CN101093866A - Clear electrode of semiconductor light emitting device of nitride, and preparation method - Google Patents
Clear electrode of semiconductor light emitting device of nitride, and preparation method Download PDFInfo
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- CN101093866A CN101093866A CNA2006100933822A CN200610093382A CN101093866A CN 101093866 A CN101093866 A CN 101093866A CN A2006100933822 A CNA2006100933822 A CN A2006100933822A CN 200610093382 A CN200610093382 A CN 200610093382A CN 101093866 A CN101093866 A CN 101093866A
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Abstract
The P type electrode is composed of a portion of semitransparent electrode of conductive metal on GaN based semiconductor layer and a portion of optical transparent crystal with rough surface. The fabricating method includes steps: on GaN based semiconductor layer, using method of electron-beam evaporation coats by vaporization metal layer in use for forming ohmic contact to P type GaN based semiconductor layer; carrying out anneal in oxygen contained atmosphere at 400 - 600 deg.C to make it become semitransparent electrode of possessing good ohmic contact with P type GaN based semiconductor layer; then, preparing transparent crystal with rough surface layer on the electrode by direct or indirect mode at 20-600 deg.C. Compared with prior art, besides good light transmittance, low resistivity, and good ohmic contact with P type GaN, the invention possesses features of raised luminous efficiency of device, greatly lowered cost, and simple technical procedure.
Description
Technical field
The present invention is relevant GaN based compound semiconductor light emitting element.
Background technology
GaN is direct transition wide bandgap semiconductor materials, and its optical transition probability is higher one more than the order of magnitude than indirect gap semiconductor material.Broad-band gap GaN base semiconductor material has a wide range of applications in luminous field, as traffic lights, and full color large scale display, the back light of liquid crystal display, laser, ultraviolet detector etc.
In default of the baseplate material that all is complementary with GaN lattice constant and thermal coefficient of expansion, GaN mainly is grown on sapphire (Sapphire), carborundum (SiC) and silicon (Si) backing material of etc.ing at present, and wherein present use the most extensively is a Sapphire Substrate.By adopting multi-quantum pit structure and optimizing growth conditions, the internal quantum efficiency of nitride LED epitaxial wafer reaches more than 70%.But, the optical refractive index of GaN material is very high, is about 2.5, calculates as can be known according to snell law (Snell Law), the light of plane GaN LED device takes out efficient approximately to be had only about 5%, causes between the internal quantum efficiency of luminescent device and the external quantum efficiency to have very big difference.
Be used to promote the technology that a kind of method that GaN LED device light takes out efficient is to use the surface coarsening technology or combines with the luminescent crystal structure, to connecing face in the device or outer surface is handled, make it have specific concaveconvex shape, destroy the total reflection of light at device inside
[1]～[3]But, no matter be GaN material itself, the material that still present widely used sapphire (sapphire) or carborundum (SiC) substrate all are the hardness height, chemical stability is good, processed is difficulty quite.Processing to them can only be used dry etching usually, and can not be with wet etching method commonly used in the general semiconductor technology.And, when roughening treatment when P type laminar surface is carried out because the P type cover layer of GaN is very thin, the degree of depth of etching is difficult to accurately control, is damaged to the luminous zone of LED device easily, reduces the efficient lighting area of material; In addition, because the uneven surface that coarsening technique causes can cause that the electric current injection is inhomogeneous in the device, the contact resistivity of electrode and storeroom rises, and is special in the poor material of the such conductance of P type GaN.
Another method that improves GaN LED device light taking-up efficient is to adopt upside-down mounting (Flip chip) technology, reduces the optical loss of P type electrode side
[5]Because its complex technical process not exclusively adapts to the requirement of large-scale production.
Another method that improves that GaN LED device light takes out efficient is with the good metal oxide of light transmission, as tin indium oxide (Indium Tin Oxide, ITO)
[6]Or zinc oxide (ZnO)
[7], (this transparent metal oxide film has level and smooth surface for Transparent Conductive Layer, the Ni/Au double-metal layer that TCL) the instead of optical transmitance is lower as transparency conducting layer.The light transmittance of General N i/Au electrode is between 60%～75%.And sull as the ITO film, can reach more than 90% the transmitance of the light of 460nm wavelength, and resistivity is low, does not need GaN semiconductor epitaxial material is carried out special processing, and preparation technology is simple relatively, echos the condition of large-scale production.But, all be n type material under these metal oxide film general conditions, it contacts with P type GaN, can form P-N junction interface with rectification characteristic, causing GaN is that the operating voltage of blue-ray LED and interface resistance between the two rise, and working temperature raises, and the element deterioration is quickened.
Another method that improves GaN LED device luminous efficiency is on the basis of adopting high light transmittance ITO film, by spraying one deck polystyrene spheres (polystyrene spheres on ITO film surface, PSs), form a kind of natural mask, utilize the ICP method to carry out etching then, make the ITO film have certain surface texture
[7]Use this LED device with ITO film of certain surface structure, under equal size of current situation, luminous intensity uses the luminous intensity of the LED device of unprocessed ITO film that further raising is arranged.But the ITO film is identical with using, and there is the operating voltage height equally in such device, element short shortcoming in useful life.In addition, by the PS mask that spraying method forms, uniformity is poor, to ICP etching condition sensitivity.When carrying out etching, easily electrode under the ITO film or GaN epitaxial loayer are produced damage with the ICP method.
List of references:
[1]T.Fujii，Y.Gao，R.Sharma，E.L.Hu，S.P.DenBaars，and?S.Nakamura，Appl.Phys.Lett.，84，855(2004)。
[2]J.Shakya，K.H.Kim，J.Y.Lin?and?H.X.Jiang，Appl.Phy.Lett.，85，142(2004)。
[3]Kenji?Orita，Satoshi?Tamura，Toshiyuki?Takizawa，Tetsuzo?Ueda，Masaaki?Yuri，Shinichi?Takigawa?and?Daisuke?Ueda，Jpn.J.Appl.Phys.，43，5809(2004)。
[4]J.J.Wierer，D.A.Steigerwald，M.R.Krames，J.J.O’Shea，M.J.Ludowise，G.Christenson，Y.-C.Shen，C.Lowery，P.S.Martin，S.Subramanya，W.Gtz，N.F.Gardner，R.S.Kern，and?S.A.Stockman，Appl.Phy.Lett.，78，3379(2001)。
[5]R.Homg，D.Wuu，Y.Lien，W.Lan，Appl.Phys.Lett.，79，2925(2001)。
[6]J.O.Song，K.K.Kim，S.J.Park，and?T.Y.Seong，Appl.Phys.Lett.，83，479(2003)。
[7]R.H.Homg，C.C.Yang，J.Y.Wu，S.H.Huang，C.E.Lee，and?D.S.Wuu，Appl.Phys.Lett.，86，221101(2005)。
Summary of the invention
The present invention provides a kind of novel GaN base luminescent device transparency electrode, can be applied to electrode at the horizontal type structure of backing material homonymy and electrode at the longitudinal type GaN of backing material heteropleural base luminescent device, it can be on the basis that does not reduce the luminescent device electric property, improve the luminous efficiency of luminescent device, and production cost is low, easily realize, be suitable for large-scale production.Its method for making is: deposited by electron beam evaporation method evaporation is used for forming with P type GaN base semiconductor interlayer the metal level of ohmic contact on the GaN based semiconductor; Then under 400 ℃～600 ℃ temperature, in oxygen containing atmosphere, anneal, metal is become with P type nitride semi-conductor material layer have the semitransparent electrode that good ohmic contacts; Then under 20 ℃～600 ℃ temperature, preparing shaggy transparent crystal layer with direct mode or indirect mode on the electrode.Compared with prior art, the present invention except have good light transmittance, low-resistivity and and P type GaN between have the characteristics of good Ohmic contact, also have the luminous efficiency that can improve device, significantly reduce cost and characteristic of simple process.
Say that more specifically this transparency electrode is mainly as the P type electrode of GaN base luminescent device, in the case, it is made up of two parts, and wherein first is the conducting metal semitransparent electrode that covers GaN base luminescent device P type laminar surface; Second portion is the optical clear crystal layer with rough surface that is layered on the aforementioned metal semitransparent electrode.The rough surface here is meant the surface with randomized profile shape or refers to surface by the crystal layer that fine structure material constituted of the specific morphology with taper or circular-arc or plane top profile.
First's metal semitransparent electrode during above-mentioned described transparency electrode is formed has excellent conducting performance, optical property and hot property, and can form good Ohmic contact with P type GaN based semiconductor, it is by 2 layers or 3 layers of metal Ni, Pd, Ti and Au or their alloy material constitute, preferred Ni/Au double-metal layer structure.
Second portion during above-mentioned described transparency electrode is formed has the optical clear crystal of rough surface surface topography, and its material is selected from ZnO, AZO, GZO, a kind of in ZITO and the ZIO material.
Metal semitransparent electrode in above-mentioned described transparency electrode part once between the material, covers the basic epi-layer surface of P type GaN at GaN base epitaxial loayer and shaggy optical clear crystal.After the annealed processing, and form good Ohmic contact between the P type GaN layer; Simultaneously, this metal semitransparent electrode partly adopts the high metal material of conductance, characteristics with low-resistivity, the easy therein diffusion profile of electric current, thereby can guarantee that nitride light-emitting device has the maximum homogenizing of lower operating voltage and light-emitting area so that the CURRENT DISTRIBUTION in the device is even.
And shaggy crystal layer is then selected semi-conducting material or the insulating material of energy gap greater than the luminous dominant wavelength energy of epitaxial material for use, and the refractive index of this material should be greater than the refractive index of luminescent device potting resin material, i.e. selective refraction rate n 〉=1.5.Shaggy crystal layer adopts wide-band gap material, can reduce this layer material to the photon that produces in the epitaxial material absorb the loss that causes again, make it have the characteristics of high permeability to the main light emission wavelength of epitaxial material; The refractive index of this crystal layer is greater than the refractive index of potting resin material, and according to the law of refraction as can be known, such selection can increase the photon that produces in the epitaxial material luminous zone enters this crystal layer from the GaN sill probability; Simultaneously, because the rough surface of this crystal layer, by reflection and the refracting process of light through this crystal layer the time, it can provide than the light shooting angle that manys big under the smooth surface situation, thereby increases the probability that photon escapes into the external space.
First kind of manufacture craft of this GaN based compound semiconductor light emitting element P type electrode is as follows:
(1) with the mocvd method n type nitride semiconductor layer (102) of on Sapphire Substrate (101), growing successively, behind luminous zone (103) and the P type nitride semiconductor layer (104), behind the growth ending, will from MOCVD equipment, take out with the sapphire material of nitride epitaxial layer;
(2) after cleaning, the deposited by electron beam evaporation device is gone up 2 layers or 3 layers Ni of evaporation at P type nitride semi-conductor material layer (104), Pd, and Ti and Au metal or their alloy material, its thickness are 5nm～30nm;
(3) sample is packed in the quick anneal oven, under 400 ℃～600 ℃ temperature, in oxygen containing atmosphere, anneal, above-mentioned metal at the last evaporation of P type nitride semi-conductor material layer (104) is become with P type nitride semi-conductor material layer have the semitransparent electrode (105) that good ohmic contacts;
(4) sample is packed in the heat evaporating device, on semitransparent electrode (105), steaming the Metal Zn of a layer thickness, perhaps containing the Metal Zn of Al element, perhaps containing the Metal Zn of Ga element at 50nm～1000nm, the Metal Zn that perhaps contains the In element, the perhaps Metal Zn of In and Sn element;
(5) during sample is packed quick anneal oven into, under 400 ℃～600 ℃ the temperature the above-mentioned metal that is steaming is being carried out oxidation processes on semitransparent electrode (105), making it be transformed into corresponding shaggy oxide crystal layer and form.
Second kind of manufacture craft divides four steps to carry out:
First three step is identical with above-mentioned technology (1)-(3).
Step 4: directly go up the transparent crystal layer that forms shaggy ZnO or AZO or GZO or ZIO or ZITO with depositional mode and form at semitransparent electrode (105).
The novel transparent electrode that above-mentioned two kinds of processes make, have when the oxide light transparent layer under the condition of high light light transmittance, compare with general P type transparency electrode, except having (1) good light transmittance, (2) have between low-resistivity and (3) and P type GaN beyond three features of good Ohmic contact, also have (4) and improve the characteristics of the light taking-up efficient of LED device by refraction or reflection, so, it can be under the condition that does not improve the LED operating voltage, and the luminous efficiency that improves device is more than 30%; If adopting with Zn is the main raw material(s) of oxide optical transparency crystal, compare with the ITO film, can significantly reduce production costs; In addition, owing to do not need the GaN material is carried out processed, technical process is simple, meets the required condition of large-scale production.
Description of drawings
Fig. 1 is the sectional drawing of P type electrode and N type electrode LED device when the backing material homonymy.
Wherein: 101 expression Sapphire Substrate, 102 expression n type nitride semiconductor layers, 103 expression luminous zones, 104 expression P type nitride semiconductor layers, 105 expression metal semitransparent electrode layers, the optical clear crystal layer that 106 presentation surfaces are coarse, 107 expression n type electrode pads, 108 expression p type electrode pads.
Fig. 2 is the sectional basic configuration of micro-structural in the rough surface crystal layer.
Fig. 3 is that thickness is about the light at room temperature fluorescence Spectra of the Zn metal level of 300nm at the ZnO crystal layer that obtained after the oxidation processes through 15 minutes under 450 ℃.
Fig. 4 is that thickness is about the light transmission curve of the Zn metal level of 300nm at the ZnO crystal layer that obtained after the oxidation processes through 15 minutes under 450 ℃.
Embodiment
Embodiment one:
Figure 1 shows that and use GaN base LED device sectional drawing of the present invention, comprising Sapphire Substrate 101, n type nitride semiconductor layer 102, luminous zone 103, P type nitride semiconductor layer 104, metal semitransparent electrode layer 105, shaggy optical clear crystal layer 106, in this embodiment, this crystalline material is ZnO, n type electrode contact pad 107, p type electrode contact pad 108.To describe the manufacturing process of P type transparency electrode part below in detail.
The first step is with MOCVD (metal-organic chemical vapor deposition) the method n type nitride semiconductor layer 102 of growing successively on Sapphire Substrate 101, behind luminous zone 103 and the P type nitride semiconductor layer 104.Behind the growth ending, above-mentioned sapphire material with nitride epitaxial layer is taken out from MOCVD equipment.
Second step is after cleaning, with electron beam (electron beam, EB) vaporising device thick Ni/Au metal level of evaporation 5nm～15nm on P type nitride semi-conductor material layer 104.
The 3rd step, this sample is packed in short annealing (RTA) stove, under 450 ℃～600 ℃ temperature, in oxygen containing atmosphere, anneal, above-mentioned Ni/Au metal is become with P type nitride semi-conductor material layer have the semitransparent electrode 105 that good ohmic contacts.
The 4th step, said sample is packed in the heat evaporating device, on Ni/Au semitransparent electrode 105, steaming layer of metal Zn, its thickness is between 50nm～1000nm, and preferred thickness is at 100nm～500nm.
The 5th step, said sample is packed in the quick anneal oven, under 400 ℃～600 ℃ temperature, the Zn metal level is carried out thermal oxidation, make it be transformed into shaggy ZnO crystal layer.Preferred thermal oxidation temperature range is 450 ℃～550 ℃.
So far, on P type nitride semi-conductor material layer, form the transparency electrode that combines by translucent conductive electrode of metal and optical transparency ZnO crystal layer.
Fig. 3 is the light at room temperature fluorescence Spectra curve of this Zn metal level after thermal oxidation.Having only a wavelength in the spectrum is the main peak of 380nm, matches with the radiative peak value of nearly band edge of ZnO material, thereby shows that the Zn metal level changes quality ZnO crystal layer preferably into after oxidation processes.
Fig. 4 has shown the light transmittance curve of this crystal layer.As can be seen from the figure, be the GaN blue-ray LED of 460nm for dominant wavelength, its light transmittance demonstrates its good light transmittance up to more than 90%.
The 6th step, by photoetching and etching process, the step of etching LED device (mesa) structure, and make N type pad 107 and P type pad 108, finish the making of LED tube core.
This LED tube core is under the situation of 20mA at operating current, compares with the LED tube core of no ZnO layer, and operating voltage is constant, is 3.4V, and still, luminous intensity has but improved about 40%.
Embodiment two:
First step is identical with embodiment one.
Second step is after cleaning, with electron beam (electron beam, EB) vaporising device thick Ti/Pd/Au metal level of evaporation 10nm～30nm on P type nitride semi-conductor material layer 104.
The 3rd step, this sample is packed in short annealing (RTA) stove, under 400 ℃～500 ℃ temperature, in oxygen containing atmosphere, anneal, above-mentioned Ti/Pd/Au metal is become with P type nitride semi-conductor material layer have the semitransparent electrode 105 that good ohmic contacts.
The 4th step, to contain Al amount is that about 4% Zn powder is raw material, in diffusion furnace, be heated to 500 ℃～850 ℃, with inert gas, argon gas (Argon), be carrier gas, by vapor transportation mode (vapor phasetransport process), in oxygen containing atmosphere, it is 50nm～2000nm that the epitaxial material surface that is coated with the Ti/Pd/Au metal level that obtains in the 3rd step forms thickness, and having specific is that the body structure surface pattern is (as taper, arcuation, plane) the transparent optical crystal layer 106 of feature, among this embodiment, this crystal layer material is Al-Doped ZnO (AZO) crystal layer.
The 5th step, by photoetching and etching process, the step of etching LED device (mesa) structure, and make N type pad 107 and P type pad 108, finish the making of LED tube core.
The wavelength that this transparent crystal layer sends the GaN blue-ray LED is that the transmitance of the dominant wavelength light of 460nm is about 75%, and corresponding LED device is compared with the LED tube core of no coarse transparent crystal layer, and luminous intensity improves about 20%, and every electrical parameter is constant.
Embodiment three:
Implementation process is identical with embodiment two.But in the 4th step, raw material are the Zn powder that contains In, and the transparent crystal layer material of formation is indium zinc oxide (ZIO).
Although the foregoing description has been explained the present invention particularly, the present invention is not limited in above-mentioned implementation content.In not departing from claim of the present invention institute restricted portion, can carry out form and details is carried out conversion to of the present invention.
Claims (7)
1, GaN based compound semiconductor light emitting element P type electrode is characterized in that described P type electrode is made of part of the conducting metal semitransparent electrode on the GaN based semiconductor and rough surface optical clear crystal block section successively;
Wherein said conducting metal semitransparent electrode part is by 2 layers or 3 layers of metal Ni, Pd, and Ti and Au or their alloy material constitute, and its thickness is 5nm～30nm;
Described rough surface optical clear crystal block section is by ZnO, AZO, and GZO, a kind of material among ZITO and the ZIO constitutes, and its thickness is 50nm～3000nm, surface roughness 〉=10nm, formation temperature is 30 ℃～600 ℃;
Has good Ohmic contact between GaN based compound semiconductor light emitting element P type electrode and the P type GaN layer.
2, according to the described GaN based compound semiconductor light emitting element of claim 1 P type electrode, it is characterized in that described conducting metal semitransparent electrode be the thick Ni/Au metal of 5nm～15nm under 400 ℃～600 ℃ temperature, annealing in oxygen containing atmosphere forms.
3, according to the described rough surface transparent crystal of claim 1 layer, its thickness is 100nm～500nm, and formation temperature is between 200 ℃～600 ℃.
4, the method for making of GaN based compound semiconductor light emitting element P type electrode is characterized in that manufacturing process is:
(1) with the mocvd method n type nitride semiconductor layer (102) of on Sapphire Substrate (101), growing successively, behind luminous zone (103) and the P type nitride semiconductor layer (104), behind the growth ending, will from MOCVD equipment, take out with the sapphire material of nitride epitaxial layer;
(2) after cleaning, the deposited by electron beam evaporation device is gone up 2 layers or 3 layers Ni of evaporation at P type nitride semi-conductor material layer (104), Pd, and Ti and Au metal or their alloy material, its thickness are 5nm～30nm;
(3) sample is packed in the quick anneal oven, under 400 ℃～600 ℃ temperature, in oxygen containing atmosphere, anneal, above-mentioned metal at the last evaporation of P type nitride semi-conductor material layer (104) is become with P type nitride semi-conductor material layer have the semitransparent electrode (105) that good ohmic contacts;
(4) sample is packed in the heat evaporating device, on semitransparent electrode (105), steaming the Metal Zn of a layer thickness, perhaps containing the Metal Zn of Al element, perhaps containing the Metal Zn of Ga element at 50nm～1000nm, the Metal Zn that perhaps contains the In element, the perhaps Metal Zn of In and Sn element;
(5) during sample is packed quick anneal oven into, under 400 ℃～600 ℃ the temperature the above-mentioned metal that is steaming is being carried out oxidation processes on semitransparent electrode (105), making it be transformed into corresponding shaggy oxide crystal layer and form.
5, according to the method for making of the described GaN based compound semiconductor light emitting element of claim 3 P type electrode, it is characterized in that describedly on semitransparent electrode (105), steaming layer of metal Zn, the Metal Zn that perhaps contains the Al element perhaps contains the Metal Zn of Ga element, and its thickness is 100nm～500nm.
6, according to the method for making of the described GaN based compound semiconductor light emitting element of claim 3 P type electrode, it is characterized in that described to Metal Zn, the Metal Zn that perhaps contains the Al element, the Metal Zn that perhaps contains the Ga element, the Metal Zn that perhaps contains the In element, perhaps the Metal Zn of In and Sn element is carried out oxidation processes, makes it be transformed into corresponding shaggy oxide crystal layer, and the temperature of oxidation processes is 400 ℃～500 ℃.
7, the method for making of GaN based compound semiconductor light emitting element P type electrode is characterized in that manufacturing process is:
(1) with the mocvd method n type nitride semiconductor layer (102) of on Sapphire Substrate (101), growing successively, behind luminous zone (103) and the P type nitride semiconductor layer (104), behind the growth ending, will from MOCVD equipment, take out with the sapphire material of nitride epitaxial layer;
(2) after cleaning, the deposited by electron beam evaporation device is gone up 2 layers or 3 layers Ni of evaporation at P type nitride semi-conductor material layer (104), Pd, and Ti and Au metal or their alloy material, its thickness are 5nm～30nm;
(3) sample is packed in the quick anneal oven, under 400 ℃～600 ℃ temperature, in oxygen containing atmosphere, anneal, above-mentioned metal at the last evaporation of P type nitride semi-conductor material layer (104) is become with P type nitride semi-conductor material layer have the semitransparent electrode (105) that good ohmic contacts;
(4) directly going up the transparent crystal layer that forms shaggy ZnO or AZO or GZO or ZIO or ZITO at semitransparent electrode (105) with depositional mode forms.
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| CN102208503A (en) * | 2011-01-25 | 2011-10-05 | 中山大学佛山研究院 | Light-emitting diode (LED) epitaxial structure and manufacturing method thereof |
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