CN104466680B - A kind of organic coordination compound laser and preparation method thereof - Google Patents
A kind of organic coordination compound laser and preparation method thereof Download PDFInfo
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- CN104466680B CN104466680B CN201410839815.9A CN201410839815A CN104466680B CN 104466680 B CN104466680 B CN 104466680B CN 201410839815 A CN201410839815 A CN 201410839815A CN 104466680 B CN104466680 B CN 104466680B
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Abstract
The invention discloses a kind of organic coordination compound laser and preparation method thereof, the organic coordination compound laser includes silica micro-loop core optical microcavity, and silica micro-loop core optical microcavity surface spin coating has one layer 4,5 diaza fluorenes metal Er complex films.By 4,5 diaza fluorenes metal Er complex are made into molar concentration for 0.9 1.1 mmol/L tetrahydrofuran solutions, organic coordination compound solution is directly spin-coated on the silica micro-loop core optical microcavity surface for having prepared by spin-coating method, certain thickness film is formed, organic coordination compound optical microcavity is made.The present invention will be combined together with the very echo wall mode optical micro-cavity of high-quality-factor and organic coordination compound luminescent material and prepare optical micro-cavity laser, have the advantages that miniaturization, integrated chip, threshold value are low, stable.
Description
Technical field
The present invention relates to semiconductor laser material and device arts, specifically a kind of organic coordination compound laser and
Its preparation method.
Background technology
Laser applications extensively, can be applied to many necks such as machining, chemical sensitisation, laser printing, modern fiber optic communication
Domain.Current laser material is generally inorganic semiconductor material, and existing inorganic semiconductor material amount is heavy, price is high and does not have
Flexible the shortcomings of；As organic coordination compound is luminous and electroluminescent discovery, organic semiconductor laser research and development are also subject to wide
General concern, as worldwide important subject.Different from inorganic semiconductor, organic semiconductor has special photo electric
Matter is prepared and processing characteristics with easy, is very potential laser material.
In existing research report, the optical micro-cavity laser on metal erbium is considerably less.Additionally, in existing laser
In device, little device has very high-quality-factor.There is presently no one by echo wall mode optical micro-cavity and 4,5- diazas
The complex of fluorene derivative is combined and prepares optical micro-cavity laser.
The content of the invention
The purpose of the present invention is directed to above-mentioned deficiency of the prior art, there is provided a kind of new diaza fluorenes Er complex light
Learn micro-cavity laser and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
4,5- diaza fluorenes have good coordination ability, are a kind of double-tooth chelate ligands, can be with rare earth ion erbium
Dione compounds react, and form metal complex luminescent material.
A kind of organic coordination compound laser, including silica micro-loop core optical microcavity, the silica micro-loop core optics are micro-
The spin coating of chamber surface has one layer of organic matches film, and the organic matches film thickness is 10-100 nm, organic cooperation
Thing is 4,5- diaza fluorenes metal Er complex.
In further design, 4, the 5- diazas fluorenes metal Er complex is with 2- thiophene trifluoroacetylacetone (TFA)s
Salt is the first part, and with 9- dicyano methylene -4,5- diazas fluorenes is the rare earth Er complex of Ligands, its molecular structure
For：
The preparation method of above-mentioned organic coordination compound laser, comprises the following steps：
Organic coordination compound 4,5- diaza fluorenes metal Er complex is made into molar concentration for 1.0 ± 0.1 mmol/L tetrahydrochysenes
Tetrahydrofuran solution, organic coordination compound solution is directly spin-coated on the silica micro-loop core optical microcavity for having prepared by spin-coating method
Surface, forms certain thickness film, is made organic coordination compound optical microcavity；Or organic coordination compound solution is passed through into spin-coating method
Certain thickness film is made in silicon chip surface, is then prepared with the method for preparing silica micro-loop core optical microcavity again organic
Complex optical microcavity, is finally assembled into organic coordination compound optical laser by organic coordination compound optical microcavity.Optical microcavity sheet
Body is exactly a device, is exactly a laser after power-up input, the method for preparing silica micro-loop core optical microcavity
Specific steps include photoetching, HF etchings, XeF2 etchings, the backflow of CO2 LASER HEATINGs, prepare the side of silica micro-loop core optical microcavity
Method is the common technology of Semiconductor Physics, and practical operation can refer to document D.K.Armani et al., Nature 421,925
（2003）.
In further design, 4, the 5- diazas fluorenes metal Er complex is with 2- thiophene trifluoroacetylacetone (TFA)s
Salt is the first part, and with 9- dicyano methylene -4,5- diazas fluorenes is the rare earth Er complex of Ligands, its preparation method
For：
（1）Volume ratio according to benzene and acetic acid is 20：3 proportions mixed solvent, under argon gas protection, adds acetic acid
The ratio between ammonium, 4,5- diazas fluorenes -9- ketone and malononitrile, amount of material of ammonium acetate, 4,5- diazas fluorenes -9- ketone and malononitrile are
26：10：15, heating reflux reaction is cooled to room temperature, rotary evaporation removal solvent, institute after 20 hours at a temperature of 70 DEG C -90 DEG C
Obtain residue chloroform column chromatography to purify, obtain yellow solid 9- dicyano methylene -4,5- diaza fluorenes；
（2）According to the ratio between the amount of material it is 1 by Er (TTA) 32H2O and 9- dicyano methylenes -4,5- diazas fluorenes：1
Ratio mixed after, after being heated to reflux at a temperature of 70 DEG C -90 DEG C 3 hours cool down, filter out the solid of precipitation, obtain with 2-
Thiophene trifluoroacetylacetone (TFA) salt is the first part, and with 9- dicyano methylene -4,5- diazas fluorenes is the rare earth erbium of Ligands
Complex.
The present invention has beneficial effect following prominent：
To be there is the present invention the very echo wall mode optical micro-cavity of high-quality-factor to be combined with organic coordination compound luminescent material
Optical micro-cavity laser is prepared together, overcomes existing inorganic semiconductor material amount weight, price high and without flexibility etc.
Shortcoming, has used light weight, inexpensive and flexible organic electronic material, low, stable etc. excellent with miniaturization, integrated chip, threshold value
Point.Semiconduction organic coordination compound has the advantage that as laser material：（1）Organic coordination compound luminescent material is relative to rare earth material
Material, it has very big stimulated emission cross section, and electronic structure is four-level system, is more easy to realize that population inversion is formed sharp
Light, therefore high-luminous-efficiency, the laser of low lasing threshold can be prepared；（2）Organic molecule species and structure are various, can be with spirit
It is living to carry out MOLECULE DESIGN and synthesis is assembled, have it is big be excited excitation cross-section and larger gain coefficient, easily realize from ultraviolet
To the stimulated emission of near-infrared region；（3）Excitation state structural relaxation causes sizable Stokes shift；（4）Concentration quenching
It is not serious.
Brief description of the drawings
Fig. 1 is 9- dicyano methylene -4,5- diaza fluorenes proton nmr spectras；
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-loop core optical microcavity preparation method；
Fig. 4 is the microcavity laser spectrum obtained in laser testing embodiment.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
Embodiment one
Step 1：40mL benzene and 6mL acetic acid are carried out to be mixed into mixed solvent, in addition three-necked bottle, under argon gas protection, to
1.00g ammonium acetates (amount of material is 13.0 mmol), the 910mg 4,5- diaza fluorenes -9- ketone (amounts of material are added in three-necked bottle
It is 5.0 mmol) and 500mg malononitrile (amount of material is 7.5 mmol), water knockout drum is installed, it is heated to reflux at a temperature of 80 DEG C
20 hours, room temperature is cooled to, rotary evaporation removal solvent, gained residue is purified with chloroform column chromatography, obtains yellow solid, right
It carries out nuclear magnetic resonance spectroscopy, and gained collection of illustrative plates is shown in Fig. 1, it is known that the yellow solid be 9- dicyano methylene -4,5- diaza fluorenes,
Yield 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 ethanol solutions, then by methanol solution and second
Alcoholic solution is mixed, and is cooled down after being heated to reflux at a temperature of 90 DEG C 3 hours, and solid is separated out, and filtering obtains yellow bulk crystals,
It with 2- thiophene trifluoroacetylacetone (TFA) salt is the first part to be, and with 9- dicyano methylene -4,5- diazas fluorenes is Ligands
Rare earth Er complex（Its molecular structure is shown in Fig. 2）, yield 45%.
Step 3：9- dicyano methylene -4,5- diaza fluorenes metal Er complex is made into 0.9 by spin-coating method
Mmol/L tetrahydrofuran solutions are directly spin-coated on the silica micro-loop core optical microcavity surface for having prepared and form thick 100nm's
Film, is made silica micro-loop core optical microcavity.
Step 4：Using silica micro-loop core optical microcavity assembling manufacturing organic coordination compound laser, with embodiment two.
Embodiment two
Step 1 is with step 2 with embodiment one.
Step 3：9- dicyano methylene -4,5- diaza fluorenes metal Er complex is made into 1.1 mmol/L tetrahydrofurans
Solution, the film that thickness is 10 nm is made by the solution by spin coating method in silicon chip surface, then carry out photoetching, HF etching,
XeF2 etchings, the backflow of CO2 LASER HEATINGs are made silica micro-loop core optical microcavity, and specific steps are as shown in Figure 3.
Step 4：Using silica micro-loop core optical microcavity assembling manufacturing organic coordination compound laser.
Laser testing embodiment
A diameter of 125 μm of single-mode fiber is heated by combustion of hydrogen, a diameter of 1~2 μm is then slowly drawn into
Micro optical fiber, and by loss control within 5%.Then the silica micro-loop core optical microcavity that will be prepared in embodiment one is put
In on three-dimensional piezoelectric console, slowly with micro optical fiber be close to for it by its position of precise control.With tunable laser as pumping
Light.First scan laser finds out the suitable pattern of micro-loop core cavity, then to each pattern distinguish pumping, find out threshold value it is minimum when
Corresponding that pattern, then its power output obtained in the case of different input power is carefully measured, test result is shown in Fig. 4.
Be can be seen that from the test result：Two characteristic emissions of rare earth Er complex can be produced in laser spectrum, 1566 nm peaks are entered
Row pumping, its power output is about 340 nW, and this wants order of magnitude lower or so than the threshold value of traditional erbium oxide, shows that this is matched somebody with somebody
Compound is a kind of excellent optical gain material.
Above is presently preferred embodiments of the present invention, all changes made according to technical solution of the present invention, produced function work
During with scope without departing from technical solution of the present invention, protection scope of the present invention is belonged to.
Claims (4)
1. a kind of organic coordination compound laser, including silica micro-loop core optical microcavity, it is characterised in that the silica micro-loop
The surface spin coating of core optical microcavity has one layer of organic matches film, and the organic coordination compound coordinates for 4,5- diaza fluorenes metals erbium
Thing, 4, the 5- diazas fluorenes metal Er complex is as the first part, with 9- dicyanos with 2- thiophene trifluoroacetylacetone (TFA) salt
Methylene -4,5- diazas fluorenes is the rare earth Er complex of Ligands, and its molecular structure is：
。
2. organic coordination compound laser according to claim 1, it is characterised in that the organic matches film thickness
It is 10-100 nm.
3. in claim 1 organic coordination compound laser preparation method, it is characterised in that comprise the following steps：
Organic coordination compound 4,5- diaza fluorenes metal Er complex is made into molar concentration for 0.9-1.1 mmol/L tetrahydrofurans
Solution, organic coordination compound solution is directly spin-coated on the silica micro-loop core optical microcavity table for having prepared by spin-coating method
Face, forms thin film, is made organic coordination compound optical microcavity；Or organic coordination compound solution is passed through into spin-coating method in silicon chip table
Face is made thin film, and it is micro- then with the method for preparing silica micro-loop core optical microcavity to prepare organic coordination compound optics again
Chamber, is finally assembled into organic coordination compound optical laser by organic coordination compound optical microcavity；Specifically preparation method is：
（1）Volume ratio according to benzene and acetic acid is 20：3 proportions mixed solvent, under argon gas protection, addition ammonium acetate,
The ratio between 4,5- diaza fluorenes -9- ketone and malononitrile, amount of material of ammonium acetate, 4,5- diazas fluorenes -9- ketone and malononitrile are 26：
10：15, heating reflux reaction is cooled to room temperature, rotary evaporation removal solvent, gained after 20 hours at a temperature of 70 DEG C -90 DEG C
Residue is purified with chloroform column chromatography, obtains yellow solid 9- dicyano methylene -4,5- diaza fluorenes；
（2）By Er (TTA)3·2H2O and 9- dicyano methylenes -4,5- diazas fluorenes are 1 according to the ratio between the amount of material：1 ratio
After example is mixed, cooled down after being heated to reflux at a temperature of 70 DEG C -90 DEG C 3 hours, filter out the solid of precipitation, obtained with 2- thiophene
Trifluoroacetylacetone (TFA) salt is the first part, and with 9- dicyano methylene -4,5- diazas fluorenes coordinates for the rare earth erbium of Ligands
Thing.
4. the preparation method of organic coordination compound laser according to claim 3, it is characterised in that described to prepare silica micro-
The specific steps of the method for ring core optical microcavity include photoetching, HF etchings, XeF2Etching, CO2LASER HEATING flows back.
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| CN108808433B (en) * | 2017-04-26 | 2020-04-07 | 中国科学院化学研究所 | Whispering gallery mode photonic device with strut support and preparation method and application thereof |
| CN108039637B (en) * | 2017-12-21 | 2021-10-12 | 河北科技大学 | Method for preparing organic echo wall type (WGM) resonant cavity |
| 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 |
| 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 |
| CN116027609B (en) * | 2023-03-27 | 2023-06-13 | 南京大学 | Microcavity with bread-ring structure and preparation method and application thereof |
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| 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 |
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