CN101494267A - Method for manufacturing gallium nitride-based light-emitting device based on substrate stripping - Google Patents
Method for manufacturing gallium nitride-based light-emitting device based on substrate stripping Download PDFInfo
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- CN101494267A CN101494267A CNA2008102378442A CN200810237844A CN101494267A CN 101494267 A CN101494267 A CN 101494267A CN A2008102378442 A CNA2008102378442 A CN A2008102378442A CN 200810237844 A CN200810237844 A CN 200810237844A CN 101494267 A CN101494267 A CN 101494267A
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- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 95
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000758 substrate Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000001039 wet etching Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 94
- 239000002585 base Substances 0.000 claims description 47
- 238000005530 etching Methods 0.000 claims description 35
- 206010040844 Skin exfoliation Diseases 0.000 claims description 22
- 229910052594 sapphire Inorganic materials 0.000 claims description 21
- 239000010980 sapphire Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 230000035618 desquamation Effects 0.000 claims description 17
- 238000005520 cutting process Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000001312 dry etching Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011241 protective layer Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- OINMNSFDYTYXEQ-UHFFFAOYSA-M 2-bromoethyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCBr OINMNSFDYTYXEQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910017083 AlN Inorganic materials 0.000 claims description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Abstract
The invention discloses a method for manufacturing a gallium nitride-based light-emitting device based on substrate stripping, which is characterized in that a GaN-based material is used as a wet etching sacrificial layer and is also used as a buffer layer for epitaxial growth of a light-emitting layer material, and the gallium nitride-based light-emitting device based on the substrate stripped by the wet etching sacrificial layer is manufactured by adopting a homogeneous sacrificial layer , and meanwhile, the higher crystal quality of the light-emitting layer is kept. The invention has the beneficial effects that: the wet etching sacrificial layer is made of the same material as the luminescent layer, so that the epitaxial growth luminescent layer can be ensured to obtain higher crystal quality, and the luminescent device based on substrate stripping with higher luminescent efficiency can be obtained.
Description
Technical field
The present invention relates to a kind of manufacture method of gallium nitride base light-emitting device, particularly a kind of manufacture method of the gallium nitride base light-emitting device based on substrate desquamation.
Background technology
Gallium nitride (GaN) based compound semiconductor is an important materials of commercially producing indigo plant, green glow and ultraviolet light-emitting diodes at present.Traditional GaN sill mainly be epitaxial growth on Sapphire Substrate, but the heat conductivility of Sapphire Substrate is relatively poor, causes the reliability of GaN based LED device to reduce.To this problem preferably solution be to peel off Sapphire Substrate.
The existing method of peeling off Sapphire Substrate mainly contains two kinds: (Laser Lift-Off LLO) peels off method with the wet etching sacrifice layer to laser lift-off.
Laser lift-off is to adopt ultraviolet pulse laser to see through Sapphire Substrate back side illuminaton GaN base epitaxial loayer and Sapphire Substrate interface, make GaN base epitaxial loayer generation thermal decomposition in the near interface certain thickness scope, thereby realize separating of Sapphire Substrate and GaN base epitaxial loayer.Laser lift-off is the substrate desquamation technology that generally adopts at present, but this method can produce thermal shock in application process, causes the epitaxial loayer damage, breaks and forms the coarse interface of peeling off.
The wet etching sacrifice layer is peeled off method and is meant by the sacrifice layer between wet etching epitaxial loayer and the Sapphire Substrate and realizes separating of Sapphire Substrate and epitaxial loayer.Traditional wet etching sacrifice layer is generally before growing GaN base epitaxial loayer, the sacrifice layer (simultaneously as resilient coating) that growth one non-GaN sill is on Sapphire Substrate earlier, then in the chip manufacturing process, use specific this sacrifice layer of solution etching, for GaN base epitaxial loayer etching not taking place then, can realize separating of GaN base epitaxial loayer and Sapphire Substrate by the selective etch sacrifice layer.Adopt this method can obtain undamaged effect and the level and smooth interface of peeling off, more superior than laser lift-off.At present known sacrificial layer material has TiN (Chinese patent application number 200710003186.6) and CrN (J-S Ha, S.W.Lee, H-J Lee, et al., The Fabrication of VerticalLight-Emitting Diodes Using Chemical Lift-Off Process, IEEE Photon.Technol.Lett., Vol.20, No.3, pp175-177,2008).Yet, peel off method for traditional wet etching sacrifice layer, because sacrifice layer that is adopted and GaN base epitaxial loayer belong to different materials system, promptly heterogeneous each other, when with this sacrifice layer as resilient coating and thereon during growing GaN base epitaxial loayer, heterogeneous resilient coating can cause the crystal mass variation, for luminescent device, more can reduce its internal quantum efficiency, thereby cause luminous efficiency to reduce.
Summary of the invention
The present invention is intended to propose a kind of manufacture method of the gallium nitride base light-emitting device based on substrate desquamation, with the GaN sill as the wet etching sacrifice layer and simultaneously as the resilient coating of luminescent layer material epitaxy growth, by adopting homogeneity sacrifice layer (resilient coating), produce based on the gallium nitride base light-emitting device at the bottom of the wet etching sacrifice layer peeling liner, simultaneously, keep higher luminescent layer crystal mass.
The manufacture method of the present invention solves that its problem proposes a kind of gallium nitride base light-emitting device based on substrate desquamation comprises step:
1) with sapphire as epitaxial growth substrate, epitaxial growth buffer, wet etch stop layer, luminescent layer successively thereon, wherein, resilient coating is unadulterated GaN sill, the wet etch stop layer is a p type GaN sill, and luminescent layer comprises n type GaN base epitaxial loayer, active layer and p type GaN base epitaxial loayer successively at least;
2) luminous mesa region of definition and Cutting Road zone, and adopt dry etching to remove the n type GaN base epitaxial loayer of p type GaN base epitaxial loayer, active layer and part on the Cutting Road zone, expose n type GaN base epitaxial loayer;
3) make multiple layer metal combination on the p of luminous mesa region type GaN base epitaxial loayer, the multiple layer metal combination covers p type GaN base epitaxial loayer;
4) adopt the etching of light assisted electrochemical to remove the n type GaN base epitaxial loayer in Cutting Road zone, and make etching stop at the wet etch stop layer;
5) make a wet etching protective layer, make it cover the luminescent layer sidewall fully;
6) the employing dry etching is removed wet etch stop layer and the resilient coating on the Cutting Road zone;
7) make a permanent substrate, make it realize engaging with the multiple layer metal combination of luminous mesa region;
8) adopt the etching of light assisted electrochemical to remove the resilient coating of luminous mesa region, make the epitaxial loayer of Sapphire Substrate and luminous mesa region realize separating;
9) adopt dry etching to remove the wet etch stop layer of luminous mesa region, expose n type GaN base epitaxial loayer;
10) make electrode, comprise and on permanent substrate, make a positive electrode respectively, on n type GaN base epitaxial loayer, make a negative electrode.
In the present invention, step 4) and 8) adopted light assisted electrochemical (PEC) etch process, promptly shine this semi-conducting material of oxidation and etching in alkaline solution by the light source of energy greater than the semi-conducting material band gap.Utilize the PEC etch process under the condition of no applying bias, not mix or n type GaN sill with speed etching faster, but can't etching p type GaN sill; Therefore, can utilize under the no applying bias condition PEC technology, select p type GaN sill as the wet etch stop layer to the selective etch of different conductivity GaN sills.Utilize step 2) and 4) the luminescent layer sidewall is exposed fully, thereby make that the wet etching protective layer can cover sidewall fully in the step 5).Wet etch stop layer and wet etching protective layer avoid it etched in step 8) the complete insulation blocking of luminescent layer.Step 6) provides the etching window for the PEC etching in the step 8), i.e. the sidewall of resilient coating (sacrifice layer), etching solution are realized peeling off of Sapphire Substrate by the infiltration etching to resilient coating (sacrifice layer) sidewall just.
In the present invention, the wet etch stop layer is low-doped p type GaN sill, and doping content is lower than 10
18Cm
-3Multiple layer metal combination has high reflectance, can form good the contact with p type GaN base epitaxial loayer, and has the character of alkali resistant etching, and its top layer metal material is selected from Pt, Au, Ni or Cr; The light source of PEC etching GaN sill is selected the ultraviolet light of wavelength less than 365nm for use, and etching solution is selected from KOH, NaOH or NH
4OH; The wet etching protective layer is the insulating properties material with alkali resistant etching, is selected from aluminium oxide, zirconia, aluminium nitride, BCB or polyimides; Permanent substrate can adopt plating or bonding mode to make, and its material of its material is selected from Cu, Ni, Si, Ge, Mo or GaAs.
The invention has the beneficial effects as follows: wet etching sacrifice layer (resilient coating) adopts and the material of luminescent layer homogeneity can guarantee that the epitaxial growth luminescent layer obtains higher crystal mass, thereby obtains the luminescent device based on substrate desquamation of higher photoluminescence efficiency.
Description of drawings
Fig. 1～Figure 10 is the schematic diagram of manufacturing process of a kind of gallium nitride base light-emitting device based on substrate desquamation of the preferred embodiment of the present invention;
Among the figure: 1: Sapphire Substrate 2:u-GaN layer
3: low-mix p-GaN layer 4:n-GaN layer
5: multiple quantum well layer 6:p-GaN layer
7:Ag/Ni/Au multiple layer metal combination 8:Al
2O
3Layer
9:Si substrate 10: positive electrode
11: negative electrode 20: luminescent layer
100: luminous mesa region 200: Cutting Road zone
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
The manufacture method of a kind of gallium nitride base light-emitting device based on substrate desquamation shown in Fig. 1～10, its making step is as follows:
As shown in Figure 1, adopt metal organic chemical vapor deposition (MOCVD) epitaxial growth u-GaN layer 2, low-mix p-GaN layer 3, n-GaN layer 4, multiple quantum well layer 5, p-GaN layer 6 successively on Sapphire Substrate 1, wherein n-GaN layer 4, multiple quantum well layer 5 and p-GaN layer 6 are formed luminescent layer 20;
According to the top plan view shown in Fig. 2 b epitaxial loayer is defined, adopt lithographic definition to go out luminous mesa region 100 and Cutting Road zone 200, and shown in accompanying drawing 2a, adopt inductively coupled plasma (ICP) dry etching to remove the n-GaN layer 4 of p-GaN layer 6, multiple quantum well layer 5 and part on the Cutting Road zone 200, expose n-GaN layer 4;
As shown in Figure 3, on the p-GaN of luminous mesa region 100 layer 6, make Ag/Ni/Au multiple layer metal combination 7, thickness is 120/50/1000nm, the luminous mesa region 100 of multiple layer metal combination 7 basic coverings, but with respect to luminous mesa region 100 do certain width in contract, expose the mesa edge part;
As shown in Figure 4, adopt the n-GaN layer 4 on the PEC technology etching removal Cutting Road zone 200, concrete process conditions comprise: " adopt the mercury lamp irradiation epi-layer surface of radiation scope at 280～350nm, power density is 50mW/cm
2, etching solution adopts the KOH solution of 2 mol, and temperature is a room temperature ", PEC etching duration 30 minutes, final etching stops on the low-mix p-GaN layer 3;
As shown in Figure 5, depositing one deck Al on the sidewall of luminescent layer 20 and on the p-GaN layer 6 of luminous mesa region frontside edge part
2O
3Layer 8, thickness is 200nm;
As shown in Figure 6, employing ICP dry etching is removed low-mix p-GaN layer 3 and the u-GaN layer 2 on the Cutting Road zone 200;
As shown in Figure 7, utilize wafer eutectic bonding technology, Si substrate 9 is joined on the multiple layer metal combination 7;
As shown in Figure 8, the u-GaN layer 2 on the luminous mesa region 100 is removed in the etching of employing PEC technology, and concrete process conditions comprise: " adopt radiation scope to see through the sapphire back side illuminaton to u-GaN layer 2 at the mercury lamp of 280～350nm, power density is 50mW/cm
2, etching solution adopts the KOH solution of 2 mol, and temperature is a room temperature ", PEC etching duration 4 hours finally makes the epitaxial loayer of Sapphire Substrate 1 and luminous mesa region 100 realize separating, and realizes that the wet method of Sapphire Substrate is peeled off;
As shown in Figure 9, adopt the ICP dry etching to remove the low-mix p-GaN layer 3 of luminous mesa region 100, expose n-GaN layer 4;
As shown in figure 10, make a positive electrode 10 on Si substrate 9, make a negative electrode 11 on n-GaN layer 4, the positive and negative electrode material is all selected Cr/Au for use, thickness 50/1000nm.
In embodiment of the present invention, epitaxially grown resilient coating (sacrifice layer) adopts conventional unadulterated GaN base u-GaN layer 2, though between resilient coating u-GaN layer 2 and luminescent layer 20, inserted etching stopping layer low-mix p-GaN layer 3, but because etching stopping layer itself also is a GaN based material and p type doping content is very low can not impact crystal mass, therefore can guarantee that the crystal mass of luminescent layer is consistent with conventional epitaxial structure, heterogeneous resilient coating (sacrifice layer) compared to non-GaN sill, epitaxially grown crystal mass is more superior on the homogeneous buffer layer, realizes that based on this sacrifice layer of etching its luminous efficiency of luminescent device of substrate desquamation is higher.
Claims (8)
1. manufacture method based on the gallium nitride base light-emitting device of substrate desquamation comprises step:
1) with sapphire as epitaxial growth substrate, epitaxial growth buffer, wet etch stop layer, luminescent layer successively thereon, wherein, resilient coating is unadulterated GaN sill, the wet etch stop layer is a p type GaN sill, and luminescent layer comprises n type GaN base epitaxial loayer, active layer and p type GaN base epitaxial loayer successively at least;
2) luminous mesa region of definition and Cutting Road zone, and be used in the n type GaN base epitaxial loayer that p type GaN base epitaxial loayer, active layer and part on the Cutting Road zone are removed in the method etching, expose n type GaN base epitaxial loayer;
3) make multiple layer metal combination on the p of luminous mesa region type GaN base epitaxial loayer, the multiple layer metal combination covers p type GaN base epitaxial loayer;
4) adopt the etching of light assisted electrochemical to remove the n type GaN base epitaxial loayer in Cutting Road zone, and make etching stop at the wet etch stop layer;
5) make a wet etching protective layer, make it cover the luminescent layer sidewall fully;
6) the employing dry etching is removed wet etch stop layer and the resilient coating on the Cutting Road zone;
7) make a permanent substrate, make it realize engaging with the multiple layer metal combination of luminous mesa region;
8) adopt the etching of light assisted electrochemical to remove the resilient coating of luminous mesa region, make the epitaxial loayer of Sapphire Substrate and luminous mesa region realize separating;
9) adopt dry etching to remove the wet etch stop layer of luminous mesa region, expose n type GaN base epitaxial loayer;
10) make electrode, comprise and on permanent substrate, make a positive electrode respectively, on n type GaN base epitaxial loayer, make a negative electrode.
2. the manufacture method of a kind of gallium nitride base light-emitting device based on substrate desquamation according to claim 1, it is characterized in that: the wet etch stop layer is that doping content is lower than 10
18Cm
-3P type GaN sill.
3. the manufacture method of a kind of gallium nitride base light-emitting device based on substrate desquamation according to claim 1, it is characterized in that: the multiple layer metal combination has the character of high reflectance and alkali resistant etching, and forming good the contact with p type GaN base epitaxial loayer, its top layer metal material is selected from Pt, Au, Ni or Cr.
4. the manufacture method of a kind of gallium nitride base light-emitting device based on substrate desquamation according to claim 1, it is characterized in that: the etching of light assisted electrochemical is to carry out under the condition of no applying bias.
5. the manufacture method of a kind of gallium nitride base light-emitting device based on substrate desquamation according to claim 1, it is characterized in that: the etching of light assisted electrochemical selects for use wavelength to shine less than the ultraviolet light of 365nm.
6. the manufacture method of a kind of gallium nitride base light-emitting device based on substrate desquamation according to claim 1, it is characterized in that: the etched etching solution of light assisted electrochemical is selected from KOH, NaOH or NH
4OH.
7. the manufacture method of a kind of gallium nitride base light-emitting device based on substrate desquamation according to claim 1; it is characterized in that: the wet etching protective layer is the insulating properties material with alkali resistant etching, is selected from aluminium oxide, zirconia, aluminium nitride, BCB or polyimides.
8. the manufacture method of a kind of gallium nitride base light-emitting device based on substrate desquamation according to claim 1 is characterized in that: permanent substrate can adopt to be electroplated or the bonding mode is made, and its material is selected from Cu, Ni, Si, Ge, Mo or GaAs.
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