CN102856450B - GaN based light-emitting diode and manufacturing method thereof - Google Patents
GaN based light-emitting diode and manufacturing method thereof Download PDFInfo
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- CN102856450B CN102856450B CN201210353406.9A CN201210353406A CN102856450B CN 102856450 B CN102856450 B CN 102856450B CN 201210353406 A CN201210353406 A CN 201210353406A CN 102856450 B CN102856450 B CN 102856450B
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Abstract
The invention discloses a GaN based light-emitting diode, which comprises a substrate, an n type contract layer, an active layer and a p type contact layer, which are overlaid sequentially. The substrate is a sapphire substrate, the n type contact layer is an n type AlGaN layer, the p type contact layer is a p type GaN layer, and the active layer is an AlGaN multi-quantum well. The invention further discloses a manufacturing method of the GaN based light-emitting diode, which comprises the steps: preparing and processing the sapphire substrate; and sequentially depositing an AlN mould layer, a low temperature GaN insertion layer, an AlGaN transitional layer, the n type contact layer, the active layer, a p type electronic barrier layer, a p type transitional layer, and the p type contact layer on the sapphire substrate. The processed sapphire substrate is used as the substrate to form the light-emitting diode, so that the breakdown field strength is enhanced, the leakage is reduced, the heat conduction is increased, the light-emitting efficiency is higher and the reliability is greater. The method can remarkably reduce the crystal defect density in the substrate of the light-emitting diode and improve the performance and the service life of the light-emitting diode.
Description
Technical field
The present invention relates to a kind of manufacture method of light-emitting diode.
Background technology
Semiconductor light-emitting-diode (LED) is a kind of diode of being made up of the compound of Ga, N, As, P etc., in the time of electronics and hole-recombination, can send visible ray, can be used for manufacturing luminescent device, because it is simple in structure, volume is little, and operating current is little, easy to use, cost is low, has been widely used at present various electro-optical systems.
Semiconductor light-emitting-diode comprises substrate and is deposited on successively P/N type epitaxial loayer, active layer and the P/N type epitaxial loayer on substrate.Substrate, as the ground of LEDZhe Zuo mansion, has important effect.Sapphire is a kind of conventional LED substrate, in Sapphire Substrate, generally all can comprise various defects, such as dislocation, gap or room etc., defect can cause crystal strain, strain meeting causes the quality of epitaxial loayer on substrate and performance to reduce, and causes the lost of life of light-emitting diode.
For many years, along with the development of semiconductor technology, process those skilled in the art studying for a long period of time and putting into practice, and have formed comparatively perfect crystal growth technique flow process, have reduced the defect concentration forming in semiconductor substrate materials growth course.But people also wish to obtain the substrate that defect concentration is lower, make the light-emitting diode that performance is better, the life-span is longer.How further to reduce or eliminate defect and become this area urgent problem.
Summary of the invention
In order to overcome the defect existing in prior art, the invention provides a kind of manufacture method of GaN base semiconductor LED, the method can significantly reduce the defect concentrations in crystals in light-emitting diode substrate, improves performance and the life-span of light-emitting diode.
GaN based light-emitting diode of the present invention comprises the substrate, N-shaped contact layer, active layer and the p-type contact layer that stack gradually;
Wherein, substrate is sapphire, and N-shaped contact layer is N-shaped AlGaN layer, and p-type contact layer is p-type GaN layer; Active layer is AlGaN Multiple Quantum Well.
Active layer is preferably the Al in 3-6 cycle
xga
1-xn/Al
yga
1-yn Multiple Quantum Well, wherein x=0-0.5, y=0.2-0.7.
The thickness of active layer is preferably 6-9nm.
Between Sapphire Substrate and N-shaped contact layer, there is AlN template layer, low temperature GaN insert layer and AlGaN transition zone.
Between active layer and p-type contact layer, also comprise p-type electronic barrier layer and p-type transition zone.Preferably, p-type electronic barrier layer 8 is p-type AlGaN layer, and p-type transition zone 9 is p-type AlGaN transition zone.
The manufacture method of GaN based light-emitting diode of the present invention comprises prepares and processes Sapphire Substrate, and in Sapphire Substrate depositing Al N template layer, low temperature GaN insert layer and AlGaN transition zone, N-shaped contact layer, active layer, p-type electronic barrier layer, p-type transition zone and p-type contact layer successively.
The method that wherein forms Sapphire Substrate comprises the steps:
(1) at normal temperatures and pressures, sapphire wafer is put into high temperature high pressure device, add transmission medium in high temperature high pressure device, this transmission medium is NaCL and liquid nitrogen;
(2) pressurization when sapphire wafer heating, being heated to temperature is 950～1020 DEG C, being forced into pressure is 4.5 ~ 4.9GPa, keeps 10～15 minutes; Wherein, the rate of heat addition is 100 DEG C/min, and compression rate is 0.2～0.3GPa/ minute.
(3) stop heating, make sapphire wafer be cooled to normal temperature; Slowly release, makes sapphire wafer return to normal pressure simultaneously.Release speed is 0.5～0.8GPa/ minute.
(4) in high temperature high pressure device, anneal after 20～30 minutes, take out sapphire wafer.
Brief description of the drawings
Fig. 1 is the structural representation of semiconductor light-emitting-diode of the present invention.
Embodiment
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
GaN based light-emitting diode of the present invention comprise the substrate 1, N-shaped contact layer 2, active layer 3 and the p-type contact layer 4 that stack gradually.
Wherein, substrate 1 is sapphire, and N-shaped contact layer 2 is N-shaped AlGaN layer, and p-type contact layer 4 is p-type GaN layer.
Active layer 3 is AlGaN Multiple Quantum Well, and preferred AlGaN active layer is the Al in 3-6 cycle
xga
1-xn/Al
yga
1-yn Multiple Quantum Well, wherein, the thickness of trap is 1-3nm, Al component x=0-0.5; The thickness of building is 5-10nm, Al component y=0.2-0.7, and it is the quantum well of transmitting deep UV (ultraviolet light) wave band.
Between Sapphire Substrate 1 and N-shaped contact layer 2, there is AlN template layer 5, low temperature GaN insert layer 6 and AlGaN transition zone 7.
Between active layer 3 and p-type contact layer 4, also comprise p-type electronic barrier layer 8 and p-type transition zone 9.Preferably, p-type electronic barrier layer 8 is p-type AlGaN layer, and p-type transition zone 9 is p-type AlGaN transition zone.
The manufacture method of GaN base semiconductor LED of the present invention, comprise and prepare and process Sapphire Substrate, and in Sapphire Substrate depositing Al N template layer, low temperature GaN insert layer and AlGaN transition zone, N-shaped contact layer, active layer, p-type electronic barrier layer, p-type transition zone and p-type contact layer successively.
The method that wherein forms Sapphire Substrate comprises the steps:
(1) at normal temperatures and pressures, sapphire wafer is put into high temperature high pressure device, add transmission medium in high temperature high pressure device, this transmission medium is NaCL and liquid nitrogen;
(2) pressurization when sapphire wafer heating, heating-up temperature is 950～1020 DEG C, moulding pressure is 4.5 ~ 4.9GPa, keeps 10～15 minutes; Moulding pressure herein may also be referred to as pressurization pressure.Wherein, the rate of heat addition is 100 DEG C/min, and compression rate is 0.2～0.3GPa/ minute.
(3) stop heating, make sapphire wafer be cooled to normal temperature; Slowly release, makes sapphire wafer return to normal pressure simultaneously.Release speed is 0.5～0.8GPa/ minute.
(4) in high temperature high pressure device, anneal after 20～30 minutes, take out sapphire wafer.
The present invention has carried out the experiment of 30 groups of different temperatures and pressure limit, and sapphire wafer carried out to high temperature high pressure process.Experimental data shows, it is 950～1020 DEG C that sapphire wafer is implemented to heating-up temperature, after moulding pressure is the high temperature high pressure process annealing of 4.5 ~ 4.9GPa, it is before treatment 25～35% that the density in its dislocation and space is reduced to, and illustrates that the method has obviously reduced the defect concentration in wafer.Experimental data also shows, defect concentration and the heating-up temperature of wafer after processing, moulding pressure are relevant, and its Main Function of temperature range and pressure limit, but heating, pressurization and decompression rate are also to its effect of the minimizing of defect concentration, above record preferred temperature and pressure scope, and preferred heating, pressurization and decompression rate.Cooling does not need to adopt specific process, stops heating rear naturally cooling.The light-emitting diode that adopts sapphire wafer after treatment to form as substrate, has increased disruptive field intensity, has reduced electric leakage, has increased thermal conductivity, and light emission effciency is higher, and reliability is larger.
Can adopt top, existing two sides and polyhedron high-pressure installation for the treatment of the high temperature high pressure device of wafer of the present invention, polyhedron high-pressure installation comprises hexahedron pressure chamber device and the octahedra chamber device of pressing.Preferably adopt two sides to push up the quiet high-pressure installation of large cavity, push up large press referred to as two sides.The shell of this device and the material of depression bar are steel alloy, and pressing the material of anvil is tungsten carbide.Adopting this two sides to push up the maximum pressure that large press can reach is 7GPa.Although its maximum pressure is compared, polyhedron high-pressure installation and diamond anvil cell ultra-high pressure apparatus are low, and because its cavity volume is large, the diameter of processing sample, from ten centimetres of left and right, is suitable for processing substrate wafer.
In this high-pressure installation, be provided with electric calorifie installation, it provides heating heat by heating wire, to heating wafer after electric calorifie installation energising.Heating-up temperature reaches as high as 1700 degrees Celsius.
Pressure medium is sodium chloride (NaCl), magnesium oxide (MgO) or liquid nitrogen, and this medium can make pressure be evenly distributed on crystal, makes non-isotropy stress minimum.
NaCl and MgO are low shearing strength solid, and its coefficient of internal friction is lower than 0.2, can well pressure transmission, play heat insulation effect simultaneously, and pressurization is beneficial to heat.Liquid nitrogen, in playing pressure transmission effect, can be restrained the decomposition of GaN in the time of heating and annealing.
In Sapphire Substrate, the concrete grammar of depositing Al N template layer, low temperature GaN insert layer and AlGaN transition zone, N-shaped contact layer, active layer, p-type electronic barrier layer, p-type transition zone and p-type contact layer is successively:
Adopt metal organic chemical vapor deposition equipment, adopt metal organic chemical vapor deposition equipment, reaction chamber temperature is elevated to 1050-1200 DEG C, at Grown on Sapphire Substrates AlN template layer; Temperature is reduced to 400-900 DEG C, and the GaN layer that under pressure 30-200torr, growth thickness is 20-50nm on AlN template layer is as low temperature GaN insert layer; Be warming up to 1050-1200 DEG C, the AlGaN transition zone of growing in low temperature GaN insert layer; Reaction chamber temperature is elevated to 1050-1200 DEG C, the AlGaN transition zone of growing in low temperature GaN insert layer; Keep temperature-resistant, on AlGaN transition zone, growing n-type AlGaN layer is as N-shaped contact layer; Keep temperature-resistant, the AlGaN active layer of growth transmitting deep UV (ultraviolet light) wave band on N-shaped AlGaN layer; Keep temperature-resistant, growing p-type AlGaN electronic barrier layer and transition zone successively on AlGaN active layer; On p-type AlGaN transition zone, growing p-type GaN layer is as p-type contact layer.
Certainly; the present invention also can have other various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art are when making according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.
Claims (3)
1. a manufacture method for GaN based light-emitting diode, comprises the steps:
Prepare and process Sapphire Substrate, and in Sapphire Substrate depositing Al N template layer, low temperature GaN insert layer and AlGaN transition zone, N-shaped contact layer, active layer, p-type electronic barrier layer, p-type transition zone and p-type contact layer successively; It is characterized in that,
The method of described processing Sapphire Substrate comprises the steps:
(1) at normal temperatures and pressures, sapphire wafer is put into high temperature high pressure device, add transmission medium in high temperature high pressure device, this transmission medium is NaCL and liquid nitrogen;
(2) pressurization when sapphire wafer heating, being heated to temperature is 950～1020 DEG C, being forced into pressure is 4.5 ~ 4.9GPa, keeps 10～15 minutes;
(3) stop heating, make sapphire wafer be cooled to normal temperature; Slowly release, makes sapphire wafer return to normal pressure simultaneously;
(4) in high temperature high pressure device, anneal after 20～30 minutes, take out sapphire wafer.
2. the manufacture method of GaN based light-emitting diode as claimed in claim 1, is characterized in that, in step (2), the rate of heat addition of heating is 100 DEG C/min, and the compression rate of pressurization is 0.2～0.3GPa/ minute.
3. the manufacture method of GaN based light-emitting diode as claimed in claim 1 or 2, is characterized in that, the release speed of described slow release is 0.5～0.8GPa/ minute.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101140867A (en) * | 2007-07-26 | 2008-03-12 | 西安电子科技大学 | GaN thin film upgrowth method based on Al3O2 substrate |
| CN101299449A (en) * | 2008-06-20 | 2008-11-05 | 华南师范大学 | GaN-based LED epitaxial wafer and preparation method thereof |
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| JP4443097B2 (en) * | 2002-06-20 | 2010-03-31 | ソニー株式会社 | GaN-based semiconductor device fabrication method |
| WO2012012010A2 (en) * | 2010-04-30 | 2012-01-26 | Trustees Of Boston University | High efficiency ultraviolet light emitting diode with band structure potential fluctuations |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101140867A (en) * | 2007-07-26 | 2008-03-12 | 西安电子科技大学 | GaN thin film upgrowth method based on Al3O2 substrate |
| CN101299449A (en) * | 2008-06-20 | 2008-11-05 | 华南师范大学 | GaN-based LED epitaxial wafer and preparation method thereof |
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