraffinic nonpolar hydrocarbon solvent is preferably used as the solvent. Preferred examples of the solvent include n-hexane, n-octane, n-nonane, n-dodecane, cyclohexane and cyclooctane.

Since the resulting intermediate polymer is insoluble in these solvents, it is convenient to separate the intermediate polymer from unreacted dichlorosilane monomer. The separated intermediate polymer is then reacted with the above-mentioned halogenated organic reagent, in which case both are dissolved in the same solvent and subjected to the reaction. In this case, aromatic solvents such as Hensen, toluene, and xylene are preferably used as the solvent.

When condensing the above-mentioned dichlorosilane monomer using the above-mentioned alkali metal catalyst to obtain a desired intermediate, the degree of polymerization of the resulting intermediate polymer can be controlled as appropriate by adjusting the reaction temperature and reaction time. . However, the reaction temperature at that time was 60
It is desirable to set the temperature between 130°C and 130°C.

General formula (1) used in the present invention described above
A desirable embodiment of the method for producing the above-mentioned polysilane compound represented by (II) will be described below.

That is, the method for producing the above-mentioned polysilane compound used in the present invention includes (i) the step of producing an intermediate polymer; and (ii) the step of producing substituents A and A' at the terminals of the intermediate polymer.
It consists of a process of introducing.

The step (i) above is performed as follows.

That is, the reaction system in the reaction vessel is completely free of oxygen and moisture and is dominated by argon and maintained at a predetermined internal pressure.
Add an oxygen-free paraffinic solvent and an oxygen-free condensation catalyst,
Next, an oxygen-free dichlorosilane monomer is added, and the whole is heated to a predetermined temperature while stirring to effect condensation of the monomer. At this time, the degree of condensation of the dichlorosilane monomer is
The reaction temperature and reaction time are adjusted to produce an intermediate polymer with a desired degree of polymerization.

In this reaction, as shown in the reaction formula (i) below, the chloro group of the dichlorosilane monomer and the catalyst cause a desalting reaction, and the Si groups repeat condensation to form a polymer, producing an intermediate polymer. do.

Catalyst nR+Rz 5ick2+mR*R4s; cz, -+R
+ R3 Cp - 1,000 Si ÷ 1 - - 1,000 Si Chi = CZ・
... (i) R2R4 The specific reaction procedure here is to prepare a condensation catalyst (alkali metal) in a paraffinic solvent,
Dichlorosilane monomer is added dropwise while stirring under heat. The degree of polymerization is confirmed by sampling the reaction solution.

Polymerization can be easily confirmed by evaporating the sampling liquid and determining whether a film can be formed.

As the condensation progresses and a polymer is formed, it becomes a white solid that precipitates out of the reaction system. Here, it is cooled, and the solvent containing the monomer is separated from the reaction system by decantation to obtain an intermediate polymer.

Next, the step (bl) described above is carried out. That is, the chlorine group at the end group of the obtained intermediate polymer is desalted and condensed using a halogenated organic agent and a condensation catalyst (alkali metal), and the polymer end group is converted to a predetermined organic The reaction at this time is represented by the following reaction formula (11).

RI R3 CIt -(S ichiT-discretionary 5t-3 薯, -C*Rz
R.

Catalyst + (2A-X or A X+A'-X)-SiR+
Rs A→SiMoT--4SiS1-A'... (11)
R2Ra Specifically, an aromatic solvent is added to an intermediate polymer obtained by condensation of dichlorosilane monomer 9 and melted. Next, a condensation catalyst (alkali metal) is added, and a halogenated organic agent is added dropwise at room temperature. At this time, in order to compete with the condensation reaction between polymer terminal groups, a halogenated organic agent is added in an excess amount of 0.01 to 0.1 times the starting amount. Gradually heat and stir at 80°C to 100°C for 1 hour to carry out the desired reaction.

After the reaction is completed, the mixture is cooled and methanol is added to remove the alkali metal of the catalyst. Next, the generated polysilane compound is extracted with toluene and purified using a silica gel column. The desired polysilane compound used in the present invention is thus obtained.

(Space below) 0 Specifications of R, R2SiCβ2 and R3RaSiCII 2): Among the following compounds, a-2 to 16, 18.20,
21°23.24 is 11. R25iC7! used for z, a-1°2.1L17, 1922, 23.25 is RJ
n Used for SiCβ2.

(CI+3)zsicj2z a-1
((CH3) 2CH) zsic n 22-22 X and A' ((C1ia) 3C) Specific example of zsic R2X (CH3) zcHcthc It CI+3 (C112) 4CI Cl3(C11,) SC1 CH3(Ctlz) + oC12 a- δ CH3(CIlz) 5Br CH:l (CH2) 1oBr −14 b=15 −i −2 −3 −4 As the catalyst, an alkali metal is preferable.

Lithium, sodium, and potassium are used as alkali metals. It is preferable that the shape is wire-like or chip-like to increase the surface area.3 4 Specific CIl of the polysilane compound used in the present invention
□CH3 27 H3 CI+3 CI+3 CI+3 8 113 113 H3 H3 H3 H3 0 C1l.

1 (CHz)z 1f3 C11° (CHJ: 1 Note): Both X and Y in the above structural formula represent polymerized units of monomers. And n is X/(x+y), and m is
Each is calculated using the formula Y/(X+Y).

1 2 AsF5゜5b to the polysilane synthesized in this way
Addition of dopants such as F1 is performed as follows.

The synthesized polysilane is placed in a sealed container, and then a dopant such as A3F4, 5bFa is placed at a predetermined q partial pressure. As a diluent gas, inert gas such as Ar or He, or Hz,
A diluent gas such as Nz may be added. In this way,
The dopant is added into the polysilane by leaving the closed container for a predetermined period of time.

In order to use the aryl group-containing polysilane doped with semiconductor impurities as a light-emitting layer, it is deposited on a substrate as follows.

The first method is to apply a hydrocarbon solution containing polysilane onto a substrate using a spinner.

In this case, the layer thickness of the polysilane that is the light-emitting layer is coated to a desired layer thickness by appropriately adjusting the rotational speed of the spinner and the concentration of polysilane in the hydrocarbon solution.

Furthermore, doping with impurities can be carried out by depositing polysilane containing an aryl group using the various methods described above, then putting the impurity into a closed container with a predetermined partial pressure, and leaving it for a predetermined time to dope the polysilane with the impurity. It is also possible.

The second conductive material used in the present invention may be either a transparent conductive layer or an opaque conductive layer when light is emitted to the support side. When emitting light to the second conductive layer side,
The second conductive layer is preferably a transparent conductive film.

The conductive material used for the second conductive layer can be the same material and deposited by the same method as the first conductive layer.

Contact and Lead The contact electrode used in the present invention is preferably made of a material that improves the electrical adhesion between the lead wire and the first and second conductive layers.Such materials include Ag, Pt, Aj!
etc.

These metals are formed by metal evaporation with a mask placed over the first and second conductive layers.

Further, the lead wire is preferably made of Au as it has low electrical resistance and is durable.

[Production example of polysilane compound used in the present invention]

Below, the polysilane compound used in the present invention will be explained with reference to a specific production example, and the usefulness of the polysilane compound will also be explained.

In addition, in the above-mentioned production examples and comparative production examples, the presence or absence of 01 group is first checked for the product, and then CI!
For those in which the presence of groups is recognized, we quantify them.
Its abundance was expressed in millimole equivalents per 1000 grams of product.

Moreover, regarding the obtained product, Si −
It was confirmed by FT-IR and/or UV spectra whether the compound was a polysilane compound having a main chain consisting of 3i bonds. Furthermore, in conjunction with this, the presence or absence of bonding of substituents in the side chains was confirmed by examining FT-IR and/or protons in the substituents by FTNMR.

5 The structure of the synthesized product was determined from the results obtained above.

The above-mentioned confirmation of the presence or absence of Cl groups in the product is carried out using a fluorescent X-ray analyzer (fully automated fluorescent X-ray analyzer system 3080).
: manufactured by Rigaku Denki Kogyo Co., Ltd.). At that time, trimethylchlorosilane (manufactured by Chisso Co., Ltd.) was prepared as a standard sample, and it was
Standard solutions were prepared by diluting each diluted twice, and each standard solution was applied to the fluorescent X-ray analyzer to measure the amount of Cl groups, and a calibration curve was determined based on the obtained results. On the other hand, regarding the product to be tested, 1 gram of the product is dissolved in dehydrated toluene to make a total volume of 10 mj2, and the test sample is prepared, and this is measured using the fluorescent X-ray analyzer, and the measurement results are used in the test. The amount of Cl groups was determined by checking the line.

For measurement by FT-IR, a KBr pellet of the test sample is prepared, and it is injected into N1colet FT-IR7.
The measurement was carried out by setting the sample size to 50 mm (manufactured by Collet Japan Co., Ltd.). In addition, for measurement by FT-NMR6, the test sample is dissolved in CD (13), and this is F"r"-NMRFX-9Q (manufactured by JEOL Ltd.).
The measurement was carried out by setting the

In addition, in the UV spectrum, if the polysilane compound is a low-molecular one, the spectrum will be on the short wavelength side, and if it is a polymer, the spectrum will be on the long wavelength side. Pure & Applied Chemistry
) 5↓, m5. pp.

104.11050 (1982).

1111 A Mitsuro flask was prepared in a blow box that had been vacuum-suctioned and replaced with argon, a reflux condenser, a thermometer, and a dropping funnel were attached to it, and argon gas was passed through the bypass pipe of the dropping funnel.

100 grams of dehydrated dodecane and 0.3 mole of wire-shaped sodium metal were placed in this Mitsuroh flask and heated to 100° C. with stirring. Next, 0.1 mole of dichlorosilane monomer (manufactured by Chisso ■) (a-7) was dissolved in 30 grams of dehydrated dodecane, and the prepared solution was slowly dropped into the reaction system.

After the dropwise addition, a white solid was precipitated by condensation polymerization at 100° C. for 1 hour. After this time it was cooled, the dodecane was decanted and an additional 100 grams of dehydrated toluene was added to dissolve the white solid and 0.01 mole of sodium metal was added.

Next, n-hexyl chloride (manufactured by Tokyo Kasei) (b3)
0.01 mole of toluene 1 Qm7! A prepared solution was slowly added dropwise to the reaction system with stirring, and the mixture was heated at 100° C. for 1 hour. Thereafter, the mixture was cooled, and 50 m4 of methanol was slowly added dropwise to remove excess metal sodium. This produced a suspended layer and a toluene layer.

Next, the toluene layer was separated, concentrated under reduced pressure, and purified by developing with a silica gel column and chromatography.
The product was obtained in a yield of . For this product, the C
As determined by the Il group content measurement method, no CZ group was found (ie, 0.00 mmol equivalent in 1000 grams of sample).

In addition, the weight average molecular weight of this product was determined by GPC method.
When it was measured by HF development, it was 75,000 (using polystyrene as a standard). Then, the product was subjected to FT-JR measurement and then FT-JR measurement using the method described above.
As a result of NMR measurement, it was found that there were no 5iCX bonds, 5i-O3i bonds, and 5i-0-R bonds, and the product was found to be a polysilane compound having the above-mentioned structure of C-1.

The above results are shown in Table 4.

Production Example 2 A three-way flask was prepared in a blow box that had been vacuum-suctioned and replaced with argon, a reflux condenser, a thermometer, and a dropping funnel were attached to it, and argon gas was passed through the bypass pipe of the dropping funnel.

In this Mitsuro flask, 100 grams of dehydrated dodecane and 1
0.3 mol of lithium metal was added and heated to 100°C with stirring. Next, a solution prepared by dissolving 0.1 mol of dichlorosilane monomer (manufactured by Chisso ■) (a-3) in 30 grams of dehydrated dodecane was slowly dropped into the reaction system. After the dropwise addition, a white solid was precipitated by condensation polymerization at 100°C for 2 hours. After this time it was cooled, the dodecane was decanted and an additional 100 grams of dehydrated toluene was added to dissolve the white solid and 0.02 mole of metallic lithium was added.

Second, chlorobenzene (manufactured by Tokyo Kasei) (b-5>0.0
A solution prepared by dissolving 2 mol in 10 mβ of toluene was slowly added dropwise to the reaction system with stirring, and 100
Heated at ℃ for 1 hour. Thereafter, the mixture was cooled, and 50 mj2 of methanol was slowly added dropwise to remove excess metal lithium. This produced a suspended layer and a toluene layer.

Next, the toluene layer was separated, concentrated under reduced pressure, and purified by development using a silica gel column and chromatography to obtain polysilane compound Yin 2 (structural formula: C-3). Yield is 7
2%, and the weight average molecular weight was 92,000. The results are shown in Table 4.

111 Prepare a Mitsuro flask in a blow box that has been vacuum-suctioned and replaced with argon, place the reflux condenser, thermometer, and dropping funnel into it, and pass argon gas through the bypass pipe of the dropping funnel. did.

100 grams of dehydrated n-hexane and 0.3 mol of 1 gram of metallic sodium were charged into this Mitsuro flask, and heated to 80° C. with stirring. Next, a solution prepared by dissolving 0.1 mol of dichlorosilane monomer (manufactured by Chisso Otoro) (a-7) in dehydrated n-hexane was slowly added dropwise to the reaction system. After the dropwise addition, a white solid was precipitated by condensation polymerization at 80° C. for 3 hours. Thereafter, it was cooled, n-hexane was decanted, and 100% of dehydrated toluene was added.
The white solid was dissolved by adding gram and 0.01 mole of sodium metal was added. Next, a solution prepared by dissolving 0.01 mol of benzyl chloride (manufactured by Tokyo Kasei) (b-12) in 10 ml of toluene was slowly added dropwise to the reaction system with stirring, and heated at 80°C for 1 hour. did. Thereafter, the mixture was cooled, and 50 m# of methanol was slowly added dropwise to remove excess metal sodium. This produced a suspended layer and a toluene layer.

Next, the toluene layer was separated, concentrated under reduced pressure, and purified by development using a silica gel column and chromatography to obtain polysilane compound Yin 3 (Structural Formula 204). Yield is 6
1%, and the weight average molecular weight was 47,000.

The results are shown in Table 4.

In addition, in this polysilane compound, unreacted 5t-
There was no TR absorption attributed to C12, by-products Si-0-3i, and 5iO-R.

Production Examples 4 and 5 Synthesis was carried out in the same manner as in Example 3 using the dichlorosilane monomer and end group treatment agent shown in Table 1 to prepare polysilane compound tooth 4 (structural formula: C-6) and polysilane compound ll.
&15 (Structural formula: C-2), 60% and 6, respectively
Obtained with a yield of 2%. In addition, in this polysilane compound, unreacted 5t-C1l and by-product S i -0-
3i, there was no TR absorption assigned to S i -0-R. The identification results are summarized in Table 4.

Polymerization was carried out in the same manner as in Example 3 using the dichlorosilane monomers shown in Table 2 and changing the reaction time as shown in Table 2. The compounds shown in Table 2 were used. The synthesized products were purified in the same manner as in Production Example 3. Thus, the polysilane compounds shown in Table 4
I got 0.

The yield and weight average molecular weight of each polysilane compound obtained were as shown in Table 4.

In addition, in any polysilane compound, unreacted 5
i-Cj! , 5t-0-3t of by-products.

There was no TR absorption assigned to 5i-0-R.

Production Examples 11 to 14 3 Synthesis was carried out in the same manner as in Example 1 using the dichlorosilane monomer and end group treatment agent shown in Table 3 to obtain polysilane compounds 11hll to 14 shown in Table 4. The yield and weight average molecular weight of each polysilane compound obtained were as shown in Table 4.

A Mitsuro flask was prepared in a blow box that had been vacuum-suctioned and replaced with argon, and a reflux condenser, thermometer, and dropping funnel were attached to it, and argon gas was passed through the bypass pipe of the dropping funnel.

100 g of dehydrated dodecane and 0.3 mol of wire-shaped sodium metal were placed in this Mitsuroh flask and heated to 100°C with stirring. Next, a solution prepared by dissolving 0.1 mole of dichlorosilane monomer (manufactured by Chisso ■) in 30 grams of dehydrated dodecane was slowly added dropwise to the reaction system. After the dropwise addition, a white solid was precipitated by condensation polymerization at 100° C. for 1 hour. Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to remove excess metal sodium.

Next, the white solid was filtered and washed repeatedly with n-hexane and methanol.
I got 1.

This polysilane compound contains toluene, chloroform, TH
It was insoluble in organic solvents such as F. The results were as shown in Table 4.

〔Example〕

The present invention will be explained in more detail below using Examples and Comparative Examples, but the present invention is not limited thereto.

As comparative example 1, Appl, Phys, Lett
42 (5LI March 1983.”Ele
ctroluminescence inhydrog
enated amorphous con-c
arbon alloyHiro Munekata
An EL light emitting device having the same structure was fabricated by the method shown in et al.

That is, silicon carbide (a-5i C1-, :H
) was deposited by a glow discharge decomposition method using a mixed gas of tetramethylsilane (TMS) and silane gas (SiH4) as a raw material gas. Y2O3 was used as the dielectric layer. Electron beam vacuum evaporation was used to deposit Y2O.

The structure of the sample is transparent electrode ITO on 7059 glass.
It has a structure in which 3000 layers of Y2O3 are used as the dielectric layer, 2000 layers of a-8ixC+-x:H are used as the light emitting layer, 3000 layers of Y2O3 are used as the dielectric layer, and /l electrodes are laminated in this order.

In the comparative example thus produced, luminescence was measured in the following manner using the measuring apparatus shown in FIG. 3, which is also used in the examples of the present invention.

The measuring device shown in FIG. 3 includes a glass chamber 301 with an Aβ vapor deposited film 302 on the outside, MgO 303 on the inside to achieve a diffuse reflectance of almost 100%, and a sample socket 305 and a sample 30 inside the chamber.
7 and attach the photocell 30 through the frosted glass 304.
6, the structure is such that the luminescence intensity of the sample is measured.

An alternating current of 200 V at 200 Hz was applied to the sample and luminescence was measured.

Example 1 The light emitting device of the present invention shown in FIG. 1 was manufactured by the manufacturing procedure shown below.

First, a transparent electrode ITO was deposited on a 7059 substrate using a sputtering apparatus shown in FIG.

For ITO sputtering, the temperature of the 7059 substrate is controlled by heater 2.
12 to 180℃, ITO target 209, 0□
Sputtering was performed using Ar gas containing 10% of . At that time, the degree of vacuum is 5 x 10-3 Torrs, and the RF power is 10
It was set to 0W. In this way, the transparent electrode IT○ is
0 people were deposited.

Next, as a first dielectric layer, 2000 layers of Y2O3 were deposited by electron beam vacuum evaporation. The back pressure at that time is 10
-'Torr.

Next, polysilane was deposited as a light emitting element.

Polysilane was synthesized by the method shown in Production Example 1.

Moreover, the average molecular weight was 75,000.

This polysilane was deposited by 5,000 people using a spinner on the substrate on which the first dielectric layer had been deposited.

7 The sample deposited up to this polysilane was placed in a sealed container, and ASF5 was introduced into the sealed container at a partial pressure of 1 Torr. Leave it in this state for 1 hour at room temperature, and add A to the polysilane.
Doped with s F s.

When a part of the polysilane sample doped with this impurity was analyzed by SIMS, it was found that the impurity was doped at about ioppm.

A second dielectric layer Y2O3 of 20% is deposited on the polysilane deposited as described above in the same manner as the first dielectric layer.
00 people deposited. Furthermore, an Al electrode was deposited on this by vacuum evaporation using 1000 people. The sample was then mounted on the diode mount and gold leads were attached.

The luminescence intensity of the EL light emitting device produced as described above was measured using the luminescence intensity measuring device shown in FIG. 3, which was explained in the comparative example.

The luminescence intensities of the comparative example and the sample of this example were compared. An alternating voltage of 200 μm was applied. The light emission intensity of the sample of this example increased by 12% compared to the comparative example.

8 When the light was emitted for 10 hours, the deterioration was 10% compared to the comparative example.
There weren't many.

As described above, better characteristics were obtained than those of the comparative example, which is a conventional technique.

Implemented Coal Amount This example was the same as Example 1 except that the first and second dielectric layers and the polysilane light emitting layer were changed.

That is, on the first and second dielectric layers, 1000 P b Ti 03, which is a ferroelectric material, was deposited by sputtering.

In addition, as a polysilane light emitting layer, CH.

The polymer was synthesized by the method of Production Example 2. The average molecular weight of the polysilane thus synthesized was 92,000.

3000 pieces of such polysilane were deposited using a spinner.

The sample in which this polysilane had been deposited was placed in a sealed container, and SbF5 was introduced into the sealed container at a partial pressure of 10 Torr. Leave it in this state for 1 hour at room temperature and apply 5
Doped with bF4.

When a part of the sample of polysilane doped with this impurity was analyzed by Sl and MS, the impurity was found to be 5Qpp.
It was doped to about m.

The luminescence intensity of the EL light emitting device formed as described above was measured using the luminescence intensity measuring device shown in FIG.

As a result, the operating voltage was reduced by 60% and the emission intensity was improved by 12% compared to the comparative example, and the deterioration of the emission intensity when operated continuously for 10 hours was reduced by 12%.

The EL light-emitting device shown in FIG. 1 was produced in the same manner as in Example 2, except that polysilane represented by Li+13 was used as the polysilane.

The polysilane of this example was synthesized by the method shown in Production Example 11. The average molecular weight was 71.000. Further, the layer thickness of the polysilane light-emitting layer was 5000 layers.

For comparison, a 5IXCI-X:H shown in Comparative Example 1
A light-emitting element was used in which the thickness of the light-emitting layer was 5,000 layers.

The EL light emitting device of this example of the present invention and the comparative example
When the luminescence intensity was compared using the luminescence intensity measuring device shown in the figure in the same manner as in Example 1, the luminescence intensity of the sample of this example was improved by 8% compared to the comparative example.

Implementation ■↓ An EL light-emitting device was produced in the same manner as in Example 3, except that the layer thickness of the polysilane light-emitting layer was changed.

The emission intensity of this EL light emitting device was measured in the same manner as in Example 3.

1 As a result, the results shown in Table 5 were obtained.

Example 5 and comparative example 2 The polysilane shown in Example 1 and the aryl group 113 The luminescence was compared with that of polysilane represented by .

H3 Synthesized by the method shown in Comparative Production Example. This polysilane was doped with AsF5 in the same manner as in Example 1.

For each polysilane, a light emitting device having the same structure as in Example 1 was produced using the same operating procedure.

In the case of Comparative Example 2 using the polysilane shown in Table H3, almost no luminescence was emitted in the visible range.

Table 1 Table 5 Table 8 [Detailed description of the invention] The light emitting device of the present invention using polysilane containing an aryl group and doped with a semiconductor impurity exhibits strong light emission in the visible range, and the luminous efficiency changes over time. It showed very good characteristics with little physical deterioration.

[Brief explanation of drawings]

FIG. 1 is a schematic explanatory diagram of a light emitting element of the present invention. FIG. 2 is a schematic illustration of a sputtering apparatus used for depositing the light emitting device of the present invention. FIG. 3 shows a luminescence intensity measuring device used to measure the light emitting element of the present invention. In FIG. 1, 100... Light emitting element, 101... Support, 102... First conductive layer, 103... First dielectric layer, 104... Light emitting layer, 105... Second dielectric layer, 106...Second conductive layer, 1.07, 109
. . . Contact electrode, 108.110 . . . Riet wire. In FIG. 2, 201...chamber, 202...
・Anode electrode with substrate holder, 203...Target 9 Cathode electrode with soto holder, 204...Insulator, 2
05... Munching box, 206... RF electrode, 207... Shutter, 208... Support, 20
9... Target for sputtering, 210... Ar gas introduction pipe for sputtering, 211... Exhaust hole, 212...
This is a heater for heating the support. In FIG. 3, 301...glass chamber 302
...A6 vapor deposited film, 303...MgO vapor deposited film, 304
...frosted glass, 305...sample socket,
306...Phototube, 307...Sample. Figure ■ Figure 3

Claims (1)

[Claims] A first conductive layer, a first dielectric layer, a light emitting layer on a support,
A light emitting device having a second dielectric layer and a second conductive layer, wherein the light emitting layer is made of polysilane containing an aryl group and doped with a semiconductor impurity.