CN103396532A - Preparation method of triphenylethylene derivative luminescent film - Google Patents
Preparation method of triphenylethylene derivative luminescent film Download PDFInfo
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- CN103396532A CN103396532A CN2013102799673A CN201310279967A CN103396532A CN 103396532 A CN103396532 A CN 103396532A CN 2013102799673 A CN2013102799673 A CN 2013102799673A CN 201310279967 A CN201310279967 A CN 201310279967A CN 103396532 A CN103396532 A CN 103396532A
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Abstract
The invention discloses a preparation method of a triphenylethylene derivative luminescent film. The preparation method comprises the following steps of: (1), dissolving carbazole triphenylethylene derivative monomer with an aggregation-induced emission effect in an electrolyte solution of an electrolytic tank; (2), starting up the electrolytic tank for carrying out electrolysis, so that the monomer is polymerized into a film, wherein in the electrolysis process, the voltage range of positive potential of a working electrode is 0.8V-1.6V, the range of the negative potential is (-)1.0V-0V; and the signal waveform is sine wave or triangular wave; (3), taking out the film after electrolytic polymerization is completed, cleaning and drying to obtain the luminescent film. The luminescent film which is prepared by the preparation method disclosed by the invention has a smooth surface, surface roughness of smaller than 3nm and can be used for solving a problem that the conventional electro-polymerization film is extremely large in surface roughness; and the obtained film has good thermal stability, the initial decomposition temperature of 376 DEG C and higher luminous efficiency. The preparation method of the triphenylethylene derivative luminescent film disclosed by the invention is simple to operate, not only capable of effectively removing impurity components, but also lower in production cost.
Description
Technical field
The present invention relates to a kind of preparation method of novel material, particularly the electrochemical polymerization of triphenylethylene derivative light-emitting film.
Background technology
Organic Light Emitting Diode (OLED), do not need backlight, and the material range of choice is wide, and is lightweight, can be made into the flexible device, and is widely good in the prospect in the fields such as demonstration, illumination, become the focus of current research exploitation.Luminous organic material is the core material of OLED, is also critical material and the bottleneck of the extensive industrialization of OLED.
As the OLED luminescent material, must under the solid film state, use, but most fluorescent substance increases in concentration, after particularly making film, owing to having formed in molecule or intermolecular excimer reduces even luminescence peak red shift, luminous intensity to disappear, this phenomenon, also referred to as the aggregation inducing cancellation, has greatly affected performance and the luminous efficiency of luminescent material.This loyal seminar of Tang found first and reported that a class has the organic compound of aggregation inducing luminous (Aggregation-induced emission, AIE) effect calendar year 2001, and its mechanism has been carried out to detailed and deep research [5].Gathering induced luminescence material has fundamentally been solved to the problem of the luminous cancellation of luminescent material gathering of always perplexing academia and industrial community, also for the performance that further improves the OLED device, laid the foundation.Henceforth, occurred having the research boom of AIE effect blue fluorescent material, but blue fluorescent material still has many defects, from application, larger distance is arranged.
Electrochemical polymerization refers to that the Applied Electrochemistry method, on negative electrode or the polyreaction of carrying out on anode, is called for short electropolymerization.But the organic molecule Direct precipitation forms polymeric film to electrode surface, and its outstanding feature is simple, economical, and provides new controllable factors (electric current or current potential, and electrode materials) for polyreaction.In recent years, the electrochemical polymerization technology has been successfully used to the synthetic polymkeric substance that specific function is arranged, is applied in the fields such as conducting polymer thin film, modified electrode, electrochromism and organic electroluminescent.At present, in the organic electroluminescent field, the electrochemical polymerization film is usually used in the hole transmission layer of organic electroluminescence device, and the report that is applied to luminescent layer seldom.The electrochemical polymerization technology is compared with vacuum evaporation technology with traditional solution processing, the advantage such as have that material use efficiency is high, technique is simple, Heat stability is good, cost are low, particularly have good application prospect aspect preparation large size patterned electricity electroluminescence device.
Existing electrochemical polymerization method, be difficult to prepare the gratifying light-emitting film of performance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of triphenylethylene derivative light-emitting film.
The technical solution used in the present invention is:
The preparation method of triphenylethylene derivative light-emitting film, comprise the steps:
The carbazole triphenylethylene derivatives monomer that 1) will have an aggregation inducing luminescent effect is dissolved in the electrolyte solution of electrolyzer;
2) start electrolyzer and carry out electrolysis, make monomer polymerization become film, in electrolytic process, the voltage range of the positive potential of working electrode is 0.8V～1.6V, and the scope of negative potential is-1.0V～0V that the waveform of signal is sine wave or choppy sea;
3) after electrolytic polymerization completes, film is taken out, clean, drying obtains light-emitting film.
Electrolyte solution is comprised of electroanalysis solvent and supporting electrolyte, electroanalysis solvent is at least a in acetonitrile, methylene dichloride, supporting electrolyte is: a kind of in tetrabutyl ammonium tetrafluoroborate, perchloric acid 4-butyl amine, lithium perchlorate, its concentration is 0.01 mol/l～1 mol/l.
The concentration of carbazole triphenylethylene derivatives monomer is 10
-2Mol/l-1mol/l, the structural formula of carbazole triphenylethylene derivatives monomer is as follows:
As a further improvement on the present invention, the waveform of signal is choppy sea, and sweep velocity is set as 200mV/s.
As a further improvement on the present invention, electroanalysis solvent is acetonitrile and the methylene dichloride mixing solutions of volume ratio 2:1, and supporting electrolyte is that the tetrafluoride boron of 0.1mol/L closes TBuA.
The invention has the beneficial effects as follows:
The light-emitting film that the inventive method prepares, smooth surface, its surfaceness can, less than 3nm, solve traditional excessive problem of electropolymerization roughness of film; The film that obtains has good thermostability, and initial decomposition temperature is at 376 ℃, and luminous efficiency is higher.
The inventive method is simple to operate, can effectively remove impurity component, and production cost is comparatively cheap.
The accompanying drawing explanation
Fig. 1 is the structural representation of electrolyzer used herein;
Fig. 2 is the infrared spectrogram of compound before and after polymerization;
Fig. 3 is the ultraviolet spectrogram of monomer and light-emitting film;
Fig. 4 is the fluorescence spectrum figure of organic light emitting film;
Fig. 5 is the photo of organic light emitting film;
Fig. 6 is the atomic force microscopy of organic light emitting film;
The electron scanning micrograph of Fig. 7 organic light emitting film.
Embodiment
The electrochemical preparation method of light-emitting film of the present invention completes in electrolyzer, as shown in Figure 1, electrolyzer consists of working electrode, supporting electrode, reference electrode, electrolyte solution etc. the structural representation of electrolyzer.
The working electrode that uses is redox noble electrode, and it can stably be worked in mensuration current potential zone.The electrode materials that uses can be the metal electrodes such as gold, platinum, lead and titanium, can be also non-metal electrode and the translucent optics electrodes of ITO such as graphite, glass carbon.
The supporting electrode Main Function is and working electrode forms a loop, so so long as redox inertia and get final product not with the electrode of solution medium reaction, as platinum, lead, gold, titanium etc., this experiment use titanium electrode is as supporting electrode.
The reference electrode that this experiment is used is " silver-silver chloride electrode ", and it is immersed in Repone K or hydrochloric acid soln and is formed by the argent that is covered with silver chloride layer, and Ag|AgCl|Cl commonly used represents.General employing filamentary silver or silver-plated platinum filament are standby in hydrochloric acid soln Anodic Oxidation legal system.This kind electrode materials can be bought and obtain with the form of commodity.
For further understanding process characteristic of the present invention, below this institute invention utilized electrochemical polymerization to prepare a kind of membrane formation mechanism with triphenylethylene derivative light-emitting film of aggregation inducing luminescent properties to be described below: adopt cyclic voltammetry the working electrode of electrolyzer to be applied to the signal of certain waveform, when working electrode is in positive potential, luminophor deposits on working electrode, form the electrochemical polymerization film, its polymerization mechanism is as follows.
After applying positive potential, carbazole group is oxidized, at 3,6, polyreaction has occurred, and with other carbazole unit's couplings, forms two polycarbazoles, and then forms the film of crosslinking structure.Apply subsequently certain negative potential, the positively charged ion in the electrochemical polymerization film is reduced again.
The aftertreatment of light-emitting film: the light-emitting film that electrochemical polymerization reaction obtains is when taking out electrolyte solution, because the luminophor that does not carry out electrochemical reaction in solution can be attached on organic light emitting film, and affect the luminous efficiency of film, so will clean film.For the solvent that cleans film, can be acetonitrile, toluene, methylene dichloride.Film after cleaning, dry under vacuum condition, temperature is 50～60 ℃, obtains dry film.
In order to understand better technical characterstic of the present invention, the present invention is further illustrated below in conjunction with embodiment.
Embodiment is intended to illustrate better technical scheme of the present invention, can not be considered as the restriction to protection domain of the present invention.
Electrochemical polymerization prepares light-emitting film
The carbazole triphenylethylene derivatives monomer with aggregation inducing luminescent effect
Be dissolved in electrolyte solution, luminophor concentration is 1 mg/ml, and supporting electrolyte is that tetrafluoride boron closes TBuA, and concentration is 0.1 mol/L, and electroanalysis solvent is the mixing solutions of acetonitrile and methylene dichloride, and volume ratio is 2:1; Working electrode is ito glass, and supporting electrode is that (working area is 1 cm to the titanium sheet
2), reference electrode is the Ag/AgCl electrode;
Apply the choppy sea electric potential signal, positive potential is 1.35V, and negative potential is-0.8V.Sweep velocity is 100mV/s, electrolysis, and the scanning number of turns is 40 circles, can be observed by working electrode surface the generation of blue membrane.
Working electrode, from electrolytic solution, taking out, is adopted to acetonitrile and methylene chloride volume than for the mixing solutions of 2:1, the electrochemical polymerization film being cleaned, and the electrochemical polymerization film after cleaning is under vacuum condition, and temperature is 50～60 ℃ of oven dry, obtains dry film.
Fig. 2 is the infrared spectrogram of compound before and after polymerization, and curve a is before polymerization, 721cm
-1And 748cm
-1Wave number is respectively the vibration absorption peak of disubstituted benzenes ring and luminous nucleon disubstituted benzenes ring on carbazole.Curve b is after polymerization, 721cm
-1Absorb the vibration peak red shift to 729 cm
-1, this is because carbazole, at 3,6, polyreaction has occurred, and with other carbazole units, is combined and forms two polycarbazoles, conjugation strengthens the signal red shift that causes; And at 801cm
-1Place has newly formed one and has absorbed vibration peak, and this belongs to the vibration peak of trisubstituted benzene ring on two polycarbazoles newly-generated after the carbazole polymerization.As can be seen here, the luminophor that is connected with the electroactive unit carbazole of electrochemical polymerization is to have carried out the electrochemistry crosslinking polymerization really.
Fig. 3 is the ultraviolet spectrogram of monomer and light-emitting film.Monomer curve a is the charateristic avsorption band of luminous nucleon at the 350nm place, and the 300nm left and right is the absorption peak of carbazyl.After electropolymerization (b), the absorption peak of carbazole is by the 300nm red shift to 303nm, and this is to cause because carbazole unit generation polymerization causes conjugation to strengthen, and the absorption peak of luminous nucleon there is no considerable change, and visible electrochemical polymerization does not affect the structure of luminous nucleon.
Fig. 4 is the fluorescence spectrum figure of organic light emitting film, and as seen from the figure, its emission wavelength is 466nm, is in the visible blue district.
Fig. 5 is the photo of organic light emitting film under ultraviolet lamp, and as can be seen from the figure film is the blue-light-emitting film.
Fig. 6 is the atomic force microscopy of organic light emitting film; The electron scanning micrograph of Fig. 7 organic light emitting film, as can be seen from the figure, organic light emitting film prepared by the inventive method, smooth surface, roughness is less than 3nm.
Claims (6)
1. the preparation method of triphenylethylene derivative light-emitting film, comprise the steps:
The carbazole triphenylethylene derivatives monomer that will have the aggregation inducing luminescent effect is dissolved in the electrolyte solution of electrolyzer;
Start electrolyzer and carry out electrolysis, make monomer polymerization become film, in electrolytic process, the voltage range of the positive potential of working electrode is 0.8V～1.6V, and the scope of negative potential is-1.0V～0V that the waveform of signal is sine wave or choppy sea;
After electrolytic polymerization completes, film is taken out, clean, drying obtains light-emitting film.
2. preparation method according to claim 1, it is characterized in that: electrolyte solution is comprised of electroanalysis solvent and supporting electrolyte, electroanalysis solvent is at least a in acetonitrile, methylene dichloride, supporting electrolyte is: a kind of in tetrabutyl ammonium tetrafluoroborate, perchloric acid 4-butyl amine, lithium perchlorate, its concentration is 0.01 mol/l～1 mol/l.
3. preparation method according to claim 1 and 2, it is characterized in that: the concentration of carbazole triphenylethylene derivatives monomer is 10
-2Mol/l-1mol/l.
4. according to claim 2 or 3 described preparation methods, it is characterized in that: the structural formula of carbazole triphenylethylene derivatives monomer is as follows:
。
5. preparation method according to claim 1 and 2, it is characterized in that: the waveform of signal is choppy sea, and sweep velocity is set as 200mV/s.
6. preparation method according to claim 2, it is characterized in that: electroanalysis solvent is acetonitrile and the methylene dichloride mixing solutions of volume ratio 2:1, supporting electrolyte is that the tetrafluoride boron of 0.1mol/L closes TBuA.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058067A (en) * | 2016-08-19 | 2016-10-26 | 深圳市华星光电技术有限公司 | Organic electroluminescence diode and preparation method of cavity transmission layer thereof |
| CN106340533A (en) * | 2016-11-29 | 2017-01-18 | 深圳市华星光电技术有限公司 | Oled display panel and manufacturing method thereof |
| CN108794382A (en) * | 2018-06-29 | 2018-11-13 | 华南师范大学 | A kind of multi-functional aggregation-induced emission enhancement compound and the preparation method and application thereof |
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| CN1822410A (en) * | 2006-01-24 | 2006-08-23 | 吉林大学 | Preparing organic light emitting film by electrochemical deposition and use in electroluminescence device |
| US20080220407A1 (en) * | 2005-04-22 | 2008-09-11 | The Hong Kong University Of Science And Technology | Fluorescent water-soluble conjugated polyene compounds that exhibit aggregation induced emission and methods of making and using same |
| CN101343539A (en) * | 2008-08-29 | 2009-01-14 | 中山大学 | Synthesis of novel organic luminescent material containing carbazolyl toluylene derivant structure and application thereof |
| CN101358367A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Electrochemical deposition preparation method of high efficient light-emitting film |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080220407A1 (en) * | 2005-04-22 | 2008-09-11 | The Hong Kong University Of Science And Technology | Fluorescent water-soluble conjugated polyene compounds that exhibit aggregation induced emission and methods of making and using same |
| CN1822410A (en) * | 2006-01-24 | 2006-08-23 | 吉林大学 | Preparing organic light emitting film by electrochemical deposition and use in electroluminescence device |
| CN101343539A (en) * | 2008-08-29 | 2009-01-14 | 中山大学 | Synthesis of novel organic luminescent material containing carbazolyl toluylene derivant structure and application thereof |
| CN101358367A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Electrochemical deposition preparation method of high efficient light-emitting film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058067A (en) * | 2016-08-19 | 2016-10-26 | 深圳市华星光电技术有限公司 | Organic electroluminescence diode and preparation method of cavity transmission layer thereof |
| US10319910B2 (en) | 2016-08-19 | 2019-06-11 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Organic electroluminescent diode and method for manufacturing hole transporting layer thereof |
| CN106340533A (en) * | 2016-11-29 | 2017-01-18 | 深圳市华星光电技术有限公司 | Oled display panel and manufacturing method thereof |
| CN106340533B (en) * | 2016-11-29 | 2019-04-30 | 深圳市华星光电技术有限公司 | OLED display panel and preparation method thereof |
| CN108794382A (en) * | 2018-06-29 | 2018-11-13 | 华南师范大学 | A kind of multi-functional aggregation-induced emission enhancement compound and the preparation method and application thereof |
| CN108794382B (en) * | 2018-06-29 | 2021-08-03 | 华南师范大学 | Multifunctional aggregation-induced emission enhancement compound and preparation method and application thereof |
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