CN103137840A - Light emitting diode of white light and manufacturing method - Google Patents
Light emitting diode of white light and manufacturing method Download PDFInfo
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- CN103137840A CN103137840A CN2013100609246A CN201310060924A CN103137840A CN 103137840 A CN103137840 A CN 103137840A CN 2013100609246 A CN2013100609246 A CN 2013100609246A CN 201310060924 A CN201310060924 A CN 201310060924A CN 103137840 A CN103137840 A CN 103137840A
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Abstract
The invention provides a light emitting diode of white light with photonic crystal. The light-emitting dioxide comprises a substrate, an n-type contact layer, an active luminescent layer, a p-type contact layer. The active luminescent layer is located in the middle of the n-type contact layer and the p-type contact layer. The multiple-hole shape photonic crystal is arranged on the surface layer of the light-emitting dioxide, fluorescent powder with a nanometer quantity is filled inside the hole, and a transparent electrode is covered on the surface. The light-emitting dioxide is arranged inside the hole of the surface layer photonic crystal. The filling particle size is yellow, red or green fluorescent powder with a nanometer quantity; the surface of the photonic crystal is covered by the indium tin oxide (ITO) transparent electrode.
Description
Technical field
The present invention relates to technical field of semiconductors, particularly relate to a kind of manufacture method with white light emitting diode of photonic crystal.
Background technology
At present III-V family photoelectric semiconductor material is described as third generation semi-conducting material.And GaN series LED owing to can produce the light-emitting diode (referred to as " LED ") of various coloured light (blue light or the purple light that especially need high energy gap) by the composition of controlling material, and becomes the emphasis of industry research.
The preparation method of gallium nitrate based white light emitting diode adopts blue light-emitting diode to add yellow fluorescent powder.Excite yellow fluorescent powder to send gold-tinted by blue light-emitting diode, then mix mutually with blue light that blue LED sends, form a kind white light source.At present adding with blue chip the method that yellow fluorescent powder prepares white light emitting diode is all yellow fluorescent powder to be mixed be placed on blue chip, is about to fluorescent material and mixes with silica gel, is filled in the space on the lens inside chip; Perhaps fluorescent material being made tabular pressure puts on light-emitting diode chip for backlight unit.Perhaps fluorescent material is mixed in ceramic substrate inside, excites ceramic substrate and luminous by blue-ray LED.
At present external more novel way is that fluorescent material is placed in packaged glass lens (as US Patent No. 7858408B2), need not to refill fluorescent material between LED chip and lens; Other method is that fluorescent material is applied to chip surface (as European patent EP 2105976A2), and yellow fluorescent powder is coated in LED chip surface, the direct excitating surface yellow fluorescent powder of the light that LED sends.But these two kinds of methods are complex manufacturing technology not only, and wastes time and energy, and has greatly increased the cost of manufacture of LED.
Summary of the invention
For this purpose, the invention provides a kind of white light emitting diode with photonic crystal, it comprises: substrate, N-shaped contact layer, active luminescent layer, p-type contact layer, described active luminescent layer are positioned in the middle of N-shaped contact layer and p-type contact layer; Described cellular photonic crystal is produced on the top layer of described light-emitting diode, and its poroid inside is filled with the fluorescent material of nanometer scale, and its surface coverage has transparency electrode.
White light LEDs manufacture method provided by the invention need not fluorescent material to be mixed with silica gel or as in glass lens again, but fluorescent material directly is placed in the pit of chip surface, and manufacture craft is simple, cost is low is another maximum characteristics of the present invention.
Description of drawings
Fig. 1 is the positive assembling structure LED structure with gallium nitride system schematic diagram that has photonic crystal in the present invention;
Fig. 2 is the vertical stratification LED structure with gallium nitride system schematic diagram with photonic crystal in the present invention.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The invention discloses a kind of light-emitting diode with photonic crystal, it comprises: substrate, N-shaped contact layer, active luminescent layer, p-type contact layer, described active luminescent layer are positioned in the middle of N-shaped contact layer and p-type contact layer; Described cellular photonic crystal is produced on the top layer of described light-emitting diode, and its poroid inside is filled with the fluorescent material of nanometer scale, and its surface coverage has transparency electrode.
Described light-emitting diode can be formal dress, upside-down mounting or vertical stratification, and in positive assembling structure, described cellular photonic crystal is produced on the p-type contact layer; In inverted structure, described cellular photonic crystal is produced in the substrate of top layer; And in vertical stratification, described cellular photonic crystal is produced on the N-shaped contact layer.
Above-mentioned light-emitting diode can be made other layer as required between N-shaped contact layer and p-type contact layer, to improve the performance of light-emitting diode, this belongs to known in the art, is not described further at this.
According to a preferred embodiment of the invention, Fig. 1 shows a kind of GaN series LED of positive assembling structure, and as shown in Figure 1, GaN series LED comprises:
One substrate 11, (Al2O3) is substrate 11 take (0001) to sapphire, and other materials that can be used for substrate 11 comprise that also alumina single crystal, 6H-SiC, 4H-SiC or the lattice constant of R-face or A-face are close to the monocrystalline oxide of nitride-based semiconductor.Adopt high-purity N H3 to do the N source in preparation, the mist of high-purity H2 and N2 is done carrier gas; Trimethyl gallium or triethyl-gallium are done the Ga source, and trimethyl indium is done the In source, and trimethyl aluminium is done the Al source; The N-shaped dopant is silane, and the p-type dopant is two luxuriant magnesium.
One gallium nitride nucleating layer 12, this gallium nitride nucleating layer 12 is produced on substrate 11.
One resilient coating 13, this resilient coating 13 is produced on nucleating layer 12, is made of gallium nitride.
One N-shaped contact layer 14, this N-shaped contact layer 14 is produced on resilient coating 13, and this N-shaped contact layer 14 is made of the N-shaped gallium nitride.
One active luminescent layer 15, this activity luminescent layer 15 is produced on N-shaped contact layer 14 and covers the part surface of described N-shaped contact layer 14, and described active luminescent layer 15 is to be made of the multiply periodic quantum well structure that indium gallium nitrogen thin layer and gallium nitride thin layer interaction cascading form.
One p-type electronic barrier layer 16, this p-type electronic barrier layer 16 are produced on the gallium nitride thin layer of active luminescent layer 15, and this p-type electronic barrier layer 16 is made of aluminum gallium nitride.
One p-type contact layer 17, this p-type contact layer 17 is produced on p-type electronic barrier layer 16, and this p-type contact layer 17 is made of the p-type gallium nitride.
One photon crystal 18, this photonic crystal are produced on p-type contact layer 17 as the top layer, and this photonic crystal is the airport structure, and hole diameter is the 50-1000 nanometer; The hole spacing is 0.1 micron-10 microns; The degree of depth in hole is: the 50-1000 nanometer; Arranging of hole can be the distribution of triangle, square, hexagon or other any shapes.
Porous photonic crystal can be to make by methods such as electron beam exposure, laser hologram exposure interference, nano impression or ps balls.
One nano-particle fluorescence powder 19, the particle diameter of this nanoscale fluorescent material are the 10-100 nanometer.Fluorescent material can be one or more mixtures in yellow, redness or green emitting phosphor.This fluorescent material is spun in photonic crystal hole.
Ultrasonic-spin-coating method is adopted in the coating of described nano-particle fluorescence powder.Concrete grammar is as follows: the epitaxial wafer level with photon crystal structure of processing is placed on carrier (annotating: with the surface of photon crystal structure up); The fluorescent material of getting a little nano particle evenly is sprinkling upon whole epitaxial wafer surface; The carrier that then will hold epitaxial wafer is placed in ultrasonic machine, low frequency ultrasound 5-10 minute.Epitaxial wafer is taken out, be positioned on sol evenning machine, under the rotating speed that 100-500 turns, at the uniform velocity rotated 5-10 minute.Afterwards, take out epitaxial wafer, dip a small amount of acetone or alcohol solution with non-dust cloth, clean gently epitaxial wafer surface, the nano-phosphor particle removal that the surface is unnecessary.Then epitaxial wafer is placed on hot plate and heated 5-10 minute under 50-100 ℃, remove residual acetone or alcohol.
One transparency electrode 20, this transparency electrode is produced on the photon crystal surface that the nano-particle fluorescence powder is housed.This transparency electrode can be indium tin oxide (ITO), zinc oxide (ZnO), nickel gold electrode etc.
One negative electrode 21, this negative electrode 21 are produced on N-shaped contact layer 14 not by on the surface of described active luminescent layer 15 coverings, are comprised of chromium platinum or titanium aluminium titanium.
One positive electrode 22, this positive electrode 22 is produced on transparency electrode 20, is comprised of chromium platinum or titanium aluminium titanium.
According to another preferred embodiment of the invention, Fig. 2 shows a kind of GaN series LED of vertical stratification, and as shown in Figure 2, the GaN series LED of vertical stratification comprises:
One substrate, with (0001) to sapphire (Al
2O
3) be substrate, other materials that can be used for substrate comprise that also alumina single crystal, 6H-SiC, 4H-SiC or the lattice constant of R-face or A-face are close to the monocrystalline oxide of nitride-based semiconductor.Adopt high-purity N H3 to do the N source in preparation, the mist of high-purity H2 and N2 is done carrier gas; Trimethyl gallium or triethyl-gallium are done the Ga source, and trimethyl indium is done the In source, and trimethyl aluminium is done the Al source; The N-shaped dopant is silane, and the p-type dopant is two luxuriant magnesium.
One gallium nitride nucleating layer, this gallium nitride nucleating layer is produced on substrate.
One resilient coating, this resilient coating is produced on nucleating layer, and this resilient coating is made of gallium nitride.
One N-shaped contact layer 23, this N-shaped contact layer 23 is produced on resilient coating, and this N-shaped contact layer 23 is made of the N-shaped gallium nitride.
One active luminescent layer 24, this activity luminescent layer 24 is produced on N-shaped contact layer 23, and described active luminescent layer 24 is to be made of the multiply periodic quantum well structure that indium gallium nitrogen thin layer and gallium nitride thin layer interaction cascading form.
One p-type electronic barrier layer 25, this p-type electronic barrier layer 25 are produced on active luminescent layer 24, and this p-type electronic barrier layer 25 is made of aluminum gallium nitride.
One p-type contact layer 26, this p-type contact layer 26 is produced on p-type electronic barrier layer 25, and this p-type contact layer 26 is made of the p-type gallium nitride.
One high-reflecting film 27, this high-reflecting film 25 is produced on p-type contact layer 26, and this high-reflecting film can be one or more in Al, Ag, Cr, Pt, Au.This high-reflecting film is completed by electron beam evaporation process.
One conductive substrates 28, this conductive substrates 28 are that the mode by thermocompression bonding or plating is produced on high-reflecting film 25.This conductive substrates 28 can be metallic copper substrate or copper-tungsten or copper molybdenum alloy.Can be also Si or other conductive substrates.
One separates substrate by the method for laser glass or chemical corrosion with the gallium nitride nucleating layer.
One removes gallium nitride nucleating layer and gallium nitride resilient coating by the method for dry etching or wet etching, until exposed N-shaped contact layer 23.
One photonic crystal 29, this photonic crystal are produced on top layer N-shaped contact layer 23, and this photonic crystal is the airport structure, and hole diameter is the 50-1000 nanometer; The hole spacing is 0.1 micron-10 microns; The degree of depth in hole is: the 50-1000 nanometer; Arranging of hole can be the distribution of triangle, square, hexagon or other any shapes.
Porous photonic crystal can be to make by methods such as electron beam exposure, laser hologram exposure interference, nano impression or ps balls.
One nano-particle fluorescence powder 30, this fluorescent material are spun in the crystal hole of top layer light.The particle diameter of this nanoscale fluorescent material is the 10-100 nanometer.Fluorescent material can be one or more mixtures in yellow, redness or green emitting phosphor.This fluorescent material is spun in the crystal hole of top layer light.
Ultrasonic-spin-coating method is adopted in the coating of nano-particle fluorescence powder 30.Concrete grammar is consistent with the painting method of the powder of nano-particle fluorescence described in Fig. 1 19.
One transparency electrode 31, this transparency electrode is produced on the photon crystal surface that nano-particle fluorescence powder 30 is housed.This transparency electrode can be indium tin oxide (ITO), zinc oxide (ZnO), titanium aluminium titanium electrode etc.
One negative electrode 32, this negative electrode 32 is produced on transparency electrode 31, is comprised of chromium platinum or titanium aluminium titanium.Complete the making of GaN series LED.
As GaN series LED as described in Fig. 1, Fig. 2, the light-emitting diode of this structure can omit fluorescent powder coating technique when making, directly send white light.Concrete principle is as follows: after energising, the light by the active luminescent layer of indium gallium nitrogen sends sees through the top layer photonic crystal.Utilize the photon band gap effect of photonic crystal that the low-order mode major part in active area is extracted, and other high-rder modes can directly appear from the surface; Utilize on the other hand the optical grating diffraction effect of photonic crystal, due to the diffraction coherent superposition, make luminous enhancing along the light of surface normal direction transmission.Therefore, adopt photon crystal structure can improve luminous efficiency to a certain extent.In addition, along the nano fluorescent powder particles of the light part excitation photon crystals of normal direction output and luminous, the light that other unabsorbed active areas the send formation white light that combines with the light that fluorescent material sends.Adjustable due to the kind of fluorescent material, color is adjustable, the kind that therefore can mix by fluorescent material, colour temperature and the color rendering index that quantity is regulated white light, thereby omit fluorescent powder coating technique, greatly simplify the manufacture craft of white light LEDs.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. light-emitting diode with photonic crystal, it comprises: substrate, N-shaped contact layer, active luminescent layer, p-type contact layer, described active luminescent layer are positioned in the middle of N-shaped contact layer and p-type contact layer; Described cellular photonic crystal is produced on the top layer of described light-emitting diode, and its poroid inside is filled with the fluorescent material of nanometer scale, and its surface coverage has transparency electrode.
2. light-emitting diode as claimed in claim 1, is characterized in that, described light-emitting diode is the light-emitting diode of formal dress, upside-down mounting or vertical stratification.
3. light-emitting diode as claimed in claim 2, is characterized in that, when described light-emitting diode was positive assembling structure, described cellular photonic crystal was produced on p-type contact layer as the top layer.
4. light-emitting diode as claimed in claim 1, is characterized in that, when described light-emitting diode was vertical stratification, described cellular photonic crystal was produced on N-shaped contact layer as the top layer.
5. light-emitting diode as claimed in claim 1, is characterized in that, the hole diameter of described cellular photonic crystal is the 50-1000 nanometer; The hole spacing is 0.1 micron-10 microns; The degree of depth in hole is the 50-1000 nanometer; Arranging of hole is triangle, square or hexagon distribution.
6. light-emitting diode as claimed in claim 1, is characterized in that, described cellular photonic crystal is made by the mode of electron beam exposure, laser hologram exposure interference, nano impression or polystyrene spheres.
7. light-emitting diode as claimed in claim 1, is characterized in that, the particle diameter of fluorescent material is the 10-100 nanometer, and described fluorescent material comprises one or more mixtures in yellow, redness or green emitting phosphor.
8. light-emitting diode as claimed in claim 1, is characterized in that, adopts ultrasonic spin-coating method that the hole that described fluorescent material is coated in described cellular photonic crystal is inner.
9. light-emitting diode as claimed in claim 1, is characterized in that, described transparency electrode is indium tin oxide or zinc oxide.
10. light-emitting diode as claimed in claim 1, is characterized in that, the material of described substrate comprises sapphire Al
2O
3, C-face, R-face or A-face alumina single crystal, 6H-SiC, 4H-SiC or lattice constant close to one of monocrystalline oxide of nitride-based semiconductor.
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CN104362232A (en) * | 2014-10-28 | 2015-02-18 | 天津三安光电有限公司 | Led |
CN104733593A (en) * | 2013-12-18 | 2015-06-24 | 晶科电子(广州)有限公司 | Quantum dot-based white LED device and manufacturing method thereof |
CN104810452A (en) * | 2014-01-23 | 2015-07-29 | 逢甲大学 | Light emitting element |
CN105405938A (en) * | 2015-12-29 | 2016-03-16 | 中国科学院半导体研究所 | Single-chip white light LED for visible light communication and preparation method therefor |
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