CN100477325C - A blue and green light emitting LED and manufacture method thereof - Google Patents
A blue and green light emitting LED and manufacture method thereof Download PDFInfo
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- CN100477325C CN100477325C CNB2007100618875A CN200710061887A CN100477325C CN 100477325 C CN100477325 C CN 100477325C CN B2007100618875 A CNB2007100618875 A CN B2007100618875A CN 200710061887 A CN200710061887 A CN 200710061887A CN 100477325 C CN100477325 C CN 100477325C
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Abstract
The related preparation method for LED with blue and green light comprises: selecting the bi(8-hydroxyquinoline)acetylacetone-Al (Alq2A) as the blue-green light material, the 4, 4', 4''-tri(2-naphthyl (phenyl)amine)triphenylamine as the hole injection layer, the N, N'-diphenyl-N, N'-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamine as the hole transmission layer, the LiF as electron transmission layer, the Al as cathode, and the conductive glass SnInO2 as the anode; applying the vacuum evaporation, form transition, gas-phase deposition, and the film growth to produce the final product. This invention has well lightness, wherein the color coordinate is X = 0. 2354, and Y = 0. 5132.
Description
Technical field
The present invention relates to a kind of light-emitting diode and preparation method of the green glow that turns blue, belong to electroluminescent organic material and the design of device architecture and preparation method's technical field.
Background technology
In today of photoelectron technology develop rapidly, its important techniques field-light Display Technique, become the front line science of the world today, novel light-emitting technology-organic electroluminescent LED OLED that the twentieth century later stage occurs succeeds in developing, form panchromatic high-resolution ultrathin display and large screen display and the new industry of solid white-light illuminating, promoted the development of flat panel display.
Organic electroluminescence device has the luminosity height, is easy to realize the large-area colour flat panel display, the low-voltage DC driven, be easy to mate with integrated circuit, and have full curing, the visual angle is wide, color is abundant, from characteristics such as main light emissions, electroluminescent organic material has obtained extensive use in light-emitting diode, common three primary colors-red, green, blue organic electroluminescent LED has been applied to high-tech and luminescence technology field.
Neutral colour-bluish-green type light-emitting diode for three primary colors-red, green, blue, it is a kind of novel organic electroluminescence device, its preparation method also is a new research topic, its luminescence mechanism, luminescent properties, luminescent device preparation, test and application all have some drawbacks and deficiency, need further profound research and discussion.
Summary of the invention
Goal of the invention
Purpose of the present invention is exactly at disadvantages of background technology, design a kind of sandwich construction, the organic electroluminescent LED of green glow turns blue, use two (oxine) acetyl acetone aluminium to make the blue green light luminescent layer, paired coupled diamine derivatives N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines is made hole transmission layer, starlike explosive 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine is made hole injection layer, lithium fluoride is made electron transfer layer, aluminium is made cathode layer, the electro-conductive glass tin indium oxide is made anode layer, adopt new preparation method, to obtain the multi-layer nano level organic electroluminescent LED of the green glow that turns blue.
Technical scheme
The chemical substance material that the present invention uses is: two (oxine) acetyl acetone aluminium, lithium fluoride, aluminium, N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 "-three [2-naphthyl (phenyl) amine] triphenylamine, absolute ethyl alcohol, toluene, acetone, watery hydrochloric acid, electro-conductive glass, mask template, adhesive tape, its combined amount ratio is: with gram, milliliter, millimeter, nanometer is unit of measurement
N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines: C
44H
32N
2NPB 2.0g ± 0.01g
Two (oxine) acetyl acetone aluminium: C
23H
19AlN
2O
4Alq2A 3.0g ± 0.02g
4,4 ', 4 " [2-naphthyl (phenyl) amine] triphenylamine: C-three
66H
48N
42-TNATA 2.0g ± 0.01g
Lithium fluoride: LiF 2.0g ± 0.01g
Aluminium: Al 4.0g ± 0.05g
Absolute ethyl alcohol: CH
3CH
2OH 120ml ± 5ml
Toluene: C
7H
8120ml ± 5ml
Acetone: CH
3COCH
3120ml ± 5ml
Watery hydrochloric acid: HCl 60ml ± 2ml
Electro-conductive glass: tin indium oxide ITO 60 * 30 * 1mm
Mask template: white plastic plate 60 * 30 * 0.5mm
Adhesive tape: 480 * 8 * 0.1mm
Blue-green light LED is 6 layers of structure, the electro-conductive glass tin indium oxide is anode layer, starlike explosive 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine is hole injection layer, diamine derivative N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines are that hole transmission layer, two (oxine) acetyl acetone aluminium is that blue green light luminescent layer, lithium fluoride are that electron transfer layer, aluminium are cathode layer.
The preparation method is as follows:
(1) selected chemical substance
To carry out selectedly to preparing required chemical substance, material, and carry out purity, fineness, size Control:
N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines: 99.9%
Two (oxine) acetyl acetone aluminium: 99.99%
4,4 ', 4 " [2-naphthyl (phenyl) amine] triphenylamine-three: 99.9%
Lithium fluoride: 99.99%
Aluminium: 99.99%
Absolute ethyl alcohol: 99.5%
Toluene: 99.5%
Acetone: 99.5%
Watery hydrochloric acid: concentration 20%
Electro-conductive glass: tin indium oxide side hinders 15 Ω/, transmissivity 90%, 60 * 30 * 1mm
Mask template: white plastic plate 60 * 30 * 0.5mm
Adhesive tape: 480 * 8 * 0.1mm
Solid feed fineness: 〉=300 orders
(2) burn into cleans electro-conductive glass
1. testing conductive glass positive and negative conductive characteristic determines that the front is a conducting surface;
2. use watery hydrochloric acid 50ml ± 2ml that the electro-conductive glass positive and negative are corroded, time 2min ± 0.1min;
3. the electro-conductive glass after wiping is corroded repeatedly with white soft fibre material;
4. clean electro-conductive glass, clean in ultrasonic cleaner with absolute ethyl alcohol, toluene, acetone respectively, order is:
Absolute ethyl alcohol: 50ml ± 2ml, time 15min ± 2min;
Toluene: 50ml ± 2ml, time 15min ± 2min;
Acetone: 50ml ± 2ml, time 15min ± 2min;
(3) make, clean the mask template
1. on the white plastic plate of 60 * 30 * 0.5mm, equidistantly symmetry is scribed the rectangle nib of 84 * 2 * 0.5mm, endoporus neat in edge;
2. clean the mask template, clean in ultrasonic cleaner with absolute ethyl alcohol, toluene, acetone respectively, order is:
Absolute ethyl alcohol: 50ml ± 2ml, time 10min ± 1min;
Toluene: 50ml ± 2ml, time 10min ± 1min;
Acetone: 50ml ± 2ml, time 10min ± 1min;
(4) vacuumize
Place vacuum drying chamber to carry out dried electro-conductive glass, mask template after cleaning, baking temperature is 30 ℃ ± 3 ℃, time 10min ± 1min;
(5) put electro-conductive glass, mask template
1. mask template and the mask aperture of the electro-conductive glass front conducting surface of 60 * 30 * 1mm and 60 * 30 * 0.5mm is overlapping, paste fixing in aggregates in the surrounding with adhesive tape;
The conducting surface that 2. will be overlapped into whole electro-conductive glass, mask template is aimed at the middle evaporation hole site of the star formula basal disc in the vacuum evaporation stove, pastes fixing with adhesive tape;
The mask aperture of mask template is aimed at the electro-conductive glass conducting surface, and mask aperture is directed downwards the evaporation hole of foresight formula basal disc;
(6) put raw chemical material
With two (oxine) acetyl acetone aluminium, lithium fluoride, aluminium, 4,4 ', 4 "-three [2-naphthyl (phenyl) amine] triphenylamine, N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines place respectively in the vapor deposition source crucible;
(7) vacuum ionic bombardment
1. close the vacuum evaporation stove, open vacuum mechanical pump, vacuum molecular pump, the vacuum degree pressure values is 3 * 10 in the control stove
-4Pa;
2. open vacuum evaporation stove ion bombardment current controller, bombarding current is 50mA, and bombardment time is 12min ± 2min, to improve the anode work function;
(8) vacuum evaporation, form conversion, film growth, vapour deposition, formed product
1. open vacuum evaporation stove heater, the furnace chamber temperature rises to 50 ℃ ± 2 ℃ by 20 ℃ ± 3 ℃, constant temperature insulation 40min ± 2min;
2. open quartzy calibrator, quartzy probe detects the vapor deposition film thickness;
3. open the star formula basal disc that electro-conductive glass, mask template are housed, make its rotation, star formula basal disc velocity of rotation is 20r/min;
4. vacuum mechanical pump, vacuum molecular pump continue to open, and pressure values continues to keep 3 * 10 in the vacuum furnace chamber
- 4Pa;
5. evaporation begins
The 1st step: evaporation hole injection layer
Connect evaporation source 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine crucible, make the interior resistor of crucible be warming up to 250 ℃ ± 10 ℃, 4,4 ', 4 "-three [2-naphthyl (phenyl) amine] triphenylamine gaseous molecular deposition growing in the mask nib of the 1st layer of electro-conductive glass becomes the 2nd layer; be hole injection layer, thickness is 10nm ± 0.02nm;
The 2nd step: evaporation hole transmission layer
Connect evaporation source N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines crucible makes the interior resistor of crucible be warming up to 250 ℃ ± 10 ℃, N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines gaseous molecular deposition growing on hole injection layer become the 3rd layer, be hole transmission layer, thickness is 50nm ± 0.1nm;
The 3rd step: evaporation blue green light luminescent layer
Connect evaporation source two (oxine) acetyl acetone aluminium crucible, make the interior resistor of crucible be warming up to 350 ℃ ± 10 ℃, two (oxine) acetyl acetone aluminium molecule becomes the 4th layer at hole transmission layer top deposition growing, i.e. blue green light luminescent layer, and thickness is 50nm ± 0.1nm;
The 4th step: evaporation electron transfer layer
Connect evaporation source lithium fluoride crucible, make that resistor is warming up to 950 ℃ ± 10 ℃ in the crucible, the lithium fluoride gaseous molecular becomes the 5th layer at blue green light luminescent layer top deposition growing, i.e. electron transfer layer, and thickness is 1nm ± 0.01nm;
The 5th step: evaporation cathode layer
Connect evaporation source aluminium crucible, make that resistor is warming up to 850 ℃ ± 10 ℃ in the crucible, the aluminium gaseous molecular becomes the 6th layer at electron transfer layer top deposition growing, i.e. cathode layer, and thickness is 120nm ± 2nm;
Chemical substance in each evaporation source crucible is carried out heat temperature raising respectively, under vacuum state, temperature changes, and carries out the form conversion, is transformed to gaseous state by solid-state, the material powder of gaseous state changes into molecular state, and gaseous molecular deposits on electro-conductive glass and generates solid-state conductive film;
In preparation process, the omnidistance unlatching of quartzy thickness meter probe measured, and control shows the thickness of each conductive layer, and by its numerical value of liquid crystal display displays;
Organic material gas phase membrane deposition rate is 0.1nm/s;
Metal material gas phase membrane deposition rate is 1nm/s;
(9) vacuum cooled
After vacuum evaporation is finished, close vacuum mechanical pump, vacuum molecular pump, close resistance heater, the product device cools off with stove, and be 6min ± 0.2min cooling time, to 20 ℃ ± 3 ℃ of normal temperature;
(10) demoulding, excision forming
Open the vacuum evaporation stove, take out electro-conductive glass, the mask template on the electro-conductive glass is removed, with specific purpose tool electro-conductive glass is cut into 8 homalographic devices, that is: 8 bluish-green type light-emitting diodes;
(11) detect, analyze, characterize
With the brightness instrument luminosity of blue green light diode is tested;
With spectrum Emanations Analysis instrument blue green light diode chromaticity coordinates is tested;
With quartzy calibrator blue green light diode conduction layer thickness is detected;
(12) encapsulation stores
Blue-green light LED to preparation encapsulates with epoxide resin material respectively, to prevent cathode oxidation, is stored in drying, the lucifuge environment, waterproof, protection against the tide, anti-oxidation, anti-soda acid to corrode 20 ℃ ± 3 ℃ of storage temperatures, relative humidity≤20%.
The preparation of described blue-green light LED is carried out in the vacuum evaporation stove, vacuum degree in the vacuum evaporation stove is by vacuum mechanical pump, vacuum molecular pump control, preparation process is finished under omnidistance vacuum state, and the vacuum degree pressure values continues to remain on 3 * 10 in the vacuum evaporation stove furnace chamber
-4Pa.
The generation of the conduction luminescent layer of described blue-green light LED is finished in the vacuum evaporation stove, the generation of hole injection layer, hole transmission layer, blue green light luminescent layer, electron transfer layer, cathode layer, finish with the molecular conformation reformulations, the chemical substance material is under the heating in vacuum state, convert gaseous molecular to by solid-state molecular, gaseous molecular is in anode layer-electro-conductive glass indium tin oxide layer vapour deposition, generate each conductive layer respectively, the form reformulations is: solid-state-gaseous state-solid-state.
Temperature value in the described vacuum evaporation stove furnace chamber in the evaporation source crucible is provided with by the chemical substance sublimation temperature, evaporation 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine is 250 ℃ ± 10 ℃, evaporation N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines are that 250 ℃ ± 10 ℃, evaporation two (oxine) acetyl acetone aluminium are that 350 ℃ ± 10 ℃, evaporation lithium fluoride are that 950 ℃ ± 10 ℃, AM aluminum metallization are 850 ℃ ± 10 ℃.
Beneficial effect
The present invention compares with background technology has tangible advance, blue-green light LED is an anode layer, hole injection layer, hole transmission layer, the blue green light luminescent layer, electron transfer layer, 6 layers of structure of cathode layer, electro-conductive glass tin indium oxide with 15 Ω/ is an anode layer, with starlike explosive 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine is a hole injection layer, with diamine derivative N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines is a hole transmission layer, with two (oxine) acetyl acetone aluminium is the blue green light luminescent layer, with the lithium fluoride is electron transfer layer, with aluminium is cathode layer, because blue green light luminescent layer-two (oxine) acetyl acetone aluminium sends out indigo plant+green glow inclined to one side, so make the diode green glow that turns blue, adopt vacuum evaporation, modality conversion, vapour deposition, the film growth method generates the conducting film of light-emitting diode, transform by solid-state-gaseous state-solid-state form, gaseous molecular generates the nanoscale solid film on electro-conductive glass, the generation of blue green light is not used dye adulterated, directly generate by inclined to one side indigo plant+green type two (oxine) acetyl acetone aluminium, directly make blue-green light LED, the method preparation technology's flow process is short, use equipment is few, an electro-conductive glass can prepare 8 diodes simultaneously, cost is low, effective, lumination of light emitting diode intensity, brightness, the efficient height, blue green light is pure, the blue green light chromaticity coordinates is: X=0.2354, Y=0.5132 is the desirable direct method for preparing blue-green light LED.
Description of drawings
Fig. 1 is a blue green light diode preparation technology flow chart
Fig. 2 is a blue green light diode conduction layer structure chart
Fig. 3 is vacuum evaporation stove and evaporation state diagram
Fig. 4 is mask formwork structure figure
Fig. 5 is the electro-conductive glass structure chart
Fig. 6 is blue green light diode electrically current density-voltage coordinate graph of a relation
Fig. 7 is blue green light led lighting brightness-voltage coordinate graph of a relation
Fig. 8 is a blue green light diode electrically photoluminescence collection of illustrative plates
Fig. 9 is blue green light diode chromaticity coordinates figure
Shown in the figure, list of numerals is as follows:
1, the stove seat, 2, control cabinet, 3, LCDs, 4, the vacuum machine switch pump, 5, the vacuum molecule switch pump, 6, the crucible temperature switch, 7, the furnace chamber temperature switch, 8, body of heater, 9, bell, 10, observation window, 11, vacuum mechanical pump, 12, vacuum molecular pump, 13, rotate suspension rod, 14, star formula basal disc, 15, electro-conductive glass+mask template, 16, crucible, 17, crucible, 18, resistance wire, 19, resistance wire, 20, quartzy Thicknesser probe, 21, the vacuum furnace chamber, 22, vacuum furnace cavity temperature transducer, 23, the mask template, 24, mask aperture, 25, electro-conductive glass, 26, the evaporation groove, 27, conducting surface, 28, nonconductive surface, 29, rotate the suspension rod switch.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be preparation technology's flow chart, each preparation parameter is wanted strict control, operation according to the order of sequence.
To preparing indigo plant+green two (oxine) acetyl acetone aluminium, lithium fluoride, the aluminium, 4 of required chemical substance material-partially, 4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine, N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines want strict selected, its purity, weight must not exceed the minimax scope.
The amount of the watery hydrochloric acid that cleaning is used to burn into, absolute ethyl alcohol, toluene, acetone wants sufficient, clean.
The electro-conductive glass tin indium oxide is the luminous carrier of blue green light, is good with 15 Ω/, transmissivity 90%.
The mask template is made of on-deformable white engineering plastics, pastes with electro-conductive glass and uses.
Adhesive tape is that fixedly electro-conductive glass, mask template will cement and tighten up in the binding material of star formula basal disc, must not come off.
It is 3 * 10 that the vacuum furnace chamber of vacuum evaporation stove will keep the vacuum degree pressure values
-4Pa, and note regulation and control vacuum mechanical pump, vacuum molecular pump, stable to keep pressure values.
Star formula basal disc will at the uniform velocity clockwise rotate in working order the time, and its rotating speed is 20r/min, must not intermittently pause.
The vacuum furnace cavity temperature will be constant all the time the time is 40min ± 2min in 50 ℃ ± 2 ℃ scopes, must not be fluctuated, and transmit temperature information and show by temperature sensor.
Quartzy Thicknesser probe will accurately be measured every layer evaporation thickness, and shows its one-tenth-value thickness 1/10 by LCDs, so that control operation, its thickness must not exceed scope of design, in order to avoid influence luminescent properties and color.
In preparation process, can once on star formula basal disc, fix one or more electro-conductive glass, the method of available adjustment displacement mask template mask aperture on electro-conductive glass is determined once to prepare the quantity of blue green light diode can once prepare 2,4,6,8.
The bottom of evaporation source crucible in the vacuum furnace chamber, respectively be provided with 5 about dividing, totally 10 crucibles, each crucible is by resistance wire UNICOM, material difference in the control cabinet 2 visual crucibles, temperature control is then different, and keeps temperature in each crucible can reach the sublimation temperature of its material, so that the metamorphosis of chemical substance material.
In evaporate process, can be at any time observe evaporate process in its vacuum chamber, and regulate and control according to circumstances with observation window.
The employed chemical substance deposition material of preparation blue green light diode is to determine in the number range that sets in advance, with gram, milliliter, millimeter, nanometer is unit of measurement, when industrialization is produced, be unit of measurement with kilogram, liter, millimeter, its light emitting layer thickness all is unit with the nanometer.
Shown in Figure 2, be blue green light diode junction composition, be 6 layers of structure, ground floor is an anode layer, be the electro-conductive glass indium tin oxide layer, the second layer is a hole injection layer, promptly starlike explosive 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine layer, the 3rd layer is hole transmission layer, i.e. diamine derivative N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines layer, the 4th layer is the blue green light luminescent layer, i.e. indigo plant+green two (oxine) acetyl acetone aluminium lamination partially, layer 5 is an electron transfer layer, i.e. the lithium fluoride layer, layer 6 is cathode layer, i.e. aluminium lamination.
Shown in Figure 3, be vacuum evaporation furnace structure and working state figure, be control cabinet 2 on the top of stove seat 1, the top of control cabinet 2 is body of heater 8, body of heater 8 tops are bell 9; The centre of control cabinet 2 is a LCDs 3, and the left part of LCDs 3 is provided with crucible temperature switch 6 successively, rotates suspension rod switch 29, furnace chamber temperature switch 7, and right part is vacuum machine switch pump 4, vacuum molecule switch pump 5; The inside of body of heater 8 is vacuum furnace chamber 21, in vacuum furnace chamber 21, on the bell 9, be provided with and rotate suspension rod 13, star formula basal disc 14, quartzy Thicknesser probe 20, bottom left-right symmetric in vacuum furnace chamber 21 respectively is provided with 5 crucibles 17,16, and each is connected by resistance wire 19,18; Be provided with observation window 10, vacuum molecular pump 12 on vacuum chamber temperature sensor 22, vacuum mechanical pump 11, the furnace wall, right side being provided with on the furnace wall, left side of body of heater 8.
Shown in Figure 4, be mask formwork structure figure, 8 rectangle masks of symmetrical spaced set nib 24 in the middle of the mask template 23, the white engineering plastics plate that mask template 23 usable intensity are good is made.
Shown in Figure 5, be the electro-conductive glass structure chart, above the electro-conductive glass 25 be conducting surface 27, following be nonconductive surface 28, conducting surface 27 is provided with the evaporation groove 26 that is equal to setting with the mask template, and behind the evaporation, vapour deposition generates blue green light diode product in evaporation groove 26, electro-conductive glass is made of the water white tin indium oxide of 15 Ω/, its transmissivity is 90%, and transmissivity is high more, and luminous intensity efficient is good more.
Shown in Figure 6, be blue green light diode electrically current density-voltage coordinate graph of a relation, among the figure as can be known: abscissa is magnitude of voltage V, and ordinate is current density value mA/cm
2, its current density is directly proportional with voltage, and its blue green light diode has good rectification characteristic.
Shown in Figure 7, be brightness of blue green light led lighting and voltage coordinate graph of a relation, among the figure as can be known: ordinate is a luminosity, and abscissa is a voltage, and when voltage reached 12.29V, maximum luminousing brightness can reach 15650cd/m
2
Shown in Figure 8, be blue green light diode electrically photoluminescence collection of illustrative plates, among the figure as can be known: ordinate is relative intensity a.u., and abscissa is wavelength nm, and the maximum emission wavelength that electroluminescence produces is in the blue green light wave band at the 513nm place.
Shown in Figure 9, be blue green light diode chromaticity coordinates figure, among the figure as can be known: its chromaticity coordinates: X=0.2354, Y=0.5132 is positioned at the blue green light zone.
Claims (2)
1, a kind of preparation method of light-emitting diode of the green glow that turns blue, it is characterized in that: the chemical substance material that preparation is used is: two (oxine) acetyl acetone aluminium, lithium fluoride, aluminium, N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine, absolute ethyl alcohol, toluene, acetone, watery hydrochloric acid, electro-conductive glass, mask template, adhesive tape, its combined amount ratio is: with gram, milliliter, millimeter is unit of measurement
N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines: C
44H
32N
2NPB 2.0g ± 0.01g
Two (oxine) acetyl acetone aluminium: C
23H
19AlN
2O
4Alq
2A 3.0g ± 0.02g
4,4 ', 4 " [2-naphthyl (phenyl) amine] triphenylamine: C-three
66H
48N
42-TNATA 2.0g ± 0.01g
Lithium fluoride: LiF 2.0g ± 0.01g
Aluminium: Al 4.0g ± 0.05g
Absolute ethyl alcohol: CH
3CH
2OH 120ml ± 5ml
Toluene: C
7H
8120ml ± 5ml
Acetone: CH
3COCH
3120ml ± 5ml
Watery hydrochloric acid: HCl 60ml ± 2ml
Electro-conductive glass: tin indium oxide ITO 60 * 30 * 1mm
Mask template: white plastic plate 60 * 30 * 0.5mm
Adhesive tape: 480 * 8 * 0.1mm
The light-emitting diode of green glow of turning blue is 6 layers of structure, the electro-conductive glass tin indium oxide is anode layer, starlike explosive 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine is hole injection layer, diamine derivative N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines are hole transmission layer, two (oxine) acetyl acetone aluminium Alq
2A is that blue green light luminescent layer, lithium fluoride LiF are that electron transfer layer, aluminium Al are cathode layer;
The preparation method is as follows:
(1) selected chemical substance
To carry out selectedly to preparing required chemical substance, material, and carry out purity, fineness, size Control:
N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines: 99.9%
Two (oxine) acetyl acetone aluminium: 99.99%
4,4 ', 4 " [2-naphthyl (phenyl) amine] triphenylamine-three: 99.9%
Lithium fluoride: 99.99%
Aluminium: 99.99%
Absolute ethyl alcohol: 99.5%
Toluene: 99.5%
Acetone: 99.5%
Watery hydrochloric acid: concentration 20%
Electro-conductive glass: tin indium oxide side hinders 15 Ω/, transmissivity 90%, 60 * 30 * 1mm
Mask template: white plastic plate 60 * 30 * 0.5mm
Adhesive tape: 480 * 8 * 0.1mm
Solid feed fineness: 〉=300 orders
(2) burn into cleans electro-conductive glass
1. testing conductive glass positive and negative conductive characteristic determines that the front is a conducting surface;
2. use watery hydrochloric acid 50ml ± 2ml that the electro-conductive glass positive and negative are corroded, time 2min ± 0.1min;
3. the electro-conductive glass after wiping is corroded repeatedly with white soft fibre material;
4. clean electro-conductive glass, clean in ultrasonic cleaner with absolute ethyl alcohol, toluene, acetone respectively, order is:
Absolute ethyl alcohol: 50ml ± 2ml, time 15min ± 2min;
Toluene: 50ml ± 2ml, time 15min ± 2min;
Acetone: 50ml ± 2ml, time 15min ± 2min;
(3) make, clean the mask template
1. on the white plastic plate of 60 * 30 * 0.5mm, equidistantly symmetry is scribed the rectangle nib of 84 * 2 * 0.5mm, endoporus neat in edge;
2. clean the mask template, clean in ultrasonic cleaner with absolute ethyl alcohol, toluene, acetone respectively, order is:
Absolute ethyl alcohol: 50ml ± 2ml, time 10min ± 1min;
Toluene: 50ml ± 2ml, time 10min ± 1min;
Acetone: 50ml ± 2ml, time 10min ± 1min;
(4) vacuumize
Place vacuum drying chamber to carry out dried electro-conductive glass, mask template after cleaning, baking temperature is 30 ℃ ± 3 ℃, time 10min ± 1min;
(5) put electro-conductive glass, mask template
1. mask template and the mask aperture of the electro-conductive glass front conducting surface of 60 * 30 * 1mm and 60 * 30 * 0.5mm is overlapping, with adhesive tape in the surrounding fixing paste in aggregates;
The conducting surface that 2. will be overlapped into whole electro-conductive glass, mask template is aimed at the middle evaporation hole site of the star formula basal disc in the vacuum evaporation stove, pastes fixing with adhesive tape;
The mask aperture of mask template is aimed at the electro-conductive glass conducting surface, and mask aperture is directed downwards the evaporation hole of foresight formula basal disc;
(6) put raw chemical material
With two (oxine) acetyl acetone aluminium, lithium fluoride, aluminium, 4,4 ', 4 "-three [2-naphthyl (phenyl) amine] triphenylamine, N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines place respectively in the vapor deposition source crucible;
(7) vacuum ionic bombardment
1. close the vacuum evaporation stove, open vacuum mechanical pump, vacuum molecular pump, the vacuum degree pressure values is 3 * 10 in the control stove
-4Pa;
2. open vacuum evaporation stove ion bombardment current controller, bombarding current is 50mA, and bombardment time is 12min ± 2min, to improve the anode work function;
(8) vacuum evaporation, form conversion, film growth, vapour deposition, formed product
1. open vacuum evaporation stove heater, the furnace chamber temperature rises to 50 ℃ ± 2 ℃ by 20 ℃ ± 3 ℃, and constant temperature time is 40min ± 2min;
2. open quartzy calibrator, quartzy probe detects the vapor deposition film thickness;
3. open the star formula basal disc that electro-conductive glass, mask template are housed, make its rotation, star formula basal disc velocity of rotation 20r/min;
4. vacuum mechanical pump, vacuum molecular pump continue to open, and pressure values continues to keep 3 * 10 in the vacuum furnace chamber
- 4Pa;
5. evaporation begins
The 1st step: evaporation hole injection layer
Connect evaporation source 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine crucible, make the interior resistor of crucible be warming up to 250 ℃ ± 10 ℃, 4,4 ', 4 "-three [2-naphthyl (phenyl) amine] triphenylamine gaseous molecular deposition growing in the mask nib of the 1st layer of electro-conductive glass becomes the 2nd layer; be hole injection layer, thickness is 10nm ± 0.02nm;
The 2nd step: evaporation hole transmission layer
Connect evaporation source N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines crucible makes the interior resistor of crucible be warming up to 250 ℃ ± 10 ℃, N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines gaseous molecular deposition growing on hole injection layer become the 3rd layer, be hole transmission layer, thickness is 50nm ± 0.1nm;
The 3rd step: evaporation blue green light luminescent layer
Connect evaporation source two (oxine) acetyl acetone aluminium crucible, make the interior resistor of crucible be warming up to 350 ℃ ± 10 ℃, two (oxine) acetyl acetone aluminium molecule becomes the 4th layer at hole transmission layer top deposition growing, i.e. blue green light luminescent layer, and thickness is 50nm ± 0.1nm;
The 4th step: evaporation electron transfer layer
Connect evaporation source lithium fluoride crucible, make that resistor is warming up to 950 ℃ ± 10 ℃ in the crucible, the lithium fluoride gaseous molecular becomes the 5th layer at blue green light luminescent layer top deposition growing, i.e. electron transfer layer, and thickness is 1nm ± 0.01nm;
The 5th step: evaporation cathode layer
Connect evaporation source aluminium crucible, make that resistor is warming up to 850 ℃ ± 10 ℃ in the crucible, the aluminium gaseous molecular becomes the 6th layer at electron transfer layer top deposition growing, i.e. cathode layer, and thickness is 120nm ± 2nm;
Chemical substance in each evaporation source crucible is carried out heat temperature raising respectively, under vacuum state, temperature changes, and carries out form and transforms, and is transformed to gaseous state by solid-state, the material powder of gaseous state changes into molecular state, and gaseous molecular deposits on electro-conductive glass and generates solid-state conductive film;
In preparation process, the omnidistance unlatching of quartzy thickness meter probe measured, and control shows hole injection layer, hole transmission layer, blue green light luminescent layer, electron transfer layer, cathode layer thickness, and by its numerical value of liquid crystal display displays;
Organic material gas phase membrane deposition rate is 0.1nm/s;
Metal material gas phase membrane deposition rate is 1nm/s;
(9) vacuum cooled
After vacuum evaporation is finished, close vacuum mechanical pump, vacuum molecular pump, close resistance heater, the product device cools off with stove, and be 6min ± 0.2min cooling time, to 20 ℃ ± 3 ℃ of normal temperature;
(10) demoulding, excision forming
Open vacuum steaming degree stove, take out electro-conductive glass, the mask template on the electro-conductive glass is removed, with specific purpose tool electro-conductive glass is cut into 8 homalographic devices, that is: 8 bluish-green type light-emitting diodes;
(11) detect, analyze, characterize
With the brightness instrument luminosity of blue green light diode is tested;
With spectrum Emanations Analysis instrument blue green light diode chromaticity coordinates is tested;
Detect with hole injection layer, hole transmission layer, blue green light luminescent layer, electron transfer layer, the cathode layer thickness of quartzy calibrator the blue green light diode;
(12) encapsulation stores
Blue-green light LED to preparation encapsulates with epoxide resin material respectively, to prevent cathode oxidation, is stored in drying, the lucifuge environment, waterproof, protection against the tide, anti-oxidation, anti-soda acid to corrode 20 ℃ ± 3 ℃ of storage temperatures, relative humidity≤20%.
The light-emitting diode of the green glow that turns blue of 2 one kinds of preparation method's preparations as claimed in claim 1, it is characterized in that: the light-emitting diode of the green glow that turns blue of preparation is 6 layers of structure, the electro-conductive glass tin indium oxide is anode layer, starlike explosive 4,4 '; 4 "-three [2-naphthyl (phenyl) amine] triphenylamine is hole injection layer, diamine derivative N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines are hole transmission layer, two (oxine) acetyl acetone aluminium Alq
2A is that blue green light luminescent layer, lithium fluoride LiF are that electron transfer layer, aluminium Al are cathode layer.
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| CN106229387A (en) * | 2016-08-02 | 2016-12-14 | 太原理工大学 | A kind of carbon quantum dot does the preparation method of the light emitting diode of luminescent layer |
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