CN104319320A - LED chip of novel composite transparent electrode and manufacturing method of LED chip - Google Patents
LED chip of novel composite transparent electrode and manufacturing method of LED chip Download PDFInfo
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- CN104319320A CN104319320A CN201410596827.3A CN201410596827A CN104319320A CN 104319320 A CN104319320 A CN 104319320A CN 201410596827 A CN201410596827 A CN 201410596827A CN 104319320 A CN104319320 A CN 104319320A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
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- 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
Abstract
The invention discloses an LED chip of a novel composite transparent electrode. The LED chip of the novel composite transparent electrode comprises a GaN buffer layer, an N-GaN layer, a quantum well layer, a P-GaN layer, a composite transparent electrode layer, SiO2 protective layers, an n-type electrode and a p-type electrode, wherein the GaN buffer layer, the N-GaN layer, the quantum well layer and the P-GaN layer are sequentially arranged on a substrate, and the n-type electrode corresponds to the p-type electrode. The LED chip of the novel composite transparent electrode is characterized in that the composite transparent electrode layer is formed by a graphene layered thin film and a ZnO transparent conducting thin film in a compounded mode. The invention further discloses a manufacturing method of the LED chip. Due to the non-ohmic contact characteristics of a ZnO material and the P-GaN layer, the application of ZnO to an LED electrode can be greatly limited. The graphene material has visible light transmittance of 97% within the visible light spectral range and excellent conductivity and mechanical performance, when the graphene material is used in a P-type electrode contact layer, the graphene material can also make good contact with the P-GaN, a layer of ZnO is grown on the graphene, the current spreading characteristic of the graphene can also be improved, after the ZnO and the graphene are compounded, an LED composite transparent electrode layer is formed, and both the contact performance and the transmittance can be greatly improved.
Description
Technical field
The present invention relates to the technical field of LED chip, particularly a kind of LED chip and preparation method thereof of NEW TYPE OF COMPOSITE transparency electrode.
Background technology
ZnO, as a kind of novel semiconductor material with wide forbidden band, has the structure identical with GaN and similar photoelectric properties, even in exciton emission performance etc., has surmounted GaN, has become the excellent candidate of high efficiency LED and ultraviolet wavelength LED.ZnO transparent conductive thin film has very high transmissivity in visible light spectrum, and its conductivity is close to metallic film, and ito thin film is closely, through the ZnO transparent conductive thin film of overdoping or compound, have can be comparable with ito thin film electrical and optical properties.In addition, compared with ITO, ZnO has nontoxic pollution-free, abundant raw material, advantage that cost is low, through the ZnO transparent conductive thin film of overdoping, have can be comparable with ito thin film electrical and optical properties, the scope more and more come into one's own at photoelectric fields such as piezoelectric device, solar cell, Light-Emitting Diodes, studied also is got over active.And In is as a kind of scarce resource, expensive, and chip technology is comparatively complicated, so ZnO conductive film is expected to replace ITO conductive film and occupy following LED market.
But the P type doping that difficult point maximum is at present exactly ZnO is difficult to realize, so its ohmic contact characteristic as transparency conducting layer and P-GaN layer is not good, makes its extensive use be subject to a definite limitation.Graphene, since successfully being prepared, has just received the favor of numerous researchers.Graphene has the characteristic and application that as graphite, perfect geometry is the same with alkene.Graphene has higher mobility, and because the scattering mechanism of its inside is mainly based on defect scattering, so mobility is a definite value in certain temperature range, theoretical value is 200000 cm
2v
-1s
-1.Moreover, Graphene has very high transmitance (up to 97%), and its electron mobility is higher than more than three times of ITO, perfect mechanical property and excellent electrology characteristic, makes it start to obtain investigation and application widely on the electrically conductive.But due to Graphene very thin thickness, so its sheet resistance is higher, then face for conductive film the problem that resistance is high, chip forward voltage is high separately.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of novel composite transparent conductive layer, effectively can solve ZnO separately as the ohmic contact problem of transparent conductive film, and avoid the problem of Graphene and current expansion high as resistance during transparent conductive film separately, and provide the manufacture method of the LED chip with this composite transparent conductive layer, a kind of LED chip of NEW TYPE OF COMPOSITE transparency conducting layer can be produced simply and easily, improve the ohmic contact characteristic of transparency conducting layer and P-GaN layer and reduce its resistance, and improving its light extraction efficiency.
Technical scheme of the present invention is: a kind of LED chip of NEW TYPE OF COMPOSITE transparency electrode; comprise the nitride buffer layer grown successively on substrate, N-GaN layer, quantum well layer, P-GaN layer and composite transparent electrode layer; it is characterized in that: described N-GaN layer is manufactured with n-type electrode; composite transparent electrode layer is manufactured with p-type electrode; chip surface outside described n-type electrode, p-type electrode deposits SiO2 protective layer, and by Graphene laminar film and growth, the ZnO transparent conductive thin film on Graphene laminar film is composited described composite transparent electrode layer.
Described SiO2 protective layer is coated on outside n-type electrode, p-type electrode, and SiO2 protective layer goes out n-type electrode and p-type electrode through etch exposed.
Described Graphene stratiform film thickness is 2 ~ 200nm, and ZnO transparent conductive thin film thickness is 100-300nm.
A manufacture method for the LED chip of NEW TYPE OF COMPOSITE transparency electrode, comprises the steps:
A, adopt MOCVD technology growing gallium nitride resilient coating, N-GaN layer, quantum well layer and P-GaN layer successively on a sapphire substrate;
B, apply one deck photoresist in the side of P-GaN layer, then carry out exposing, developing, opposite side etches into the table top of N-GaN by ICP method;
C, on P-GaN layer, be manufactured with composite transparent electrode layer (TCL), composite transparent electrode layer is composited by Graphene laminar film and ZnO transparent conductive thin film;
D, by photoetching process, the composite transparent electrode layer of side obtains P electrode, the N-GaN layer of side obtains N electrode;
E, use PECVD deposit one deck SiO on electrode
2after protective layer, then by etching, P electrode and N electrode are exposed, complete the making of LED chip.
In described step C, the manufacture method of composite transparent electrode layer comprises following steps:
C1, first a kind of material in Graphene or graphene oxide and polymethyl methacrylate (PMMA) material are carried out Homogeneous phase mixing, composite material is coated in chip die, Graphene or graphene oxide tightly can be fitted on wafer in reacting furnace, do not blown away by carrier gas or protective gas, and PMMA also plays the mechanical support effect to product-Graphene;
C2, the chip die being coated with composite material is placed in middle temperature tube furnace, take H2 as carrier gas, N2 is protective gas, obtain Graphene laminar film with chemical vapour deposition technique (CVD);
C3, Graphene laminar film obtained for above-mentioned steps is dipped in acetone soln, low temperature (less than 55 DEG C) heats, and gets rid of the PMMA on surface, after repeatedly cleaning, dries under room temperature;
C4, on laminar film, grow layer of ZnO transparent conductive film by USP method (ultrasonic spray pyrolysis) or mocvd method.
In described step C1, PMMA is realized and Graphene or graphene oxide Homogeneous phase mixing by ultrasonic method.
In described step C3, the method that laminar film cleans repeatedly adopts acetone, isopropyl alcohol and deionized water repeatedly to clean.
In described step C4; the manufacture method of ZnO transparent conductive thin film take zinc ethide as zinc source; pass into N2 as protective gas and purge gas, O2 as reacting gas; control growth temperature is 450-500 DEG C; gas flow controls be 10000-15000sccm; reaction chamber pressure is 10-20torr, and the electric current that interior China and foreign countries three are enclosed remains on the level of homogeneous constant, thus obtains compactness and transmitance preferably ZnO transparent conductive thin film.
In described step C4, the manufacture method of ZnO transparent conductive thin film adopts USP method, using zinc acetate as zinc source, ethanol is as solvent, high-temperature region is sprayed into after the metal salt solution that reaction generates is atomized in the chamber, control temperature is at about 500-650 DEG C, and the concentration of metal salt solution is preferably 0.1-1mol/L, thus in chip die, obtain layer of ZnO conductive film.
Beneficial effect of the present invention is: the compound transparent electricity conductive film being obtained Graphene/ZnO by simple chemical vapour deposition technique, the Homogeneous phase mixing of material is realized by ultrasonic method, then the laminated film of Graphene and ZnO is freely spread on P-GaN layer, technique is simple, easy to operate, both the ohmic contact problem of zinc-oxide film and P-GaN had been efficiently solved, effectively can avoid again Graphene separately as the problem of high value during conductive film and current expansion, and after Graphene and ZnO compound, form the composite transparent electrode layer of LED, contact performance and transmissivity can be largely increased.
accompanying drawing explanation
Fig. 1 is the structural representation with the LED chip of NEW TYPE OF COMPOSITE transparency electrode of the present invention.
In figure, 1-substrate, 2-resilient coating, 3-N-GaN layer, 4-quantum well layer, 5-P-GaN layer, 6-Graphene laminar film, 7-ZnO conductive film, 8-P electrode, 9-N electrode, 10-SiO
2protective layer.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further:
embodiment 1:as shown in Figure 1, a kind of LED chip of NEW TYPE OF COMPOSITE transparency electrode, adopts mocvd method at Al
2o
3or (1) growing gallium nitride resilient coating (2), N-GaN layer (3), quantum well layer (4), P-GaN layer (5) successively in GaN substrate; P-GaN layer applies one deck photoresist, then carries out exposing, developing, by ICP(reactive ion etching method) side of P-GaN layer is etched into N-GaN layer (3); First graphene oxide and polymethyl methacrylate (PMMA) material are carried out Homogeneous phase mixing, it is coated in substrate wafer, graphene oxide tightly can be fitted on wafer in reacting furnace, do not blown away by carrier gas or protective gas, and PMMA also plays the mechanical support effect to product-Graphene; Above-mentioned material is placed in middle temperature tube furnace, with H
2for carrier gas, N
2for protective gas, obtain the laminar film (6) of Graphene with chemical vapour deposition technique; The laminar film (6) that above-mentioned steps is obtained is dipped in acetone soln, 45 DEG C of low-temperature heats, gets rid of the PMMA on surface, repeatedly after cleaning, dries under room temperature; With the MOCVD that First ZnO is special, be zinc source with zinc ethide, pass into N
2as protective gas and purge gas, O
2as reacting gas, control growth temperature is 450-500 DEG C, and gas flow controls be 13000sccm, and reaction chamber pressure is 10-20torr, the electric current that interior China and foreign countries three are enclosed remains on the level of homogeneous constant, thus obtains compactness and transmitance preferably ZnO transparent conductive thin film (7); By photoetching process, on the composite electrode layers of side, prepare P electrode (8), the N-GaN layer (3) of opposite side prepares N electrode (9); After using PECVD to deposit one deck SiO2 protective layer (10) on electrode, then by etching, P electrode (8) and N electrode (9) are exposed, complete the making of the LED chip of Graphene and ZnO composite transparent electrode.
embodiment 2:as shown in Figure 1, a kind of LED chip of NEW TYPE OF COMPOSITE transparency electrode, adopts mocvd method at Al
2o
3or (1) growing gallium nitride resilient coating (2), N-GaN layer (3), quantum well layer (4), P-GaN layer (5) successively in GaN substrate; P-GaN layer applies one deck photoresist, then carries out exposing, developing, by ICP(reactive ion etching method) side of P-GaN layer is etched into N-GaN layer (3); First Graphene and polymethyl methacrylate (PMMA) material are carried out Homogeneous phase mixing, it is coated in substrate wafer, Graphene tightly can be fitted on wafer in reacting furnace, do not blown away by carrier gas or protective gas, and PMMA also plays the mechanical support effect to product-Graphene; Above-mentioned material is placed in middle temperature tube furnace, and take H2 as carrier gas, N2 is protective gas, obtains the laminar film (6) of Graphene with chemical vapour deposition technique; The laminar film (6) that above-mentioned steps is obtained is dipped in acetone soln, 45 DEG C of low-temperature heats, gets rid of the PMMA on surface, repeatedly after cleaning, dries under room temperature; With the MOCVD that First ZnO is special, take zinc ethide as zinc source, pass into N2 as protective gas and purge gas, O2 as reacting gas, control growth temperature is 450-500 DEG C, gas flow controls be 13000sccm, reaction chamber pressure is 10-20torr, and the electric current that interior China and foreign countries three are enclosed remains on the level of homogeneous constant, thus obtains compactness and transmitance preferably ZnO transparent conductive thin film (7); By photoetching process, on the composite electrode layers of side, prepare P electrode (8), the N-GaN layer (3) of opposite side prepares N electrode (9); After using PECVD to deposit one deck SiO2 protective layer (10) on electrode, then by etching, P electrode (8) and N electrode (9) are exposed, complete the making of the LED chip of Graphene and ZnO composite transparent electrode.
embodiment 3:as shown in Figure 1, a kind of LED chip of NEW TYPE OF COMPOSITE transparency electrode, adopts mocvd method at Al
2o
3or (1) growing gallium nitride resilient coating (2), N-GaN layer (3), quantum well layer (4), P-GaN layer (5) successively in GaN substrate; P-GaN layer applies one deck photoresist, then carries out exposing, developing, by ICP(reactive ion etching method) side of P-GaN layer is etched into N-GaN layer (3); First graphene oxide and polymethyl methacrylate (PMMA) material are carried out Homogeneous phase mixing, it is coated in substrate wafer, graphene oxide tightly can be fitted on wafer in reacting furnace, do not blown away by carrier gas or protective gas, and PMMA also plays the mechanical support effect to product-Graphene; Above-mentioned material is placed in middle temperature tube furnace, and take H2 as carrier gas, N2 is protective gas, obtains the laminar film (6) of Graphene with chemical vapour deposition technique; The laminar film (6) that above-mentioned steps is obtained is dipped in acetone soln, 45 DEG C of low-temperature heats, gets rid of the PMMA on surface, repeatedly after cleaning, dries under room temperature; Adopt USP method, using zinc acetate as zinc source, ethanol, as solvent, sprays into high-temperature region after the metal salt solution of the 0.1-1mol/L concentration of reaction generation is atomized in the chamber, control temperature at about 500-650 DEG C, thus obtains layer of ZnO conductive film (7) on above-mentioned wafer; By photoetching process, on the composite electrode layers of side, prepare P electrode (8), the N-GaN layer (3) of opposite side prepares N electrode (9); After using PECVD to deposit one deck SiO2 protective layer (10) on electrode, then by etching, P electrode (8) and N electrode (9) are exposed, complete the making of the LED chip of Graphene and ZnO composite transparent electrode.
embodiment 4:as shown in Figure 1, a kind of LED chip of NEW TYPE OF COMPOSITE transparency electrode, adopts mocvd method at Al
2o
3or (1) growing gallium nitride resilient coating (2), N-GaN layer (3), quantum well layer (4), P-GaN layer (5) successively in GaN substrate; P-GaN layer applies one deck photoresist, then carries out exposing, developing, by ICP(reactive ion etching method) side of P-GaN layer is etched into N-GaN layer (3); First Graphene and polymethyl methacrylate (PMMA) material are carried out Homogeneous phase mixing, it is coated in substrate wafer, Graphene tightly can be fitted on wafer in reacting furnace, do not blown away by carrier gas or protective gas, and PMMA also plays the mechanical support effect to product-Graphene; Above-mentioned material is placed in middle temperature tube furnace, and take H2 as carrier gas, N2 is protective gas, obtains the laminar film (6) of Graphene with chemical vapour deposition technique; The laminar film (6) that above-mentioned steps is obtained is dipped in acetone soln, 45 DEG C of low-temperature heats, gets rid of the PMMA on surface, repeatedly after cleaning, dries under room temperature; Adopt USP method, using zinc acetate as zinc source, ethanol, as solvent, sprays into high-temperature region after the metal salt solution of the 0.1-1mol/L concentration of reaction generation is atomized in the chamber, control temperature at about 500-650 DEG C, thus obtains layer of ZnO conductive film (7) on above-mentioned wafer; By photoetching process, on the composite electrode layers of side, prepare P electrode (8), the N-GaN layer (3) of opposite side prepares N electrode (9); After using PECVD to deposit one deck SiO2 protective layer (10) on electrode, then by etching, P electrode (8) and N electrode (9) are exposed, complete the making of the LED chip of Graphene and ZnO composite transparent electrode.
What describe in above-described embodiment and specification just illustrates principle of the present invention and most preferred embodiment; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.
Claims (9)
1. the LED chip of a NEW TYPE OF COMPOSITE transparency electrode; comprise the nitride buffer layer grown successively on substrate, N-GaN layer, quantum well layer, P-GaN layer and composite transparent electrode layer; it is characterized in that: described N-GaN layer is manufactured with n-type electrode; composite transparent electrode layer is manufactured with p-type electrode; chip surface outside described n-type electrode, p-type electrode deposits SiO2 protective layer, and by Graphene laminar film and growth, the ZnO transparent conductive thin film on Graphene laminar film is composited described composite transparent electrode layer.
2. the LED chip of NEW TYPE OF COMPOSITE transparency electrode according to claim 1, is characterized in that: described SiO2 protective layer is coated on outside n-type electrode, p-type electrode, and SiO2 protective layer goes out n-type electrode and p-type electrode through etch exposed.
3. the LED chip of NEW TYPE OF COMPOSITE transparency electrode according to claim 1, is characterized in that: described Graphene stratiform film thickness is 2 ~ 200nm, and ZnO transparent conductive thin film thickness is 100-300nm.
4. a manufacture method for the LED chip of NEW TYPE OF COMPOSITE transparency electrode, comprises the steps:
A, adopt MOCVD technology growing gallium nitride resilient coating, N-GaN layer, quantum well layer and P-GaN layer successively on a sapphire substrate;
B, apply one deck photoresist at P-GaN layer, then carry out exposing, developing, etched into the table top of N-GaN in side by ICP method;
C, on P-GaN layer, be manufactured with composite transparent electrode layer (TCL), composite transparent electrode layer is composited by the laminar film of Graphene and ZnO transparent conductive thin film;
D, by photoetching process, the composite transparent electrode layer of side obtains P electrode, the N-GaN layer of opposite side obtains N electrode;
E, use PECVD deposit one deck SiO on electrode
2after protective layer, then by etching, P electrode and N electrode are exposed, complete the making of LED chip.
5. the manufacture method of the LED chip of NEW TYPE OF COMPOSITE transparency electrode according to claim 4, it is characterized in that: in described step C, the manufacture method of composite transparent electrode layer comprises following steps:
C1, first a kind of material in Graphene or graphene oxide and polymethyl methacrylate (PMMA) material are carried out Homogeneous phase mixing, composite material is coated in chip die;
C2, the chip die being coated with composite material is placed in middle temperature tube furnace, take H2 as carrier gas, N2 is protective gas, obtain Graphene laminar film with chemical vapour deposition technique (CVD);
C3, Graphene laminar film obtained for above-mentioned steps is dipped in acetone soln, low-temperature heat, gets rid of the PMMA on surface, repeatedly after cleaning, dries under room temperature;
C4, on laminar film, grow layer of ZnO transparent conductive film with USP method or mocvd method.
6. the manufacture method of the LED chip of NEW TYPE OF COMPOSITE transparency electrode according to claim 5, is characterized in that: in described step C1, and PMMA is realized and Graphene or graphene oxide Homogeneous phase mixing by ultrasonic method.
7. the manufacture method of the LED chip of NEW TYPE OF COMPOSITE transparency electrode according to claim 5, is characterized in that: in described step C3, and the method that laminar film cleans repeatedly adopts acetone, isopropyl alcohol and deionized water repeatedly to clean.
8. the manufacture method of the LED chip of NEW TYPE OF COMPOSITE transparency electrode according to claim 5, is characterized in that: in described step C4, the manufacture method of ZnO transparent conductive thin film take zinc ethide as zinc source, passes into N
2as protective gas and purge gas, O
2as reacting gas, control growth temperature is 450-500 DEG C, and gas flow controls as 10000-15000sccm, and reaction chamber pressure is 10-20torr.
9. the manufacture method of the LED chip of NEW TYPE OF COMPOSITE transparency electrode according to claim 5, it is characterized in that: in described step C4, the manufacture method of ZnO transparent conductive thin film adopts USP method, using zinc acetate as zinc source, ethanol is as solvent, spray into high-temperature region after the metal salt solution that reaction generates is atomized in the chamber, control temperature at about 500-650 DEG C, thus obtains layer of ZnO conductive film in chip die.
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| CN108198922A (en) * | 2017-12-29 | 2018-06-22 | 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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| CN104319320B (en) | 2018-06-22 |
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