CN104466680A - Organic complex laser and manufacturing method thereof - Google Patents
Organic complex laser and manufacturing method thereof Download PDFInfo
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- CN104466680A CN104466680A CN201410839815.9A CN201410839815A CN104466680A CN 104466680 A CN104466680 A CN 104466680A CN 201410839815 A CN201410839815 A CN 201410839815A CN 104466680 A CN104466680 A CN 104466680A
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Abstract
The invention discloses an organic complex laser and a manufacturing method of the organic complex laser. The organic complex laser comprises a silicon oxide micro-ring-core optical micro-cavity, the surface of the silicon oxide micro-ring-core optical micro-cavity is coated with a layer of 4,5-diazafluorene metal erbium complex thin film in a spinning mode. The 4,5-diazafluorene metal erbium complex thin film is prepared into a tetrahydrofuran solution with the molar concentration of 0.9-1.1 mmol/L, the surface of the prepared silicon oxide micro-ring-core optical micro-cavity is directly coated with the organic complex solution in a spinning mode through a spin-coating method, the thin film with a certain thickness is formed, and the organic complex optical micro-cavity is manufactured. According to the organic complex laser and the manufacturing method of the organic complex laser, the echo wall type micro-cavity with the high quality factor and organic complex light-emitting materials are combined to prepare the optical micro-cavity laser together. The organic complex laser and the manufacturing method of the organic complex laser have the advantages that miniaturization is achieved, chip integration is achieved, the threshold value is low, and stability is achieved.
Description
Technical field
The present invention relates to semiconductor laser material and device arts, is a kind of organic coordination compound laser and preparation method thereof specifically.
Background technology
Laser applications is extensive, can be applicable to the numerous areas such as machining, chemical sensitisation, laser printing, modern optical fiber communication.Current laser material is generally inorganic semiconductor material, and existing inorganic semiconductor material amount is heavy, price is high and do not have the shortcomings such as flexible; Along with organic coordination compound is luminous and electroluminescent discovery, organic semiconductor laser research and development are also subject to extensive concern, become worldwide important subject.Different from inorganic semiconductor, organic semiconductor has special photoelectric property and easy preparation and fabrication characteristic, is very potential laser material.
In existing research report, the optical micro-cavity laser about metal erbium is considerably less.In addition, in existing laser, little device has very high-quality-factor.Also do not have at present an example to be combined by the complex of echo wall mode optical micro-cavity and 4,5-diaza fluorene derivative and prepare optical micro-cavity laser.
Summary of the invention
The object of the invention is for above-mentioned deficiency of the prior art, a kind of novel diaza fluorenes Er complex optical micro-cavity laser and preparation method thereof is provided.
The object of the invention is to be achieved through the following technical solutions:
4,5-diaza fluorenes has good coordination ability, is a kind of double-tooth chelate ligand, can react with the dione compounds of rare earth ion erbium, forms metal complex luminescent material.
A kind of organic coordination compound laser, comprise the micro-ring core optical microcavity of silica, the micro-ring core optical microcavity surface spin coating of described silica has one deck organic matches film, and described organic matches film thickness is 10-100 nm, described organic coordination compound is 4,5-diaza fluorenes metal Er complex.
In further design, described 4,5-diaza fluorenes metal Er complex are for being the first part with 2-thiophene trifluoroacetylacetone (TFA) salt, and take 9-dicyano methylene-4,5-diaza fluorenes as the rare earth erbium complex of Ligands, its molecular structure is:
The preparation method of above-mentioned organic coordination compound laser, comprises the following steps:
By organic coordination compound 4, it is 1.0 ± 0.1 mmol/L tetrahydrofuran solutions that 5-diaza fluorenes metal Er complex is made into molar concentration, by spin-coating method, organic coordination compound solution is directly spin-coated on the micro-ring core optical microcavity surface of the silica prepared, form certain thickness film, make organic coordination compound optical microcavity; Or organic coordination compound solution is made certain thickness film by spin-coating method at silicon chip surface, and then prepare organic coordination compound optical microcavity by the method preparing the micro-ring core optical microcavity of silica, finally organic coordination compound optical microcavity is assembled into organic coordination compound optical laser.Optical microcavity is individual device inherently, be exactly a laser after powering up input, the described concrete steps preparing the method for the micro-ring core optical microcavity of silica comprise photoetching, HF etching, XeF2 etching, the backflow of CO2 LASER HEATING, the method preparing the micro-ring core optical microcavity of silica is the common technology of Semiconductor Physics, practical operation can refer to document D.K.Armani et al., Nature 421,925(2003).
In further design, described 4,5-diaza fluorenes metal Er complex are for being the first part with 2-thiophene trifluoroacetylacetone (TFA) salt, and take 9-dicyano methylene-4,5-diaza fluorenes as the rare earth erbium complex of Ligands, its preparation method is:
(1) according to the volume ratio of benzene and acetic acid be the proportions mixed solvent of 20:3, under argon shield, add ammonium acetate, 4,5-diaza fluorenes-9-ketone and malononitrile, ammonium acetate, 4, the ratio of the amount of substance of 5-diaza fluorenes-9-ketone and malononitrile is 26:10:15, and at 70 DEG C of-90 DEG C of temperature, heating reflux reaction is after 20 hours, is cooled to room temperature, rotary evaporation removes solvent, gained residue chloroform column chromatography is purified, and obtains yellow solid 9-dicyano methylene-4,5-diaza fluorenes;
(2) by Er (TTA) 32H2O and 9-dicyano methylene-4, after 5-diaza fluorenes mixes according to the ratio that the ratio of amount of substance is 1:1, add hot reflux at 70 DEG C of-90 DEG C of temperature to cool after 3 hours, filter out the solid of precipitation, obtaining with 2-thiophene trifluoroacetylacetone (TFA) salt is the first part, with the rare earth erbium complex that 9-dicyano methylene-4,5-diaza fluorenes is Ligands.
The present invention has following outstanding beneficial effect:
The echo wall mode optical micro-cavity and organic coordination compound luminescent material with very high-quality-factor combine and prepare optical micro-cavity laser by the present invention, overcome existing inorganic semiconductor material amount weight, price is high and do not have the shortcomings such as flexible, employ light weight, inexpensive and flexible organic electronic material, there is the advantages such as microminiaturization, integrated chip, threshold value be low, stable.Semiconduction organic coordination compound has following advantage as laser material: (1) organic coordination compound luminescent material is relative to rare earth material, it has very large stimulated emission cross section, electronic structure is four level system, more easily realize population inversion and form laser, therefore can prepare the laser of high-luminous-efficiency, low lasing threshold; (2) organic molecule kind and structure various, MOLECULE DESIGN and synthesis assembling can be carried out flexibly, have large excitation cross-section and the larger gain coefficient of being excited, easily realize the stimulated emission from ultraviolet to near-infrared region; (3) excitation state structural relaxation causes sizable Stokes shift; (4) concentration quenching is not serious.
Accompanying drawing explanation
Fig. 1 is 9-dicyano methylene-4,5-diaza fluorenes proton nmr spectra;
Fig. 2 is the molecular structure of 9-dicyano methylene-4,5-diaza fluorenes metal Er complex;
Fig. 3 is the preparation flow of silica micro-ring core optical microcavity preparation method;
Fig. 4 is the microcavity laser spectrum obtained in laser testing embodiment.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment one
Step 1: 40mL benzene and 6mL acetic acid are carried out being mixed into mixed solvent, add in three-necked bottle, under argon shield, 1.00g ammonium acetate (amount of substance is 13.0 mmol) is added in three-necked bottle, 910mg 4, 5-diaza fluorenes-9-ketone (amount of substance is 5.0 mmol) and 500mg malononitrile (amount of substance is 7.5 mmol), install water knockout drum, hot reflux 20 hours are added at 80 DEG C of temperature, be cooled to room temperature, rotary evaporation removes solvent, gained residue chloroform column chromatography is purified, obtain yellow solid, nuclear magnetic resonance spectroscopy is carried out to it, Fig. 1 is shown in by gained collection of illustrative plates, this yellow solid known is 9-dicyano methylene-4, 5-diaza fluorenes, productive rate 61%.Fusing point: 279-280 ° C.
Step 2: in single port bottle, 0.6 mmol Er (TTA) 32H2O is dissolved in 50 mL methanol solutions, by 0.6 mmol yellow solid 9-dicyano methylene-4, 5-diaza fluorenes is dissolved in 50 mL ethanolic solutions, then methanol solution is mixed with ethanolic solution, add hot reflux at 90 DEG C of temperature to cool after 3 hours, solid is separated out, filter, obtain yellow bulk crystals, namely be the first part with 2-thiophene trifluoroacetylacetone (TFA) salt, with 9-dicyano methylene-4, 5-diaza fluorenes is the rare earth erbium complex (its molecular structure is shown in Fig. 2) of Ligands, productive rate 45%.
Step 3: by spin-coating method by 9-dicyano methylene-4,5-diaza fluorenes metal Er complex is made into 0.9 mmol/L tetrahydrofuran solution and is directly spin-coated on the film that the silica prepared micro-ring core optical microcavity surface forms thick 100nm, makes the micro-ring core optical microcavity of silica.
Step 4: utilize silica micro-ring core optical microcavity assembling manufacturing organic coordination compound laser, with embodiment two.
Embodiment two
Step 1 and step 2 are with embodiment one.
Step 3: by 9-dicyano methylene-4,5-diaza fluorenes metal Er complex is made into 1.1 mmol/L tetrahydrofuran solutions, this solution is made at silicon chip surface the film that thickness is 10 nm by spin coating method, then carry out photoetching, HF etching, XeF2 etching, CO2 LASER HEATING backflow make the micro-ring core optical microcavity of silica, concrete steps are as shown in Figure 3.
Step 4: utilize silica micro-ring core optical microcavity assembling manufacturing organic coordination compound laser.
Laser testing embodiment
By the monomode fiber that combustion of hydrogen heating diameter is 125 μm, be then slowly drawn into the micro optical fiber that diameter is 1 ~ 2 μm, and by loss control within 5%.Then micro-for the silica prepared in embodiment one ring core optical microcavity is put on three-dimensional piezoelectric control desk, accurately controls its position, slowly that itself and micro optical fiber is close.With tunable laser as pump light.The suitable pattern in micro-ring core chamber found out by first scan laser, then to the pumping respectively of each pattern, find out threshold value minimum time corresponding that pattern, more carefully measure its power output obtained in different input power situation, test result is shown in Fig. 4.As can be seen from this test result: the characteristic emission that can produce two rare earth erbium complexs in laser spectrum, pumping is carried out to 1566 nm peaks, its power output is about 340 nW, this number magnitude lower than the threshold value of traditional erbium oxide, shows that this complex is a kind of excellent optical gain material.
Be more than preferred embodiment of the present invention, all changes done according to technical solution of the present invention, when the function produced does not exceed the scope of technical solution of the present invention, all belong to protection scope of the present invention.
Claims (6)
1. an organic coordination compound laser, comprises the micro-ring core optical microcavity of silica, it is characterized in that, the micro-ring core optical microcavity surface spin coating of described silica has one deck organic matches film, and described organic coordination compound is 4,5-diaza fluorenes metal Er complex.
2. organic coordination compound laser according to claim 1, is characterized in that, described organic matches film thickness is 10-100 nm.
3. organic coordination compound laser according to claim 1, it is characterized in that, described 4,5-diaza fluorenes metal Er complex is for being the first part with 2-thiophene trifluoroacetylacetone (TFA) salt, with 9-dicyano methylene-4,5-diaza fluorenes is the rare earth erbium complex of Ligands, and its molecular structure is:
。
4. the preparation method of organic coordination compound laser in claim 1, is characterized in that, comprise the following steps:
By organic coordination compound 4, it is 0.9-1.1 mmol/L tetrahydrofuran solution that 5-diaza fluorenes metal Er complex is made into molar concentration, by spin-coating method, organic coordination compound solution is directly spin-coated on the micro-ring core optical microcavity surface of the silica prepared, form certain thickness film, make organic coordination compound optical microcavity; Or organic coordination compound solution is made certain thickness film by spin-coating method at silicon chip surface, and then prepare organic coordination compound optical microcavity by the method preparing the micro-ring core optical microcavity of silica, finally organic coordination compound optical microcavity is assembled into organic coordination compound optical laser.
5. the preparation method of organic coordination compound laser according to claim 4, it is characterized in that, described 4,5-diaza fluorenes metal Er complex is for being the first part with 2-thiophene trifluoroacetylacetone (TFA) salt, with 9-dicyano methylene-4,5-diaza fluorenes is the rare earth erbium complex of Ligands, and its preparation method is:
(1) according to the volume ratio of benzene and acetic acid be the proportions mixed solvent of 20:3, under argon shield, add ammonium acetate, 4,5-diaza fluorenes-9-ketone and malononitrile, ammonium acetate, 4, the ratio of the amount of substance of 5-diaza fluorenes-9-ketone and malononitrile is 26:10:15, and at 70 DEG C of-90 DEG C of temperature, heating reflux reaction is after 20 hours, is cooled to room temperature, rotary evaporation removes solvent, gained residue chloroform column chromatography is purified, and obtains yellow solid 9-dicyano methylene-4,5-diaza fluorenes;
(2) by Er (TTA) 32H2O and 9-dicyano methylene-4, after 5-diaza fluorenes mixes according to the ratio that the ratio of amount of substance is 1:1, add hot reflux at 70 DEG C of-90 DEG C of temperature to cool after 3 hours, filter out the solid of precipitation, obtaining with 2-thiophene trifluoroacetylacetone (TFA) salt is the first part, with the rare earth erbium complex that 9-dicyano methylene-4,5-diaza fluorenes is Ligands.
6. the preparation method of organic coordination compound laser according to claim 4, is characterized in that, the described concrete steps preparing the method for the micro-ring core optical microcavity of silica comprise photoetching, HF etching, XeF2 etching, the backflow of CO2 LASER HEATING.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108039637A (en) * | 2017-12-21 | 2018-05-15 | 河北科技大学 | A kind of organic echo wall type（WGM）The preparation method of resonator |
| CN108808433A (en) * | 2017-04-26 | 2018-11-13 | 中国科学院化学研究所 | A kind of Whispering-gallery-mode photonic device and its preparation method and application with pillar support |
| CN110975924A (en) * | 2019-11-19 | 2020-04-10 | 上海应用技术大学 | Catalyst for preparing cyclohexanone by catalytic oxidation of cyclohexene, preparation method and application thereof |
| CN111740308A (en) * | 2020-06-04 | 2020-10-02 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of on-chip micro-ring white light laser based on rare earth doped nanocrystalline |
| CN113526458A (en) * | 2020-04-16 | 2021-10-22 | 清华大学 | Method for preparing micro-core ring cavity by wet silicon etching |
| CN116027609A (en) * | 2023-03-27 | 2023-04-28 | 南京大学 | Microcavity with bread-ring structure and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10231476A (en) * | 1997-02-19 | 1998-09-02 | Oki Electric Ind Co Ltd | Organic el element |
| CN1350049A (en) * | 2000-10-19 | 2002-05-22 | 中国科学院长春光学精密机械与物理研究所 | Organic RE light emitting material with narrow emission band in infrared band |
| CN101257185A (en) * | 2008-02-28 | 2008-09-03 | 复旦大学 | Method for manufacturing organic and inorganic composite echo wall mode optical micro-cavity laser |
| CN103694265A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Novel light-emitting beta-diketone rare earth complex crystal form material |
-
2014
- 2014-12-30 CN CN201410839815.9A patent/CN104466680B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10231476A (en) * | 1997-02-19 | 1998-09-02 | Oki Electric Ind Co Ltd | Organic el element |
| CN1350049A (en) * | 2000-10-19 | 2002-05-22 | 中国科学院长春光学精密机械与物理研究所 | Organic RE light emitting material with narrow emission band in infrared band |
| CN101257185A (en) * | 2008-02-28 | 2008-09-03 | 复旦大学 | Method for manufacturing organic and inorganic composite echo wall mode optical micro-cavity laser |
| CN103694265A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Novel light-emitting beta-diketone rare earth complex crystal form material |
Non-Patent Citations (2)
| Title |
|---|
| 杨春和 等: "二氮杂芴化学及其在有机光电器件中的应用", 《液晶与显示》 * |
| 蒋维 等: "三[α-噻吩甲酰三氟丙酮]-9-[烷基亚胺基-4,5-二氮杂芴]合铕（Ⅲ）荧光三元配合物的合成与表征", 《中国稀土学报》 * |
Cited By (8)
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| CN108808433A (en) * | 2017-04-26 | 2018-11-13 | 中国科学院化学研究所 | A kind of Whispering-gallery-mode photonic device and its preparation method and application with pillar support |
| CN108039637A (en) * | 2017-12-21 | 2018-05-15 | 河北科技大学 | A kind of organic echo wall type（WGM）The preparation method of resonator |
| CN110975924A (en) * | 2019-11-19 | 2020-04-10 | 上海应用技术大学 | Catalyst for preparing cyclohexanone by catalytic oxidation of cyclohexene, preparation method and application thereof |
| CN110975924B (en) * | 2019-11-19 | 2021-12-07 | 上海应用技术大学 | Catalyst for preparing cyclohexanone by catalytic oxidation of cyclohexene, preparation method and application thereof |
| CN113526458A (en) * | 2020-04-16 | 2021-10-22 | 清华大学 | Method for preparing micro-core ring cavity by wet silicon etching |
| CN113526458B (en) * | 2020-04-16 | 2024-04-09 | 清华大学 | Method for preparing micro-core annular cavity by wet etching silicon |
| CN111740308A (en) * | 2020-06-04 | 2020-10-02 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of on-chip micro-ring white light laser based on rare earth doped nanocrystalline |
| CN116027609A (en) * | 2023-03-27 | 2023-04-28 | 南京大学 | Microcavity with bread-ring structure and preparation method and application thereof |
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