Semiconductor light-emitting-diode and preparation method thereof
Technical field:
The present invention relates to a kind of light emitting semiconductor device and method for making thereof, especially a kind of semiconductor light-emitting-diode and preparation method thereof.
Background technology:
Semiconductor light-emitting-diode (LED) is that the semiconductor light-emitting-diode of the solid light source of low-cost long-life, particularly visible light wave range has widely in room lighting, flat panel display, junction service each side such as light interconnection in the computer and uses.Though semiconductor light-emitting-diode (LED) has very high internal light emission efficiency, common LED only has the light extraction efficiency of a few percent, how will take out owing to the high-index semiconductor inner total reflection is confined to interior most of light, the light-emitting diode of developing and produce high light-emitting efficiency is the difficult problem that people need to be resolved hurrily always, causes people's extensive concern and research.
Over past ten years,, obtained a series of achievements, as utilized the surface to become crude, transparent substrates and upper caldding layer, photon recirculation, coherent scattering and microcavity effect etc. for improving the light-emitting diode light extraction efficiency.Thereby proposed various ways, wherein had random texturing of (1) nano surface level and bottom to add speculum combine (I.Schnitzer, E.Yablonovitch, etc, Appl.Phys.Lett.63 (16), 2174 (1993); ); (2) microcavity LED (F.Schubert, Y.H.Wang, etc, Appl.Phys.Lett., 60,921 (1992), J.J.Wierer, D.A.Kellogg, and N.Holonyak, Jr.Appl.Phys.Lett., 74,926 (1999)); (3) two-dimensional photon crystal structure (M.Boroditsky for example, T.F.Krauss, etc, Appl.Phys.Lett.75,1036, (1999); And A.A.Erchak, D.J.Ripin, etc, Appl.Phys.Lett., 78,563 (2001)) etc. method.These methods make the LED light extraction efficiency all obtain effectively improving.But method (1) is the random microstructure that forms the deep-submicron yardstick on LED surface, also the semiconductor LED heteroepitaxy multilayer film of several micron thickness only " must be peeled off " from its substrate base, transfers on the mirror substrate; Prague (Bragg) mirror surface that method (2) need replace by the epitaxy technology growing multiple layer film of accurate control, the requirement of growing technology is also very high; Method (3) is the forward position achievement in research that obtains under optical pumping recently, will adopt the technology of " peeling off " or growth Bragg speculum equally, and not make the practicability LED that electricity injects at present as yet.The common feature of these methods is technology complexity, and difficulty is big, and in addition, the LED (near infrared band and red-light LED) of GaAs base is mainly studied and prepare to these methods with son at present.Therefore if adopt the shorter visible light emitting diode of said method development wavelength, little processing or epitaxially grown requirement and technical difficulty are all higher.
On the other hand, GaN base short wavelength's (purple light is to blue green light) light-emitting diode is the light-emitting diode that a class has broad prospect of application, and therefore improving its light extraction efficiency is an important topic equally.Recently, H.X.Jiang group confirms that InGaN base little dish-type (about 10 microns of diameter) blue light-emitting diode has the quantum efficiency higher than large area LED, and the emission effciency of little dish-type LED of interconnection is only high by 60% (referring to S.X.Jin than common LED of the same area, J.Li, J.Y.Lin, and H.X.Jiang, Appl.Phys.Lett., 77.3236 (2001)).(J.Cryst.Growth 201/202 for S.Nakamura, the exiting surface of GaN base blue green light LED 290 (1999)) has adopted the practice of transparency electrode beyond the contact of p-type electrode, solved the scaling problem of injection current, its cost is the light extraction efficiency that has reduced LED.
Summary of the invention:
The purpose of this invention is to provide and a kind ofly have the high light-emitting efficiency simple semiconductor light-emitting-diode of preparation technology simultaneously, and the method for preparing this semiconductor light-emitting-diode.
Semiconductor light-emitting-diode of the present invention, its top surface has the two-dimensional and periodic micro-structural; This two-dimensional and periodic micro-structural can be periodically honeycomb or periodically concentric ring structure.
Semiconductor light-emitting-diode light-emitting area of the present invention has the electrode contact area, and luminous table top is a disk structure.
The cycle of described two-dimensional and periodic micro-structural is submicron order or micron order; Depth of microstructure reaches the n type district of semiconductor light-emitting-diode.
The method for preparing the said structure semiconductor light-emitting-diode of the present invention has two kinds, and first kind is the preparation method of common photoetching and the little processing combination of etching, and its step comprises:
1) designs the semiconductor light-emitting-diode lithographic cell domain that top surface has the two-dimensional and periodic micro-structural;
2) epitaxial growth light-emitting diode substrate;
3) on substrate, carry out the deposit of p metal ohmic contact multilayer film;
4) carry out photoetching according to domain;
5) etching;
6) make n type metallized multilayer film ohmic contact;
7) alloying obtains the semiconductor light-emitting-diode core.
The cycle of two-dimensional and periodic micro-structural is submicron order or micron order in the described cell design domain; Luminous table top is a disk structure; Light-emitting area has the electrode contact area.
Etching is a dry etching, and the degree of depth reaches n type district; Make the back side or positive n type metallized multilayer film ohmic contact as required.
The method that another kind of the present invention prepares the said structure semiconductor light-emitting-diode is focused ion beam (FIB) preparation method, and its step comprises:
1) designs semiconductor light-emitting-diode photoetching and FIB cell layout with two-dimensional and periodic micro-structural;
2) epitaxial growth semiconductor light-emitting-diode substrate;
3) on substrate, carry out the deposit of p type metal ohmic contact multilayer film;
4) table top photoetching;
5) etching;
6) make n type metallized multilayer film ohmic contact;
7) alloying;
8) on p type table top, carry out the FIB etching, obtain the semiconductor light-emitting-diode core.
The luminous table top of described light-emitting diode is a disk structure; Light-emitting area has the electrode contact area.
The two-dimensional and periodic micro-structural can be periodically honeycomb or periodically concentric ring structure in the described cell design domain; The described cycle is submicron order or micron order;
Described etching is dry method or wet etching, and the degree of depth reaches the n type district of semiconductor light-emitting-diode; Make the back side or positive n metallized multilayer film ohmic contact as required.
Principle of the present invention and good effect analysis:
Different with the square mesa basic structure of S.Nakamura and general GaN base blue-green light LED, the present invention has adopted the disc type mesa structure.Because the disc pattern that exists in the disc type table top more helps increasing output intensity, the present invention proposes an imagination on the basis of disc type luminous substantially chamber mode configuration and p type metal electrode maturation process, promptly utilize on the light-emitting area certain two-dimensional and periodic micro-structural to come out from LED top coupling platform because of the light that total reflection is confined in light-emitting diode inside.For this reason, the present invention proposes two kinds of concrete schemes, a kind of is to form the honeycomb type light-emitting diode with micro-processing technology manufacturing cycle micron order cavity dot matrix on the disc type table top; Another kind is to etch the concentric annular groove of micron order width and form concentric ring-like light-emitting diode on the disc type table top.Simultaneously, the electricity that the contact of p type metal electrode is set in light emitting diode disc formula mesa designs structure injects contact, and guarantees the expansion of injection current on light-emitting diode p face.
That is to say that the present invention adopts the microstructure graph design of the deep hole or the concentric ring deep trouth that have two-dimensional and periodic on the p-type light-emitting area of the basic ray structure of existing square light-emitting diode; By to the light-emitting diode substrate with the micro-processing technology that carries out common photoetching and etching phase combination, perhaps focused ion beam (FIB) process technology produces and comprises the semiconductor light-emitting-diode with honeycomb type or concentric ring-like micro-structural.
The above-mentioned design that has the semiconductor light-emitting-diode of two-dimensional and periodic micro-structural at two kinds of different preparation methods of common photoetching and FIB, is adopted two class design layout.The common feature of its layout design is the luminous round platform of luminous tube, micro-structural to be contacted in etching procedure with the electric injecting electrode in p district finish simultaneously.Light extraction efficiency is increased substantially, both simplified process simultaneously, reduced requirement again craft precision.
No matter adopt the light-emitting diode that has micro-structural of project organization domain of the present invention and preparation method preparation, be honeycomb type light-emitting diode or concentric ring-like light-emitting diode, all obtained excellent characteristic and positive effect.These two kinds luminous intensities that have the disc type light-emitting diode of micro-structural of experiment confirm have all obtained tangible improvement.(seeing the luminous comparison of accompanying drawing 6-10)
Major advantage of the present invention comprises:
(1) the of the same area common square that on identical epitaxial wafer, prepares of beam intensity ratio do not have a micro-structural light-emitting diode 1.6-8 doubly.Therefore light-emitting diode light extraction efficiency of the present invention has obtained effective raising;
(2) design layout of the present invention is simple with the technological process of working out.As adopt the ordinary semiconductor micro fabrication, only need 2-3 piece lithography design domain.On epitaxial substrate, only need to finish light-emitting diode chip for backlight unit through p electrode evaporation, micro-structural photoetching and etching and n electrode alignment and a small amount of operation of evaporation.If adopt the FIB technology, more can on submicron-scale, change microstructure design pattern, size and etching parameters flexibly, at the concrete structure of each epitaxial wafer, light-emitting diode is optimized design and processing.
(3) solved transparency electrode in the preparation of InGaN base blue LED lowly influences light extraction efficiency because of transmitance problem.
(4) the present invention is not only applicable to InGaN base blue green light and InGaAlP red light-emitting diode, and can be used for other wave band and the semiconductor light-emitting-diode of material system and making, research and the production of Organic Light Emitting Diode.
Therefore the present invention has opened up new thinking for the light extraction efficiency that improves semiconductor light-emitting-diode, a kind of new method for preparing high efficiency, high-brightness LED has been proposed, have tangible economic benefit, can be applicable to the manufacturing of various semiconductor light-emitting-diodes, promote the development of led technology.
Description of drawings:
Fig. 1 has nitrogenize thing based light-emitting diode structural representation now
1---Sapphire Substrate 2---GaN resilient coating 3---n type GaN 4---InGaN/GaN mqw active layer 5---p type GaN 7---p type ohmic contact layer 11---n type ohmic contact layer 12---p type ohmic contact transparency electrode
The nitride based light emitting diode construction schematic diagram of Fig. 2 the present invention
The nitride based concentric round light emitting diode construction schematic diagram of Fig. 2 (a) the present invention
1---Sapphire Substrate 2---GaN resilient coating 3---n type GaN 4---InGaN/GaN mqw active layer 5---p type GaN 7---p type ohmic contact layer 10---two-dimensional and periodic concentric ring groove 11---n type ohmic contact layer 13---p type electrode contact area
The nitride based honeycomb type light emitting diode construction of Fig. 2 (b) the present invention schematic diagram
9---two-dimensional and periodic honeycomb type micropore
Fig. 3 GaAs of the present invention (or other semiconductor) based light-emitting diode structural representation
The concentric ring-like light emitting diode construction schematic diagram of Fig. 3 (a) the present invention GaAs based (or other semiconductor)
21---Semiconductor substrate 22---epitaxial buffer layer 23---n type epitaxial loayer 24---mqw active layer 25---p type epitaxial loayer 27---p type ohmic contact layer 30---two-dimensional and periodic concentric ring groove 31---n type ohmic contact layer 33---p type electrode contact area
Fig. 3 (b) the present invention GaAs based (or other semiconductor) honeycomb type light emitting diode construction schematic diagram
29---two-dimensional and periodic honeycomb type micropore
Fig. 4 cell design domain
Fig. 4 (a) concentric ring microstructure unit design layout
Fig. 4 (b) honeycomb type microstructure unit design layout
Fig. 4 (c) n type ohmic contact hole cell design domain
Fig. 4 (d) p type round table surface cell design domain
Fig. 5 method---(nitride based luminous tube is an example) main technique schematic flow sheet
Fig. 5 (a) spares glue
The 8---photoresist
Fig. 5 (b) photoetching
Fig. 5 (c) etching
Fig. 5 (d) makes n type ohmic contact
The luminous pattern of the nitride based blue light-emitting diode of Fig. 6 is (injection current 2mA) relatively
The common square light-emitting diode of Fig. 6 (a)
The concentric ring-like light-emitting diode of Fig. 6 (b) the present invention
Fig. 6 (c) honeycomb type light-emitting diode of the present invention
The nitride based blue light-emitting diode luminosity of Fig. 7 relatively
Fig. 7 (a) spectrogram
"-" line style is represented common square LED, and "---" line style is represented concentric ring-like LED, " ... " line style is represented honeycomb type LED
Fig. 7 (b) integration light intensity and injection current graph of a relation
" ■-" line style is represented common square LED, and " ●-" line style is represented concentric ring-like LED, and " ▲-" line style is represented honeycomb type LED
The luminous pattern of the GaAs based red light-emitting diode of Fig. 8 is (injection current 2mA) relatively
The common square light-emitting diode of Fig. 8 (a)
The concentric ring-like light-emitting diode of Fig. 8 (b) the present invention
Fig. 8 (c) honeycomb type light-emitting diode of the present invention
The GaAs based red light-emitting diode luminosity of Fig. 9 relatively
Fig. 9 (a) spectrogram
"-" line style is represented common square LED, and "---" line style is represented concentric ring-like LED, " ... " line style is represented honeycomb type LED
Fig. 9 (b) relative integral light intensity and injection current graph of a relation
" ■-" line style is represented common square LED, and " ●-" line style is represented concentric ring-like LED, and " ▲-" line style is represented honeycomb type LED
The luminous pattern of the nitride based blue light-emitting diode of Figure 10 is (injection current 80mA) relatively
The common light-emitting diode of the no micro-structural of Figure 10 (a)
The concentric ring-like light-emitting diode of Figure 10 (b) FIB of the present invention
The nitride based blue light-emitting diode luminosity of Figure 11 relatively
Figure 11 (a) spectrogram
"-" line style is represented the concentric ring-like LED of FIB, " ... " the no micro-structural LED of line style representative
Figure 11 (b) relative integral light intensity and injection current graph of a relation
"-●-" line style represents the concentric ring-like LED of FIB, the no micro-structural LED of " △-" line style representative
Specific embodiments:
Embodiment 1
Honeycomb type and concentric ring-like InGaN based quantum well blue light-emitting diode
1. adopt metal oxide chemical vapor deposition (MOCVD) equipment growing InGaN Multiple Quantum Well (MQW) epitaxial wafer, the hierarchical structure of epitaxial wafer is:
P-GaN (thickness d=50-300nm, carrier concentration p=3-5 * 10
17Cm
-3)/P-AlGaN (aluminum gallium nitride) (d=5-20nm, p=1-3 * 10
17Cm
-3)/3 quantum well [In
xGa
1-xN (indium component x=0.18-0.25, d=20-30nm)/GaN (d=70-100nm)] QW/n-GaN (d=2000-3000nm, carrier concentration n=2 * 10
18Cm
-3)/GaN resilient coating (d=25-30m)/Sapphire Substrate;
2. with direct current sputtering deposition techniques p type ohmic contact double-level-metal film gold (5-500 nanometer)/nickel (5-40 nanometer);
3. adopt the normal optical lithography on sample, to form Fig. 4 (a) or figure (b);
4. be mask with the photoresist, successively carry out argon (Ar) ion beam etching and boron chloride (BCl
3) reactive ion etching, carry out the photoetching alignment with Fig. 4 (c) domain;
5. with direct current sputtering and lift-off technology deposition n type ohmic contact double-level-metal film gold (100-500 nanometer)/titanium (20-40 nanometer);
6. short annealing forms ohmic contact.Annealing (condition 450-500 ℃, 2-5 minute) under blanket of nitrogen.
Embodiment 2
Honeycomb type and concentric ring-like InGaAlP quantum well red light-emitting diode
1. adopt MOCVD InGaAlP quantum well (QW) epitaxial wafer;
2. use vacuum thermal evaporation deposition techniques p type ohmic contact double-level-metal film gold (100-500 nanometer)/chromium (20-40 nanometer), and under the nitrogen and hydrogen mixture atmosphere, carry out in-situ alloy (400-450 ℃, 2-5 minute);
3. adopt the normal optical lithography on sample, to form domain Fig. 4 (a) or figure (b);
4. be mask with the photoresist, successively carry out the Ar ion beam etching, total etching depth reaches n type district;
5. back side n type ohmic contact alloy film gold germanium nickel (AuGeNi) vacuum thermal evaporation and alloy (400-450 ℃, 2-5 minute).
Embodiment 3
The concentric ring-like InGaN based quantum well blue light-emitting diode preparation process of FIB:
1. adopt MOCVD equipment growing InGaN Multiple Quantum Well (MQW) epitaxial wafer (with embodiment 1);
2. with embodiment 1 step 2;
3. adopt the normal optical lithography on epitaxial wafer, to form the figure of domain 4 (d);
4. be mask with the photoresist, carry out BCl
3Reactive ion etching, total etching depth reaches n type district;
5. carry out the photoetching alignment with domain 4 (c);
6. with direct current sputtering and lift-off technology deposition n type ohmic contact double-level-metal film gold (5-500 nanometer)/titanium (5-40 nanometer)
7. the blanket of nitrogen short annealing forms ohmic contact (450-500 ℃, 2-5 minute);
8.p-carry out the FIB etching by domain 4 (a) or 4 (b) on district's round table surface, etching depth reaches n type district.