CN104319320B - A kind of LED chip with composite transparent electrode and preparation method thereof - Google Patents
A kind of LED chip with composite transparent electrode and preparation method thereof Download PDFInfo
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0016—Processes relating to electrodes
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Led Devices (AREA)
Abstract
The invention discloses a kind of LED chips of NEW TYPE OF COMPOSITE transparent electrode; including setting gradually nitride buffer layer, N GaN layers, quantum well layer, P GaN layers, composite transparent electrode layer and SiO2 protective layers on substrate; and corresponding n-type electrode and p-type electrode, it is characterised in that：The composite transparent electrode layer is combined by graphene laminar film and ZnO transparent conductive thin film, the production method for also describing the chip.The non-ohmic contact characteristic of ZnO material and P GaN layers so that applications of the ZnO in LED electrode is very limited.Grapheme material has the visible light transmittance for being up to 97% and excellent electric conductivity and mechanical performance in the range of visible light spectrum, good contact can be formed when it is used for P-type electrode contact layer between P GaN again, layer of ZnO is grown on graphene, the current expansion characteristic of graphene can be improved again, the composite transparent electrode layer of LED is formed after the two is compound, contact performance and transmissivity can be largely increased.
Description
Technical field
The present invention relates to the technical field of LED chip, particularly a kind of LED chip and its system with composite transparent electrode
Make method.
Background technology
ZnO has the structure identical with GaN and similar photo electric as a kind of novel semiconductor material with wide forbidden band
It can or even surmount GaN in exciton emission performance etc., become the excellent candidate of high efficiency LED and ultraviolet wavelength LED
Person.ZnO transparent conductive thin film has very high transmissivity in visible light spectrum, and conductivity is thin close to metallic film and ITO
Film is very close, and through overdoping or compound ZnO transparent conductive thin film, having can be with comparable electrical and optical of ito thin film
Characteristic.In addition to this, compared with ITO, ZnO has nontoxic and pollution-free, abundant raw material, advantage at low cost, the ZnO through overdoping
Transparent conductive film with electrical and optical properties that can be comparable with ito thin film, in piezoelectric device, solar cell, shines
The range that the photoelectric fields such as diode are increasingly taken seriously, study also more becomes active.And In is as a kind of scarce resource, price
Costliness, and chip technology is complex, so ZnO conductive films are expected to substitution ITO conductive films and occupy following LED cities
.
But maximum difficult point is exactly that the p-type doping of ZnO is difficult to realize at present, so it is as transparency conducting layer and P-GaN
The ohmic contact characteristic of layer is bad, is subject to certain restrictions its extensive use.Graphene since by since successfully preparing, just by
The favor of numerous researchers.Graphene has perfect characteristic and application of the geometry as alkene as graphite.Graphene
With higher mobility, since its internal scattering mechanism is mainly based on defect scattering, so in certain temperature range
Mobility be a definite value, theoretical value 200000cm2V-1S-1.Moreover, graphene has very high transmitance (up to
97%), and more than three times of its electron mobility higher than ITO, perfect mechanical property and excellent electrology characteristic open it
Beginning is widely studied and is applied on the electrically conductive.But due to graphene very thin thickness, so its sheet resistance is higher, individually
The problem of resistance is high, chip forward voltage is high is then faced for conductive film.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of novel composite transparent conductive layer, and it is mono- effectively to solve ZnO
Solely Ohmic contact problem as transparent conductive film, and when avoiding graphene separately as transparent conductive film resistance value height and
It the problem of current expansion, and the production method for providing the LED chip with the composite transparent conductive layer, can be simply and easily
Produce a kind of LED chip of NEW TYPE OF COMPOSITE transparency conducting layer, improve transparency conducting layer and P-GaN layers of ohmic contact characteristic,
And its resistance is reduced, and improve its light extraction efficiency.
The technical scheme is that：A kind of LED chip with composite transparent electrode, including growing successively on substrate
Nitride buffer layer, N-GaN layers, quantum well layer, P-GaN layers and composite transparent electrode layer, it is characterised in that：The N-
Being made in GaN layer has n-type electrode, and being made on composite transparent electrode layer has p-type electrode, on the outside of the n-type electrode, p-type electrode
Chip surface deposition has SiO2Protective layer, the composite transparent electrode layer is by graphene laminar film and is grown in graphene layer
ZnO transparent conductive thin film on shape film is combined.
The SiO2Protective layer is coated on n-type electrode, p-type electrode outside, and SiO2Protective layer is etched to expose N-shaped
Electrode and p-type electrode.
The graphene stratiform film thickness is 2~200nm, and ZnO transparent conductive thin film thickness is 100-300nm.
A kind of production method of the LED chip with composite transparent electrode, includes the following steps：
A, using MOCVD technologies on a sapphire substrate successively growing gallium nitride buffer layer, N-GaN layers, quantum well layer and
P-GaN layers；
B, one layer of photoresist is coated, then be exposed, develop P-GaN layers of side, opposite side is etched by ICP method
The table top of N-GaN；
C, being made on P-GaN layers has composite transparent electrode layer (TCL), and composite transparent electrode layer is by graphene laminar film
It is combined with ZnO transparent conductive thin film；
D, by photoetching process, P electrode is obtained on the composite transparent electrode layer of side, on the N-GaN layers of side
To N electrode；
E, one layer of SiO is deposited on the electrode using PECVD2After protective layer, then by etching P electrode and N electrode dew
Go out, complete the making of LED chip.
In the step C, the production method of composite transparent electrode layer comprises the following steps：
C1, first by a kind of material in graphene or graphene oxide and polymethyl methacrylate (PMMA) material into
Row uniformly mixing, mixing material be coated in chip die on, allow graphene or graphene oxide in reacting furnace tightly
It is fitted on wafer, is not blown away by carrier gas or protective gas, and PMMA also acts as the mechanical support to reaction product-graphene
Effect；
C2, the chip die coated with mixing material is placed in medium temperature tube furnace, with H2For carrier gas, N2For protective gas,
Graphene laminar film is obtained with chemical vapour deposition technique (CVD)；
C3, graphene laminar film made from above-mentioned steps is dipped in acetone soln, (less than 55 DEG C) heating of low temperature are gone
The PMMA on surface is removed, after cleaning repeatedly, is dried at room temperature；
C4, that layer of ZnO electrically conducting transparent is grown on laminar film with USP methods (ultrasonic spray pyrolysis) or mocvd method is thin
Film.
In the step C1, PMMA is to realize uniformly to mix with graphene or graphene oxide by ultrasonic method.
In the step C3, the method that laminar film cleans repeatedly is carried out using acetone, isopropanol and deionized water
It cleans repeatedly.
In the step C4, the production method of ZnO transparent conductive thin film is using zinc ethide as zinc source, is passed through N2 as guarantor
Gas and purge gas, O2 are protected as reaction gas, control growth temperature is 450-500 DEG C, gas flow control for
10000-15000sccm, reaction chamber pressure 10-20torr, the electric current of inside and outside three circle are maintained at the level of homogeneous constant,
So as to obtain compactness and the preferable ZnO transparent conductive thin film of transmitance.
In the step C4, the production method of ZnO transparent conductive thin film is to use USP methods, using zinc acetate as zinc source,
Ethyl alcohol sprays into high-temperature region, control temperature exists as solvent after the metal salt solution of reaction generation is atomized in the chamber
500-650 DEG C or so, the concentration of metal salt solution is preferably 0.1-1mol/L, is led so as to obtain layer of ZnO in chip die
Conductive film.
Beneficial effects of the present invention are：The composite transparent that graphene/ZnO is obtained by simple chemical vapour deposition technique is led
Conductive film is realized the uniform mixing of material by ultrasonic method, the laminated film of graphene and ZnO is freely then spread over P-
It is simple for process, easy to operate in GaN layer, not only efficiently solved the problems, such as zinc-oxide film and the Ohmic contact of P-GaN, but also can have
High value and current expansion when effect avoids the problem that graphene separately as conductive film, and graphene and the compound rear shapes of ZnO
Into the composite transparent electrode layer of LED, contact performance and transmissivity can be largely increased.
Description of the drawings
Fig. 1 is the structure diagram of the present invention with the LED chip with composite transparent electrode.
In figure, 1- substrates, 2- buffer layers, 3-N-GaN layers, 4- quantum well layers, 5-P-GaN layers, 6- graphene laminar films,
7-ZnO conductive films, 8-P electrodes, 9-N electrodes, 10-SiO2Protective layer.
Specific embodiment
The specific embodiment of the present invention is described further below in conjunction with the accompanying drawings：
Embodiment 1：As shown in Figure 1, a kind of LED chip with composite transparent electrode, using mocvd method in Al2O3Or
(1) growing gallium nitride buffer layer (2), N-GaN layers (3), quantum well layer (4), P-GaN layers (5) successively in GaN substrate；In P-GaN
One layer of photoresist is coated on layer, then is exposed, develops, P-GaN layers of side is etched by ICP (reactive ion etching method)
To N-GaN layers (3)；Graphene oxide and polymethyl methacrylate (PMMA) material are uniformly mixed first, it is applied
It overlays in substrate wafer, graphene oxide is allow tightly to be fitted on wafer in reacting furnace, not by carrier gas or protective gas
It blows away, and PMMA also acts as the mechanical support effect to reaction product-graphene；Above-mentioned material is placed on medium temperature tube furnace
In, with H2For carrier gas, N2For protective gas, the laminar film (6) of graphene is obtained with chemical vapour deposition technique；Above-mentioned steps
Laminar film (6) obtained is dipped in acetone soln, 45 DEG C of low-temperature heats, gets rid of the PMMA on surface, after cleaning repeatedly, room temperature
Under dry；With the dedicated MOCVD of First ZnO, using zinc ethide as zinc source, it is passed through N2As protective gas and purge gas, O2
As reaction gas, control growth temperature is 450-500 DEG C, and for 13000sccm, reaction chamber pressure is for gas flow control
10-20torr, the electric current of inside and outside three circle is maintained at the level of homogeneous constant, preferable so as to obtain compactness and transmitance
ZnO transparent conductive thin film (7)；By photoetching process, P electrode (8), the N- of opposite side are prepared on the composite electrode layers of side
N electrode (9) is prepared in GaN layer (3)；Deposit one layer of SiO on the electrode using PECVD2After protective layer (10), then pass through etching
So that P electrode (8) and N electrode (9) are exposed, the making of the LED chip of graphene and ZnO composite transparent electrodes is completed.
Embodiment 2：As shown in Figure 1, a kind of LED chip with composite transparent electrode, using mocvd method in Al2O3Or
(1) growing gallium nitride buffer layer (2), N-GaN layers (3), quantum well layer (4), P-GaN layers (5) successively in GaN substrate；In P-GaN
One layer of photoresist is coated on layer, then is exposed, develops, P-GaN layers of side is etched by ICP (reactive ion etching method)
To N-GaN layers (3)；Graphene and polymethyl methacrylate (PMMA) material are uniformly mixed first, it is coated in
In substrate wafer, graphene is allow tightly to be fitted on wafer in reacting furnace, do not blown away by carrier gas or protective gas, and
PMMA also acts as the mechanical support effect to reaction product-graphene；Above-mentioned material is placed in medium temperature tube furnace, with H2To carry
Gas, N2For protective gas, the laminar film (6) of graphene is obtained with chemical vapour deposition technique；Stratiform made from above-mentioned steps
Film (6) is dipped in acetone soln, 45 DEG C of low-temperature heats, gets rid of the PMMA on surface, after cleaning repeatedly, is dried at room temperature；With
The dedicated MOCVD of First ZnO using zinc ethide as zinc source, are passed through N2 as protective gas and purge gas, O2 as reaction
Gas, control growth temperature are 450-500 DEG C, and gas flow control is for 13000sccm, reaction chamber pressure 10-
20torr, the electric current of inside and outside three circle is maintained at the level of homogeneous constant, saturating so as to obtain compactness and the preferable ZnO of transmitance
Bright conductive film (7)；By photoetching process, P electrode (8), the N-GaN layers of opposite side are prepared on the composite electrode layers of side
(3) N electrode (9) is prepared on；Deposit one layer of SiO on the electrode using PECVD2After protective layer (10), then by etching P
Electrode (8) and N electrode (9) are exposed, and complete the making of the LED chip of graphene and ZnO composite transparent electrodes.
Embodiment 3：As shown in Figure 1, a kind of LED chip with composite transparent electrode, using mocvd method in Al2O3Or
(1) growing gallium nitride buffer layer (2), N-GaN layers (3), quantum well layer (4), P-GaN layers (5) successively in GaN substrate；In P-GaN
One layer of photoresist is coated on layer, then is exposed, develops, P-GaN layers of side is etched by ICP (reactive ion etching method)
To N-GaN layers (3)；Graphene oxide and polymethyl methacrylate (PMMA) material are uniformly mixed first, it is applied
It overlays in substrate wafer, graphene oxide is allow tightly to be fitted on wafer in reacting furnace, not by carrier gas or protective gas
It blows away, and PMMA also acts as the mechanical support effect to reaction product-graphene；Above-mentioned material is placed on medium temperature tube furnace
In, with H2For carrier gas, N2For protective gas, the laminar film (6) of graphene is obtained with chemical vapour deposition technique；Above-mentioned steps
Laminar film (6) obtained is dipped in acetone soln, 45 DEG C of low-temperature heats, gets rid of the PMMA on surface, after cleaning repeatedly, room temperature
Under dry；Using USP methods, using zinc acetate as zinc source, ethyl alcohol is as solvent, the gold of the 0.1-1mol/L concentration of reaction generation
Belong to and high-temperature region is sprayed into after salting liquid is atomized in the chamber, control temperature is at 500-650 DEG C or so, so as on above-mentioned wafer
Obtain layer of ZnO conductive film (7)；By photoetching process, P electrode (8), opposite side are prepared on the composite electrode layers of side
N-GaN layers (3) on prepare N electrode (9)；Deposit one layer of SiO on the electrode using PECVD2After protective layer (10), then pass through
Etching completes the making of the LED chip of graphene and ZnO composite transparent electrodes so that P electrode (8) and N electrode (9) exposing.
Embodiment 4：As shown in Figure 1, a kind of LED chip with composite transparent electrode, using mocvd method in Al2O3Or
(1) growing gallium nitride buffer layer (2), N-GaN layers (3), quantum well layer (4), P-GaN layers (5) successively in GaN substrate；In P-GaN
One layer of photoresist is coated on layer, then is exposed, develops, P-GaN layers of side is etched by ICP (reactive ion etching method)
To N-GaN layers (3)；Graphene and polymethyl methacrylate (PMMA) material are uniformly mixed first, it is coated in
In substrate wafer, graphene is allow tightly to be fitted on wafer in reacting furnace, do not blown away by carrier gas or protective gas, and
PMMA also acts as the mechanical support effect to reaction product-graphene；Above-mentioned material is placed in medium temperature tube furnace, with H2To carry
Gas, N2For protective gas, the laminar film (6) of graphene is obtained with chemical vapour deposition technique；Stratiform made from above-mentioned steps
Film (6) is dipped in acetone soln, 45 DEG C of low-temperature heats, gets rid of the PMMA on surface, after cleaning repeatedly, is dried at room temperature；It adopts
With USP methods, using zinc acetate as zinc source, ethyl alcohol is as solvent, the metal salt solution of the 0.1-1mol/L concentration of reaction generation
High-temperature region is sprayed into after being atomized in the chamber, control temperature is at 500-650 DEG C or so, so as to obtain one layer on above-mentioned wafer
ZnO conductive films (7)；By photoetching process, P electrode (8), the N-GaN of opposite side are prepared on the composite electrode layers of side
N electrode (9) is prepared on layer (3)；Deposit one layer of SiO on the electrode using PECVD2After protective layer (10), then by etching make
It obtains P electrode (8) and N electrode (9) is exposed, complete the making of the LED chip of graphene and ZnO composite transparent electrodes.
The above embodiments and description only illustrate the principle of the present invention and most preferred embodiment, is not departing from this
Under the premise of spirit and range, various changes and improvements may be made to the invention, these changes and improvements both fall within requirement and protect
In the scope of the invention of shield.
Claims (7)
1. a kind of LED chip with composite transparent electrode, including growing nitride buffer layer, N-GaN on substrate successively
Layer, quantum well layer, P-GaN layers and composite transparent electrode layer, it is characterised in that：Being made on the N-GaN layers has n-type electrode,
Being made on composite transparent electrode layer has p-type electrode, and the chip surface deposition on the outside of the n-type electrode, p-type electrode has SiO2Protection
Layer, the composite transparent electrode layer is by graphene laminar film and the ZnO electrically conducting transparents being grown on graphene laminar film
Film laminated forms, and the graphene laminar film mixes system with polymethyl methacrylate by graphene or graphene oxide
；The SiO2Protective layer is coated on n-type electrode, p-type electrode outside, and SiO2Protective layer is etched expose n-type electrode and
P-type electrode.
2. the LED chip according to claim 1 with composite transparent electrode, it is characterised in that：The graphene layer
Shape film thickness is 2~200nm, and ZnO transparent conductive thin film thickness is 100-300nm.
3. a kind of production method of the LED chip with composite transparent electrode, includes the following steps：
A, using MOCVD technologies growing gallium nitride buffer layer, N-GaN layers, quantum well layer and P-GaN successively on a sapphire substrate
Layer；
B, one layer of photoresist is coated at P-GaN layers, then is exposed, develops, etch into the platform of N-GaN by ICP method in side
Face；
C, being made on P-GaN layers has a composite transparent electrode layer (TCL), composite transparent electrode layer by graphene laminar film and
ZnO transparent conductive thin film is combined；
D, by photoetching process, P electrode is obtained on the composite transparent electrode layer of side, N electricity is obtained on the N-GaN layers of opposite side
Pole；
E, one layer of SiO is deposited on the electrode using PECVD2It is complete after protective layer, then by etching P electrode and N electrode exposing
Into the making of LED chip；
In the step C, the production method of composite transparent electrode layer comprises the following steps：
C1, a kind of material in graphene or graphene oxide and polymethyl methacrylate materials are uniformly mixed first
It closes, mixing material is coated in chip die；
C2, the chip die coated with mixing material is placed in medium temperature tube furnace, with H2For carrier gas, N2For protective gas, with change
It learns vapour deposition process (CVD) and obtains graphene laminar film；
C3, graphene laminar film made from above-mentioned steps is dipped in acetone soln, low-temperature heat, gets rid of the poly- first on surface
Base methyl acrylate after cleaning repeatedly, dries at room temperature；
C4, layer of ZnO transparent conductive film is grown on laminar film with USP methods or mocvd method.
4. the production method of the LED chip according to claim 3 with composite transparent electrode, it is characterised in that：It is described
Step C1 in, polymethyl methacrylate is to realize uniformly to mix with graphene or graphene oxide by ultrasonic method.
5. the production method of the LED chip according to claim 3 with composite transparent electrode, it is characterised in that：It is described
Step C3 in, the method that laminar film cleans repeatedly is cleaned repeatedly using acetone, isopropanol and deionized water.
6. the production method of the LED chip according to claim 3 with composite transparent electrode, it is characterised in that：It is described
Step C4 in, the production method of ZnO transparent conductive thin film is using zinc ethide as zinc source, is passed through N2As protective gas and purging
Gas, O2As reaction gas, control growth temperature is 450-500 DEG C, and gas flow control is 10000-15000sccm, instead
It is 10-20torr to answer chamber pressure.
7. the production method of the LED chip according to claim 3 with composite transparent electrode, it is characterised in that：It is described
Step C4 in, the production method of ZnO transparent conductive thin film is using USP methods, and using zinc acetate as zinc source, ethyl alcohol is as molten
Agent sprays into high-temperature region after the metal salt solution of reaction generation is atomized in the chamber, controls temperature at 500-650 DEG C, from
And layer of ZnO conductive film is obtained in chip die.
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| CN105591001B (en) * | 2015-12-25 | 2018-09-21 | 安徽三安光电有限公司 | A kind of light emitting diode and preparation method thereof |
| CN108198922B (en) * | 2017-12-29 | 2019-07-23 | 湘能华磊光电股份有限公司 | A kind of high brightness LED chip and preparation method thereof |
| CN110797440A (en) * | 2018-08-03 | 2020-02-14 | 山东浪潮华光光电子股份有限公司 | Preparation method of light-emitting diode chip with zinc oxide as current expansion layer |
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