CN101515616A - Multiple quantum well uv-LED device on SiC substrate and manufacturing method - Google Patents
Multiple quantum well uv-LED device on SiC substrate and manufacturing method Download PDFInfo
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Abstract
The invention discloses a multiple quantum well uv-LED device on a SiC substrate and a manufacturing method, relating to the technical field of micro-electronics and mainly solving the problem that the light-emitting efficiency of uv LED is low. The device comprises a low-temperature AlN nucleating layer, a high-temperature AlN nucleating layer, an intrinsic AlGaN epitaxial layer, an n-AlGaN barrier layer, an active area, a p-AlGaN barrier layer, a low Al component p-shaped AlGaN layer, a p-shaped GaN capping layer and a window area (A) arranged on the p-shaped GaN capping layer from bottom to top in sequence. The device etches the p-GaN capping layer to an electronic p-AlGaN barrier layer by a dry method to form a cylindrical emergent light window, thus changing the path of the emergent light and greatly reducing the loss of light in the process of spread. The device has the advantages of high light-emitting efficiency, simple process, low cost, good repeatability and high reliability and can be applied in different fields such as water processing, medical treatment, biomedicine occasion and white light illumination, etc.
Description
Technical field
The invention belongs to microelectronics technology, relate to semiconductor device, particularly a kind of implementation method of uv-LED device of new A lGaN based multiple quantum well can be used for water treatment, medical treatment and biomedicine and white-light illuminating field.
Background technology
The III-V group iii v compound semiconductor material is as the outstanding representative of third generation semi-conducting material, have a lot of excellent characteristic, especially aspect optical application, { (Al, In) N} can cover whole visible region and black light district to Ga to the alloy of being made up of Ga, Al, In, N.And the III group-III nitride of wurtzite structure all is direct band gap, is very suitable for the application of opto-electronic device.Particularly at ultraviolet region, the uv-LED of AlGaN based multiple quantum well has demonstrated huge advantage, becomes one of focus of present ultraviolet light photo device development.Yet, along with shortening of LED emission wavelength, the Al component is more and more higher in the GaN base LED active layer, the preparation of high-quality AlGaN material has great difficulty, the AlGaN material causes the external quantum efficiency of uv-LED and luminous power all very low, becoming the bottleneck of uv-LED development, is current urgent problem.
AlGaN based multiple quantum well uv-LED device has broad application prospects.At first, GaN base blue green light LED has been obtained breakthrough progress, and high brightness blue green light LED commercialization has at present all shown powerful potentiality in fields such as Landscape Lighting, large-screen backlight, optical communications.Secondly, the white light LEDs solid-state illumination is like a raging fire especially, has caused the revolution of throwing light on for the third time.Once more, along with reaching its maturity of visible light field, the researcher shifts research emphasis gradually to short wavelength's ultraviolet light, and ultraviolet light all has major application to be worth in fields such as silk screen printing, polymer cure, environmental protection, white-light illuminating and military detections.
At present, at home and in the world, mainly be to adopt some new material growth methods, or adopt new structure to reduce the destruction of stress to the AlGaN quality of materials, improve the growth quality of AlGaN material, thereby improved the luminescent properties of uv-LED, these methods comprise:
2002, first uv-LED that is lower than 300nm realizes in South Carolina, USA state university, they have made the LED of wavelength 285nm on Sapphire Substrate, 200 μ * 200 μ chips power under the 400mA pulse current is 0.15mW, after improving p type and n type contact resistance, maximum power reaches 0.25mW.Referring to document V.Adivarahan, J.P.Zhang, A.Chitnis, et al, " sub-Milliwatt Power III-N Light EmittingDiodes at 285nm, " Jpn JAppl Phy, 2002,41:L435.Subsequently, they have obtained a series of breakthroughs again, have realized the emission wavelength of 280nm, 269nm, 265nm successively, and the LED maximum power surpasses 1mW.Referring to document W H Sun, J P Zhang, V Adivarahan, et al. " AlGaN-based 280nm light-emittingdiodes with continuous wave powers in excess of 1.5mW " Appl Phys Lett, 2004,85 (4): 531; V Adivarahan, S Wu, JP Zhang, et al. " High-efficiency 269nm emission deepultraviolet light-emitting diodes " Appl Phys Lett, 2004,84 (23): 4762; Y Bilenko, A Lunev, X Hu, et al. " 10Milliwatt Pulse Operation of 265nm AlGaN Light Emitting Diodes " JpnJ Appl Phys, 2005,44:L98. in order to improve current delivery, reduce thermal effect, they are to the small size chip of 100 μ m * 100 μ m, connect according to 2 * 2 array patterns, and adopting the flip-chip structure, the power of 280nm wavelength can reach 24mW, maximum external quantum efficiency 0.35%.Referring to document W H Sun, J P Zhang, V Adivarahan, et al. " AlGaN-based 280nm light-emitting diodes with continuous wave powers in excessof 1.5mW " Appl Phys Lett, 2004,85 (4): 531.2004, made the LED of 250nm again, the chip maximum power of 200 μ * 200 μ is near 0.6mW, but external quantum efficiency only has 0.01%.Referring to document VAdivarahan, W H Sun, A Chitnis, et al. " 250nm AlGaN light-emitting diodes " Appl PhysLett, 2004,85 (12): 2175,
2004, Northwestern Univ USA, University of Kansas also deep ultraviolet particularly the 280-290nm wave band obtained bigger progress.Fischer A J, Allerman A A, et al.Room-temperature direct current operationof 290nm Light-emitting diodes with milliwatt power level[J] .Appl Phys Lett, 2004, adopt slotting thread contact improve the current expansion of chip internal at 84 (17): 3394., flip-chip bonded structure improves the heat-sinking capability of LED, made the high-power ultraviolet LED of 1mm * 1mm, emission wavelength 290nm, luminous power under the 300mA direct current reaches 1.34mW, external quantum efficiency 0.11%.Kim K H, Fan Z Y, Khizar M, et al.AlGaN-based ultraviolet light-emitting diodes grown on AlN epilayers[J] .Appl PhysLett, change traditional square chip discoid at 2004,85 (20): 4777., reduced cut-in voltage, power is increased substantially, the chip of 210 μ m diameters, power has surpassed 1mW.
The same year, South Carolina, USA state university develops 250 and the deep ultraviolet uv-LED of 255nm again, bottom buffer layer adopts the AlGaN/AlN superlattice structure, grow high-quality AlGaN barrier layer, made the deep ultraviolet LED of 200 * 200 μ m, under the pulse current of 300mA and 1000mA, its luminous power reaches 0.16mW and 0.57mW respectively, but owing to adopt the mode of bottom bright dipping, its luminous efficiency is still lower.Referring to document V Adivarahan, W H Sun, A Chitnis, M Shatalov, S Wu, H P Maruska, M AsifKhan. " 250nm AlGaN light-emitting diodes " Appl Phys Lett, 2004,85 (12): 2175.
2007, the beautiful university of Japan's Saitama has obtained further progress in the research of the deep ultraviolet LED of 231-261nm wave band, owing to adopt Pulsed growth AlN resilient coating, further reduced the dislocation defect of AlN layer, thereby grow the AlGaN layer of high Al component, make the luminous power of deep ultraviolet LED of 261nm and external quantum efficiency distribute and reach 1.65mW and 0.23%.Referring to document Hirayama Hideki, Yatabe Tohru, NoguchiNorimichi, Ohashi Tomoaki, Kamata Norihiko. " 231-261nm AlGaN deep-ultravioletlight-emitting diodes fabricated on AlN multilayer buffers grown by ammonia pulse-flowmethod on sapphire " Appl Phys Lett, 2007,91 (7): 071901-1.
Indulge the above, current, the making of AlGaN base deep uv-LED device all is the mode that adopts the bottom bright dipping in the world, and is less to the research of top bright dipping.Along with the minimizing of emission wavelength, bottom buffer layer is more and more to the absorption of ultraviolet light, has had a strong impact on emergent light power and external quantum efficiency.Also there is very big shortcoming at present in the technology of existing bottom bright dipping, and the one, the outgoing path of light is long, and the loss of light midway is excessive, often causes the external quantum efficiency of light low excessively; The 2nd, the crystalline quality of bottom AlN resilient coating is all relatively poor, causes the non-radiative recombination center of material to increase, and is more to the absorption of ultraviolet light; The 3rd, bottom buffer layer is under the electric stress effect, and the defective of capturing photon increases, and has had a strong impact on the reliability of device.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, propose that a kind of reliability height, cost are low, multiple quantum well uv-LED device and manufacture method on the simple SiC substrate of technology, to reduce the outgoing path of light, improve the power and the external quantum efficiency of output light, realize the making of great power LED device.
For achieving the above object, multiple quantum well uv-LED device on the SiC substrate provided by the invention: comprise that AlN nucleating layer, intrinsic AlGaN epitaxial loayer, n type AlGaN barrier layer, active area, p type AlGaN barrier layer, low Al component p type AlGaN layer and p type GaN emit layer, wherein p type GaN emits the center of layer to be etched with the bar shape window region, is used to change the path of emergent light.
Described window region bottom is positioned at 3/4ths places of p type AlGaN barrier layer.
The degree of depth of described window region and the ratio of width are 1: 1000.
For achieving the above object, the invention provides following two kinds of methods of making the multiple quantum well uv-LED device on the SiC substrate.
Technical scheme 1, the method for making the multiple quantum well uv-LED device on the SiC substrate comprises the steps:
I. material growth step: on the SiC substrate, utilize MOCVD technology, successively the high Al component p type AlGaN barrier layer of growing low temperature AlN nucleating layer, high temperature AlN nucleating layer, AlGaN epitaxial loayer, n-AlGaN barrier layer, active area, 40%-60%, low Al component p type AlGaN layer and the p type GaN layer of 10%-25%;
II. element manufacturing step:
1) make by lithography earlier be positioned at p type GaN emit the layer circular window, adopt chloro ICP technology etching window district to p type AlGaN barrier layer again, form cylindrical light-emitting window, its etching technics parameter is respectively: the upper electrode power of 240W-600W, the bias voltage of 0-80V, the pressure of 1-3Pa, the etch period of 100-180s;
2) make the figure of n type electrode by lithography at the back side of n type SiC substrate, adopt electron beam evaporation process,, form n type electrode at electrode pattern district evaporation n type metal ohmic contact;
3) emit layer photoetching to go out the figure of p type electrode at p type GaN, adopt electron beam evaporation process,, form p type electrode, finish element manufacturing at electrode pattern district evaporation p type metal ohmic contact.
Technical scheme 2, the method for making the multiple quantum well uv-LED device on the SiC substrate comprises the steps:
I. material growth step: on the SiC substrate, utilize MOCVD technology, successively the high Al component p type AlGaN barrier layer of growing low temperature AlN nucleating layer, high temperature AlN nucleating layer, AlGaN epitaxial loayer, n-AlGaN barrier layer, active area, 40%-60%, low Al component p type AlGaN layer and the p type GaN layer of 10%-25%;
II. element manufacturing step:
1) emit layer center to make circular window earlier by lithography at p type GaN, adopt the secondarily etched window region of chloro RIE technology to p type AlGaN barrier layer again, form cylindrical light-emitting window, its etching technics parameter is respectively: the electrode power of 150W-400W, the bias voltage of 230-550V, the chamber pressure of 5-10mT, the etch period of 100-240s;
2) make the figure of n type electrode by lithography at the back side of n type SiC substrate, adopt electron beam evaporation process,, form n type electrode at window region evaporation n type metal ohmic contact;
3) emit layer photoetching to go out the figure of p type electrode at p type GaN, adopt electron beam evaporation process,, form p type electrode, finish element manufacturing at window region evaporation p type metal ohmic contact.
The present invention compared with prior art has following advantage:
(1) the present invention forms the light-emitting window of cylindrical shape owing to emit layer to p type AlGaN barrier layer by etching p-GaN, makes the ultraviolet luminous energy that sends radiate from the top, effectively raises the power output of light and the external quantum efficiency of device.
(2) the present invention has further improved the outgoing efficient of emergent light owing to the surface coarsening that adopts the dry etching window region, make the electron barrier layer p-AlGaN that is positioned at the window region bottom.
(3) device of the present invention has been owing to adopted the top window structure, even electric stress increases the defective in the AlN resilient coating of device, also can not influence the power of emergent light, and this will greatly advance the practicalization of AlGaN based multiple quantum well ultraviolet LED.
(4) manufacture craft of the present invention fully can with the blue light GaN of maturation base LED device preparation technology compatibility.
Description of drawings
Fig. 1 is the cross-sectional view of device of the present invention;
Fig. 2 is the process chart of material growth of the present invention;
Fig. 3 is a device making technics flow chart of the present invention.
With reference to Fig. 1, the orlop of device of the present invention is the SiC substrate, it is low temperature AI N nucleating layer on the SiC substrate, it is the high temperature nucleating layer on the low temperature AI N nucleating layer, be the AlGaN epitaxial loayer on the high temperature AlN nucleating layer, being N-shaped AlGaN barrier layer on the AlGaN epitaxial loayer, is active area on the N-shaped AlGaN barrier layer, and this active area is by the Al of multi-quantum pit structurexGa
1-xN/Al
yGa
1-yN forms, and is high Al contents p-type AlGaN barrier layer on the active area, its Upper p-type AlGaN layer for low Al component emits layer for p-type GaN topmost. P-type GaN emits layer place to be provided with window Oral region A makes the light of generation emit layer to send by the top. This window region A is shaped as cylinder, and its bottom is positioned at p 3/4ths places of type AlGaN barrier layer thickness. The degree of depth of window region A and the ratio of width are 1: 1000, n The type electrode is positioned on the n-AlGaN table top, and the p-type electrode is positioned at p-type GaN and emits on the layer.
Below provide 6 kinds of embodiment of element manufacturing of the present invention:
Embodiment one, and the making of device of the present invention comprises material growth and two steps of element manufacturing.
With reference to Fig. 2, material growth step of the present invention is as follows:
Step 1 on the SiC substrate, is utilized MOCVD technology, growing low temperature AlN nucleating layer.
Underlayer temperature is reduced to 600 ℃, keeps growth pressure 50Torr, hydrogen flowing quantity is 1500sccm, and ammonia flow is 1500sccm, and feeding flow to reative cell is the aluminium source of 28 μ mol/min, and growth thickness is the low temperature AI N nucleating layer of 3nm.
Step 2, on low temperature AI N nucleating layer, growth high temperature AlN nucleating layer.
Growth temperature is elevated to 1050 ℃, keeps growth pressure 50Torr, hydrogen flowing quantity is 1500sccm, and ammonia flow is 1500sccm, and feeding flow to reative cell is the aluminium source of 28 μ mol/min, and growth thickness is the high temperature AlN nucleating layer of 20nm.
Step 3, on high temperature AlN nucleating layer, growth AlGaN epitaxial loayer.
Growth temperature remains on 1050 ℃, the maintenance growth pressure is 110Torr, and hydrogen flowing quantity is 1500sccm, and ammonia flow is 1100sccm, feeding flow to reative cell is the aluminium source of 50 μ mol/min and the gallium source of 80 μ mol/min, and growth thickness is the AlGaN epitaxial loayer of the non-doping of 1200nm.
Step 4, on the AlGaN epitaxial loayer, growth Si doped n type AlGaN barrier layer.
Growth temperature remains on 1050 ℃, keep growth pressure 110Torr, hydrogen flowing quantity is 1500sccm, ammonia flow 1500sccm, feed the aluminium source that flow is 55 μ mol/min, the gallium source of 65 μ mol/min and the Si source of 1-3 μ mol/min simultaneously to reative cell, growth thickness is the AlGaN barrier layer that the Si of 600nm mixes.
Step 5, on n type AlGaN barrier layer, growth Multiple Quantum Well Al
xGa
1-xN/Al
yGa
1-yThe N layer, (x＜y).
Growth temperature remains on 1050 ℃, keeps growth pressure 120Torr, and hydrogen flowing quantity is 1500sccm, and ammonia flow 1500sccm feeds aluminium source that flow is 65 μ mol/min and the gallium source of 80 μ mol/min simultaneously to reative cell, and growth thickness is the Al of 2-7nm
xGa
1-xThe N potential well layer; Growth temperature remains on 1050 ℃, keeps growth pressure 70Torr, and hydrogen flowing quantity is 1500sccm, and ammonia flow 1500sccm feeds the aluminium source that flow is 80 μ mol/min simultaneously to reative cell, the gallium source of 65 μ mol/min, and growth thickness is the Al of 2-10nm
yGa
1-yThe N barrier layer, the cycle of quantum well is 3-5.
Step 6 is at Multiple Quantum Well Al
xGa
1-xN/Al
yGa
1-yOn the N layer, the high Al component p type AlGaN barrier layer of growth 40%-60%.
Growth temperature remains on 1000 ℃, keep growth pressure 100Torr, hydrogen flowing quantity is 1500sccm, ammonia flow 1500sccm, feed the aluminium source that flow is 100 μ mol/min, the gallium source of 70 μ mol/min simultaneously to reative cell, and the Mg source of 3-5 μ mol/min, growth thickness is the p type AlGaN barrier layer of the high Al component of 70nm.
Step 7, on p type barrier layer, the low Al component p type AlGaN layer of growth 10%-25%.
Growth temperature remains on 1000 ℃, keep growth pressure 100Torr, hydrogen flowing quantity is 1500sccm, ammonia flow 1500sccm, feed the aluminium source that flow is 80 μ mol/min, the gallium source of 120 μ mol/min and the Mg source of 3-5 μ mol/min simultaneously to reative cell, growth thickness is the p type AlGaN barrier layer of the low Al component of 60nm.
Step 8, on described low Al component p type AlGaN layer, growing p-type GaN emits layer.
Growth temperature remains on 950 ℃, keeps growth pressure 70Torr, and hydrogen flowing quantity is 1500sccm, ammonia flow 1500sccm, feed the gallium source that flow is 65 μ mol/min simultaneously to reative cell, and the Mg source of 3-5 μ mol/min, growth thickness is that the p type GaN of 60nm emits layer.
With reference to Fig. 3, element manufacturing step of the present invention is as follows:
(1) first step is emitted at p type GaN to make a circular window on the layer by lithography, adopts ICP etching window district to p type AlGaN barrier layer, forms cylindrical light-emitting window A.
(2) to the print positive-glue removing, rotating speed is 5000 commentaries on classics/min, and then dries by the fire 15min in 90 ℃ baking oven, by the photoetching and the required light-emitting window of formation etching that develops;
(3) adopt ICP dry etching p type GaN layer to p type AlGaN barrier layer, the gas that etching adopts is Cl
2/ BCl
3, etching depth is 135nm, and the electrode power that etching adopts is 240W, and bias voltage is 80V, and pressure is 1Pa, etch period is 180s, forms cylindrical light-emitting window A.
Second goes on foot, and makes the figure of n type electrode by lithography at the back side of n type SiC substrate, adopts electron beam evaporation process, at electrode pattern district evaporation n type metal ohmic contact, forms n type electrode.
(1) for stripping metal better, at first get rid of binder on print, rotating speed is 8000 commentaries on classics/min, and the time is 30s, dries by the fire 20min in temperature is 160 ℃ high temperature oven; And then on this print positive-glue removing, rotating speed is 5000 commentaries on classics/min, at last dries by the fire 10min in temperature is 80 ℃ high temperature oven, photoetching obtains n type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, this step has improved the rate of finished products of peeling off greatly, then adopts VPC-1000 electron beam evaporation equipment deposit Ni/Au double layer of metal;
(3) carry out sonicated after in acetone, soaking more than the 40min, dry up with nitrogen then;
(4) print is put in the quick anneal oven, at first fed about nitrogen 10min in annealing furnace, under nitrogen atmosphere, temperature is the high annealing that carries out 65s under 1000 ℃ of conditions then, forms n type electrode.
In the 3rd step, GaN emits the figure that makes p type electrode on the layer by lithography in the p type, adopts electron beam evaporation process, at electrode pattern district evaporation p type metal ohmic contact, forms p type electrode.
(1) at first get rid of binder on print, the rotating speed of whirl coating platform is 8000 commentaries on classics/min, and the time is 30s, puts it into temperature and be in 160 ℃ the high temperature oven to dry by the fire 20min; Positive-glue removing on this print more afterwards, the rotating speed of whirl coating platform is 5000 commentaries on classics/min, and the high temperature oven of putting into temperature and be 80 ℃ dries by the fire 10min, and photoetching obtains p type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, on p type electrode pattern, adopt VPC-1100 electron beam evaporation equipment evaporation Ni/Au double layer of metal to be used as p type electrode;
(3) print that will finish above-mentioned processing is put into acetone and is soaked 20min and carry out sonicated after above, dry up with nitrogen then, again this print is put in the quick anneal oven afterwards, under air atmosphere, temperature is the high annealing that carries out 10min under 560 ℃ of conditions, form p type electrode, finish element manufacturing.
Embodiment two, and the making of device of the present invention comprises material growth and two steps of element manufacturing.
Wherein the material growth step is identical with embodiment one, as shown in Figure 2.
Element manufacturing as shown in Figure 3, concrete steps are as follows:
The first step is emitted at p type GaN to make a circular window on the layer by lithography, adopts ICP etching window district to p type AlGaN barrier layer, forms cylindrical light-emitting window A.
(1) on rotating speed is the whirl coating platform of 5000 commentaries on classics/min, print is carried out whirl coating, in 90 ℃ baking oven, dry by the fire 15min again, by photoetching and develop and form the required light-emitting window of etching;
(2) adopt ICP dry etching p type GaN layer to p type AlGaN barrier layer, etching depth is 135nm, and the gas that etching adopts is Cl
2/ BCl
3, the electrode power that etching adopts is 450W, and bias voltage is 60V, and pressure is 2Pa, and etch period is 140s, forms cylindrical light-emitting window A.
Second goes on foot, and makes the figure of n type electrode by lithography at the back side of n type SiC substrate, adopts electron beam evaporation process, at electrode pattern district evaporation n type metal ohmic contact, forms n type electrode.
(1) for stripping metal better, at first get rid of binder on print, rotating speed is 8000 commentaries on classics/min, and the time is 30s, dries by the fire 20min in temperature is 160 ℃ high temperature oven; Positive-glue removing on this print again, rotating speed is 5000 commentaries on classics/min; At last dry by the fire 10min in temperature is 80 ℃ high temperature oven, photoetching obtains n type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, this step has improved the rate of finished products of peeling off greatly, then adopts VPC-1000 electron beam evaporation equipment deposit Ni/Au double layer of metal;
(3) carry out sonicated after in acetone, soaking more than the 40min, dry up with nitrogen then;
(4) print is put in the quick anneal oven, at first fed about nitrogen 10min in annealing furnace, under nitrogen atmosphere, temperature is the high annealing that carries out 65s under 1000 ℃ of conditions then, forms n type electrode.
In the 3rd step, GaN emits the figure that makes p type electrode on the layer by lithography in the p type, adopts electron beam evaporation process, at electrode pattern district evaporation p type metal ohmic contact, forms p type electrode.
(1) at first get rid of binder on print, the rotating speed of whirl coating platform is 8000 commentaries on classics/min, and the time is 30s, puts it into temperature and be in 160 ℃ the high temperature oven to dry by the fire 20min; Positive-glue removing on this print more afterwards, the rotating speed of whirl coating platform is 5000 commentaries on classics/min, and the high temperature oven of putting into temperature and be 80 ℃ dries by the fire 10min, and photoetching obtains p type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, on p type electrode pattern, adopt VPC-1100 electron beam evaporation equipment evaporation Ni/Au double layer of metal to be used as p type electrode;
(3) print that will finish above-mentioned processing is put into acetone and is soaked 20min and carry out sonicated after above, dry up with nitrogen then, again this print is put in the quick anneal oven afterwards, under air atmosphere, temperature is the high annealing that carries out 10min under 560 ℃ of conditions, form p type electrode, finish element manufacturing.
Embodiment three, and the making of device of the present invention comprises material growth and two steps of element manufacturing.
Wherein the material growth step is identical with embodiment one, as shown in Figure 2.
Element manufacturing as shown in Figure 3, concrete steps are as follows:
The first step is emitted at p type GaN to make a circular window on the layer by lithography, adopts ICP etching window district to p type AlGaN barrier layer, forms cylindrical light-emitting window A.
(1) to the print positive-glue removing, rotating speed is 5000 commentaries on classics/min, and then dries by the fire 15min in 90 ℃ baking oven, by the photoetching and the required light-emitting window of formation etching that develops;
(2) adopt ICP dry etching p type GaN layer to p type AlGaN barrier layer, etching depth is 135nm, and the gas that etching adopts is Cl
2/ BCl
3, the electrode power that etching adopts is 600W, and bias voltage is 0V, and pressure is 3Pa, and etch period is 100s, forms cylindrical light-emitting window A.
Second goes on foot, and makes the figure of n type electrode by lithography at the back side of n type SiC substrate, adopts electron beam evaporation process, at electrode pattern district evaporation n type metal ohmic contact, forms n type electrode.
(1) for stripping metal better, at first get rid of binder on print, rotating speed is 8000 commentaries on classics/min, and the time is 30s, dries by the fire 20min in temperature is 160 ℃ high temperature oven; And then on this print positive-glue removing, rotating speed is 5000 commentaries on classics/min, at last dries by the fire 10min in temperature is 80 ℃ high temperature oven, photoetching obtains n type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, this step has improved the rate of finished products of peeling off greatly, then adopts VPC-1000 electron beam evaporation equipment deposit Ni/Au double layer of metal;
(3) carry out sonicated after in acetone, soaking more than the 40min, dry up with nitrogen then;
(4) print is put in the quick anneal oven, at first fed about nitrogen 10min in annealing furnace, under nitrogen atmosphere, temperature is the high annealing that carries out 65s under 1000 ℃ of conditions then, forms n type electrode.
In the 3rd step, GaN emits the figure that makes p type electrode on the layer by lithography in the p type, adopts electron beam evaporation process, at electrode pattern district evaporation p type metal ohmic contact, forms p type electrode.
(1) at first get rid of binder on print, the rotating speed of whirl coating platform is 8000 commentaries on classics/min, and the time is 30s, puts it into temperature and be in 160 ℃ the high temperature oven to dry by the fire 20min; Positive-glue removing on this print more afterwards, the rotating speed of whirl coating platform is 5000 commentaries on classics/min, and the high temperature oven of putting into temperature and be 80 ℃ dries by the fire 10min, and photoetching obtains p type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, on p type electrode pattern, adopt VPC-1100 electron beam evaporation equipment evaporation Ni/Au double layer of metal to be used as p type electrode;
(3) print that will finish above-mentioned processing is put into acetone and is soaked 20min and carry out sonicated after above, dry up with nitrogen then, again this print is put in the quick anneal oven afterwards, under air atmosphere, temperature is the high annealing that carries out 10min under 560 ℃ of conditions, form p type electrode, finish element manufacturing.
Embodiment four, and the making of device of the present invention comprises material growth and two steps of element manufacturing.
Wherein the material growth step is identical with embodiment one, as shown in Figure 2.
Element manufacturing as shown in Figure 3, concrete steps are as follows:
The first step is emitted at p type GaN to make a circular window on the layer by lithography, adopts RIE etching window district to p type AlGaN barrier layer, forms cylindrical light-emitting window A.
(1) coating photoresist on the print surface, is to carry out whirl coating on the whirl coating platform of 5000 commentaries on classics/min at rotating speed, dries by the fire 15min then in 90 ℃ baking oven, by photoetching and develop and form the required light-emitting window of etching;
(2) adopt RIE dry etching p type GaN layer to p type AlGaN barrier layer, etching depth is 135nm, and the gas that etching adopts is Cl
2/ BCl
3, the electrode power that etching adopts is 150W, and bias voltage is 230V, and pressure is 10mT, and etch period is 240s, forms the cylinder light-emitting window A of bottom at p type AlGaN barrier layer.
Second goes on foot, and makes the figure of n type electrode by lithography at the back side of n type SiC substrate, adopts electron beam evaporation process, at electrode pattern district evaporation n type metal ohmic contact, forms n type electrode.
(1) for stripping metal better, at first get rid of binder on print, rotating speed is 8000 commentaries on classics/min, and the time is 30s, dries by the fire 20min in temperature is 160 ℃ high temperature oven; And then on this print positive-glue removing, rotating speed is 5000 commentaries on classics/min, at last dries by the fire 10min in temperature is 80 ℃ high temperature oven, photoetching obtains n type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, this step has improved the rate of finished products of peeling off greatly, then adopts VPC-1000 electron beam evaporation equipment deposit Ni/Au double layer of metal;
(3) carry out sonicated after in acetone, soaking more than the 40min, dry up with nitrogen then;
(4) print is put in the quick anneal oven, at first fed about nitrogen 10min in annealing furnace, under nitrogen atmosphere, temperature is the high annealing that carries out 55s under 1000 ℃ of conditions then, forms n type electrode.
In the 3rd step, GaN emits the figure that makes p type electrode on the layer by lithography in the p type, adopts electron beam evaporation process, at electrode pattern district evaporation p type metal ohmic contact, forms p type electrode.
(1) at first get rid of binder on print, the rotating speed of whirl coating platform is 8000 commentaries on classics/min, and the time is 30s, puts it into temperature and be in 160 ℃ the high temperature oven to dry by the fire 20min; Positive-glue removing on this print more afterwards, the rotating speed of whirl coating platform is 5000 commentaries on classics/min, and the high temperature oven of putting into temperature and be 80 ℃ dries by the fire 10min, and photoetching obtains p type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, on p type electrode pattern, adopt VPC-1100 electron beam evaporation equipment evaporation Ni/Au double layer of metal to be used as p type electrode;
(3) print that will finish above-mentioned processing is put into acetone and is soaked 20min and carry out sonicated after above, dry up with nitrogen then, again this print is put in the quick anneal oven afterwards, under air atmosphere, temperature is the high annealing that carries out 10min under 560 ℃ of conditions, form p type electrode, finish element manufacturing.
Embodiment five, and the making of device of the present invention comprises material growth and two steps of element manufacturing.
Wherein the material growth step is identical with embodiment one, as shown in Figure 2.
Element manufacturing as shown in Figure 3, concrete steps are as follows:
The first step is emitted at p type GaN to make a circular window on the layer by lithography, adopts RIE etching window district to p type AlGaN barrier layer, forms cylindrical light-emitting window A.
(1) coating photoresist on the print surface, is to carry out whirl coating on the whirl coating platform of 5000 commentaries on classics/min at rotating speed, dries by the fire 15min then in 90 ℃ baking oven, by photoetching and develop and form the required light-emitting window of etching;
(2) adopt RIE dry etching p type GaN layer to p type AlGaN barrier layer, etching depth is 135nm, and the gas that etching adopts is Cl
2/ BCl
3, the electrode power that etching adopts is 320W, and bias voltage is 410V, and pressure is 8mT, and etch period is 180s, forms the cylinder light-emitting window A of bottom at p type AlGaN barrier layer.
Second goes on foot, and makes the figure of n type electrode by lithography at the back side of n type SiC substrate, adopts electron beam evaporation process, at electrode pattern district evaporation n type metal ohmic contact, forms n type electrode.
(1) for stripping metal better, at first get rid of binder on print, rotating speed is 8000 commentaries on classics/min, and the time is 30s, dries by the fire 20min in temperature is 160 ℃ high temperature oven; And then on this print positive-glue removing, rotating speed is 5000 commentaries on classics/min, at last dries by the fire 10min in temperature is 80 ℃ high temperature oven, photoetching obtains n type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, this step has improved the rate of finished products of peeling off greatly, then adopts VPC-1000 electron beam evaporation equipment deposit Ni/Au double layer of metal;
(3) carry out sonicated after in acetone, soaking more than the 40min, dry up with nitrogen then;
(4) print is put in the quick anneal oven, at first fed about nitrogen 10min in annealing furnace, under nitrogen atmosphere, temperature is the high annealing that carries out 55s under 1000 ℃ of conditions then, forms n type electrode.
In the 3rd step, GaN emits the figure that makes p type electrode on the layer by lithography in the p type, adopts electron beam evaporation process, at electrode pattern district evaporation p type metal ohmic contact, forms p type electrode.
(1) at first get rid of binder on print, the rotating speed of whirl coating platform is 8000 commentaries on classics/min, and the time is 30s, puts it into temperature and be in 160 ℃ the high temperature oven to dry by the fire 20min; Positive-glue removing on this print more afterwards, the rotating speed of whirl coating platform is 5000 commentaries on classics/min, and the high temperature oven of putting into temperature and be 80 ℃ dries by the fire 10min, and photoetching obtains p type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, on p type electrode pattern, adopt VPC-1100 electron beam evaporation equipment evaporation Ni/Au double layer of metal to be used as p type electrode;
(3) print that will finish above-mentioned processing is put into acetone and is soaked 20min and carry out sonicated after above, dry up with nitrogen then, again this print is put in the quick anneal oven afterwards, under air atmosphere, temperature is the high annealing that carries out 10min under 560 ℃ of conditions, form p type electrode, finish element manufacturing.
Embodiment six, and the making of device of the present invention comprises material growth and two steps of element manufacturing.
Wherein the material growth step is identical with embodiment one, as shown in Figure 2.
Element manufacturing as shown in Figure 3, concrete steps are as follows:
The first step is emitted at p type GaN to make a circular window on the layer by lithography, adopts RIE etching window district to p type AlGaN barrier layer, forms cylindrical light-emitting window A.
(1) coating photoresist on the print surface, is to carry out whirl coating on the whirl coating platform of 5000 commentaries on classics/min at rotating speed, dries by the fire 15min then in 90 ℃ baking oven, by photoetching and develop and form the required light-emitting window of etching;
(2) adopt RIE dry etching p type GaN layer to p type AlGaN barrier layer, etching depth is 135nm, and the gas that etching adopts is Cl
2/ BCl
3, the electrode power that etching adopts is 400W, and bias voltage is 550V, and pressure is 5mT, and etch period is 100s, forms the cylinder light-emitting window A of bottom at p type AlGaN barrier layer.
Second goes on foot, and makes the figure of n type electrode by lithography at the back side of n type SiC substrate, adopts electron beam evaporation process, at electrode pattern district evaporation n type metal ohmic contact, forms n type electrode.
(1) for stripping metal better, at first get rid of binder on print, rotating speed is 8000 commentaries on classics/min, and the time is 30s, dries by the fire 20min in temperature is 160 ℃ high temperature oven; And then on this print positive-glue removing, rotating speed is 5000 commentaries on classics/min, at last dries by the fire 10min in temperature is 80 ℃ high temperature oven, photoetching obtains n type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, this step has improved the rate of finished products of peeling off greatly, then adopts VPC-1000 electron beam evaporation equipment deposit Ni/Au double layer of metal;
(3) carry out sonicated after in acetone, soaking more than the 40min, dry up with nitrogen then;
(4) print is put in the quick anneal oven, at first fed about nitrogen 10min in annealing furnace, under nitrogen atmosphere, temperature is the high annealing that carries out 55s under 1000 ℃ of conditions then, forms n type electrode.
In the 3rd step, GaN emits the figure that makes p type electrode on the layer by lithography in the p type, adopts electron beam evaporation process, at electrode pattern district evaporation p type metal ohmic contact, forms p type electrode.
(1) at first get rid of binder on print, the rotating speed of whirl coating platform is 8000 commentaries on classics/min, and the time is 30s, puts it into temperature and be in 160 ℃ the high temperature oven to dry by the fire 20min; Positive-glue removing on this print more afterwards, the rotating speed of whirl coating platform is 5000 commentaries on classics/min, and the high temperature oven of putting into temperature and be 80 ℃ dries by the fire 10min, and photoetching obtains p type electrode pattern;
(2) adopt the DQ-500 equipment for burning-off photoresist by plasma to remove the photoresist thin layer that graph area is not developed clean, on p type electrode pattern, adopt VPC-1100 electron beam evaporation equipment evaporation Ni/Au double layer of metal to be used as p type electrode;
(3) print that will finish above-mentioned processing is put into acetone and is soaked 20min and carry out sonicated after above, dry up with nitrogen then, again this print is put in the quick anneal oven afterwards, under air atmosphere, temperature is the high annealing that carries out 10min under 560 ℃ of conditions, form p type electrode, finish element manufacturing.
Claims (6)
1. the multiple quantum well uv-LED device on the SiC substrate, comprise that AlN nucleating layer, intrinsic AlGaN epitaxial loayer, n type AlGaN barrier layer, active area, p type AlGaN barrier layer, low Al component p type AlGaN layer and p type GaN emit layer, it is characterized in that p type GaN emits the center of layer to be etched with bar shape window region (A), is used to change the path of emergent light.
2. multiple quantum well uv-LED device according to claim 1, it is two-layer to it is characterized in that the AlN nucleating layer is divided into, and ground floor is 500 ℃-600 ℃ a low temperature nucleating layer, and the second layer is 900 ℃-1000 ℃ a high temperature nucleating layer.
3. multiple quantum well uv-LED device according to claim 1 is characterized in that the bottom of window region (A) is positioned at 3/4ths places of p type AlGaN barrier layer thickness.
4. multiple quantum well uv-LED device according to claim 1 is characterized in that the degree of depth of window region (A) and the ratio of width are 1: 1000.
5. the manufacture method of multiple quantum well uv-LED device on the SiC substrate comprises:
I. material growth step: on the SiC substrate, utilize MOCVD technology, successively the high Al component p type AlGaN barrier layer of growing low temperature AlN nucleating layer, high temperature AlN nucleating layer, AlGaN epitaxial loayer, n-AlGaN barrier layer, active area, 40%-60%, low Al component p type AlGaN layer and the p type GaN layer of 10%-25%;
II. element manufacturing step:
1) make by lithography earlier be positioned at p type GaN emit the layer circular window, adopt chloro ICP technology etching window district to p type AlGaN barrier layer again, form cylindrical light-emitting window, its etching technics parameter is respectively: the upper electrode power of 240W-600W, the bias voltage of 0-80V, the pressure of 1-3Pa, the etch period of 100-180s;
2) make the figure of n type electrode by lithography at the back side of n type SiC, adopt electron beam evaporation process,, form n type electrode at electrode pattern district evaporation n type metal ohmic contact;
3) emit layer photoetching to go out the figure of p type electrode at p type GaN, adopt electron beam evaporation process,, form p type electrode, finish element manufacturing at electrode pattern district evaporation p type metal ohmic contact.
6. the manufacture method of multiple quantum well uv-LED device on the SiC substrate comprises:
I. material growth step: on the SiC substrate, utilize MOCVD technology, successively the high Al component p type AlGaN barrier layer of growing low temperature AlN nucleating layer, high temperature AlN nucleating layer, AlGaN epitaxial loayer, n-AlGaN barrier layer, active area, 40%-60%, low Al component p type AlGaN layer and the p type GaN layer of 10%-25%;
II. element manufacturing step:
1) emit layer center to make circular window earlier by lithography at p type GaN, adopt chloro RIE technology etching window district to p type AlGaN barrier layer again, form cylindrical light-emitting window, its etching technics parameter is respectively: the electrode power of 150W-400W, the bias voltage of 230-550V, the chamber pressure of 5-10mT, the etch period of 100-240s;
2) make the figure of n type electrode by lithography at the back side of n type SiC, adopt electron beam evaporation process,, form n type electrode at window region evaporation n type metal ohmic contact;
3) emit layer photoetching to go out the figure of p type electrode at p type GaN, adopt electron beam evaporation process,, form p type electrode, finish element manufacturing at window region evaporation p type metal ohmic contact.
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| CN2009100217648A CN101515616B (en) | 2009-03-31 | 2009-03-31 | Multiple quantum well uv-LED device on SiC substrate and manufacturing method |
| PCT/CN2009/073519 WO2010111854A1 (en) | 2009-03-31 | 2009-08-26 | Uv led and method for fabricating the same |
| US13/262,049 US8525198B2 (en) | 2009-03-31 | 2009-08-26 | Ultraviolet light emitting diode devices and methods for fabricating the same |
| JP2012502421A JP2012522388A (en) | 2009-03-31 | 2009-08-26 | Ultraviolet light emitting diode device and manufacturing method thereof |
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| CN102185064A (en) * | 2011-04-19 | 2011-09-14 | 武汉华炬光电有限公司 | AlGaN base deep ultraviolet light-emitting diode (LED) device using multiple quantum well electronic barrier layer to improve luminescent efficiency and manufacturing method of AlGaN base deep ultraviolet LED device |
| CN103165775A (en) * | 2013-04-07 | 2013-06-19 | 中国科学院半导体研究所 | Ultraviolet light-emitting diode with high reflection film and manufacturing method of ultraviolet light-emitting diode |
| CN103199164A (en) * | 2013-04-07 | 2013-07-10 | 中国科学院半导体研究所 | Ultraviolet light-emitting diode with distributed bragg reflector (DBR) and preparation method thereof |
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| CN102185064A (en) * | 2011-04-19 | 2011-09-14 | 武汉华炬光电有限公司 | AlGaN base deep ultraviolet light-emitting diode (LED) device using multiple quantum well electronic barrier layer to improve luminescent efficiency and manufacturing method of AlGaN base deep ultraviolet LED device |
| CN103296156A (en) * | 2013-01-09 | 2013-09-11 | 长春理工大学 | Novel ultraviolet light-emitting diode structure |
| CN103165775A (en) * | 2013-04-07 | 2013-06-19 | 中国科学院半导体研究所 | Ultraviolet light-emitting diode with high reflection film and manufacturing method of ultraviolet light-emitting diode |
| CN103199164A (en) * | 2013-04-07 | 2013-07-10 | 中国科学院半导体研究所 | Ultraviolet light-emitting diode with distributed bragg reflector (DBR) and preparation method thereof |
| CN103199164B (en) * | 2013-04-07 | 2016-03-02 | 中国科学院半导体研究所 | A kind of have ultraviolet light-emitting diode of DBR high reverse--bias structure and preparation method thereof |
| CN104900767A (en) * | 2015-04-07 | 2015-09-09 | 圆融光电科技股份有限公司 | Light-emitting diode P-type doped layer growth method |
| CN104900767B (en) * | 2015-04-07 | 2017-10-20 | 圆融光电科技股份有限公司 | LED P-type doped layer growing method |
| CN110459658A (en) * | 2018-05-08 | 2019-11-15 | 山东浪潮华光光电子股份有限公司 | A kind of UV LED chip of p-type GaN layer and preparation method thereof |
| CN110137321A (en) * | 2019-04-19 | 2019-08-16 | 西安电子科技大学 | Vertical structure UV LED and preparation method based on bulk aluminum nitride substrate |
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