JP4771720B2 - Organic semiconductor laser - Google Patents

Description

  The present invention relates to a current excitation type organic semiconductor laser using an organic dye polymer material.

  In order to realize an advanced information society, high-speed and large-capacity optical communication technology is indispensable, and one of the important devices that support this technology is a laser. At present, inorganic semiconductor lasers are used, but there is a problem of solving the high cost due to complicated manufacturing processes.

  On the other hand, recently, an organic electroluminescence (EL) element has been developed and is expected to be put to practical use for a color display panel of a mobile phone soon. Although organic EL has a simpler device structure than inorganic semiconductors, it can emit multicolor light. In particular, since light having a short wavelength (400 nm to 550 nm) can be obtained as compared with the wavelength of light (generally 620 nm to 800 nm) obtained with an inorganic semiconductor laser, for example, a large capacity (higher recording density) can be achieved. Since it can be expected to be applied in various fields, it is expected that it will be developed into an organic semiconductor laser in the future, and many studies and reports have been made so far.

Examples of such documents include S.I. R. Forrest, et al. , Nature 389, 362 (1997) [Non-Patent Document 1], R.A. E. Slusher, et al. , Appl. Phys. Lett. 71,230 (1997) [Non-Patent Document 2], S.A. R. Forrest, et al. , Appl. Phys. Lett. 72, 144 (1998) [Non-Patent Document 3].
However, since the organic semiconductor laser exemplified above uses a low molecular compound as a light emitting material, film formation by a vacuum process is required, and a complicated manufacturing process is required as in the case of an inorganic semiconductor laser.

  In addition, the film formation process of these organic low molecular weight compounds by the vacuum evaporation method forms a microcrystalline polycrystalline thin film, and the problems such as pinholes associated therewith cannot be avoided. It is difficult to obtain efficiently.

S. R. Forrest, et al. , Nature 389, 362 (1997) R. E. Slusher, et al. , Appl. Phys. Lett. 71,230 (1997) S. R. Forrest, et al. , Appl. Phys. Lett. 72, 144 (1998)

  In view of the above problems, it is an object of the present invention to provide an organic semiconductor laser that does not require the formation of an organic thin film layer by a vacuum process and has excellent film formability without a pinhole.

  The inventors of the present invention have made extensive studies in order to realize an organic semiconductor laser that can be easily manufactured by forming an organic thin film layer easily by a wet method. As a result, it was found that an organic polymer material can be used for the light emitting layer, and the present invention has been completed.

That is, the said subject is solved by following (1)-(15) of this invention.
(1) “In an organic semiconductor laser in which at least a positive electrode layer, a light emitting layer, and a negative electrode layer are laminated in this order, the light emitting layer includes at least a polymer material having a repeating unit represented by the following general formula (I) An organic semiconductor laser.

（式中、Ａｒ^１及びＡｒ^２は、それぞれ独立に置換若しくは無置換の芳香族炭化水素または置換若しくは無置換の複素芳香環化合物の２価基であり、Ａｒ^３は、置換若しくは無置換の芳香族炭化水素または置換若しくは無置換の複素芳香環化合物の１価基であり、Ｒ^１からＲ^８は、それぞれ独立に、水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、及び置換または無置換のアルキルチオ基からなる群より選択される基であり、ｘ及びｙは、それぞれ独立に１以上３以下の整数を表わす。
ｘまたはｙが２以上の整数の場合、ｘ個のＲ^３はそれぞれ異なっていてもよく、ｙ個のＲ^４もそれぞれ異なっていてもよい。）」；
（２）「少なくとも陽電極層、発光層、陰電極層がこの順で積層された有機半導体レーザにおいて、該発光層に少なくとも下記一般式（II）で表わされる繰返し単位を有する高分子材料が含まれることを特徴とする有機半導体レーザ。

(Wherein Ar ¹ and Ar ² are each independently a divalent group of a substituted or unsubstituted aromatic hydrocarbon or a substituted or unsubstituted heteroaromatic ring compound, and Ar ³ is a substituted or unsubstituted aromatic group. R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, or a monovalent group of a substituted or unsubstituted heteroaromatic compound. It is a group selected from the group consisting of an alkoxy group and a substituted or unsubstituted alkylthio group, and x and y each independently represents an integer of 1 or more and 3 or less.
When x or y is an integer of 2 or more, x R ^{3 s} may be different from each other, and y R ^{4 s} may be different from each other. ) ”;
(2) “In an organic semiconductor laser in which at least a positive electrode layer, a light emitting layer, and a negative electrode layer are laminated in this order, the light emitting layer includes a polymer material having at least a repeating unit represented by the following general formula (II) An organic semiconductor laser.

（式中、Ｒ^１からＲ^１１は、それぞれ独立に水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、及び置換または無置換のアルキルチオ基からなる群より選択される基を表わす。ｘ及びｙは、それぞれ独立に１以上３以下の整数を表わし、ｕ及びｖは、それぞれ独立に１以上４以下の整数を表わし、ｗは１以上５以下の整数を表わす。
ｕ、ｖ、ｗ、ｘ、ｙがそれぞれ２以上の整数の場合、ｕ個のＲ^９、ｖ個のＲ^１０、ｗ個のＲ^１１、ｘ個のＲ^３、ｙ個のＲ^４はそれぞれ異なっていてもよい。）」；
（３）「少なくとも陽電極層、発光層、陰電極層がこの順で積層された有機半導体レーザにおいて、該発光層に少なくとも下記一般式（III）で表わされる繰返し単位を有する高分子材料が含まれることを特徴とする有機半導体レーザ。

Wherein R ¹ to R ¹¹ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted alkylthio group. X and y each independently represents an integer of 1 to 3, u and v each independently represent an integer of 1 to 4, and w represents an integer of 1 to 5.
When u, v, w, x, and y are integers of 2 or more, u R ⁹ , v R ¹⁰ , w R ¹¹ , x R ³ , and y R ⁴ are different from each other. It may be. ) ”;
(3) “In an organic semiconductor laser in which at least a positive electrode layer, a light emitting layer, and a negative electrode layer are laminated in this order, the light emitting layer includes a polymer material having at least a repeating unit represented by the following general formula (III) An organic semiconductor laser.

（式中、Ｒ^１からＲ^１０およびＲ^１２からＲ^１５は、それぞれ独立に水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、及び置換または無置換のアルキルチオ基からなる群より選択される基を表わす。ｓ、ｘ及びｙは、それぞれ独立に１以上３以下の整数を表わし、ｔ、ｕ及びｖは、それぞれ独立に１以上４以下の整数を表わす。
ｓ、ｔ、ｕ、ｖ、ｘ、ｙがそれぞれ２以上の整数の場合、ｓ個のＲ^１２、ｔ個のＲ^１３、ｕ個のＲ^９、ｖ個のＲ^１０、ｘ個のＲ^３、ｙ個のＲ^４はそれぞれ異なっていてもよい。）」；
（４）「前記繰り返し単位は、置換または無置換で１個以上２５個以下の炭素原子を含む直鎖または分岐鎖のアルキル基、置換または無置換で１個以上２５個以下の炭素原子を含む直鎖または分岐鎖のアルコキシ基、及び／又は置換または無置換で１個以上２５個以下の炭素原子を含む直鎖または分岐鎖のアルキルチオ基を前記芳香族環上または飽和炭化水素環上に有することを特徴とする前記第（１）項乃至第（３）項のいずれかに記載の有機半導体レーザ」；
（５）「該陽電極層と発光層との間に正孔輸送層が設けられ、該発光層と陰電極層との間に電子輸送層が設けられていることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載の有機半導体レーザ」；
（６）「該正孔輸送層の厚みが１００〜２０００ｎｍであることを特徴とする前記第（５）項に記載の有機半導体レーザ」；
（７）「上記電子輸送層の厚みが１００〜２０００ｎｍであることを特徴とする前記第（５）項に記載の有機半導体レーザ」；
（８）「該陽電極層と発光層との間に反射層が設けられていることを特徴とする前記第（１）項乃至第（５）項のいずれかに記載の有機半導体レーザ」；
（９）「該発光層と陰電極層との間に反射層が設けられていることを特徴とする前記第（８）項に記載の有機半導体レーザ」；
（１０）「該陽電極層の一方の面に共振器が設けられていることを特徴とする前記第（１）項乃至第（７）項のいずれかに記載の有機半導体レーザ」；
（１１）「基板上に、陰電極層側を該基板の反対側に向けて設けられていることを特徴とする前記第（１）項乃至第（１０）項のいずれかに記載の有機半導体レーザ」；
（１２）「該発光層が正孔輸送物質を含むことを特徴とする前記第（１）項乃至第（１１）項のいずれかに記載の有機半導体レーザ」；
（１３）「該発光層が電子輸送物質を含むことを特徴とする前記第（１）項乃至第（１１）項のいずれかに記載の有機半導体レーザ」；
（１４）「該発光層が正孔輸送物質および電子輸送物質を含むことを特徴とする前記第（１）項乃至第（１１）項のいずれかに記載の有機半導体レーザ」；
（１５）「該発光層が湿式法により成膜されることを特徴とする前記第（１）項乃至第（１４）項のいずれかに記載の有機半導体レーザ」。

Wherein R ¹ to R ¹⁰ and R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted alkylthio group. Represents a group selected from the group consisting of: s, x and y each independently represents an integer of 1 to 3, and t, u and v each independently represents an integer of 1 to 4.
When s, t, u, v, x, and y are integers of 2 or more, s R ¹² , t R ¹³ , u R ⁹ , v R ¹⁰ , x R ³ , The y R ^{4 s} may be different from each other. ) ”;
(4) "The repeating unit is a substituted or unsubstituted linear or branched alkyl group containing 1 to 25 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms. A linear or branched alkoxy group and / or a substituted or unsubstituted linear or branched alkylthio group containing 1 to 25 carbon atoms on the aromatic ring or saturated hydrocarbon ring; An organic semiconductor laser according to any one of the items (1) to (3),
(5) wherein the hole transport layer is provided between the positive electrode layer and the light emitting layer, and the electron transport layer is provided between the light emitting layer and the negative electrode layer. The organic semiconductor laser according to any one of 1) to 4);
(6) “The organic semiconductor laser as described in (5) above, wherein the hole transport layer has a thickness of 100 to 2000 nm”;
(7) "The organic semiconductor laser as described in (5) above, wherein the electron transport layer has a thickness of 100 to 2000 nm";
(8) "The organic semiconductor laser according to any one of (1) to (5) above, wherein a reflective layer is provided between the positive electrode layer and the light emitting layer";
(9) “Organic semiconductor laser according to item (8), wherein a reflective layer is provided between the light emitting layer and the negative electrode layer”;
(10) "The organic semiconductor laser according to any one of (1) to (7) above, wherein a resonator is provided on one surface of the positive electrode layer";
(11) The organic semiconductor according to any one of (1) to (10) above, wherein the negative electrode layer side is provided on the substrate so as to face the opposite side of the substrate. laser";
(12) "The organic semiconductor laser according to any one of (1) to (11) above, wherein the light emitting layer contains a hole transport material";
(13) "The organic semiconductor laser according to any one of (1) to (11) above, wherein the light emitting layer contains an electron transporting substance";
(14) "The organic semiconductor laser according to any one of (1) to (11) above, wherein the light-emitting layer includes a hole transport material and an electron transport material";
(15) “The organic semiconductor laser according to any one of items (1) to (14), wherein the light emitting layer is formed by a wet method”.

  Since the organic semiconductor laser of the present invention uses a polymer material for the light emitting layer, it is easy to manufacture and has excellent practicality.

Hereinafter, the present invention will be described in detail.
In the organic semiconductor laser of the present invention, at least a positive electrode layer, a light emitting layer, and a negative electrode layer are laminated in this order. An organic semiconductor laser having such a configuration is conventionally known, but the organic semiconductor laser of the present invention is characterized in that the light emitting layer contains at least a polymer material represented by the following general formula. With this configuration, the organic semiconductor laser of the present invention can be easily manufactured even with a simple manufacturing process.

  That is, in the device of the present invention, the organic semiconductor layer (hereinafter also referred to as a light emitting layer) contains a polymer having a repeating unit represented by the following general formula (I) as a main component.

Ａｒ^１及びＡｒ^２は、それぞれ独立に置換若しくは無置換の芳香族炭化水素または置換若しくは無置換の複素芳香環化合物の２価基であり、Ａｒ^３は、置換若しくは無置換の芳香族炭化水素または置換若しくは無置換の複素芳香環化合物の１価基であり、Ｒ^１からＲ^８は、それぞれ独立に水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、及び置換または無置換のアルキルチオ基からなる群より選択される基であり、ｘ及びｙは、それぞれ独立に、１以上３以下の整数を表わす。
ｘまたはｙが２以上の整数の場合、ｘ個のＲ^３はそれぞれ異なっていてもよく、ｙ個のＲ^４もそれぞれ異なっていてもよい。

Ar ¹ and Ar ² are each independently a substituted or unsubstituted aromatic hydrocarbon or a divalent group of a substituted or unsubstituted heteroaromatic compound, Ar ³ is a substituted or unsubstituted aromatic hydrocarbon or A monovalent group of a substituted or unsubstituted heteroaromatic ring compound, wherein R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted Or a group selected from the group consisting of unsubstituted alkylthio groups, and x and y each independently represents an integer of 1 to 3.
When x or y is an integer of 2 or more, x R ^{3 s} may be different from each other, and y R ^{4 s} may be different from each other.

  The organic semiconductor material of the present invention may have a substituent on the aromatic ring or the saturated hydrocarbon ring. From the viewpoint of improving solubility, an alkyl group, an alkoxy group, an alkylthio group, and the like can be given. As the number of carbons in these substituents increases, the solubility will improve, but on the other hand, the carrier mobility will decrease. It is preferable to do. Examples of suitable substituents in that case include linear or branched alkyl groups, alkoxy groups, and alkylthio groups having 1 to 25 carbon atoms. Furthermore, a linear or branched alkyl group, alkoxy group and alkylthio group having 2 to 18 carbon atoms are preferable. A plurality of the same substituents may be introduced, or a plurality of different substituents may be introduced.

  In addition, these alkyl groups, alkoxy groups and alkylthio groups are further halogen atoms, cyano groups, aryl groups, hydroxyl groups, carboxyl groups, linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, alkoxy groups, alkylthio groups. It may contain further substituents such as an aryl group substituted with a group.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, hexyl group, Heptyl, octyl, nonyl, decyl, 3,7-dimethyloctyl, 2-ethylhexyl, trifluoromethyl, 2-cyanoethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, A cyclopentyl group, a cyclohexyl group, etc. can be mentioned as an example, As an alkoxy group and an alkylthio group, what made an alkoxy group and an alkylthio group by inserting an oxygen atom or a sulfur atom in the bond position of the said alkyl group is mentioned as an example. It is done.

  The polymer is further improved in solubility in a solvent due to the presence of an alkyl group, an alkoxy group, or an alkylthio group. It is important to improve the solubility of these materials because the manufacturing tolerance of the film wet film forming process is increased. For example, the choice of coating solvent is expanded, the temperature range during solution preparation is expanded, the temperature and pressure range during solvent drying is expanded, and the high processability results in high purity and uniformity. The possibility of obtaining a high-quality thin film is increased.

As the divalent groups Ar ¹ and Ar ² of the substituted or unsubstituted aromatic hydrocarbon or the substituted or unsubstituted heteroaromatic compound in the polymer of the present invention, a monocyclic group, a polycyclic group (condensed polycyclic group) And a non-condensed polycyclic group), and examples thereof include a divalent group of an aromatic ring represented by the following formula (a).

Ｙ、Ｚはそれぞれ、Ｏ、Ｓ、および、Ｎ（Ｒ）を表わし、Ｙ’は、Ｏ、Ｓ、Ｃ（Ｒ^２）、および、Ｎ（Ｒ）を表わす（ここでＲは置換若しくは無置換の芳香族炭化水素または置換若しくは無置換の複素芳香環化合物の１価基、またはアルキル基を表わす）。
また、本発明の重合体における置換若しくは無置換の芳香族炭化水素または置換若しくは無置換の複素芳香環化合物の１価基Ａｒ^３の例としては、上記芳香環の１価基が挙げられる。

Y and Z represent O, S, and N (R), respectively, and Y ′ represents O, S, C (R ² ), and N (R) (where R is substituted or unsubstituted) Or a monovalent group or an alkyl group of a substituted or unsubstituted heteroaromatic ring compound).
In addition, examples of the monovalent group Ar ³ of the substituted or unsubstituted aromatic hydrocarbon or the substituted or unsubstituted heteroaromatic ring compound in the polymer of the present invention include the monovalent group of the aromatic ring.

Moreover, the monovalent group and divalent group of these aromatic hydrocarbons, and the monovalent group and divalent group of the heterocyclic compound may have the following substituents.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) A linear or branched alkyl group or alkoxy group having 1 to 25 carbon atoms. These alkyl groups and alkoxy groups may be further substituted with a halogen atom, a cyano group, a phenyl group, a hydroxy group, a carboxyl group, an alkoxy group, or an alkylthio group.
(3) Aryloxy group. (Examples include aryloxy groups having a phenyl group or a naphthyl group as the aryl group. These aryloxy groups may contain a halogen atom as a substituent, and may be a linear or branched chain having 1 to 25 carbon atoms. An alkyl group, an alkoxy group or an alkylthio group may be contained as a substituent, specifically, a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group. , 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group, etc.)
(4) An alkylthio group or an arylthio group. (Specific examples of the alkylthio group or arylthio group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.)
(5) An alkyl-substituted amino group. (Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group And a urolidyl group.)
(6) Acyl group. (Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.)

  Of the polymers mainly containing the repeating unit represented by the general formula (I), a more preferred embodiment is a polymer mainly containing the repeating unit represented by the following general formula (II).

一般式（II）において、Ｒ^１からＲ^１１は、それぞれ独立に水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、及び置換または無置換のアルキルチオ基からなる群より選択される基を表わす。ｘ及びｙは、それぞれ独立に１以上３以下の整数を表わし、ｕ及びｖは、それぞれ独立に１以上４以下の整数を表わし、ｗは１以上５以下の整数を表わす。
ｕ、ｖ、ｗ、ｘ、ｙがそれぞれ２以上の整数の場合、ｕ個のＲ^９、ｖ個のＲ^１０、ｗ個のＲ^１１、ｘ個のＲ^３、ｙ個のＲ^４はそれぞれ異なっていてもよい。

In the general formula (II), R ¹ to R ¹¹ are each independently a group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted alkylthio group. Represents a group selected from x and y each independently represent an integer of 1 to 3, u and v each independently represent an integer of 1 to 4, and w represents an integer of 1 to 5.
When u, v, w, x, and y are integers of 2 or more, u R ⁹ , v R ¹⁰ , w R ¹¹ , x R ³ , and y R ⁴ are different from each other. It may be.

  Among the polymers mainly containing the repeating unit represented by the general formula (I), a more preferred second embodiment is a polymer mainly containing the repeating unit represented by the following general formula (III).

一般式（III）において、Ｒ^１からＲ^１０およびＲ^１２からＲ^１５は、それぞれ独立に水素原子、ハロゲン原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基、及び置換または無置換のアルキルチオ基からなる群より選択される基を表わす。ｓ、ｘ及びｙは、それぞれ独立に１以上３以下の整数を表わし、ｔ、ｕ及びｖは、それぞれ独立に１以上４以下の整数を表わす。
ｓ、ｔ、ｕ、ｖ、ｘ、ｙがそれぞれ２以上の整数の場合、ｓ個のＲ^１２、ｔ個のＲ^１３、ｕ個のＲ^９、ｖ個のＲ^１０、ｘ個のＲ^３、ｙ個のＲ^４はそれぞれ異なっていてもよい。

In the general formula (III), R ¹ to R ¹⁰ and R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted group. Represents a group selected from the group consisting of alkylthio groups. s, x, and y each independently represent an integer of 1 to 3, and t, u, and v each independently represent an integer of 1 to 4.
When s, t, u, v, x, and y are integers of 2 or more, s R ¹² , t R ¹³ , u R ⁹ , v R ¹⁰ , x R ³ , The y R ^{4 s} may be different from each other.

The method for producing the polymer containing the repeating unit represented by the general formulas (I), (II), and (III) includes, for example, Wittig-Horner reaction using a carbonyl compound and a phosphonate, and Wittig using a carbonyl compound and a phosphonium salt. Reaction, Heck reaction using a vinyl-substituted product and a halide, Suzuki-Miyaura coupling reaction using a vinylboronic acid derivative and a halide, and the like can be used, and they can be produced by a known method.
A detailed method for producing the polymer according to the present invention is described in Japanese Patent Application No. 2004-174088.

The organic semiconductor material according to the present invention is not substantially oxidized even in air in a solid or solution state.
The preferable molecular weight of the polymer material represented by the general formulas (I), (II), and (III) is 1000 to 1000000 in terms of polystyrene-equivalent number average molecular weight, and more preferably 2000 to 500000. If the molecular weight is too small, it will be cracked during film formation and become less practical. On the other hand, when the molecular weight is too large, the solubility in a general solvent is deteriorated, the viscosity of the solution becomes high and coating becomes difficult, and the practicality is also poor.

  Next, the layer structure of the organic semiconductor laser of the present invention will be described with reference to FIGS. 1 to 4 are sectional views of the organic semiconductor laser of the present invention.

As shown in FIG. 1, the organic semiconductor laser of the present invention includes at least a positive electrode layer (2), a light emitting layer (3), and a negative electrode layer (4) laminated in this order. And the light emitting layer (3) and the negative electrode layer (4) are usually laminated so that the positive electrode layer (2) is in contact with the substrate (1) on the substrate (1) (negative electrode layer (4)). With the side facing away from the substrate (1). Since the organic semiconductor laser of the present invention is configured in this way, holes are injected from the positive electrode layer (2) provided on the substrate (1) into the light emitting layer (3), and the negative electrode layer Electrons are injected from (4) into the light emitting layer (3), and light is obtained by recombination of the holes and electrons in the light emitting layer (3). This light can be reflected between the layers (specifically, the contact surface between the positive electrode layer (2) and the light emitting layer (3) and / or the contact surface between the light emitting layer (3) and the negative electrode layer (4)). Thus, it is amplified by repeating reflection and emitted as laser light.
Generally as said board | substrate (1), glass, a plastic film, etc. can be used.

In the present invention, the positive electrode layer (2) injects holes into the light emitting layer (3) (as will be described later, when a hole transport layer is provided, the hole transport layer is injected into the light emitting layer (3)). Have The positive electrode layer (2) is preferably formed of a metal having a large work function (4 eV or more), an alloy thereof, an electrically conductive compound, and a mixture thereof. Specific examples of such electrode materials include metals such as Au, and conductive materials such as CuI, ITO (indium tin oxide), SnO ₂ , and ZnO. The thickness of the positive electrode layer (2) is usually 10 nm to 1 μm, preferably 50 to 200 nm. As a method for forming the positive electrode layer (2), a conventionally known method such as vapor deposition or sputtering can be used.

In the present invention, the negative electrode layer (4) has an action of injecting electrons into the light emitting layer (3) (when an electron transporting layer is provided, as will be described later, through the electron transporting layer to the light emitting layer (3)). . The negative electrode layer (4) is preferably formed of a metal having a small work function (4 eV or less) or an alloy thereof, an electrically conductive compound, and a mixture thereof. Specific examples of such electrode materials include Na, Na · K alloy, Mg, Li, Mg / Cu mixture, Mg · Ag alloy, Al·Li alloy, Al / Al ₂ O ₃ mixture, In, rare earth metal, etc. Is mentioned. The thickness of the negative electrode layer (3) is usually 10 nm to 1 μm, preferably 50 to 200 nm. As a method for forming the negative electrode layer, a conventionally known method such as vapor deposition or sputtering can be used.

In the present invention, the light emitting layer (3) has a function of generating light by recombining holes injected from the positive electrode layer (2) and electrons injected from the negative electrode layer (4). The light emitting layer (2) of this invention contains the polymeric material mentioned above. Moreover, when forming the light emitting layer (3) for the purpose of improving electrical characteristics, an electron transport material or a hole transport material described later may be included together with the polymer material.
There is no restriction | limiting in particular in the film thickness of a light emitting layer, Although it can select suitably, Usually, it is preferable to set it as the range of 5-500 nm.

  The light emitting layer (2) in the present invention can be formed by coating and drying in the form of a coating solution containing the material therefor. In the present invention, the light emitting layer (2) is formed using this coating solution. The method is referred to as “wet method”. In the present invention, the light emitting layer (2) can be easily thinned by a known method such as a spin coating method, a casting method, an inkjet method, a dipping method, a blade coating method, a spray coating method, etc. It is. The polymer material used in the present invention is easily dissolved in an organic solvent such as dichloromethane, tetrahydrofuran, chloroform, toluene, dichlorobenzene and xylene. Therefore, if a solution having an appropriate concentration is prepared with an appropriate solvent capable of dissolving the polymer material and applied by the above method or the like, the light emitting layer (2) can be easily prepared.

  In the organic semiconductor laser of the present invention, as shown in FIG. 2, a hole transport layer (5) is provided between the positive electrode layer (2) and the light emitting layer (3), and the light emitting layer (3) and the negative electrode layer (3) are negatively connected. It is preferable that an electron transport layer (6) is provided between the electrode layer (4). If comprised in this way, light will be generated in a light emitting layer (3) by applying a voltage between a positive electrode layer (2) and a negative electrode layer (4), and this light will be carried out to a positive hole transport layer. The light is amplified by repeating total reflection on the contact surface between (5) and the light emitting layer (3) and / or the contact surface between the electron transport layer (6) and the light emitting layer (3), and then the light is emitted from the light emitting layer. It can discharge | release from the edge part of (3).

  Examples of hole transport materials used for the hole transport layer (5) include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine. Derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilanes And electroconductive polymer oligomers such as thiophene compounds, polyvinylcarbazole derivatives, aniline copolymers, thiophene oligomers, and polythiophenes.

Examples of the electron transport material used for the electron transport layer (6) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbodiimides, and fluorenylidenemethane. Derivatives, andraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like. Further, epidolidine, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, 4,4-bis (5,7-di-t-pentyl--) described in JP-A-59-194393. 2-Benzoxazolyl) stilbene, 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) stilbene, 2,2 ′ (1,4-phenylenedivinylene-benzothiazole) 2,2 ′-(4,4′-biphenylene) bisbenzothiazole, bis (8-hydroxyquinolino) magnesium, 2,5-bis [5- (α, α′-dimethylpentyl) -2-benzoxa A series of electron transport compounds such as [zolyl] thiophene can also be used as the electron transport material.

  Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc, etc., and the central metals of these metal complexes are In, Mg, Cu, Metal complexes replaced with Ca, Sn, Ga, or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having a terminal substituted with an alkyl group or a sulfonic acid group can also be used as the electron transport material. Distyrylpyrazine derivatives can also be used as an electron transport material, and inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as an electron transport material.

  The electron transport layer (6) made of the above electron transport material has an electron donating donor made of a compound such as an alkali metal or alkaline earth metal, and a fluoride, chloride or iodide of the alkali metal or alkaline earth metal. Is preferably 0.1 to 30 mol%.

  In the present invention, the electron transport layer (5) and the hole transport layer (6) exemplified above can be formed by a conventionally known method such as a spin coating method, a casting method, a vapor deposition method, or a sputtering method. However, it is preferable to use a vapor deposition method.

  The thickness of the hole transport layer 5 is preferably 100 to 2000 nm, and more preferably 200 to 500 nm. Moreover, it is preferable that the thickness of the said electron carrying layer (6) is 100-2000 nm, and it is more preferable that it is 200-500 nm. As long as the thickness of the hole transport layer (5) and the thickness of the electron transport layer (6) are within such ranges, the light emitting layer (3) at the contact surface between the hole transport layer (5) and the light emitting layer (3) Laser light can be obtained by totally reflecting the emitted light. If the thickness of the hole transport layer (5) or the electron transport layer (6) is too thin, there is a possibility that the light emitted from the contact surface is totally reflected, and laser light cannot be obtained. There is a risk that the transport capacity will be reduced.

  In the organic semiconductor laser of the present invention, as shown in FIG. 3, it is preferable that a reflective layer (7) is provided between the positive electrode layer (2) and the light emitting layer (3). With this configuration, light is repeatedly reflected and amplified between the reflective layer (7) and the negative electrode layer (4) (waveguide effect), and thus amplified from the end face of the organic semiconductor laser. Laser light can be extracted. From this viewpoint, it is preferable that a reflective layer (not shown) is also provided between the light emitting layer (3) and the negative electrode layer (4).

  As an example of a material that can be used for the reflective layer (7), it is preferable to use a metal having high reflectance. Examples of the metal include those similar to those used for the negative electrode layer (4) shown above.

  In the organic semiconductor laser of the present invention, it is preferable that a resonator (8) is provided on one surface of the positive electrode layer (3) in order to obtain laser light amplified more efficiently. Specifically, as shown in FIG. 4, a resonator (8) is provided on a substrate (1), and a positive electrode layer (2), a light emitting layer (3), a negative electrode layer ( 4) are preferably laminated in this order. The resonator may be provided on the positive electrode layer (3) (between the positive electrode layer (2) and the light emitting layer (3)). Thereby, the light generated in the light emitting layer (3) is amplified and reflected in the diffraction grating waveguide in the resonator, and is efficiently extracted as laser light.

  As an example of the resonator structure used in the present invention, it is preferable to use a distributed feedback resonator such as DFB (Distributed Feedback) or DBR (Distributed Bragg Reflector). The diffraction grating for obtaining these resonators can be manufactured by a conventionally known lithography technique.

2 to 4, the laminate composed of the positive electrode layer (2) or the like is placed on the substrate (1) with the positive electrode layer (2) side facing the substrate (1) (negative electrode). The layer (4) side is preferably formed (toward the opposite side of the substrate (1)), and as the material constituting the substrate (1), those described in the embodiment of FIG. 1 are preferably used.

  The present invention will be described in detail by the following examples, but the present invention is not limited thereto.

[Example 1]
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm is cleaned with boiling alcohol, and the surface is further surface-treated with oxygen plasma (the plasma treatment conditions are: output: 500 W, reflected wave rate: 1.2% or less) Oxygen gas flow rate: 70 cc / min., Treatment time: 30 minutes). An organic positive photoresist was applied onto this substrate, and a diffraction grating (resonator) with a pitch of 500 nm was produced by lithography. After vapor-depositing 250 nm of N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine (TPD) as a hole transport layer thereon. As a polymer material represented by the general formula used in the present invention, a 1.5 wt% dichloromethane solution of the polymer material represented by the following formula (1) was prepared and filtered through a membrane filter having a pore size of 0.1 μm. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, after depositing 250 nm of 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole as an electron transport layer, An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, it was confirmed that laser light was emitted.

[Synthesis of polymer material of general formula (1)]
The polymer used in the example used in Example 1 was synthesized as follows.

In a 200 ml four-necked flask, 1.106 g (2.648 mmol) of the above dialdehyde and 1.681 g (2.648 mmol) of diphosphonate were placed, and the atmosphere was replaced with nitrogen. 80 ml of tetrahydrofuran and 14.1 mg (0.132 mmol) of benzaldehyde Was added. To this solution, 8.00 ml (8.00 mmol) of 1.0 mol dm ^-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then 60.5 mg (0.265 mmol) of diethyl benzylphosphonate was added. The mixture was further stirred for 1 hour. About 1 ml of acetic acid was added to complete the reaction, and the reaction solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 1.682 g of the above polymer. Yield 85%.
Elemental analysis value (calculated value); C: 90.68 (90.40%), H: 7.48% (7.72%), N: 1.91% (1.88%).
The glass transition temperature determined from differential scanning calorimetry was 194.6 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 17300, and the weight average molecular weight was 56000.

[Example 2]
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 250 nm of TPD as a hole transport layer on this substrate, the polymer material represented by the general formula used in the present invention is represented by the following formula (2). A 1.5 wt% dichloromethane solution of the polymer material was prepared and filtered through a membrane filter having a pore size of 0.1 μm. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, after depositing 250 nm of 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole as an electron transport layer, An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, it was confirmed that laser light was emitted from the edge of the light emitting layer.

[Synthesis of polymer material of general formula (2)]
The polymer used in Example 2 was synthesized as follows.

In a 200 ml four-necked flask, 0.837 g (2.655 mmol) of the above dialdehyde and 1.585 g (2.655 mmol) of diphosphonate were placed, and the atmosphere was replaced with nitrogen, 80 ml of tetrahydrofuran, and 14.1 mg (0.132 mmol) of benzaldehyde. Was added. To this solution, 8.00 ml (8.00 mmol) of 1.0 mol dm ^-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then 60.5 mg (0.265 mmol) of diethyl benzylphosphonate was added. The mixture was further stirred for 1 hour. About 1 ml of acetic acid was added to complete the reaction, and the reaction solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 1.386 g of the above polymer. Yield 81%.
Elemental analysis value (calculated value); C: 90.11 (89.81%), H: 7.92% (8.01%), N: 2.01% (2.18%).
The glass transition temperature determined from differential scanning calorimetry was 182.9 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 14400, and the weight average molecular weight was 42600.

Example 3
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. 250 nm of N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine (TPD) was deposited on this substrate as a hole transport layer. Thereafter, a 1.5 wt% dichloromethane solution of the polymer material represented by the following formula (3) was prepared and filtered through a membrane filter having a pore size of 0.1 μm. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, after depositing 250 nm of 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole as an electron transport layer, an MgAg alloy as a cathode Was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, it was confirmed that laser light was emitted from the edge of the light emitting layer.

[Synthesis of polymer material of general formula (3)]
The polymer used in Example 3 was synthesized as follows.

In a 200 ml four-necked flask, 0.977 g (2.534 mmol) of the above dialdehyde and 1.609 g (2.534 mmol) of diphosphonate were placed, and the atmosphere was replaced with nitrogen to give 80 ml of tetrahydrofuran and 13.4 mg (0.127 mmol) of benzaldehyde. Was added. To this solution, 8.00 ml (8.00 mmol) of a 1.0 mol dm ^-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then 57.7 mg (0.253 mmol) of diethyl benzylphosphonate was added. The mixture was further stirred for 1 hour. About 1 ml of acetic acid was added to complete the reaction, and the reaction solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 1.580 g of the polymer. Yield 88%.
Elemental analysis value (calculated value); C: 89.70 (89.40%), H: 8.44% (8.63%), N: 2.01% (1.97%).
The glass transition temperature determined from differential scanning calorimetry was 142.4 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 11600, and the weight average molecular weight was 31900.

Example 4
A glass substrate provided with an ITO film having a thickness of 150 nm was washed with boiling alcohol, and the surface was surface-treated with oxygen plasma. After depositing 250 nm of TPD as a hole transport layer on this substrate, the polymer material represented by the above formula (1) was mixed with 5 wt% Alq ₃ (tris (8-quinolinol) aluminum) and 5 wt% TPD. The prepared 1.5 wt% dichloromethane solution was filtered through a membrane filter having a pore size of 0.1 μm. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, Alq ₃ was deposited as an electron transport layer by 250 nm, and then an MgAg alloy was formed as a cathode at 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, it was confirmed that laser light was emitted from the edge of the light emitting layer.

Example 5
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 100 nm of TPD as a hole transport layer on this substrate, a 1.5 wt% dichloromethane solution of a polymer material represented by the above formula (1) was prepared. It filtered with the 0.1 micrometer membrane filter. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, after depositing 250 nm of 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole as an electron transport layer, An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, it was confirmed that laser light was emitted from the edge of the light emitting layer.

Example 6
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 250 nm of TPD as a hole transport layer on this substrate, a 1.5 wt% dichloromethane solution of the polymer material represented by the above formula (1) was prepared. It filtered with the 0.1 micrometer membrane filter. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficient drying, 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole was deposited as an electron transport layer to a thickness of 100 nm, and then the cathode layer was formed. An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, it was confirmed that laser light was emitted from the edge of the light emitting layer.

Example 7
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 1800 nm of TPD as a hole transport layer on this substrate, a 1.5 wt% dichloromethane solution of the polymer material represented by the above formula (2) was prepared. It filtered with the 0.1 micrometer membrane filter. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, after depositing 250 nm of 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole as an electron transport layer, An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, it was confirmed that laser light was emitted from the edge of the light emitting layer.

Example 8
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 250 nm of TPD as a hole transport layer on this substrate, a 1.5 wt% dichloromethane solution of the polymer material represented by the above formula (2) was prepared. It filtered with the 0.1 micrometer membrane filter. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficient drying, 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole was deposited as an electron transport layer at 1800 nm, and then the negative electrode layer was used. An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, it was confirmed that laser light was emitted from the edge of the light emitting layer.

[Comparative Example 1]
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 50 nm of TPD as a hole transport layer on this substrate, a 1.5 wt% dichloromethane solution of the polymer material represented by the above formula (1) was prepared. It filtered with the 0.1 micrometer membrane filter. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole was deposited as an electron transport layer to a thickness of 500 nm, and then the negative electrode layer was formed. An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, no emission of laser light was confirmed from the edge of the light emitting layer.

[Comparative Example 2]
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 500 nm of TPD as a hole transport layer on this substrate, a 1.5 wt% dichloromethane solution of the polymer material represented by the above formula (1) was prepared. It filtered with the 0.1 micrometer membrane filter. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole was deposited as an electron transport layer by 50 nm, An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, no emission of laser light was confirmed from the edge of the light emitting layer.

[Comparative Example 3]
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 2500 nm of TPD as a hole transport layer on this substrate, a 1.5 wt% dichloromethane solution of the polymer material represented by the above formula (3) was prepared. It filtered with the 0.1 micrometer membrane filter. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, after depositing 250 nm of 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole as an electron transport layer, An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, no emission of laser light was confirmed from the edge of the light emitting layer.

[Comparative Example 4]
A glass substrate provided with an ITO film (positive electrode layer) having a thickness of 150 nm was washed with boiling alcohol, and the surface was further treated with oxygen plasma. After depositing 10 nm of Au as a reflective layer and 500 nm of TPD as a hole transport layer on this substrate, a 1.5 wt% dichloromethane solution of the polymer material represented by the above formula (3) was prepared. It filtered with the 0.1 micrometer membrane filter. Using this solution, a light emitting layer was formed on the TPD film by spin coating to a thickness of 100 nm. After sufficiently drying, 2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole was deposited as an electron transport layer at 2500 nm, and then the cathode layer was formed. An MgAg alloy was formed to 200 nm. When a voltage of 30 V was applied to the organic semiconductor laser produced in this way, no emission of laser light was confirmed from the edge of the light emitting layer.

It is sectional drawing for showing an example of the organic-semiconductor laser of this invention. It is sectional drawing for showing another example of the organic-semiconductor laser of this invention. It is sectional drawing for showing another example of the organic-semiconductor laser of this invention. It is sectional drawing for showing another example of the organic-semiconductor laser of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Positive electrode layer 3 Light emitting layer 4 Negative electrode layer 5 Hole transport layer 6 Electron transport layer 7 Reflective layer 8 Resonator

Claims (15)

In an organic semiconductor laser in which at least a positive electrode layer, a light emitting layer, and a negative electrode layer are laminated in this order, the light emitting layer contains at least a polymer material having a repeating unit represented by the following general formula (I) An organic semiconductor laser.

(Wherein Ar ¹ and Ar ² are each independently a divalent group of a substituted or unsubstituted aromatic hydrocarbon or a substituted or unsubstituted heteroaromatic ring compound, and Ar ³ is a substituted or unsubstituted aromatic group. R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, or a monovalent group of a substituted or unsubstituted heteroaromatic compound. It is a group selected from the group consisting of an alkoxy group and a substituted or unsubstituted alkylthio group, and x and y each independently represents an integer of 1 or more and 3 or less.
When x or y is an integer of 2 or more, x R ^{3 s} may be different from each other, and y R ^{4 s} may be different from each other. ) In an organic semiconductor laser in which at least a positive electrode layer, a light emitting layer, and a negative electrode layer are laminated in this order, the light emitting layer includes at least a polymer material having a repeating unit represented by the following general formula (II) An organic semiconductor laser.

Wherein R ¹ to R ¹¹ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted alkylthio group. X and y each independently represents an integer of 1 to 3, u and v each independently represent an integer of 1 to 4, and w represents an integer of 1 to 5.
When u, v, w, x, and y are integers of 2 or more, u R ⁹ , v R ¹⁰ , w R ¹¹ , x R ³ , and y R ⁴ are different from each other. It may be. ) In an organic semiconductor laser in which at least a positive electrode layer, a light emitting layer, and a negative electrode layer are laminated in this order, the light emitting layer includes at least a polymer material having a repeating unit represented by the following general formula (III) An organic semiconductor laser.

Wherein R ¹ to R ¹⁰ and R ¹² to R ¹⁵ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted alkylthio group. Represents a group selected from the group consisting of: s, x and y each independently represents an integer of 1 to 3, and t, u and v each independently represents an integer of 1 to 4.
When s, t, u, v, x, and y are integers of 2 or more, s R ¹² , t R ¹³ , u R ⁹ , v R ¹⁰ , x R ³ , The y R ^{4 s} may be different from each other. )   The repeating unit is a substituted or unsubstituted linear or branched alkyl group containing 1 to 25 carbon atoms, a substituted or unsubstituted linear group or branched chain containing 1 to 25 carbon atoms. It has a chain alkoxy group and / or a linear or branched alkylthio group containing 1 to 25 carbon atoms, which is substituted or unsubstituted, on the aromatic ring or the saturated hydrocarbon ring. The organic semiconductor laser according to claim 1.   The hole transporting layer is provided between the positive electrode layer and the light emitting layer, and the electron transporting layer is provided between the light emitting layer and the negative electrode layer. An organic semiconductor laser according to claim 1.   6. The organic semiconductor laser according to claim 5, wherein the hole transport layer has a thickness of 100 to 2000 nm.   6. The organic semiconductor laser according to claim 5, wherein the electron transport layer has a thickness of 100 to 2000 nm.   6. The organic semiconductor laser according to claim 1, wherein a reflective layer is provided between the positive electrode layer and the light emitting layer.   9. The organic semiconductor laser according to claim 8, wherein a reflective layer is provided between the light emitting layer and the negative electrode layer.   8. The organic semiconductor laser according to claim 1, wherein a resonator is provided on one surface of the positive electrode layer.   11. The organic semiconductor laser according to claim 1, wherein the organic semiconductor laser is provided on the substrate with the negative electrode layer side facing away from the substrate.   12. The organic semiconductor laser according to claim 1, wherein the light emitting layer contains a hole transport material.   12. The organic semiconductor laser according to claim 1, wherein the light emitting layer contains an electron transport material.   12. The organic semiconductor laser according to claim 1, wherein the light emitting layer contains a hole transport material and an electron transport material. 15. The organic semiconductor laser according to claim 1, wherein the light emitting layer is formed by a wet method.

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