CN101771114A - Vertical light-emitting diode with new compound stacked barrier layer metal structure and preparation method thereof - Google Patents
Vertical light-emitting diode with new compound stacked barrier layer metal structure and preparation method thereof Download PDFInfo
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- CN101771114A CN101771114A CN200910013721A CN200910013721A CN101771114A CN 101771114 A CN101771114 A CN 101771114A CN 200910013721 A CN200910013721 A CN 200910013721A CN 200910013721 A CN200910013721 A CN 200910013721A CN 101771114 A CN101771114 A CN 101771114A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
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- 238000000137 annealing Methods 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
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- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910004166 TaN Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005234 chemical deposition Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
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Abstract
The invention discloses a vertical light-emitting diode with a new compound stacked barrier layer metal structure and a preparation method thereof. A new compound stacked barrier layer metal structure is deposited under a p type ohmic contact reflecting metal film in an active layer and between heat radiating substrates; the diffusion property, corrosion resistance, oxidation resistance, adhesion property and thermal stability of the metal barrier are comprehensively considered; oxidation of Ag can be completely and effectively prevented and interdiffusion of the Ag and solder metal can be blocked; the Ag is ensured to have high reflectivity and low contact resistance; simultaneously the connection strength between a GaN based extension and the heat radiating substrate is ensured; and the electric and thermal long-term stability and reliability of a high efficiency light-emitting diode with a vertical structure are realized.
Description
Technical field
The present invention relates to a kind of GaN based vertical light emitting diode, particularly a kind of vertical LED and preparation method thereof with new compound stacked barrier layer metal structure.
Background technology
Present most GaN base extension mainly is to be grown on the Sapphire Substrate, because sapphire poor electric conductivity, common GaN base luminescent device adopts transversary, promptly two electrodes are in the same side of device, the electric current distance that lateral flow does not wait in the n-GaN layer, exist electric current to stop up, produce heat; In addition, the heat conductivility of Sapphire Substrate is low, has therefore limited the luminous power and the efficient of GaN base device.Sapphire Substrate is removed, and luminescent device is made vertical stratification can effectively solve heat radiation, bright dipping and problem such as antistatic.For vertical LED, the light of active layer emission downwards makes progress from the bright dipping of n type epitaxial surface after the reflection of p type extension contacting metal, therefore in order to obtain efficient vertical LED, need make the high reflectance ohmic contact metal layer in p type GaN base extension bottom, be absorbed by metal level with the light that reduces the downward emission of active layer.For visible light wave range, silver (Ag) reflectivity is the highest in all metal materials, and can form good Ohmic contact with p type GaN base epitaxial loayer, but the shortcoming of Ag is and semi-conductive poor adhesion, electricity and poor heat stability, easily oxidized and chemical corrosion etc.For the light-emitting diode of making vertical stratification; before peeling off Sapphire Substrate, usually GaN base extension is transferred on Si or the metal substrate by the heating and pressurizing mode; if speculum Ag surface shortage effectively stops and protects; this high temperature transfer process can promote the oxidation of Ag and the counterdiffusion of Ag and weld metal storeroom; cause light reflectivity decline, the contact resistance of Ag to become big, reduced the luminous efficiency of device.And the light emitting diode with vertical structure with good heat-radiating substrate is more prone to be applied in big electric current, high voltage occasion, therefore very high to the requirement on barrier layer, if the barrier layer process window is big inadequately, the ability of anti-long-term ageing then will produce phenomenons such as light efficiency decline even inefficacy after the long term device work.
Summary of the invention
For solving the above-mentioned light efficiency and electric, hot long-time stability and reliability problems that causes vertical LED because of the counterdiffusion between speculum Ag poor stability and Ag and solder metal, the present invention proposes a kind of vertical LED with new compound stacked barrier layer metal structure and preparation method thereof with innovating.
A kind of vertical LED with new compound stacked barrier layer metal structure comprises:
One heat-radiating substrate,
The heat-radiating substrate lower surface forms bottom electrode,
The heat-radiating substrate upper surface forms weld metal,
GaN base extension lower surface forms p type ohmic contact reflecting metallic film,
GaN base extension upper surface forms top electrode,
It is characterized in that: the reflecting metallic film lower surface forms the compound stacked barrier layer metal, comprises two or two above first barrier metal, second barrier metal, the 3rd barrier metal and one or above the 4th barrier metal, the 5th barrier metals of one-period of cycle in order;
Multiple-level stack formula barrier metal lower surface forms down weld metal;
GaN base extension is connected on the heat-radiating substrate by weld metal on following weld metal and the heat-radiating substrate.
The present invention prepares the method for above-mentioned vertical LED, the steps include:
1) epitaxial growth GaN base blue-ray LED luminescent material on Sapphire Substrate, luminescent material comprises n type GaN based semiconductor, active layer and p type GaN based semiconductor successively;
2) on p type GaN based semiconductor, deposit the ohmic contact reflecting metallic film, comprise the alloy of Ag or Ag;
3) deposition first barrier metal on above-mentioned reflecting metallic film;
4) stop deposition second barrier metal first;
5) repeated deposition first barrier metal on second barrier metal further comprises repeated deposition second barrier metal, the repetition period two or more;
6) after step 5), deposit the 3rd barrier metal;
7) sequential aggradation the 4th barrier metal and the 5th barrier metal above the 3rd barrier metal, the repetition period one or more;
8) deposit weld metal above the above-mentioned multilayer barrier layer metal, comprising the alloy of Au or Au;
9) get a heat-radiating substrate and weld metal under the surface deposition thereon, comprise the alloy of Au or Au;
10) by the pressuring method of heating with step 1)～6) the GaN based epitaxial film that forms is welded to completing steps 7) and heat-radiating substrate on;
11) Sapphire Substrate is removed;
12) at n type GaN base semiconductor laminar surface middle section deposition top electrode;
13) at heat-radiating substrate lower surface deposition bottom electrode.
GaN base LED luminescent material of the present invention is to form by the organic gas chemistry precipitation of metal (MOCVD) method; Heat-radiating substrate prepares material and is selected from GaAs, Ge, Si, Cu or Mo.First barrier metal is selected from one of W, Ta, TaN, WN, TiN, WTi, WTiN or aforesaid combination in any, thickness 10～500nm.Second barrier metal is selected from Mo, Nb, Ru, Rh or Pt, thickness 10～500nm.Comprise further that after step 5) Ag is carried out high-temperature thermal annealing handles 400～500 ℃ of annealing temperatures, annealing time 10～30min.The 3rd barrier metal is selected from one of Pd, Ni, Co or aforesaid combination in any, thickness 10～1000nm.The 4th barrier metal is selected from one of Cr, Ti, W, Ta, TaN, WN, TiN, WTi, WTiN or aforesaid combination in any, thickness 10～500nm.The 5th barrier metal is selected from Mo, Nb, Ru, Rh or Pt, thickness 10～500nm.The barrier metal depositional mode adopts evaporation, sputter or chemical deposition.Wherein welding manner can adopt fusion bonding or eutectic bonding wafer bond techniques.Sapphire Substrate removing method wherein select for use laser lift-off, grinding, wet etching or aforementioned in any two kinds of technology combinations.Top electrode and bottom electrode depositional mode adopt evaporation, sputter or chemical deposition.
Step 3) to step 8) is an innovation part of the present invention in the inventive method, the high melting point metal materials that the evaporation multilayer is different forms stacked barrier layer metal structure, wherein: 1. first barrier metal has higher fusing point than second barrier metal, its counterdiffusion to the Ag and second barrier metal plays barrier effect, suppresses decline of Ag reflectivity and ohmic contact degeneration that its heat and electric diffusion cause; Adopt the high-melting-point alloy material that contains Ti or Ta can improve the adhesive force of second barrier metal and Ag as first barrier metal simultaneously.2. adopt anticorrosive materials with high melting point preferably as second barrier metal, can protect Ag not corroded by the technical process chemicals.3. step 5) repeats alternating deposit first barrier metal and the second barrier metal mode, can reduce thermal stress to the adhering destruction of intermetallic, avoids single-layer metal deposition blocked up appearance easily to peel off.4. step 6) is handled by high-temperature thermal annealing, promotes Ag and p type GaN surface to form ohmic contact, and improves the adhesiveness of itself and the basic extension of GaN; Because the fusing point of first barrier metal and second barrier metal is higher, has good oxidization resistance, can stop the high-temperature annealing process oxygen atom to enter the Ag layer, stop the oxidated back of Ag to the reflectivity of Ag and the destruction that contacts with p type GaN extension.5. the 3rd barrier metal has than first and second barrier metals and stops the characteristic that spreads in the solder metal better, stop solder metal interior diffusion couple Ag reflectivity and with the destruction of p type contact resistance.6. the 3rd barrier layer is if deposit thickness is blocked up, then may cause peeling off (peeling) because stress is excessive, if thickness low LCL, be not enough to stop fully the interior diffusion of solder metal, can reflectivity and the p type GaN contact of Ag be damaged, and the interior diffusion of solder metal also can have influence on the weld strength between GaN base extension and heat-radiating substrate, therefore above the 3rd barrier metal, continue deposition the 4th and the 5th barrier metal and can solve the problem that diffusion causes in above-mentioned stress and the scolder on the one hand, the metal material that wherein adopts higher melt is as the 4th barrier metal, not only can improve the adhesive force of the 5th barrier metal and the 3rd barrier metal, also can suppress heat and electric diffusion between them.By step 3)～8) new compound stacked barrier layer metal structure that forms is to have taken into full account to stop diffusion property, corrosion resistance, non-oxidizability, adhesiveness and thermal stability, the combination that connects to each barrier metal, the counterdiffusion that stops Ag and solder metal in full force and effect, guarantee that Ag has high reflectivity and low contact resistance, guarantee the weld strength of GaN base extension and heat-radiating substrate simultaneously, realized the electricity of high light efficiency light emitting diode with vertical structure, the long-time stability and the reliability of heat.
The invention has the beneficial effects as follows: innovation ground adopts new compound stacked barrier layer metal structure, metal barrier diffusion property, corrosion resistance, non-oxidizability, adhesiveness and thermal stability have been taken all factors into consideration, can in full force and effectly stop the oxidation of Ag and stop Ag and the counterdiffusion of solder metal, guarantee that Ag has high reflectivity and low contact resistance, guarantee the bonding strength between GaN base extension and heat-radiating substrate simultaneously, realized the electricity of efficient light emitting diode with vertical structure, the long-time stability and the reliability of heat.
Description of drawings
Fig. 1 a to Fig. 1 g is the schematic cross-section of preparation process of the vertical LED with new compound stacked barrier layer metal structure of the preferred embodiment of the present invention;
Part description in the accompanying drawing:
100: Sapphire Substrate; 110:GaN base extension; 120: reflecting metallic film
130: the compound stacked barrier layer metal; 131: the first barrier metals; 132: the second barrier metals
133: the three barrier metals; 134: the four barrier metals; 135: the five barrier metals;
140: go up weld metal; 150: top electrode; 160: bottom electrode; 200: heat-radiating substrate;
210: following weld metal.
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
A kind of vertical LED shown in Fig. 1 g with new compound stacked barrier layer metal structure, one heat-radiating substrate 200 is provided, heat-radiating substrate 200 lower surfaces form bottom electrode 160, heat-radiating substrate 200 upper surfaces form weld metal 140, GaN base extension 110 lower surfaces form p type ohmic contact reflecting metallic film 120, and GaN base extension 110 upper surfaces form top electrode 150; Reflecting metallic film 120 lower surfaces form compound stacked barrier layer metal 130, comprise first barrier metal 131, second barrier metal 132, the 3rd barrier metal 133, the 4th barrier metal 134, the 5th barrier metal 135 in order; Multiple-level stack formula barrier metal 130 lower surfaces form down weld metal 210; GaN base extension 110 is connected on the heat-radiating substrate 200 by weld metal 140 on following weld metal 210 and the heat-radiating substrate.
Preparation method's step of above-mentioned vertical LED is as follows:
As shown in Figure 1a, adopt MOCVD method epitaxial growth GaN base LED luminescent material 110 on Sapphire Substrate 100, luminescent material comprises n type GaN based semiconductor, active layer and p type GaN based semiconductor successively;
Shown in Fig. 1 b, adopt electron beam evaporation plating deposition of reflective metal film 120 on the p-GaN surface, select Ag for use, thickness is between 100nm～120nm, and under nitrogen atmosphere, anneal, 400～500 ℃ of annealing temperatures, annealing time 10～30min, annealing makes reflecting metallic film 120 and p type GaN based semiconductor form good Ohmic contact and adhesion strength;
Shown in Fig. 1 c, adopt electron beam evaporation plating on reflecting metallic film 120, alternately to deposit first barrier metal 131 and second barrier metal 132, select WTi (N) and Pt respectively for use, thickness is respectively 100nm and 50nm; Repeat above 4 times (cycle) of deposition; Deposition the 3rd barrier metal 133 is selected Ni for use above second barrier metal 132 of top, and thickness is 100nm; Sequential aggradation the 4th barrier metal 134 and the 5th barrier metal 135 above the 3rd barrier metal 133, thickness is respectively 100nm and 50nm; So far form compound stacked barrier layer metal structure 130;
Shown in Fig. 1 d, adopt electron beam evaporation plating weld metal 140 on the deposition of multiple-level stack formula barrier metal film 130 tops, select Ti/Au for use, thickness is 50/1000nm; Get a Si substrate simultaneously as heat-radiating substrate 200, weld metal layers 210 under the electron beam evaporation plating thereon, and material selection Cr/Ni/Au/AuSn, thickness are 20/50/150/500nm, and wherein the AuSn ratio is 80: 20;
Shown in Fig. 1 e, adopt the eutectic bonding mode the above-mentioned GaN extension for preparing to be connected on the Si substrate 200 280 ℃ of key and temperature, pressure 5000N;
Shown in Fig. 1 f, adopt 248nm KrF excimer laser to peel off and remove Sapphire Substrate 100, the about 1J/cm of laser energy density
2
Shown in Fig. 1 g, electron beam evaporation plating top electrode 150 on n type GaN based semiconductor, electron beam evaporation plating bottom electrode 160 on Si substrate 200 back sides is all selected Cr/Pt/Au for use.So far finish the preparation of vertical LED of the present invention, its structure is shown in Fig. 1 g.
Claims (13)
1. vertical LED with new compound stacked barrier layer metal structure comprises:
One heat-radiating substrate,
The heat-radiating substrate lower surface forms bottom electrode,
The heat-radiating substrate upper surface forms weld metal,
GaN base extension lower surface forms p type ohmic contact reflecting metallic film,
GaN base extension upper surface forms top electrode,
It is characterized in that: the reflecting metallic film lower surface forms the compound stacked barrier layer metal, comprises two or two above first barrier metal, second barrier metal, the 3rd barrier metal and one or above the 4th barrier metal, the 5th barrier metals of one-period of cycle in order;
Multiple-level stack formula barrier metal lower surface forms down weld metal;
GaN base extension is connected on the heat-radiating substrate by weld metal on following weld metal and the heat-radiating substrate.
2. preparation method with vertical LED of new compound stacked barrier layer metal structure comprises step:
1) epitaxial growth GaN base blue-ray LED luminescent material on Sapphire Substrate, luminescent material comprises n type GaN based semiconductor, active layer and p type GaN based semiconductor successively;
2) on p type GaN based semiconductor, deposit the ohmic contact reflecting metallic film, comprise the alloy of Ag or Ag;
3) deposition first barrier metal on above-mentioned reflecting metallic film;
4) stop deposition second barrier metal first;
5) repeated deposition first barrier metal on second barrier metal further comprises repeated deposition second barrier metal, the repetition period two or more;
6) after step 5), deposit the 3rd barrier metal;
7) sequential aggradation the 4th barrier metal and the 5th barrier metal above the 3rd barrier metal, the repetition period one or more;
8) deposit weld metal above the above-mentioned multilayer barrier layer metal, comprising the alloy of Au or Au;
9) get a heat-radiating substrate and weld metal under the surface deposition thereon, comprise the alloy of Au or Au;
10) by the pressuring method of heating with step 1)～6) the GaN based epitaxial film that forms is welded to completing steps
7) on the heat-radiating substrate;
11) Sapphire Substrate is removed;
12) at n type GaN base semiconductor laminar surface middle section deposition top electrode;
13) at heat-radiating substrate lower surface deposition bottom electrode.
3. the preparation method of vertical LED as claimed in claim 2 is characterized in that: GaN base LED luminescent material is to form by the organic gas chemistry precipitation of metal (MOCVD) method; Heat-radiating substrate prepares material and is selected from GaAs, Ge, Si, Cu or Mo.
4. the preparation method of vertical LED as claimed in claim 2, it is characterized in that: first barrier metal is selected from one of W, Ta, TaN, WN, TiN, WTi, WTiN or aforesaid combination in any, thickness 10～500nm.
5. the preparation method of vertical LED as claimed in claim 2, it is characterized in that: second barrier metal is selected from Mo, Nb, Ru, Rh or Pt, thickness 10～500nm.
6. the preparation method of vertical LED as claimed in claim 2 is characterized in that: comprise further that after step 5) Ag is carried out high-temperature thermal annealing handles 400～500 ℃ of annealing temperatures, annealing time 10～30min.
7. the preparation method of vertical LED as claimed in claim 2, it is characterized in that: the 3rd barrier metal is selected from one of Pd, Ni, Co or aforesaid combination in any, thickness 10～1000nm.
8. the preparation method of vertical LED as claimed in claim 2, it is characterized in that: the 4th barrier metal is selected from one of Cr, Ti, W, Ta, TaN, WN, TiN, WTi, WTiN or aforesaid combination in any, thickness 10～500nm.
9. the preparation method of vertical LED as claimed in claim 2, it is characterized in that: the 5th barrier metal is selected from Mo, Nb, Ru, Rh or Pt, thickness 10～500nm.
10. the preparation method of vertical LED as claimed in claim 2 is characterized in that: the employing of barrier metal depositional mode evaporation, sputter or chemical deposition.
11. the preparation method of vertical LED as claimed in claim 2 is characterized in that: wherein welding manner can adopt fusion bonding or eutectic bonding wafer bond techniques.
12. the preparation method of vertical LED as claimed in claim 2 is characterized in that: Sapphire Substrate removing method wherein select for use laser lift-off, grinding, wet etching or aforementioned in any two kinds of technology combinations.
13. the preparation method of vertical LED as claimed in claim 2 is characterized in that: top electrode and bottom electrode depositional mode adopt evaporation, sputter or chemical deposition.
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| CN102610728A (en) * | 2012-03-21 | 2012-07-25 | 厦门市三安光电科技有限公司 | Light-emitting diode (LED) with back silver-plated reflecting layer and manufacturing method of LED |
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| JP3304541B2 (en) * | 1993-09-08 | 2002-07-22 | 住友電気工業株式会社 | Method of forming ohmic electrode |
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| CN102610728A (en) * | 2012-03-21 | 2012-07-25 | 厦门市三安光电科技有限公司 | Light-emitting diode (LED) with back silver-plated reflecting layer and manufacturing method of LED |
| CN102610728B (en) * | 2012-03-21 | 2014-10-29 | 厦门市三安光电科技有限公司 | Light-emitting diode (LED) with back silver-plated reflecting layer and manufacturing method of LED |
| CN103618035A (en) * | 2013-11-14 | 2014-03-05 | 南昌黄绿照明有限公司 | GaN-based LED thin-film chip with stress modulation layer and manufacturing method thereof |
| CN104091821A (en) * | 2014-07-16 | 2014-10-08 | 上海和辉光电有限公司 | Flexible display device and folding-resistant metal wire |
| CN112846495A (en) * | 2019-11-27 | 2021-05-28 | 山东大学齐鲁医院 | High-precision electron beam radiation field stop block |
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| CN101771114B (en) | 2012-03-07 |
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