CN108808448A - A kind of organic laser thin-film device and preparation method thereof - Google Patents

A kind of organic laser thin-film device and preparation method thereof Download PDF

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Publication number
CN108808448A
CN108808448A CN201810602042.0A CN201810602042A CN108808448A CN 108808448 A CN108808448 A CN 108808448A CN 201810602042 A CN201810602042 A CN 201810602042A CN 108808448 A CN108808448 A CN 108808448A
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China
Prior art keywords
film
organic laser
gain media
substrate
laser thin
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CN201810602042.0A
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Chinese (zh)
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赖文勇
陆婷婷
黄维
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南京邮电大学
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Priority to CN201810602042.0A priority Critical patent/CN108808448A/en
Publication of CN108808448A publication Critical patent/CN108808448A/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01SDEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00Semiconductor lasers
    • H01S5/10Construction or shape of the optical resonator, e.g. extended or external cavity, coupled cavities, bent-guide, varying width, thickness or composition of the active region
    • H01S5/12Construction or shape of the optical resonator, e.g. extended or external cavity, coupled cavities, bent-guide, varying width, thickness or composition of the active region the resonator having a periodic structure, e.g. in distributed feedback [DFB] lasers
    • H01S5/125Distributed Bragg reflector [DBR] lasers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01SDEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00Semiconductor lasers
    • H01S5/30Structure or shape of the active region; Materials used for the active region
    • H01S5/36Structure or shape of the active region; Materials used for the active region comprising organic materials

Abstract

The invention discloses a kind of organic laser thin-film devices and preparation method thereof, belong to laser technology field.The thin-film device is based on monodispersed multi-arm structure three, and simultaneously simultaneously indene derivative is deposited on substrate to form organic laser film device as gain media, and by certain way for indene derivative or diphenylamines end group modification three.In wider excitation wavelength range, effective light amplification and excellent photostability and thermal stability may be implemented.Obtained organic laser thin-film device not only realizes excellent gain of light performance, but also can improve the photoelectric properties of organic electroluminescent LED.Method of the invention is of low cost, it is simple and fast to prepare, and can be applied to realize high-performance organic laser apparatus.

Description

A kind of organic laser thin-film device and preparation method thereof
Technical field
The invention belongs to laser technology fields, and in particular to a kind of organic laser thin-film device and preparation method thereof.
Background technology
Over the last couple of decades, excellent with convenient, easily fabricated, transmitting polychrome etc. is gently taken due to discharge-pumped laser Point makes people have been devoted to the research of electric pump organic semiconductor laser (OSL).However pass through development for many years, due to Organic emitters part is difficult to realize high carrier mobility, high-luminous-efficiency and low pumping threshold simultaneously, therefore realize electric pump Organic laser is still a prodigious challenge.Main cause or devices difficult high electric property and high optical property it Between realize tradeoff, and these be realize the most important condition of electric pump organic laser.
In order to solve these problems, first, changing device architecture promotes electric property, such as increase polyvinyl carbazole (PVK) Hole transmission layer, but this can increase the complexity of making, and can there is a phenomenon where mutually melt in spin coating plural layers.Separately One strategy is by end group modification promotion device performance, such as carbazole, diphenylamines, triphenylamine etc., these groups are conducive to adjust The energy level of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) is to promote the transmission and injection of carrier Ability.Wherein, diphenylamino group be widely used to organic hair due to having very strong electron-withdrawing energy and excellent luminous efficiency In optical diode (OLED).However extensive research is not yet received in its influence to optical property.
Invention content
Goal of the invention:In order to overcome the deficiencies in the prior art, the present invention to provide a kind of organic laser thin-film device And preparation method thereof, in wider excitation wavelength range, may be implemented effective light amplification and excellent photostability and Thermal stability.
Technical solution:To achieve the above object, the technical solution adopted by the present invention is:
The device is made of following functional layer:Substrate, gain media.The rigid substrate or flexible substrate It is a kind of;The gain media is organic-based gain media.The gain media is the starlike macromolecular optical gain medium of monodisperse Material, has the characteristics that be easy to that purification, chemical constitution is clear, thermal stability is excellent.The gain media introduces electron End moieties are modified.
Further, the rigid substrate is sapphire, silicon chip, quartz, metal coating, ITO (partly lead by indium tin oxide Body) one kind in film, distributed Feedback Bragg grating (DFB) or Distributed Bragg Reflection chamber (DBR).
Specifically, the starlike macromolecular optical gain medium material of the monodisperse, nuclear structure be selected from benzene, triazine, pyrroles, One kind in pyridine, pyrene, three and indenes, three and carbazole, spiro fluorene;Its arm configuration is selected from low polystyrene, Oligopoly thiophene, oligocene With one kind in oligomerization fluorenes.
Further, the gain media, which introduces electron end moieties, improves the electric property of device, simultaneously selected from three One kind in carbazole, diphenylamines or triphenylamine.
Further, the starlike macromolecular optical gain medium material selection of monodisperse in the gain media is with three and indenes For nuclear structure, using oligomerization fluorenes as six arm configuration of branch arm monodisperse;Or using diphenylamines as end group modification macromolecular optical gain medium Material;With the general formula structure being shown below:
Wherein R is C1-C20Linear alkyl chain or branched alkyl chain in one kind;N is the natural number between 1~10.
In the above-mentioned technical solutions, the thickness as preferred gain media is in 80~200nm.
Advantageous effect:A kind of organic laser thin-film device provided by the invention and preparation method thereof, compared with prior art, It has the advantage that:The organic laser thin-film device of the present invention, it is simple in structure, easily designed, simple process, of low cost.? In wider excitation wavelength range, the thin-film device of gained can realize effective light amplification and excellent photostability and heat Stability.Excellent gain of light performance is not only realized, but also the photoelectric properties of organic electroluminescent LED can be improved.This The method of invention is of low cost, it is simple and fast to prepare, and can be applied to realize high-performance organic laser apparatus.
Description of the drawings
Fig. 1 is the structure chart of the made thin-film device of test;
Fig. 2 is the starlike macromolecular optical gain medium material structure example of monodisperse:(a)TrnD;(b)Trn;
Fig. 3 is the spontaneous radiation enlarged drawing of gain material in quartz substrate;
Fig. 4 is gain coefficient test chart;
Fig. 5 is the laser activity test chart of two series materials.
Specific implementation mode
The organic laser thin-film device of the present invention is based on monodispersed multi-arm structure three and indene derivative is as gain media 1 or diphenylamines end group modification three and indene derivative as gain media 2.And it is deposited on substrate and is formed with by certain way Machine laser film device.In wider excitation wavelength range, effective light amplification and excellent photostability may be implemented And thermal stability.Obtained organic laser thin-film device not only realizes excellent gain of light performance, but also can improve The photoelectric properties of organic electro luminescent diode.Method of the invention is of low cost, it is simple and fast to prepare, and can be applied to realize high property It can organic laser apparatus.
The present invention is further described with reference to the accompanying drawings and examples.
Embodiment
According to following embodiments, the present invention can be better understood from.However, as it will be easily appreciated by one skilled in the art that real It applies specific material proportion, process conditions and its result described in example and is merely to illustrate the present invention, without that should will not limit The present invention described in detail in claims processed.
The present invention provides a kind of organic laser thin-film device, prepares organic laser gain media thin-film device, the device by Substrate (1) and gain media (2) composition;Organic laser gain media is uniformly deposited on substrate, the structure of thin-film device As shown in Figure 1.The gain media (2) by determine molecular structure starlike core and it is multiple have adjust intramolecular interaction Organic conjugate arm composition.The gain media (2) introduces electron end moieties and is modified.
The starlike core has benzene, triazine, pyrroles, pyridine, pyrene, three, and simultaneously indenes, three and carbazole, spiro fluorene etc. are the more of nuclear structure Arm configuration monodisperse macromolecular optical gain medium material.
The rigid substrate includes sapphire, silicon chip, quartz, metal coating, ITO (indium tin oxide semiconductor) film, Distributed Feedback Bragg grating (DFB) or Distributed Bragg Reflection chamber (DBR) etc..
The depositional mode of the laser gain medium (2) is spin coating, coining, spray printing, vacuum evaporation or inkjet printing plating In one kind.
Thin-film device preparation is as follows:
The first step:Substrate cleans, and substrate (1), substrate is selected to use acetone, ethyl alcohol, ultra-pure water to be cleaned by ultrasonic successively 1 time, wash It is put into after complete in baking oven dry.
Second step:Solution is prepared, by selecting solution of the chloroform solvent to gain media (2) compound concentration for 15mg/ml, Clean magneton is added in the solution prepared and is placed on thermal station stirring, heating temperature is 60 DEG C, stir speed (S.S.) 1000rpm, when stirring Between 2h or more.
Third walks:Prepared by device, select the substrate needed, gain media (2) is uniformly spin-coated on substrate using sol evenning machine On, spin coating rotating speed is 2000rpm, spin-coating time 60s, spin coating acceleration are 4000rpm/s, and the film thickness of preparation is 80- 150nm.It is the solvent that removal film surface is extra after spin coating is complete, the device made is placed in thermal station and is annealed 10 points for 50 DEG C Clock.
Embodiment 1
Select suprasil as substrate, selecting high-performance, simultaneously indenes is core using three, using oligomerization fluorenes as six arm of branch arm monodisperse Optical gain medium 1 (Trn, n=1-3) of the starlike macromolecular of structure as device, uses diphenylamines end group modification gain media 2 Starlike macromolecular as gain media 2 (TrnD, n=1-3), it is as shown in Figure 2 that product is made.Sample preparation such as specific embodiment party Shown in formula.By the above-mentioned thin-film device made, optical pumping is carried out using YAG laser.The pumping that Trn series materials use swashs The a length of 355nm of light wave, the pumping laser wavelength that TrnD series materials use are 390nm.Fig. 3 shows based on both gains (ASE) figure is amplified in the spontaneous radiation of dielectric tests, it is found that both thin-film devices can realize effective light amplification.Wherein TrX The ASE threshold values of display are 4.4-16.1 μ J/cm2, the TrXD after introducing diphenylamines, ASE threshold values drop to 2.1-4.3 μ J/cm2, Show that superior gain of light performance is had based on the amine-modified starlike macromolecular of hexichol.
Embodiment 2
Select suprasil as substrate, selecting high-performance, simultaneously indenes is core using three, using oligomerization fluorenes as six arm of branch arm monodisperse Optical gain medium 1 (Trn, n=1-3) of the starlike macromolecular of structure as device, uses diphenylamines end group modification gain media 2 Starlike macromolecular as gain media 2 (TrnD, n=1-3).Sample preparation is as shown in specific implementation mode.Use YAG laser Device carries out optical pumping.The pumping laser wavelength that Trn series materials use is 355nm, the pumping laser that TrnD series materials use Wavelength is 390nm.Fig. 4 is the gain coefficient test chart based on two kinds of material film devices, it can be seen that has been added based on TrnD's Thin-film device has higher gain performance compared to the thin-film device of TrX.
Embodiment 3
It is substrate to select transparent DFB gratings, and DFB gratings are one-dimensional second-order DFB grating, and grating duty ratio is 50%, Etching depth 100nm, period 280nm.Selecting high-performance, simultaneously indenes is core using three, using oligomerization fluorenes as six arm configuration of branch arm monodisperse Optical gain medium 1 (Tr3) of the starlike macromolecular as device, use the big point starlike of diphenylamines end group modification gain media 2 Son is used as gain media 2 (Tr3D).
Sample preparation is embodied:
The first step:DFB gratings clean, and in the environment of glove box, required DFB gratings are firstly placed on spin coating instrument, The speed of spin coating about 4000rps, spin-coating time 60s, spin coating acceleration 4000rpm/s;Liquid-transfering gun draws about 50 μ l- of chloroform solvent 100 μ l are dropped on grating, and start spin coating cleaning.It changes isopropanol after spin coating into and carries out identical operation, it is clear to complete grating It washes.
Second step:Solution is prepared, and uses chloroform for solvent gain material Tr3 and Tr3D, concentration of ordinary dissolution 30mg/ml,
Third walks:Different film thicknesses is formed by different spin coating rotating speeds (3000rpm and 4000rpm).Then will The solution dissolved is spin-coated on the grating of just cleaned DFB.
Fig. 5 is the laser activity test chart of two series materials.Swashed at room temperature by the YAG laser of 390nm Hair.It can be seen that the laser threshold minimum based on Tr3D devices is measured as 0.31kw/cm2, wavelength 465nm;The laser threshold of Tr3 Minimum is measured as 0.86kw/cm2, wavelength 438nm.It can be seen that having using DFB gratings as the organic laser thin-film device of substrate bright Aobvious laser spectrum output.
The above is only a preferred embodiment of the present invention, it should be pointed out that:For the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (9)

1. a kind of organic laser thin-film device, which is characterized in that by substrate (1) and gain media made of uniform deposition thereon (2) it constitutes, wherein the substrate (1) is one kind of rigid substrate or flexible substrate;The gain media (2) is multi-arm The starlike macromolecular optical gain medium material of structure monodisperse, the gain media (2) introduce electron end moieties.
2. a kind of organic laser thin-film device according to claim 1, which is characterized in that the rigid substrate be include indigo plant Jewel, silicon chip, quartz, metal coating, indium tin oxide semiconductor ito film, distributed Feedback Bragg grating or distributed cloth One of which including glug reflection cavity.
3. a kind of organic laser thin-film device according to claim 1, which is characterized in that the multi-arm structure monodisperse Starlike macromolecular optical gain medium material, nuclear structure are selected from benzene, triazine, pyrroles, pyridine, pyrene, three simultaneously indenes, three and carbazole, spiral shell One kind in fluorenes;The one kind of its arm configuration in low polystyrene, Oligopoly thiophene, oligocene and oligomerization fluorenes.
4. a kind of organic laser thin-film device according to claim 3, which is characterized in that the gain media (2) The starlike macromolecular optical gain medium material selection of multi-arm structure monodisperse using three and indenes as nuclear structure, using oligomerization fluorenes as single point of branch arm Six arm configurations are dissipated, general formula structure is:
Wherein R is C1-C20Linear alkyl chain or branched alkyl chain in one kind;N is the natural number between 1~10.
5. a kind of organic laser thin-film device according to claim 1 or 4, which is characterized in that the gain media (2) End moieties selected from three and carbazole, diphenylamines or triphenylamine in one kind.
6. a kind of organic laser thin-film device according to claim 5, which is characterized in that the gain media (2) is Using diphenylamines as end group modification macromolecular optical gain medium material, general formula structure is:
Wherein R is C1-C20Linear alkyl chain or branched alkyl chain in one kind;N is the natural number between 1~10.
7. a kind of organic laser thin-film device according to claim 1 or 4, which is characterized in that the gain media (2) Thickness be 80~200nm.
8. a kind of organic laser thin-film device according to claim 1, which is characterized in that the gain media (2) Depositional mode is one kind in spin coating, coining, spray printing, vacuum evaporation or inkjet printing.
9. a kind of preparation method of organic laser thin-film device according to claim 1 or 8, which is characterized in that specific step It is rapid as follows:
The first step:Substrate cleans, and substrate uses acetone, ethyl alcohol, ultra-pure water to be cleaned by ultrasonic successively, then the drying in baking oven;
Second step:Solution is prepared, and is gain media (2) solution of 15mg/mL by solvent compound concentration of chloroform, thermal station stirring, Heating temperature is 60 DEG C, stir speed (S.S.) 1000rpm, mixing time 2h or more;
Third walks:Prepared by device, on substrate by the uniform spin coating of gain media (2) solution, spin coating rotating speed is 2000rpm, spin coating Time is 60s, spin coating acceleration is 4000rpm/s, is the solvent that removal film surface is extra after spin coating is complete, by what is made Device is placed in thermal station and is annealed 10 minutes for 50 DEG C.
CN201810602042.0A 2018-06-12 2018-06-12 A kind of organic laser thin-film device and preparation method thereof CN108808448A (en)

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Publication number Priority date Publication date Assignee Title
CN109378709A (en) * 2018-12-13 2019-02-22 中国科学院半导体研究所 Flexible VCSEL array device and preparation method thereof

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CN106905102A (en) * 2017-02-28 2017-06-30 南京邮电大学 A kind of fluorenes arylation pyrene derivatives material and preparation method and application
CN107445849A (en) * 2017-06-14 2017-12-08 南京邮电大学 One kind three and indenyl organic semiconductor laser material and preparation method and application

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Application publication date: 20181113