CN103178168A - Preparation method of air-gap photonic crystal implanted gallium nitride-based light emitting diode - Google Patents
Preparation method of air-gap photonic crystal implanted gallium nitride-based light emitting diode Download PDFInfo
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- CN103178168A CN103178168A CN2013100883240A CN201310088324A CN103178168A CN 103178168 A CN103178168 A CN 103178168A CN 2013100883240 A CN2013100883240 A CN 2013100883240A CN 201310088324 A CN201310088324 A CN 201310088324A CN 103178168 A CN103178168 A CN 103178168A
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Abstract
The invention discloses a preparation method of an air-gap photonic crystal implanted gallium nitride-based light emitting diode. The preparation method comprises the following steps of: laying single-layer self-assembly close-spaced globules on an n-GaN template; reducing the single-layer self-assembly close-spaced globules to form single-layer non-close-spaced globules; evaporating a masking layer on the n-GaN template on which the single-layer non-close-spaced globules are laid, wherein the single-layer non-close-spaced globules are covered by the masking layer with certain thickness to form a globule-on masking layer, and forming masking layer meshes at gaps of the single-layer non-close-spaced globules; removing the single-layer non-close-spaced globules and the globule-on masking layer, and leaving back the masking layer meshes; transferring hole patterns of the masking layer meshes to the n-GaN template, and removing the masking layer meshes to form the n-GaN template with the hole patterns, wherein the n-GaN template with the hole patterns grows into an epitaxial wafer of the air-gap photonic crystal implanted gallium nitride-based light emitting diode.
Description
Technical field
The invention belongs to technical field of semiconductors, refer to especially a kind of method of utilizing the self-assembling technique preparation to implant the gallium nitride based light emitting diode of air-gap photonic crystal.
Background technology
Gallium nitride (GaN) based light-emitting diode (LED) is because its high light efficiency, low power consumption and pollution-free etc. good characteristic have been widely studied and have been entered the large-scale commercial applications growth.Traditional LED epitaxial wafer surfacing, because the refractive index of GaN higher (2.52) own, serious with the total reflection effect of air interface, cause the light that active area sends to escape out from LED, light extraction efficiency is on the low side is a bottleneck realizing efficient LED always.People have also developed a lot of methods that are used for improving light extraction efficiency, comprise graph substrate, the p-GaN surface coarsening, the current extending surface coarsening and in the LED structure integrated PhC structure etc., all obtained obvious effect.But, improve in the method for light extraction efficiencies at these, most by electron beam exposure or the costliness of nano impression, complicated technology, this has limited the application of these coarsening techniques in business LED greatly.In addition, also by the technique of plasma etching, this can introduce etching defect to most method for coarsening surface, brings the absorption of photon and the degeneration of electric property.In a word, seek a kind of low cost, large tracts of land and improve the method for the light extraction efficiency of LED without the making micro-nano graph of etching injury, seem has using value very much.
Natural lithography is a kind of cycle or the technology that aperiodic masking layer comes performance period or aperiodic micro-nano figure to shift of utilizing self-assembling formation that occurs the beginning of the nineties in last century.Compare traditional lithographic technique, the natural lithography technical matters is simple, with low cost.Along with the fast-developing and progress of chemical field self-assembling technique in recent years, article and the patent of utilizing the self-assembled nanometer ball to do photoetching transfer (NSL) occur one after another, not only have greatly improved on the figure transfer mass, and obtain a lot of gratifying achievements on the innovation and application that figure shifts.Utilize the NSL technology can realize even nano-scale pattern transfer of sub-micron, also realize making and the transfer of 3-D graphic.
The natural lithography technology is applied to make photonic crystal (PhC) structure to improve the LED light extraction efficiency in LED, be a study hotspot in the past few years.The scientific research personnel makes the PhC structure on the p-GaN of LED or current extending, all the LED light extraction efficiency is had clear improvement.But do micro-nano structure on the LED surface, since the device electric property is had damage possibly, two improve the limited space of LED extraction efficiency.People have begun again the device inside at LED, such as implanting the PhC structure in n-GaN, have obtained very good effect.
Summary of the invention
The object of the invention is to, provide a kind of self-assembling technique that utilizes to implant air-gap PhC structure to improve the method for LED light extraction efficiency in the n-GaN of LED layer.
The invention discloses a kind of preparation method who implants the gallium nitride based light emitting diode of air-gap photonic crystal, it comprises:
Step 1: at n-GaN template upper berth individual layer self assembly solid matter bead;
Step 2: individual layer self assembly solid matter bead is dwindled, form the non-solid matter bead of individual layer;
Step 3: evaporation masking layer on the n-GaN template that is covered with the non-solid matter bead of described individual layer, wherein covered certain thickness masking layer on the non-solid matter bead of individual layer, form masking layer on ball, the place forms the masking layer grid at the non-solid matter globular spaces of Czermak of described individual layer;
Step 4: remove masking layer on the non-solid matter bead of described individual layer and ball, stay the masking layer grid;
Step 5: the hole figure of masking layer grid is transferred to the n-GaN template, and removes the masking layer grid, form the n-GaN template with the hole figure;
Step 6: at described gallium nitride based light emitting diode (LED) epitaxial wafer that becomes to implant air-gap PhC structure with the n-GaN template growth of hole figure.
Said method disclosed by the invention utilizes Chemical self-assembly method transition diagram to the air-gap PhC structure that n-GaN makes, and makes the part light conduction mode in the LED epitaxial structure become the escape pattern, has greatly improved the extraction efficiency of LED.And the LED electric property that the method is made is not degenerated.And the method processing step is simple, with low cost, effective, for the LED of people low-cost production high extracting efficiency provides a good method.
Description of drawings
Fig. 1 is the method flow diagram that in the present invention, the gallium nitride based light emitting diode of air-gap photonic crystal is implanted in preparation;
Structural representation when preparing the gallium nitride based light emitting diode of implanting the air-gap photonic crystal in Fig. 2 the present invention after n-GaN template upper berth individual layer solid matter self assembly bead;
Fig. 3 when preparing the gallium nitride based light emitting diode of implanting the air-gap photonic crystal in the present invention dwindles into self assembly bead etching the structural representation of the non-solid matter bead of individual layer;
Fig. 4 be when in the present invention, the gallium nitride based light emitting diode of air-gap photonic crystal is implanted in preparation on the n-GaN template that is covered with the non-solid matter bead of individual layer the structural representation of covering metal layer;
Fig. 5 removes the structural representation with the n-GaN template of metal grill that forms after metal level on bead and ball when in the present invention, the gallium nitride based light emitting diode of air-gap photonic crystal is implanted in preparation;
Fig. 6 is that the present invention is the structural representation that forms when preparing the gallium nitride based light emitting diode of implanting the air-gap photonic crystal with the n-GaN template of hole figure;
Fig. 7 is the structural representation of the gallium nitride based LED epitaxial slice of the implantation air-gap photonic crystal for preparing in the present invention.
Fig. 8 implants scanning electron microscopy (SEM) cross-section photograph of air-gap photon crystal structure in n-GaN 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.
Fig. 1 shows the method flow diagram that the gallium nitride based light emitting diode of air-gap photonic crystal is implanted in preparation that the present invention proposes.As shown in Figure 1, the invention provides a kind of preparation method who implants the gallium nitride based light emitting diode of air-gap photonic crystal, in the described gallium nitride based light emitting diode process of preparation, the present invention utilizes self-assembling technique to implant air-gap photonic crystal (PhC) to improve the light extraction efficiency of LED in N-shaped gallium nitride (n-GaN) layer of light-emitting diode (LED).Fig. 2-7 show the present invention at the structural representation of the different phase of the gallium nitride based light emitting diode of preparation implantation air-gap photonic crystal.Particularly, in one embodiment of the present invention, the method comprises the following steps:
Step 1: select a slice certain thickness n-GaN template 10 of having grown, the n-GaN template thickness will be determined according to the height of implanting air-gap and the transfer degree of depth of hole figure, usually between the hundreds of nanometer was to several microns, its LED that mixes concentration and commercialization was suitable;
Step 2: at n-GaN template 10 upper berth individual layer self assembly solid matter beads 20, the small ball's diameter is namely the cycle of photonic crystal (PhC), and the size in cycle is determined the size of light extraction efficiency impact according to the PhC structure of implanting different cycles; Described individual layer self assembly solid matter bead can be polystyrene PS bead, silicon dioxide SiO
2One of self assembly bead of bead or other materials; Generally, the diameter of ball is between 100 nanometers to 3 micron; Fig. 2 shows the structural representation of spreading after individual layer solid matter self assembly bead 20;
Step 3: individual layer self assembly solid matter bead 20 etchings are dwindled, form the non-solid matter bead 30 of individual layer; The degree that etching is dwindled is determined the size of light extraction efficiency impact and the actual process condition of evaporation masking layer according to the PhC that implants different duty; Fig. 3 shows the structural representation that described self assembly solid matter bead is dwindled into the non-solid matter bead of individual layer;
Step 4: evaporation masking layer 40 on the n-GaN template that is covered with the non-solid matter bead 30 of individual layer, wherein also covered certain thickness masking layer above the non-solid matter bead 30 of individual layer, form masking layer 41 on ball, non-solid matter bead 30 gap locations have formed masking layer grid 42, and Fig. 4 shows the structural representation after evaporation masking layer 40 on the n-GaN template that is covered with the non-solid matter bead 30 of individual layer; Carry out the etching technics compatibility that the hole figure shifts in the material of the masking layer of institute's evaporation and step 6, in the n-GaN template, certain depth hole figure shifts needed thickness to its thickness greater than bearing; And evaporation masking layer mode comprises one of electron beam evaporation (EB evaporation), magnetron sputtering (Magnetron sputtering) or other modes.
Step 5: remove masking layer 41 on described non-solid matter bead 30 and ball, stay masking layer grid 42; Removing the method for masking layer on bead and ball can determine according to the characteristic of bead and the characteristic of masking layer, such as if described individual layer self assembly solid matter bead is selected polystyrene PS bead, adopt masking layer on the ultrasonic removal of toluene PS bead and ball, perhaps can directly have masking layer 41 on certain adhering tape stripping PS bead and ball with blue film or other; If the individual layer self assembly solid matter bead 20 of paving is SiO
2Bead can be with the non-solid matter SiO of the ultrasonic removal individual layer of solution of hydrofluoric acid
2On bead and ball, masking layer 41, also can use tape stripping.Fig. 5 shows and removes the structural representation after masking layer 41 on described non-solid matter bead 30 and ball;
Step 6: the hole figure of masking layer grid 42 is transferred on n-GaN template 10, the hole figure has certain depth, then remove masking layer grid 42, form the n-GaN template 60 with hole figure 61, Fig. 6 shows the structural representation that forms with the n-GaN template 60 of empty figure 61; Wherein, transfer method can be the method for ICP etching or other transition diagrams; Transfer to the hole figure degree of depth on n-GaN template 10 and can be 500 nanometers to 3 micron, the concrete degree of depth will be improved size to light extraction efficiency and jointly determines according to carrying out the air-gap height that stays in the n-GaN template after regrowth and the size of implanting air-gap photonic crystal PhC in template thickness, step 7.Masking layer grid 42 will be removed totally, with anti-pollution MOCVD chamber;
Step 7: will put into the MOCVD reative cell with the n-GaN template 60 of hole figure, grow into the epitaxial wafer 70 of the gallium nitrate based reflective diode of having implanted air-gap PhC71 structure, Fig. 7 shows the structural representation after the epitaxial wafer that grows into the gallium nitrate based reflective diode of having implanted air-gap PhC structure.The growth of epitaxial wafer 70 is included in described with the certain thickness n-GaN72 of regrowth, Multiple Quantum Well (MQWs) 73, p-type gallium nitride (p-GaN) 74 homepitaxy layers in order on the n-GaN of empty figure.The thickness of regrowth n-GaN72 will according to implant air-gap PhC structure apart from the active area distance on light extraction efficiency affect size and regrowth n-GaN thickness is determined jointly on the quality of LED device electric property impact; The follow-up epitaxial structure such as quantum well can be the epitaxial structure that uses in any business LED.
The below provides another preferred embodiment of preparation method of the gallium nitride based light emitting diode of the implantation air-gap photonic crystal that the present invention proposes, and the method comprises:
Step 1: select the grown n-GaN template of 2 micron thickness of a slice;
Step 2: at n-GaN template upper berth individual layer self assembly solid matter PS bead;
Step 3: individual layer self assembly solid matter PS bead is dwindled with the RIE etching, form the non-solid matter PS of individual layer bead;
Step 4: evaporation thickness is the metal level Ni of 200 nanometers on the non-solid matter PS of individual layer bead, has wherein also covered certain thickness metal level above the non-solid matter PS of individual layer bead, forms Ni metal level on ball, and non-solid matter PS globular spaces of Czermak place is the Ni metal grill;
Step 5: remove Ni metal level on non-solid matter PS bead and ball, stay the Ni metal grill;
Step 6: the hole figure of Ni metal grill is transferred on the n-GaN template, and then dark 1 micron of hole figure removes the Ni metal grill, forms the n-GaN template with the hole figure;
Step 7: will put into the MOCVD reative cell with the n-GaN template of hole figure, the regrowth n-GaN layer of regrowth 1 micron thickness, 5 pairs of MQWs, the p-A1GaN layer of 20 nanometer thickness and the p-GaN layers of 130 nanometer thickness form the LED epitaxial wafer of having implanted air-gap PhC structure in n-GaN.
Fig. 8 shows by implant scanning electron microscopy (SEM) cross-section photograph of air-gap photon crystal structure in this another preferred embodiment in n-GaN by said method.
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 (11)
1. preparation method who implants the gallium nitride based light emitting diode of air-gap photonic crystal, it comprises:
Step 1: at n-GaN template upper berth individual layer self assembly solid matter bead;
Step 2: individual layer self assembly solid matter bead is dwindled, form the non-solid matter bead of individual layer;
Step 3: evaporation masking layer on the n-GaN template that is covered with the non-solid matter bead of described individual layer, wherein covered certain thickness masking layer on the non-solid matter bead of individual layer, form masking layer on ball, the place forms the masking layer grid at the non-solid matter globular spaces of Czermak of described individual layer;
Step 4: remove masking layer on the non-solid matter bead of described individual layer and ball, stay the masking layer grid;
Step 5: the hole figure of masking layer grid is transferred to the n-GaN template, and removes the masking layer grid, form the n-GaN template with the hole figure;
Step 6: at described gallium nitride based light emitting diode (LED) epitaxial wafer that becomes to implant air-gap PhC structure with the n-GaN template growth of hole figure.
2. preparation method as claimed in claim 1, is characterized in that, the thickness of the template of n-GaN described in step 1 is that the hundreds of nanometer is to several microns.
3. preparation method as claimed in claim 1, is characterized in that, the self assembly of individual layer described in step 1 solid matter bead is polystyrene PS bead, silicon dioxide SiO
2One of self assembly bead of bead or other materials; The diameter of ball is between 100 nanometers to 3 micron.
4. preparation method as claimed in claim 1, is characterized in that, dwindles described individual layer self assembly solid matter bead by reactive ion etching (RIE) or inductively coupled plasma (ICP) etching mode in step 2; Wherein, etching gas determines according to the material of described individual layer self assembly solid matter bead, and the sphere gap of etching after dwindling determined according to mode and the parameter of the masking layer of evaporation in step 3 from scope.
5. preparation method as claimed in claim 1, it is characterized in that, carry out the etching technics compatibility that the hole figure shifts in step 3 in the material of the masking layer of institute's evaporation and step 6, in the n-GaN template, certain depth hole figure shifts needed thickness to its thickness greater than bearing; And evaporation masking layer mode comprises electron beam evaporation (EB evaporation) or magnetron sputtering (Magnetron sputtering) mode.
6. preparation method as claimed in claim 1, is characterized in that, removes the mode of masking layer on the non-solid matter bead of individual layer and ball described in step 4 and determine according to different types of bead.
7. preparation method as claimed in claim 6, it is characterized in that, described individual layer self assembly solid matter bead is selected polystyrene PS bead, adopt masking layer on toluene ultrasonic removal PS bead and ball in step 4, perhaps directly have masking layer on certain adhering tape stripping PS bead and ball with blue film or other.
8. preparation method as claimed in claim 6, is characterized in that, described individual layer self assembly solid matter bead is selected silicon dioxide SiO
2Adopt the ultrasonic removal of the solution SiO of hydrofluoric acid in bead, step 4
2Masking layer on bead and ball is perhaps directly used the described SiO of tape stripping
2Masking layer on bead and ball.
9. preparation method as claimed in claim 1, it is characterized in that, adopt ICP etching mode that the hole figure of described metal grill is transferred on the n-GaN template in step 5, its degree of depth is determined the improvement size of light extraction efficiency jointly according to the size of the air-gap height that stays in n-GaN template thickness, regrowth n-GaN and implantation air-gap photonic crystal.
10. preparation method as claimed in claim 1, it is characterized in that, in step 6 by putting into the MOCVD reative cell with the n-GaN template of hole figure, after regrowth n-GaN, Multiple Quantum Well, p-GaN epitaxial loayer, grow into the epitaxial wafer of the gallium nitride based light emitting diode of having implanted the air-gap photon crystal structure.
11. preparation method as claimed in claim 1, it is characterized in that, the thickness of the n-GaN of regrowth described in step 6 according to implantation air-gap PhC structure apart from the distance of active area on light extraction efficiency affect size and regrowth n-GaN thickness is determined jointly on the quality of the electric property impact of LED device.
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Application publication date: 20130626 |