CN102255009A - Light-emitting diode (LED) chip manufacturing method - Google Patents
Light-emitting diode (LED) chip manufacturing method Download PDFInfo
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- CN102255009A CN102255009A CN2011101722177A CN201110172217A CN102255009A CN 102255009 A CN102255009 A CN 102255009A CN 2011101722177 A CN2011101722177 A CN 2011101722177A CN 201110172217 A CN201110172217 A CN 201110172217A CN 102255009 A CN102255009 A CN 102255009A
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Abstract
The invention discloses a light-emitting diode (LED) chip manufacturing method, which comprises the following steps of: providing a semiconductor substrate, and sequentially growing a nitride nucleating layer, an undoped nitride layer, an N-type nitride layer, a multi-quantum well and a P-type nitride layer on the semiconductor substrate by adopting metal-organic chemical vapor deposition; depositing a mask layer on the P-type nitride layer; etching the mask layer to form a periodical pattern structure window, wherein the P-type nitride layer is exposed in the periodical pattern structure window; forming a doped conical structure in the periodical pattern structure window and on the surface of the P-type nitride layer by adopting a metal-organic chemical vapor deposition epitaxy method; and removing the mask layer, and forming a P-type epitaxial layer consisting of the P-type nitride layer and the doped conical structure. By the LED chip manufacturing method provided by the invention, the light extraction efficiency of a nitride light-emitting diode is improved.
Description
Technical field
The present invention relates to a kind of manufacture method of led chip, relate in particular to metal organic chemical vapor deposition (MOCVD) epitaxy method grow doping pyramidal structure, get the manufacture method of optical efficiency with raising.
Background technology
Need in traditional fluorescent lamp to use mercury vapour and lead composition, if the fluorescent lamp fragmentation, mercury vapour and lead then can evaporate in the atmosphere, become continuous air-polluting source, and human body is damaged.Therefore, people are seeking the lighting source of a new generation.1964, arsenic phosphorus (GaAsP) light-emitting diode (LED sows in first red III-V family in the world, Light Emitting Diode) is born, this is also just indicating the arriving in solid luminescence epoch, and then orange, yellow and yellow green LED also come out one after another, and the vacancy of blue-ray LED causes always and can not realize panchromatic demonstration only.1994, develop gallium nitride (GaN) LED, realized that blue-light semiconductor is luminous, make LED can send from the infrared ray to the blue light between the light of different wave length, thereby may realize changing into the white light LEDs of white light by the blue-light semiconductor luminescent material.White light LEDs need not to use mercury vapour and lead, and easily reclaims, and can not pollute environment, thereby environment is played a protective role.Because LED not only has energy-saving and environmental protection, long three big advantages of life-span, also have advantages such as volume is little, driving voltage is low, response is quick, colour is adjustable, the optically focused performance is good, therefore, along with improving constantly of LED luminous intensity, application also constantly enlarges, and progressively enters lighting field.
Along with the exploitation of using based on the high-brightness LED of nitride, new generation of green environmental protection solid light source nitride LED has become the emphasis of research, is the exploitation of the blue led of representative with third generation semiconductor gallium nitride (GaN) especially.Having characteristics such as wide direct band gap, interior external quantum efficiency height, high heat conductance, high temperature resistant, anticorrosive, shock resistance, high strength and high rigidity based on the III hi-nitride semiconductor material of GaN, InGaN (InGaN) and aluminium gallium nitride alloy (AlGaN) alloy, is the ideal material of making the high brightness luminescent device in the world at present.
Because transversary is generally adopted in the manufacturing of LED device, build is a cuboid, two sides, the left and right sides is parallel to each other, though the wide part that active area sends is from the top outgoing of p type island region, but, because the refractive index difference of semi-conducting material and air is bigger, cause LED light when the big chip of refractive index is transmitted into the little air of refractive index, full emission can take place at the interface of semiconductor and air, undressed semiconductor LED body structure surface approximately has only seldom a part of light to escape out from chip internal, thereby causes the light extraction efficiency of chip very low.Because the light extraction efficiency of chip is the main cause of the luminous efficiency of decision semiconductor lighting chip, therefore, promotes the luminous efficiency of nitride LED and the taking-up efficient of increase light and the external quantum efficiency that improves device is played a part very crucial.
In order to improve external quantum efficiency, people are attempting to attempt technically the various methods that can improve the chip light-emitting rate, such as surface coarsening (Surface roughing), destroy the total reflection of light in semiconductor and air interface, increase the outgoing efficient of light, improve the light extraction efficiency of chip.In addition, the method for relatively more successful raising light taking-up efficient is that led chip is made inverted pyramid shape, taper etc.When being made into inverted pyramid (TIP, Truncated Inverted Pyramid) during shape (side and vertical direction are angled), four sides of chip no longer are parallel to each other, can be so that be mapped to the light of chip sides, the end face that reflexes to through the side is with the angle outgoing less than the cirtical angle of total reflection; Simultaneously, be mapped to the light from the side outgoing of end face, thereby improved the light extraction efficiency of chip greatly greater than the cirtical angle of total reflection.The formation of surface coarsening or inverted pyramid type is generally to be corrosion depth, shape and the gradient by process reform surfaces such as etchings, therefore causes on all directions corrosion inhomogeneous easily, even causes corrosion insufficient and cross the phenomenon of erosion.Therefore, in the led chip structure, be difficult to form the degree of depth, shape and the gradient of uniformity, improve the inclined plane of getting optical efficiency and also be difficult to accurate control.Also can cause problems such as sliver, reduce the yield of production.
In order to address the above problem, improve internal quantum and light extraction efficiency that III group-III nitride luminescent device comes, in the implementation process of reality, still there is sizable barrier, demand introducing the new method that effectively to improve above-mentioned defective urgently, use the topmost problem that faces to solve third generation semi-conducting material.
The utility model content
Technical problem to be solved by this invention provides a kind of manufacture method that realizes led chip, to improve the optical efficiency of getting of nitride LED.
For addressing the above problem, a kind of manufacture method that realizes led chip that the present invention proposes comprises the steps:
Semiconductor substrate is provided, on Semiconductor substrate, adopts MOCVD (Metal-organic Chemical Vapor Deposition) growing nitride nucleating layer, non-doped nitride layer, N type nitride layer, Multiple Quantum Well, P type nitride layer successively;
Deposition mask layer on P type nitride layer;
Etch mask layer exposes P type nitride layer to form the periodic pattern topology window in the described periodic pattern topology window;
Adopt the method for metal organic chemical vapor deposition extension, in the periodic pattern topology window, on the P type nitride layer surface, form the doping pyramidal structure;
Remove mask layer, form the P type epitaxial loayer that constitutes by P type nitride layer and doping pyramidal structure.
From technique scheme as seen, adopt the method for MOCVD extension, the doping pyramidal structure of having grown in the periodic pattern topology window of mask layer, on the P type nitride layer after removing mask layer, has formed P type epitaxial loayer by P type nitride layer and doping pyramidal structure.Owing to after having prepared opening size size unanimity, the uniform periodic pattern topology window of spacing on the mask layer,, just can obtain the periodic doping pyramidal structure that shape is identical, size is unified in conjunction with described MOCVD epitaxy method.And by adjusting the MOCVD growth conditions, height and shape that also can the controlled doping pyramidal structure be unified the inclined plane of doping pyramidal structure and the angle of vertical direction, get the inclined plane of optical efficiency to improve accurate control.
Usually, adopt wet method or dry method etch technology that surface coarsening is formed pyramidal structure.Yet, because etching not only all produces etching action downwards but also to left and right sides all directions, therefore be difficult to corrosion depth, shape and the gradient by technology controlling and process surfaces such as etchings, form height and the uniform pyramidal structure of lateral dimension.Moreover, the method for etching has been destroyed semi-conducting material itself, has caused highdensity crystal defect, forms the non-radiative recombination center of photon easily, thereby reduces the luminous efficiency of LED device.The present invention forms the uniform hatch frame of size by adopting general mask+corroding method in the production on the surface of P type nitride.Then, reuse the MOCVD method, prepare the pyramidal structure of being expected, thereby avoided the defective of etch process, enlarged the critical angle of light when semiconductor and the full emission of air interface generation, thereby improved light extraction efficiency; The periodic doping pyramidal structure owing on P type nitride layer surface, grown, improved the uneven shortcoming of the isostructural density distribution of pyramid, taper that corrosion in the past forms, obtain the density distribution pyramidal structure of mixing uniformly, improved the light-emitting uniformity and the light extraction efficiency of nitride LED element.
Description of drawings
Fig. 1 has shown the making flow process of a kind of nitride LED structure of the present invention.
Fig. 2 a to Fig. 2 e has shown the manufacture method of Fig. 1 flow process.
Fig. 3 has shown cone-shaped polyhedral schematic diagram of a kind of MOCVD of the present invention constituency secondary epitaxy growth.
Fig. 4 has shown that a kind of cone-shaped structure of the present invention gets the optical efficiency schematic diagram.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing.
A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention is not subjected to the restriction of following public concrete enforcement.
Secondly, the present invention utilizes schematic diagram to be described in detail, when the embodiment of the invention is described in detail in detail; for ease of explanation; the profile of expression device architecture can be disobeyed general ratio and be done local the amplification, and described schematic diagram is example, and it should not limit the scope of protection of the invention at this.The three dimensions size that in actual fabrication, should comprise in addition, length, width and the degree of depth.
Be example with making flow process shown in Figure 1 below, 2a to 2e in conjunction with the accompanying drawings is described in detail the manufacture craft of led chip.
S100: Semiconductor substrate 10 is provided, on Semiconductor substrate 10, adopts MOCVD growing nitride nucleating layer 11, non-doped nitride layer 12, N type nitride layer 13, Multiple Quantum Well 16, P type nitride layer 19 successively.
Referring to Fig. 2 a, Semiconductor substrate 10 is provided, on Semiconductor substrate 10, adopt common mocvd method, growing nitride nucleating layer 11, unadulterated non-doped nitride layer 12, the N type nitride layer 13 that mixes successively, then, growth Multiple Quantum Well 16, growing P-type nitride layer 19 on Multiple Quantum Well 16 at last on N type nitride layer 13.Wherein, first nitride layer 17 of the doping of growing successively on Multiple Quantum Well 16 and second nitride layer 18 that mixes have constituted P type nitride layer 19.Said process is specific as follows:
At first, on Semiconductor substrate 10 surfaces, form the nitride nucleating layer 11 that a layer thickness is even, have an even surface, to change Semiconductor substrate 10 surface engagement types, in order to follow-up other materials growth.Nitride nucleating layer 11 can be for GaN film, thickness
Secondly, the unadulterated non-doped nitride layer 12 of growth on the nitride nucleating layer 11 aggregates into the base layer of continuous formation in order to crystallization.Non-doped nitride layer 12 can be for GaN film, thickness
Then, the N type nitride layer 13 of grow doping on non-doped nitride layer 12.Doped N-type nitride layer 13 can be for GaN film, thickness
Its alloy can be N type alloy, and N type alloy can be Si or other, preferred Si, and its doping content is 5 * 1017cm-3 to 1 * 1019cm-3.Si since doping techniques simple, be easy to control, so be the normal N type dopant that uses in the N type nitride.
Then, growth Multiple Quantum Well 16 on the N type nitride layer 13 that mixes is as active area.Contain the periodicity of the nitride film 15 of the low energy gap width nitride film 14 of In and broad stopband width by adjustment, and allow the nitride film 14 of low energy gap width and the nitride film 15 of broad stopband width alternately arrange, formed described Multiple Quantum Well 16.Wherein, the low energy gap width nitride film 14 that contains In can be the InGaN film, and thickness is
Formation temperature is 700～900 ℃; The nitride film 15 of broad stopband width can be the GaN film, and thickness is
Formation temperature is 700～900 ℃.
And then, first nitride layer 17 of grow doping on Multiple Quantum Well 16, first nitride layer 17 that mixes can be for aluminium gallium nitride alloy (AlGaN), thickness
Its alloy can be P type alloy, and P type alloy can be magnesium (Mg) or zinc (Zn) or other, and its doping content is 1 * 1018cm-3 to 5 * 1019cm-3;
At last, second nitride layer 18 of grow doping on first nitride layer 17 that mixes, second nitride layer 18 that mixes can be for GaN film, thickness
Its alloy can be P type alloy, and P type alloy can be Mg or Zn or other, and its doping content is 1 * 1018cm-3 to 5 * 1019cm-3;
In first nitride layer 17 and second nitride layer 18, mix, improve hole concentration, improve the conductivity of P type nitride layer 19, mix, improved LED architecture quality based on nitride material thereby obtained high-quality P type.
The N type nitride layer 13 that mixes is the electronics source of Multiple Quantum Well 16, first nitride layer 17 that mixes is the source, hole of Multiple Quantum Well 16, and electronics and hole are limited in the Multiple Quantum Well 16, in active area electronics and hole-recombination, give off energy, and then send light.Simultaneously, the electronics of the N type nitride layer 13 that first nitride layer 17 of doping utilizes the high energy gap of AlGaN film to stop to derive from doping overflows from Multiple Quantum Well 16, has strengthened the efficient of hole and electron recombination, improves luminous intensity.
S101: deposition mask layer 20 on P type nitride layer 19.
Referring to Fig. 2 b, using plasma strengthens chemical vapour deposition (CVD) (PECVD, Plasma Enhanced Chemical Vapor Deposition) deposition mask layer 20 on P type nitride layer 19.
The PECVD method is to utilize reacting gas to take place to decompose in plasma and the process that deposits on substrate.Utilize the amorphous silicon quality height of PECVD preparation, raw materials consumption is few, and cost is low, and technology is simple.
Described mask layer 20 can be an amorphous silicon, and this amorphous silicon can be silicon dioxide (SiO2) or silicon nitride (SixNy), preferred SiO2, and thickness is respectively
S102: etch mask layer 20 exposes P type nitride layer 19 to form periodic pattern topology window 21 in the described periodic pattern topology window 21.
Referring to Fig. 2 c, deposition photoresist (not shown) on mask layer 20, adopt common photoetching method to form the photoresist of periodic pattern window, expose mask layer 20 surfaces, with the photoresist is that mask carries out wet etching to mask layer 20, expose P type nitride layer 19 surfaces, thereby in mask layer 20, prepared periodic pattern topology window 21.Wherein, the size of periodic pattern topology window 21 (CD) is
The size unanimity of each window 21, spacing are even.
On mask layer 20, can use photoetching technique, preferred nano-imprinting method (NIL, Nano Imprint Lithography) photoresist is handled, produce the photoresist of periodic pattern topology window, periodic pattern topology window 21 can be periodic circular open or other, and the diameter of circular open is
S103: in the periodic pattern topology window 21 of mask layer 20, on P type nitride layer 19 surfaces, adopt the method for MOCVD extension, grow doping pyramidal structure 22.
Referring to Fig. 2 d, after led chip adopts usual way to be cleaned, utilize the method for MOCVD constituency secondary epitaxy, carry out epitaxial growth on the device architecture surface shown in Fig. 2 c, because the material of mask layer 20 is an amorphous silicon, when adopting MOCVD constituency secondary epitaxy, do not react on the mask layer 20, therefore, through after this epitaxial growth steps, only in the periodic pattern topology window 21 of mask layer 20, form doping pyramidal structure 22 on P type nitride layer 19 surfaces, promptly realize the interior epitaxial growth in constituency (window 21).Described doping pyramidal structure 22 can be GaN, and its cone height is
Its alloy can be P type alloy, and P type alloy can be Mg or Zn or other, and its doping content is 1 * 1018cm-3 to 5 * 1019cm-3;
Described doping pyramidal structure 22 can be for having pyramid, taper, pointed cone pyramid or other structure at the top, as long as guarantee that the build of led chip no longer is that two sides, the left and right sides is parallel to each other, but there is the gradient side, improves the purpose of getting optical efficiency thereby reach.
The concrete technological parameter of described MOCVD constituency secondary epitaxy method comprises: reative cell pressure is 100 millitorr to 500 millitorrs, reaction temperature is 750 degrees centigrade to 1050 degrees centigrade, reactant is NH3 (ammonia) and TMGa (trimethyl gallium), and wherein, NH 3 is 500 to 2000 with the mol ratio of TMGa.
S104: remove mask layer 20, form the P type epitaxial loayer 24 that constitutes by P type nitride layer 19 and doping pyramidal structure 22.
Referring to Fig. 2 e, adopt common wet etching to remove mask layer 20, expose P type nitride layer 19, and on P type nitride layer 19 surfaces, expose doping pyramidal structure 22 fully.
After MOCVD constituency secondary epitaxy method finishes, led chip is placed on 500 to 800 ℃ and carry out high annealing under the atmosphere of nitrogen or air, adopt the P type epitaxial loayer 24 of dopant growth to utilize annealing process, to activate the alloy in the P type epitaxial loayer 24, realize that the P type mixes, and has obtained the uniform P type of concentration epitaxial loayer 24.
Then, reuse the MOCVD method, the pyramidal structure that preparation is expected has enlarged the critical angle of light when semiconductor and the full emission of air interface generation, thereby has improved light extraction efficiency;
By general mask+corroding method in adopt producing, in the surface preparation of P type nitride 19 the uniform hatch frame of size.Then, reuse the MOCVD method, the pyramidal structure 22 that preparation is expected, thereby the defective of having avoided etch process to cause.And because crystal growth itself, referring to Fig. 3, (referring to Fig. 4) also unified with the angle theta of vertical direction in the inclined plane 23 of doping pyramidal structure 22.This shows, can adjust the MOCVD growth conditions according to actual needs and improve the unsettled defective of etching process inclined plane 23 angle θ in the past, improve light extraction efficiency simultaneously.The periodic size pyramidal structure 22 of mixing uniformly owing on P type nitride layer 19 surfaces, grown, pyramid, taper isodensity shortcoming pockety have in the past been improved, obtain the density distribution pyramidal structure 22 of mixing uniformly, improved the optical efficiency of getting of nitride LED element.
At last, adopt common nitride LED device fabrication, the LED epitaxial wafer is made P type electrode and N type electrode.The surface of P type epitaxial loayer 24 can provide the interface of P type electrode engagement.N type nitride layer 13 can be the metal contact layer of N type electrode.P type epitaxial loayer 24 is based on the hole, and N type nitride layer 13 mainly is an electronics.After applying forward bias on the electrode at led chip, inject in the P type epitaxial loayer 24 respectively and send light with the form of photon when electronics in the N type nitride layer 13 and hole-recombination.
Though the present invention with preferred embodiment openly as above; but it is not to be used for limiting claim; any those skilled in the art without departing from the spirit and scope of the present invention; can make possible change and modification, so protection scope of the present invention should be as the criterion with the scope that claim of the present invention was defined.
Claims (18)
1. the manufacture method of a led chip comprises the steps:
Semiconductor substrate is provided, on Semiconductor substrate, adopts metal organic chemical vapor deposition growing nitride nucleating layer, non-doped nitride layer, N type nitride layer, Multiple Quantum Well, P type nitride layer successively;
Deposition mask layer on P type nitride layer;
Etch mask layer exposes P type nitride layer to form the periodic pattern topology window in the described periodic pattern topology window;
Adopt the method for metal organic chemical vapor deposition extension, in the periodic pattern topology window, on the P type nitride layer surface, form the doping pyramidal structure;
Remove mask layer, form the P type epitaxial loayer that constitutes by P type nitride layer and doping pyramidal structure.
2. the manufacture method of led chip according to claim 1, it is characterized in that: described nitride nucleating layer is a gallium nitride, and thickness is
3. the manufacture method of led chip according to claim 1, it is characterized in that: described non-doped nitride layer is a gallium nitride, and thickness is
4. the manufacture method of led chip according to claim 1, it is characterized in that: described N type nitride layer is a N type doped gallium nitride layer, and thickness is
5. the manufacture method of led chip according to claim 4, it is characterized in that: the alloy in the described N type doped gallium nitride layer is a silicon, and doping content is 5 * 10
17Cm
-3To 1 * 10
19Cm
-3
6. the manufacture method of led chip according to claim 1 is characterized in that: described P type nitride layer to down and on constitute by mix first nitride layer and second nitride layer that mixes.
7. the manufacture method of led chip according to claim 6, it is characterized in that: described doping first nitride layer is a P type doped aluminum nitride gallium layer, and thickness is
8. the manufacture method of led chip according to claim 6, it is characterized in that: described doping first nitride layer is a P type doped aluminum nitride gallium layer of mixing magnesium or zinc, and wherein the doping content of magnesium or zinc is 1 * 10
18Cm
-3To 5 * 10
19Cm
-3
9. the manufacture method of led chip according to claim 6, it is characterized in that: described doping second nitride layer is a P type doped gallium nitride layer, and thickness is
10. the manufacture method of led chip according to claim 6, it is characterized in that: described doping second nitride layer is the P type doped gallium nitride layer of mixing magnesium or zinc, and wherein the doping content of magnesium or zinc is 1 * 10
18Cm
-3To 5 * 10
19Cm
-3
11. the manufacture method of led chip according to claim 1 is characterized in that: described mask layer is the silicon dioxide of amorphous silicon, and thickness is
12. the manufacture method of led chip according to claim 1 is characterized in that: described mask layer is the silicon nitride of amorphous silicon, and thickness is
13. the manufacture method of led chip according to claim 1 is characterized in that: described periodic pattern topology window is periodic opening.
14. the manufacture method of led chip according to claim 1 is characterized in that: the size of described periodic pattern topology window is
15. the manufacture method of led chip according to claim 1 is characterized in that: the top of described doping pyramidal structure is taper.
16. the manufacture method according to claim 1 or 15 described led chips is characterized in that: described doping pyramidal structure is a P type doped gallium nitride material, and cone height is
17. the manufacture method of led chip according to claim 16 is characterized in that: described doping pyramidal structure is the P type doped gallium nitride layer of mixing magnesium or zinc, and wherein the doping content of magnesium or zinc is 1 * 10
18Cm
-3To 5 * 10
19Cm
-3
18. the manufacture method of led chip according to claim 1 is characterized in that: the epitaxially grown reative cell pressure of described metal organic chemical vapor deposition is 100 millitorr to 500 millitorrs, and reaction temperature is 750 degrees centigrade to 1050 degrees centigrade, and reactant is NH
3With TMGa, wherein, NH
3With the mol ratio of TMGa be 500 to 2000.
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| CN104300062A (en) * | 2013-07-18 | 2015-01-21 | Lg伊诺特有限公司 | Light emitting device |
| CN105185879A (en) * | 2015-10-10 | 2015-12-23 | 厦门市三安光电科技有限公司 | Three-dimensional doped nitride LED, and manufacturing method thereof |
| CN107394018A (en) * | 2017-08-10 | 2017-11-24 | 湘能华磊光电股份有限公司 | A kind of LED epitaxial growth methods |
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Application publication date: 20111123 |