CN103346229B - A kind of based on Cu2O/TiO2The luminescent device of the brilliant film of core-shell nano - Google Patents
A kind of based on Cu2O/TiO2The luminescent device of the brilliant film of core-shell nano Download PDFInfo
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Abstract
A kind of based on Cu2O/TiO2The luminescent device of nano-crystal film, by ito glass layer, Cu2O/TiO2Core-shell nano polycrystalline thin film layer and aluminium negative electrode are formed by stacking, and its preparation method is spin coating Cu on the ITO of clean dried substrate2O/TiO2The brilliant toluene solution of core-shell nano, then 400 ° of C annealing 1h in argon gas atmosphere, thick quinoline aluminum thin layer and the thick Al electrode of 150nm of 30nm on last vacuum thermal evaporation successively. Advantage of the present invention is: the TiO that the present invention adds2Nano material and Al electrode form Ohmic contact, make the injection of electronics easier; Simultaneously increase again hole injection barrier, effectively prevented that hole from injecting too fast compound at electrode place, increased Cu2The recombination probability of hole and electronics in O, significantly strengthens luminous efficiency and luminous intensity; In addition, by adding the TiO of broad-band gap2Increase Cu2The stability of O.
Description
Technical field
The present invention relates to luminescent device field, be specifically related to a kind of based on Cu2O/TiO2Luminescent device of the brilliant film of core-shell nano and preparation method thereof.
Background technology
The ancient times mankind just start to note natural luminescence phenomenon, august lightning, and glorious aurora, mysterious phosphorescence, because there is light, just has the bright and colourful boundless universe. Marvellous optical phenomena has been carried the too many illusion of the mankind, to the worship of light, is the enormous motivation of human progress to bright pursuit with to the exploration of optics essence. The luminescence phenomenon that causes solid under electric field or the function of current is referred to as electroluminescent (EL), is the electric light conversion phenomena that electric energy is directly changed into luminous energy. Electroluminescent has three kinds of forms by typoiogical classification: powder, film and transistor junction type device; Junction device is all low tension photoluminescence, for example light emitting diode and solid state laser, and typical operating voltage only has several volts, luminous by the electric current injection generation of PN junction, also referred to as current mode device, conventionally uses direct voltage drive. Powder and film are all High-Field devices, form luminous electric field up to 106v/cm, and this class device, also referred to as voltage-type device, drives (can certainly use direct voltage drive) with alternating voltage conventionally.
Cuprous oxide (Cu2O) be a kind of P-type semiconductor, energy gap is only 2.2eV, has special optics, photoelectricity and catalytic performance, is with a wide range of applications in fields such as solar cell, catalyst, sensor, lithium ion battery electrode materials. Compared with macroscopic material, micro/nano material has more excellent physicochemical property, and therefore, the preparation of nano/micron particle at present has become a domestic and international active research field.
Cu2Be positioned at-3.1eV of the conduction band of O, differs larger with the work function (4.3eV) of aluminium, and what form with Al is Schottky contacts, has potential barrier, and therefore electronic injection is more difficult, and Cu2The work function of O valence band and ITO is very approaching, and hole is injected easily, and hole is at Cu2Mobility in O is higher than electronics, and this just causes electronics and hole injection is uneven and then cause luminous efficiency low; And TiO2Conduction band be-4.1eV, more approaching with the work function (4.3eV) of aluminium, and with Al form be Ohmic contact. Therefore TiO2The effect of having played step has reduced the potential barrier of electronic injection, makes the injection of electronics easier; Simultaneously increase again hole injection barrier, effectively prevented that hole from injecting too fast compound at electrode place, increased at Cu2In O, with the recombination probability of electronics, relevant luminous intensity is strengthened.
Summary of the invention
The object of the invention is for Cu2Cu in O luminescent device2O is easily oxidized and lose activity, and light induced electron and hole are easily compound, and have Schottky barrier with Al electrode, cause electron hole to inject unbalanced problem, provide a kind of based on Cu2O/TiO2The luminescent device of the brilliant film of core-shell nano, TiO in this luminescent device2Be N-shaped semiconductor, with gap is wider is 3.0eV, stable performance, and TiO2Approach with the work function of Al, can play step effect, the two combination both can have been improved to Cu2The stability of O, can make again Cu2Electron hole injection balance in O, strengthens luminous intensity.
Technical scheme of the present invention:
A kind of based on Cu2O/TiO2The luminescent device of the brilliant film of core-shell nano, by glassy layer, ITO layer, Cu2O/TiO2Core-shell nano polycrystalline thin film layer, quinoline aluminum (Alq3) layer and metal negative electrode be formed by stacking. Wherein ITO layer thickness is 100-200 nanometer, TiO2/Cu2The thickness of O core-shell nano polycrystalline thin film layer is 100-500 nanometer, and quinoline aluminum layer thickness is 10-40 nanometer, and metal negative electricity very aluminium electrode and thickness is 100-200 nanometer.
A kind of described based on Cu2O/TiO2The preparation method of the luminescent device of the brilliant film of core-shell nano, step is as follows:
1) by the glass substrate that deposits ITO first after after liquid detergent, deionized water, acetone, isopropyl alcohol and ethanol ultrasonic cleaning, in vacuum drying chamber at 80 DEG C dry 30 minutes;
2) Cu of preparation 10mg/ml2O/TiO2The brilliant toluene solution of core-shell nano is as spin coating liquid, Cu2O and TiO2Mol ratio be 1:1-2;
3) dried ITO is cooled to after 18-25 ° of C, be put on sol evenning machine, drips above-mentioned spin coating liquid 5-6 thereon and drip, stop 3-5s, distinguish spin coating 6 seconds and 20 seconds at slow-speed of revolution 700rpm and high rotating speed 2000rpm;
4) by the good Cu of above-mentioned spin coating2O/TiO2The brilliant film of core-shell nano is placed in dry 30min at 70 DEG C of vacuum drying chambers;
5) step 3 and step 4 are repeated 5 times;
6) Cu spin coating being completed2O/TiO2The brilliant film of core-shell nano is annealed 1 hour under 400 ° of C under argon shield;
7) Cu annealing being completed2O/TiO2The brilliant film of core-shell nano is 10 in vacuum-4Under Pa, evaporation thickness is that the quinoline aluminium lamination of 10-40 nanometer is as electron transfer layer;
8) be 10 in vacuum again-4Under Pa, evaporation thickness is the metal A l electrode of 100 nanometer-200 nanometers, and completing making should be based on Cu2O/TiO2The luminescent device of the brilliant film of core-shell nano.
Described Cu2O/TiO2The preparation method of core-shell nano crystalline substance is as follows: take 0.852g(0.005mol) CuCl2·2H2O joins in the deionized water of 100mL and it is fully dissolved, under stirring condition, adding 30mL concentration is the ammoniacal liquor of 0.5 mol/L, drip again the NaOH that 10mL concentration is 1 mol/L (0.01mol) solution, generate after blue precipitation, stir again 5min, the 1mL butyl titanate ethanolic solution that dropping contains 0.1mL ammoniacal liquor, then adding 10mL concentration is the aqueous ascorbic acid of 1 mol/L, at 70 DEG C, react 1 hour, centrifugal, then clean and centrifugal 3 times with deionized water and alcohol, dryly at 40 DEG C in a vacuum within 3 hours, obtain Cu russet2O/TiO2Core-shell nano crystalline flour end.
Principle of the present invention and foundation:
Cu2Be positioned at-3.1eV of the conduction band of O, differs larger with the work function (4.3eV) of aluminium, and what form with Al is Schottky contacts, has potential barrier, and therefore electronic injection is more difficult, and Cu2The work function of O valence band and ITO is very approaching, and hole is injected easily, and hole is at Cu2Mobility in O is higher than electronics, and this just causes electronics and hole injection is uneven and then cause luminous efficiency low; And TiO2Conduction band be-4.1eV, more approaching with the work function (4.3eV) of aluminium, and with Al form be Ohmic contact. Therefore TiO2The effect of having played step has reduced the potential barrier of electronic injection, makes the injection of electronics easier; Simultaneously increase again hole injection barrier, effectively prevented that hole from injecting too fast compound at electrode place, increased at Cu2In O, with the recombination probability of electronics, relevant luminous intensity is strengthened.
Advantage of the present invention is:
The present invention is by adding TiO2, make to form Ohmic contact with Al electrode, make the injection of electronics easier; Simultaneously increase again hole injection barrier, effectively prevented that hole from injecting too fast compound at electrode place, increased at Cu2In O, with the recombination probability of electronics, luminous efficiency and luminous intensity are significantly strengthened, simultaneously by adding the TiO of broad-band gap2Increase Cu2The stability of O.
Brief description of the drawings
Fig. 1 is this luminescent device structural representation.
In figure: 1. glassy layer 2.ITO layer 3.Cu2O/TiO2Core-shell nano polycrystalline thin film layer 4. quinoline aluminium lamination 5. metal negative electrodes
Fig. 2 a is based on Cu2Electroluminescent (EL) spectrum of O nano-crystal film luminescent device, the different magnitude of voltage that in figure, digitized representation adds to device: 1.4V2.4.5V3.5V4.5.5V5.6V.
Fig. 2 b is based on Cu2O/TiO2Electroluminescent (EL) spectrum of the brilliant thin-film light emitting device of core-shell nano, in figure, the voltage of digitized representation is respectively: 1.4V2.4.5V3.5V4.5.5V5.6V.
Detailed description of the invention
Embodiment:
A kind of based on Cu2O/TiO2The luminescent device of the brilliant film of core-shell nano, as shown in Figure 1, by glassy layer 1, ITO layer 2, Cu2O/TiO2Core-shell nano polycrystalline thin film layer 3, quinoline aluminum (Alq3) layer 4 and metal negative electrode 5 be formed by stacking, wherein Cu2O/TiO2The thickness of core-shell nano polycrystalline thin film layer is 200 nanometers, quinoline aluminum (Alq3) thickness of layer is 30 nanometers, metal negative electricity very aluminium electrode and thickness is 100 nanometers.
A kind of described based on Cu2O/TiO2The preparation method of the luminescent device of the brilliant film of core-shell nano, step is as follows:
1) by the glass substrate that deposits ITO first after after liquid detergent, deionized water, acetone, isopropyl alcohol and ethanol ultrasonic cleaning, in vacuum drying chamber at 80 DEG C dry 30 minutes;
2) Cu of preparation 10mg/ml2O/TiO2The brilliant toluene solution of core-shell nano is as spin coating liquid, Cu2O and TiO2Mol ratio be 1.67, Cu2O/TiO2The preparation method of core-shell nano crystalline substance is as follows:
Take 0.852g(0.005mol) CuCl2·2H2O joins in the deionized water of 100mL and it is fully dissolved, under stirring condition, adding 30mL concentration is the ammoniacal liquor of 0.5 mol/L, drip again the NaOH that 10mL concentration is 1 mol/L (0.01mol) solution, generate after blue precipitation, stir again 5min, the 1mL butyl titanate ethanolic solution that dropping contains 0.1mL ammoniacal liquor, then adding 10mL concentration is the aqueous ascorbic acid of 1 mol/L, at 70 DEG C, react one hour, centrifugal, clean and centrifugal three times with deionized water and alcohol, dryly at 40 DEG C in a vacuum within three hours, obtain Cu russet2O/TiO2Core-shell nano crystalline flour end;
3) will after dried ITO cool to room temperature, be put on sol evenning machine, drip above-mentioned spin coating liquid 5-6 thereon and drip, stop 3-5 second, spin coating 6s and 20s respectively under 2000 rpms of 700 rpms of the slow-speed of revolution and high rotating speeds;
4) by the good Cu of above-mentioned spin coating2O/TiO2The brilliant film of core-shell nano is placed at 70 DEG C of vacuum drying chambers dry 30 minutes;
5) step 3 is repeated 5 times to step 4;
6) Cu spin coating being completed2O/TiO2The brilliant film of core-shell nano is annealed 1 hour under 400 ° of C under argon shield;
7) Cu annealing being completed2O/TiO2The brilliant film of core-shell nano is 10 in vacuum-4Under Pa, evaporation thickness is that the quinoline aluminium lamination of 30 nanometers is as electron transfer layer;
8) be 10 in vacuum again-4Under Pa, evaporation thickness is the metal A l electrode of 150 nanometers, and completing making should be based on Cu2O/TiO2The luminescent device of the brilliant film of core-shell nano.
Monitor at normal temperatures the electroluminescent spectrum of this device with JY-FL3-2-2 XRF.
Fig. 2 a is based on Cu2Electroluminescent (EL) spectrum of O nano-crystal film luminescent device, the different magnitude of voltage that in figure, digitized representation adds to device: 1.4V2.4.5V3.5V4.5.5V5.6V.
Fig. 2 b is based on Cu2O/TiO2Electroluminescent (EL) spectrum of the brilliant thin-film light emitting device of core-shell nano, in figure, the voltage of digitized representation is respectively: 1.4V2.4.5V3.5V4.5.5V5.6V.
As shown in Fig. 2 a and Fig. 2 b contrast, with simple Cu2O nano-crystal film luminescent device is compared, with TiO2Cu after compound2O/TiO2The luminous intensity of core-shell nano trichite optical device is by 10-1The order of magnitude brings up to 103The order of magnitude, shows through TiO2After coated, increase the recombination probability in electronics and hole, thereby the luminous intensity of device is significantly strengthened.
Claims (2)
1. one kind based on Cu2O/TiO2The preparation method of the luminescent device of the brilliant film of core-shell nano, described based onCu2O/TiO2The luminescent device of the brilliant film of core-shell nano is by glassy layer, ITO layer, Cu2O/TiO2Core-shell nano crystalline substanceThin layer, quinoline aluminium lamination and metal negative electrode are formed by stacking, and wherein ITO layer thickness is 100-200 nanometer, withCu2O is core, TiO2For the thickness of the nano-crystalline thin rete of shell is 100-500 nanometer, quinoline aluminum layer thickness is10-40 nanometer, metal negative electricity very aluminium electrode and thickness is 100-200 nanometer; It is characterized in that preparation processAs follows:
1) by the glass substrate that deposits ITO first after through liquid detergent, deionized water, acetone, isopropyl alcohol and secondAfter alcohol ultrasonic cleaning, in vacuum drying chamber, at 80 DEG C, be dried 30 minutes;
2) Cu of preparation 10mg/ml2O/TiO2The brilliant toluene solution of core-shell nano is as spin coating liquid, Cu2O withTiO2Mol ratio be 1:1-2;
3) will after dried ITO cool to room temperature, be put on sol evenning machine, drip above-mentioned spin coating liquid 5-6 thereonDrip, stop 3-5 second, difference spin coating 6 seconds and 20 seconds under slow-speed of revolution 700rpm and high rotating speed 2000rpm;
4) by the good Cu of spin coating2O/TiO2The brilliant film of core-shell nano is placed at 70 DEG C of vacuum drying chambers dry30min；
5) step 3 and step 4 are repeated 5 times;
6) Cu spin coating being completed2O/TiO2The brilliant film of core-shell nano anneals 1 at 400 DEG C under argon shieldHour;
7) Cu annealing being completed2O/TiO2The brilliant film of core-shell nano is 10 in vacuum-4Evaporation thickness under PaFor the quinoline aluminium lamination of 10-40 nanometer is as electron transfer layer;
8) be 10 in vacuum again-4Under Pa, evaporation thickness is the metal A l electrode of 100 nanometer-200 nanometers,Completing making should be based on Cu2O/TiO2The luminescent device of the brilliant film of core-shell nano.
2. according to claim 1 based on Cu2O/TiO2The preparation side of the luminescent device of the brilliant film of core-shell nanoMethod, is characterized in that: step 2) in Cu2O/TiO2The preparation method of core-shell nano crystalline substance is as follows: take 0.852The CuCl of g2·2H2O joins in the deionized water of 100mL and it is fully dissolved, and under stirring condition, addsEnter the ammoniacal liquor that 30mL concentration is 0.5 mol/L, then to drip 10mL concentration be that the NaOH of 1 mol/L is moltenLiquid, generates after blue precipitation, then stirs 5min, drips the 1mL butyl titanate second that contains 0.1mL ammoniacal liquorAlcoholic solution, then adding 10mL concentration is the aqueous ascorbic acid of 1 mol/L, at 70 DEG C, reacts 1Hour, centrifugal, clean and centrifugal 3 times at 40 DEG C dry 3 hours in a vacuum with deionized water and alcoholObtain Cu russet2O/TiO2Core-shell nano crystalline flour end.
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Citations (3)
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|---|---|---|---|---|
| US5834894A (en) * | 1995-09-14 | 1998-11-10 | Casio Computer Co., Ltd. | Carrier injection type organic electro-luminescent device which emits light in response to an application of a voltage |
| EP1013740A2 (en) * | 1998-12-25 | 2000-06-28 | Konica Corporation | Electroluminescent material, electroluminescent element and color conversion filter |
| CN102916097A (en) * | 2011-08-01 | 2013-02-06 | 潘才法 | Electroluminescent device |
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| TWI408834B (en) * | 2010-04-02 | 2013-09-11 | Miin Jang Chen | Nanocrystal-based optoelectronic device and method of fabricating the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5834894A (en) * | 1995-09-14 | 1998-11-10 | Casio Computer Co., Ltd. | Carrier injection type organic electro-luminescent device which emits light in response to an application of a voltage |
| EP1013740A2 (en) * | 1998-12-25 | 2000-06-28 | Konica Corporation | Electroluminescent material, electroluminescent element and color conversion filter |
| CN102916097A (en) * | 2011-08-01 | 2013-02-06 | 潘才法 | Electroluminescent device |
Non-Patent Citations (2)
| Title |
|---|
| p-Cu2O-shell/n-TiO2-nanowire-core heterostucture photodiodes;Tsung-Ying Tsai1等;《Nanoscale Research Letters》;20111031;第6卷;全文 * |
| Solution synthesis of Cu2O/TiO2 core-shell nanocomposites;Xiaodan Su等;《Colloids and Surfaces A》;20091005;第349卷(第1-3期);全文 * |
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