CN105185883A - Coarsened-sidewall AlGaInP-base LED and manufacture method thereof - Google Patents
Coarsened-sidewall AlGaInP-base LED and manufacture method thereof Download PDFInfo
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- CN105185883A CN105185883A CN201510653644.5A CN201510653644A CN105185883A CN 105185883 A CN105185883 A CN 105185883A CN 201510653644 A CN201510653644 A CN 201510653644A CN 105185883 A CN105185883 A CN 105185883A
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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
- H01L33/02—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 semiconductor bodies
- H01L33/20—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 semiconductor bodies with a particular shape, e.g. curved or truncated substrate
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
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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
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
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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
- H01L33/0093—Wafer bonding; Removal of the growth substrate
Abstract
The invention relates to a coarsened-sidewall AlGaInP-base LED and a manufacture method thereof and belongs to the technical field of semiconductors. The method comprises steps of: bonding an epitaxial wafer on a permanent substrate by using a metallic bonding layer on the epitaxial wafer and a metallic bonding layer on the permanent substrate in order to form a bonded semi-finished product; removing a temporary substrate, a buffer layer, and a cutoff layer on the bonded semi-finished product in order to expose an ohmic contact layer; etching and patterning the ohmic contact layer, and manufacturing a n-type expansion electrode, a main electrode, and a back electrode; and etching a cutting channel at least reaching a p-GaP window layer on the periphery of the epitaxial layer of each LED chip, coarsening the surface and the sidewall of the epitaxial layer in order that the surface and the sidewall of the epitaxial layer are coarsened. The manufacture method is simple in technology, convenient in production, and capable of increasing electro-optical conversion efficiency, prolonging the service life of the LED, enlarging a visual angle, and improving the display effect of an LED screen.
Description
Technical field
The present invention relates to structure and the manufacture method of a kind of AlGaInP base LED of sidewall alligatoring, belong to technical field of semiconductors.
Background technology
The AlGaInP sill mated with GaAs substrate lattice is a kind of direct gap semiconductor, and by adjusting the ratio of Al and Ga, energy gap can change between 1.9eV to 2.3eV, and the wave-length coverage of AlGaInP base LED can cover 550nm-650nm.Therefore, AlGaInP sill has been widely used in the manufacture of ruddiness, orange light, green-yellow light LED.Because the refractive index n of AlGaInP sill is up to 3.0 to 3.5, far above LED conventional encapsulation materials such as epoxy resin, silica gel (n ≈ 1.5).According to the total reflection law of light, light enters optically thinner medium from optically denser medium can produce total reflection phenomenon in interface, and the refractive index difference of both sides, interface is larger, and the cirtical angle of total reflection is less.This makes the light extraction efficiency of AlGaInP base LED very low.In fact, this problem is also present in GaAsLED and GaNLED.
To this, I.Schnitzer etc. propose the method [Appl.Phys.Lett., Vol.63, No.16,2174-2176, (1993)] that surface coarsening improves the external quantum efficiency of GaAsLED.The optical coupling that S.Fan etc. propose to adopt 2 D photon crystal to be sent active area exports, thus improves light extraction efficiency [Phys.Rev.Lett., Vol.78, No.17,3294-3297, (1997)].AlGaInPLED chip cutting is become rescinded angle reverse pyramid (truncated-inverted-pyramid) by M.R.Krames etc., thus the angle changed between the light of directive sidewall and sidewall normal direction, reduce interface total reflection, improve light extraction efficiency [Appl.Phys.Lett., Vol.75, No.16,2365-2367, (1999)].C.S.Chang etc. adopt optical graving for mask pattern, then adopt ICP to be dry-etched in GaNLED sidewall to form semicircle periodic patterns, improve light extraction efficiency [IEEEPhotonic.Technol.Lett., Vol.16, No.3,750-752, (2004)].
In the above-mentioned methods, the method being improved LED light extraction efficiency by surface coarsening is extensively adopted by industry, becomes a kind of conventional techniques of LED industry.In AlGaInP base LED, prior art mainly carries out alligatoring to epi-layer surface, and sidewall method of roughening only has a small amount of report.A left side causes the people of grade far away and proposes to adopt optical graving for mask pattern, and recycling wet etching, in the method for AlGaInPLED sidewall formation periodic pattern, is shown in Chinese Patent Application No. 201310108349.2.
But to so far, the random submicron-scale figure of aperiodicity is that conventional lithographic is prepared mask pattern method and cannot be realized.
Summary of the invention
For above-mentioned mention cause the problem that the light extraction efficiency of AlGaInP base LED is very low due to interface total reflection phenomenon, on the basis of existing surface texture technology, the present invention proposes a kind of AlGaInP based LED construction of sidewall alligatoring.
The present invention is disposed with metal bonding layer, ODR speculum, epitaxial loayer, N-shaped expansion electrode and main electrode in the permanent substrate with back electrode; ODR speculum is made up of metallic reflector and media coating, and media coating is connected with epitaxial loayer; Metallic reflector is connected with metal bonding layer; N-shaped expansion electrode is connected with main electrode electricity; Be characterized in that epi-layer surface and sidewall are all in alligatoring shape.
Beneficial effect of the present invention has: (1) can improve the light extraction efficiency of AlGaInP base LED further, and LED chip brightness is improved 10% to 30%, thus improves electro-optical efficiency; (2) because light extraction efficiency improves, the light that LED material itself absorbs reduces, and caloric value is corresponding reduction also, thus can extend the life-span of LED; (3) because sidewall alligatoring makes the corresponding increase of the lighting angle of LED chip, this is for LED display, can increase visible angle, improves the display effect of LED screen.
Further, the pattern of alligatoring shape of the present invention is acyclic random figure, and described dimension of picture is submicron order.This submicron order figure has the size comparable with visible wavelength range 380nm to 760nm.Acyclic random figure, can have scattering and diffracting effect to the light of different wave length, if periodic regular figure, then only effective to the light of specific wavelength.Because LED of the present invention is visible LED, the figure of submicron order can produce scattering and diffraction to the light of this wave band more effectively.
Described dimension of picture is 100nm ~ 1 μm.
Epitaxial loayer of the present invention can adopt conventional expitaxial layer, comprising: p-GaP Window layer, p-AlGaInP limiting layer, MQW multiple quantum well active layer, n-AlGaInP limiting layer, n-AlGaInP current extending, N-shaped roughened layer, n-GaAs ohmic contact layer.
The present invention is along the thickness direction of LED, and the p-GaP Window layer sidewall of described epitaxial loayer is non-alligatoring, or part alligatoring, or any one in complete alligatoring.If Cutting Road etch depth just arrives p-GaP surface in production and processing, then p-GaP sidewall will be non-alligatoring state; If Cutting Road etches into the inner certain depth of p-GaP, then p-GaP sidewall will be part alligatoring state; If Cutting Road runs through p-GaP, then p-GaP sidewall will be complete alligatoring state, and these three kinds of states are all normal.
The media coating of described ODR speculum is SiO
2, Si
3n
4, MgF
2, in ITO at least any one, metallic reflector be in Ag, Al, Au, AuZn alloy, AuBe alloy at least any one.The starting point of this design is the ODR speculum in order to obtain high reflectance, and described media coating and metallic reflector can carry out different combinations.
Another object of the present invention proposes with the manufacture method of the AlGaInP based light-emitting diode of upper side wall alligatoring.
Comprise the following steps:
1) epitaxial growth buffer, cutoff layer, n-GaAs ohmic contact layer, N-shaped roughened layer, n-AlGaInP current extending, n-AlGaInP limiting layer, MQW multiple quantum well active layer, p-AlGaInP limiting layer, p-GaP Window layer successively on temporary substrates, forms epitaxial wafer;
The p-GaP Window layer of epitaxial wafer makes ODR speculum and metal bonding layer successively;
2) metal bonding layer is made in permanent substrate front;
3) by the metal bonding layer on epitaxial wafer and the metal bonding layer in permanent substrate, by wafer bonding in permanent substrate, the semi-products of bonding are formed;
4) remove temporary substrates, resilient coating and the cutoff layer on the good semi-products of bonding, expose n-GaAs ohmic contact layer;
5) etch patterned n-GaAs ohmic contact layer, and make N-shaped expansion electrode on n-GaAs ohmic contact layer surface;
6) on expansion electrode, main electrode is made;
7) back electrode is made at the permanent substrate back side.
The feature of present invention process is: after described step 6), etches in the surrounding of each LEDs chip epitaxial loayer the Cutting Road at least reaching p-GaP Window layer, then does roughening treatment to the surface of epitaxial loayer and sidewall.
The present invention is common process substantially, just by first etching Cutting Road, then does roughening treatment to the surface of epitaxial loayer and sidewall.So the present invention has the advantage that technique is simple, facilitate production operation.
In addition, the solution that the present invention does roughening treatment to the surface of epitaxial loayer and sidewall is HCl, H
2sO
4, H
3pO
4, HNO
3, HBr, I
2, CH
3cOOH, HF, NH
4f, NH
4oH, H
2o
2in at least one.
Accompanying drawing explanation
Fig. 1 is the structural representation having made ODR speculum and metal bonding layer in manufacturing process on epitaxial wafer surface.
Fig. 2 is the structural representation made metal bonding layer in manufacturing process in permanent substrate after.
Fig. 3 is a kind of cross-sectional view of the present invention.
Fig. 4 is the vertical view of Fig. 3.
Fig. 5 is the another kind of vertical view of Fig. 3.
Fig. 6 be scanning electron microscopy shooting epi-layer surface of the present invention or sidewall alligatoring after typical surface pattern.
Embodiment
One, be the structural representation of preferred embodiment of the present invention in manufacturing process as illustrated in fig. 1 and 2, manufacturing step is as follows:
1, as shown in Figure 1, adopt MOCVD device at GaAs temporary substrates 101 growing epitaxial layers, epitaxial loayer comprises resilient coating 102, GaInP cutoff layer 103, n-GaAs ohmic contact layer 104, n-AlGaInP roughened layer 105, n-AlGaInP current extending 106, n-AlGaInP limiting layer 107, MQW multiple quantum well active layer 108, p-AlGaInP limiting layer 109, p-GaP Window layer 110.
Wherein n-GaAs ohmic contact layer 104 preferred thickness is 20nm to 100nm, and doping content is 1 × 10
19cm
-3above, doped chemical is Si, to form good ohmic contact with N-shaped expansion electrode 204.The preferred thickness of p-GaP Window layer 110 is 600nm to 8000nm, and doping content is 1 × 10
18cm
-3above, doped chemical is Mg, to ensure the ohmic contact that p face is good and current expansion ability.
Adopt acetone, isopropyl alcohol, deionized water to clean the p-GaP Window layer 110 in epitaxial wafer front successively, nitrogen dries up, and p-GaP Window layer deposits SiO
2media coating 111, by spin coating positive photoresist, exposure, mask pattern is made in development, adopts BOE solution by SiO
2(or Si
3n
4, MgF
2, any one or combination in ITO) media coating 111 etches conductive hole, is that the Al of AuZn and 500nm of 300nm is as metallic reflector 112 at the surperficial evaporation thickness of media coating 111.Metallic reflector 112 also can adopt any one or combination in Ag, Al, Au, AuZn alloy, AuBe alloy.By SiO
2media coating 111 and AuZn/Al metallic reflector 112 form ODR speculum jointly, simultaneously SiO
2in deielectric-coating conductive hole, AuZn and p-GaP Window layer forms good electricity contact through 440 DEG C of annealing 10min.
On the ODR speculum made, evaporation thickness is that the Au of 1000nm is as metal bonding layer 113.
2, as shown in Figure 2, in permanent substrate---on Si substrate 201, evaporation thickness is that the Au of 1000nm is as metal bonding layer 202.
Permanent substrate also can adopt in Mo substrate, Cu substrate, SiC substrate, Ge substrate, molybdenum-copper substrate or tungsten-copper alloy substrate any one.
3, the goods that goods step 1 made and step 2 are made immerse ultrasonic cleaning 10min in acetone soln, and then use isopropyl alcohol and deionized water rinsing respectively totally, nitrogen dries up.By relative with 202 for metal bonding layer 113,300 DEG C, through 20min, both are bonded to together under the effect of 5000kg pressure.
The temporary substrates of the goods 4, utilizing mechanical lapping mode step 3 to be made---GaAs substrate 101 is thinned to residue about 20 μm, then is the NH of 1:5 by volume ratio
4oH and H
2o
2mixed solution etching 10min, remove GaAs temporary substrates 101 and resilient coating 102, chemical etching stops on GaInP cutoff layer 103, then immerses HCl and H that volume ratio is 1:2
3pO
4etch 1min in mixed solution, remove GaInP cutoff layer 103, expose n-GaAs ohmic contact layer 104.
5, by spin coating positive photoresist on n-GaAs ohmic contact layer 104, after soft baking, exposure, development, hard baking, then the H that volume ratio is 1: 2: 2 is immersed
3pO
4, H
2o
2and H
2the mixed solution of O, etches n-GaAs ohmic contact layer 104 figure, then removes photoresist, cleans.
6, on the n-GaAs ohmic contact layer 104 making figure, adopt the mode evaporation thickness of electron beam evaporation plating to be the AuGeNi alloy material of 400nm, then through gluing, photoetching, adopt after the techniques such as development volume ratio be 1: 2: 5 I
2, KI and H
2the mixed solution of O etches N-shaped expansion electrode 204.Carry out annealing 10min process by 350 DEG C of nitrogen atmosphere annealing furnaces, make N-shaped expansion electrode 204 and n-GaAs ohmic contact layer 104 form good electricity and contact.
First GaAs can be etched figure, then make N-shaped expansion electrode, also first can make N-shaped expansion electrode on n-GaAs ohmic contact layer surface, then n-GaAs is etched figure.
7, the goods made after N-shaped expansion electrode 204 are immersed acetone soln ultrasonic cleaning 10min, then use isopropyl alcohol and deionized water rinsing successively, nitrogen dries up.Carry out photolithographic procedures again, spin coating negative photoresist, soft baking, exposure, develop, be spin-dried for, then carry out plasma and play glue, the Au that evaporation is 4 μm covers on n-AlGaInP roughened layer 105 and N-shaped expansion electrode 204, forms main electrode 205 after peeling off.Main electrode 205 can be that part covers or covers N-shaped expansion electrode 204 completely, respectively as shown in Figure 4 and Figure 5.
In Fig. 4, main electrode 205 part covers main electrode 205 in expansion electrode 204, Fig. 5 and covers expansion electrode 204 completely.
The figure of the n-GaAs ohmic contact layer 104 etched and the figure of N-shaped expansion electrode 204 both can be the same or different.
8, at the surperficial spin coating positive photoresist with N-shaped expansion electrode 204 and main electrode 205, soft baking, exposure, development, firmly to dry, form masking layer figure during etching Cutting Road, adopt ICP dry etching epitaxial loayer again, the degree of depth reaches p-GaP Window layer 110, form Cutting Road, then remove photoresist, clean.
Also any one method in wet etching, blade cuts, laser cutting can be adopted during etching Cutting Road.
9, the goods making Cutting Road being immersed volume ratio is the H of 1: 1: 7
3pO
4, H
2sO
4and CH
3in the mixed solution of COOH, roughening treatment is carried out to n-AIGaInP roughened layer 105 surface and Cutting Road sidewall, form the random submicron-scale pattern of aperiodicity, typical case's shape characteristic as shown in Figure 6, dimension of picture is submicron order, has the size comparable with visible wavelength range 380nm to 760nm.
Along Cutting Road depth direction, p-GaP Window layer 110 sidewall of epitaxial loayer can be non-alligatoring, or part alligatoring, or any one in complete alligatoring.
10, in permanent substrate---the mode that Si substrate 201 back side adopts electron beam hot evaporation respectively evaporation thickness is Ti, Au of 20nm and 100nm, completes the making of device back electrode.
When permanent substrate is any one in Si substrate, Ge substrate, SiC substrate, step 10 needs to comprise substrate thinning, back electrode evaporation, back electrode alloy three contents.
Two, the product structure feature made:
As shown in Fig. 3,4,5, the permanent substrate 201 with back electrode 203 is disposed with metal bonding layer 202 and 113, ODR speculum 112 and 111, epitaxial loayer 104-110, N-shaped expansion electrode 204 and main electrode 205.
Wherein, ODR speculum is made up of metallic reflector 112 and media coating 111, and media coating 111 is connected with epitaxial loayer; Metallic reflector 112 is connected with metal bonding layer 113; N-shaped expansion electrode 204 is connected with main electrode 205 electricity.
Epitaxial loayer comprises: p-GaP Window layer 110, p-AlGaInP limiting layer 109, MQW multiple quantum well active layer 108, n-AlGaInP limiting layer 107, n-AlGaInP current extending 106, N-shaped roughened layer 105, n-GaAs ohmic contact layer 104.LED chip epi-layer surface and sidewall are alligatoring, and pattern is acyclic random figure, and pattern character size is 100nm ~ 1 μm, is a kind of sub-micrometer scale, has the size comparable with visible wavelength range 380nm to 760nm.
Claims (8)
1. the AlGaInP base LED of sidewall alligatoring, the permanent substrate with back electrode is disposed with metal bonding layer, ODR speculum, epitaxial loayer, N-shaped expansion electrode and main electrode; ODR speculum is made up of metallic reflector and media coating, and media coating is connected with epitaxial loayer; Metallic reflector is connected with metal bonding layer; N-shaped expansion electrode is connected with main electrode electricity; The surface and the sidewall that it is characterized in that epitaxial loayer are alligatoring shape.
2. the AlGaInP base LED of sidewall alligatoring according to claim 1, it is characterized in that the pattern of described alligatoring shape is acyclic random figure, described dimension of picture is submicron order.
3. the AlGaInP base LED of sidewall alligatoring according to claim 2, is characterized in that described dimension of picture is 100nm ~ 1 μm.
4. the AlGaInP base LED of sidewall alligatoring according to claim 1 or 2 or 3, is characterized in that described epitaxial loayer comprises: p-GaP Window layer, p-AlGaInP limiting layer, MQW multiple quantum well active layer, n-AlGaInP limiting layer, n-AlGaInP current extending, N-shaped roughened layer, n-GaAs ohmic contact layer.
5. the AlGaInP base LED of sidewall alligatoring according to claim 4, is characterized in that the thickness direction along LED, and the p-GaP Window layer sidewall of described epitaxial loayer is non-alligatoring, or part alligatoring, or any one in complete alligatoring.
6. the AlGaInP base LED of sidewall alligatoring according to claim 1, is characterized in that the media coating of described ODR speculum is SiO
2, Si
3n
4, MgF
2, in ITO at least any one, metallic reflector be in Ag, Al, Au, AuZn alloy, AuBe alloy at least any one.
7. the manufacture method of the AlGaInP based light-emitting diode of sidewall alligatoring as claimed in claim 1, comprises the following steps:
1) epitaxial growth buffer, cutoff layer, n-GaAs ohmic contact layer, N-shaped roughened layer, n-AlGaInP current extending, n-AlGaInP limiting layer, MQW multiple quantum well active layer, p-AlGaInP limiting layer, p-GaP Window layer successively on temporary substrates, forms epitaxial wafer;
The p-GaP Window layer of epitaxial wafer makes ODR speculum and metal bonding layer successively;
2) metal bonding layer is made in permanent substrate front;
3) by the metal bonding layer on epitaxial wafer and the metal bonding layer in permanent substrate, by wafer bonding in permanent substrate, the semi-products of bonding are formed;
4) remove temporary substrates, resilient coating and the cutoff layer on the good semi-products of bonding, expose n-GaAs ohmic contact layer;
5) etch patterned n-GaAs ohmic contact layer, and make N-shaped expansion electrode on n-GaAs ohmic contact layer surface;
6) on N-shaped expansion electrode, main electrode is made;
7) back electrode is made at the permanent substrate back side;
It is characterized in that: after described step 6), etch in the surrounding of each LEDs chip epitaxial loayer the Cutting Road at least reaching p-GaP Window layer, then roughening treatment is done to the surface of epitaxial loayer and sidewall.
8. manufacture method according to claim 7, is characterized in that: the solution surface of epitaxial loayer and sidewall being done to roughening treatment is HCl, H
2sO
4, H
3pO
4, HNO
3, HBr, I
2, CH
3cOOH, HF, NH
4f, NH
4oH, H
2o
2in at least one.
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