CN107134512B - Based on the face c Al2O3The light emitting diode of III group-III nitride of the face N of substrate - Google Patents
Based on the face c Al2O3The light emitting diode of III group-III nitride of the face N of substrate Download PDFInfo
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- H—ELECTRICITY
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- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
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- H10H20/01—Manufacture or treatment
- H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
- H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
- H10H20/0137—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials the light-emitting regions comprising nitride materials
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- H—ELECTRICITY
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- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
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- H10H20/822—Materials of the light-emitting regions
- H10H20/824—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP
- H10H20/825—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP containing nitrogen, e.g. GaN
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Abstract
本发明公开了一种基于c面Al2O3衬底的N面Ⅲ族氮化物的发光二极管，主要解决现有LED器件生长步骤繁多，工艺周期长的问题。其自下而上包括：c面Al2O3衬底层、10‑40nm厚的高温AlN成核层、700‑2000nm厚的发光层和电极，其中发光层为一层N面Ⅲ族氮化物层，该Ⅲ族氮化物层采用GaN或AlN或AlGaN材料，分别获得发紫外光、极紫外光和深紫外光不同颜色的发光二极管。本发明利用N面Ⅲ族氮化物薄膜内的反型畴代替传统LED的量子阱结构发光，简化了器件结构和制作流程，缩短了工艺周期，可用于照明，显示屏和背光源。
The invention discloses a light emitting diode of N-plane III nitride based on a c-plane Al 2 O 3 substrate, which mainly solves the problems of numerous growth steps and long process cycle of the existing LED device. It includes from bottom to top: a c-plane Al 2 O 3 substrate layer, a high-temperature AlN nucleation layer with a thickness of 10-40 nm, a light-emitting layer with a thickness of 700-2000 nm, and an electrode, wherein the light-emitting layer is an N-face group III nitride layer. , the group III nitride layer adopts GaN or AlN or AlGaN material to obtain light-emitting diodes with different colors of ultraviolet light, extreme ultraviolet light and deep ultraviolet light respectively. The invention utilizes the inversion domain in the N-face III nitride film to replace the quantum well structure of the traditional LED to emit light, simplifies the device structure and fabrication process, shortens the process cycle, and can be used for lighting, display screens and backlight sources.
Description
Technical field
The invention belongs to technical field of microelectronic devices, in particular to a kind of to be based on the face c Al2O3III race of the face N of substrate nitrogenizes
The light emitting diode of object can be used for illuminating, the various optical applications of display screen and backlight.
Technical background
Light-emitting diode LED is due to the advantages that its is high-efficient, and the service life is long, energy conservation and environmental protection, so that LED illumination develops rapidly.
Someone says that incandescent lamp illuminated for 20th century, and LED can then illuminate 21 century.Nitride has simultaneously as direct band-gap semicondictor
Biggish forbidden bandwidth, the ratio forbidden bandwidth by adjusting each component in material can change between 0.7ev to 6.2ev,
The wavelength band from infrared to extreme ultraviolet is covered, is widely used in LED application.Wherein, III group-III nitride is partly led
Body material is the most common material for preparing LED, such as AlN base, GaN base, InN base semiconductor material.The III of wurtzite structure
Hi-nitride semiconductor material usually has the polar axis in the c-axis for being parallel to structure cell (0001) direction, due to along polar axis
Center inversion symmetry is not present in direction, therefore can be divided into III group nitride material of the face N and metal covering by the difference of polar orientation
III group nitride material.The intersection of III group-III nitride of III group-III nitride of the face N and metal covering, referred to as transoid farmland IDB.
P.J.Schuck et al. had studied the optical characteristics on transoid farmland in GaN, the i.e. luminous intensity on transoid farmland in 2001
More than the face body GaN region an order of magnitude, accordingly, during which thinks that transoid farmland can regard that a high efficient radiation is compound as
Transoid farmland can theoretically be regarded as Quantum Well, and the GaN film on the transoid farmland with certain density, can be used for making by the heart
LED greatly reduces processing step without grown quantum well structure in this way.Based on above-mentioned conclusion, due to polar in the face N
In III group-III nitride film, there is the transoid farmlands of certain density for itself, therefore can make of III group-III nitride film of the face N polarity
Novel LED.
Metallo-organic compound chemical gaseous phase deposition MOCVD technology is outside current most commonly used III group-III nitride semiconductor
Prolong technology.By MOCVD technique in the face c Al2O3III group-III nitride film of epitaxial growth generally has metal covering pole on substrate
Property.Nicholas A.Fichtenbaum is mentioned in doctoral thesis within 2008, using MOCVD growth mechanism in the face c Al2O3Lining
GaN is grown on bottom, after high-temperature ammonolysis processing step, acquisition is the polar GaN material in the face N；And it uses at low temperature nitride
After managing step, acquisition is the polar GaN material in the face Ga.Using above-mentioned theory, the face N III can be obtained with MOCVD technology growth
Group-III nitride film, for making the LED of novel no quantum well structure.
The luminous carrier radiation recombination by well layer/barrier layer quantum well structure of LED component at present, and Quantum Well knot
Structure needs to grow plural layers such as InGaN/GaN Quantum Well, and growth step is various, and process cycle is long.
Summary of the invention
It is a kind of based on the face c Al it is an object of the invention in view of the above shortcomings of the prior art, propose2O3The face N of substrate
The light emitting diode of III group-III nitride shortens process cycle to simplify device architecture and production process.
Technical thought of the invention is: have the characteristics that good luminous characteristic using transoid farmland, to substitute quantum well radiation,
Using including that III group-III nitride of the face the N production on transoid farmland does not include the LED of quantum well structure, implementation is as follows:
1. one kind is based on the face c Al2O3The light emitting diode of III group-III nitride of the face N of substrate, includes: the face c from bottom to top
Al2O3Substrate layer, high-temperature AlN nucleating layer, luminescent layer and electrode, it is characterised in that: luminescent layer is one layer of III group-III nitride of the face N
Layer.
Above-mentioned film, it is characterised in that: the high-temperature AlN nucleating layer with a thickness of 20-50nm.
Above-mentioned film, it is characterised in that: the III group-III nitride film of the face N with a thickness of 700-2000nm.
Above-mentioned film, it is characterised in that: III group iii nitride layer of the face N, any one using GaN, in AlN and AlGaN.
2. one kind is based on the face c Al2O3The preparation method of the light emitting diode of III group-III nitride of the face N of substrate, including walk as follows
It is rapid:
1) it is heat-treated:
By the face c Al2O3Substrate is placed in metal organic chemical vapor deposition MOCVD reaction chamber, and the vacuum degree of reaction chamber is dropped
Low to less than 2 × 10-2Torr；It is passed through hydrogen to reaction chamber again, is reached for 20-760Torr condition in MOCVD chamber pressure
Under, it is 900-1200 DEG C by silicon to temperature, and keep 5-10min, completes the heat treatment to substrate base；
2) high-temperature ammonolysis:
Substrate after heat treatment is placed in the reaction chamber that temperature is 1000-1100 DEG C, being passed through flow is 3000-
The ammonia of 4000sccm continues 3-5min and is nitrogenized；
3) high-temperature AlN nucleating layer is grown:
It uses MOCVD technique under conditions of reaction chamber temperature is 950-1100 DEG C on substrate after nitridation, leads to simultaneously
The silicon source that the ammonia and flow that inbound traffics are 3000-4000sccm are 20-40sccm, growth thickness are the high temperature of 20- 50nm
AlN nucleating layer；
4) III group iii nitride layer of the face N N-shaped is grown:
Use MOCVD technique growth thickness for III group iii nitride layer of the face N N-shaped of 700-2000nm on AlN nucleating layer, then
Using III group iii nitride layer of photoetching process etch away sections N-shaped to high-temperature AlN nucleating layer；
5) III group iii nitride layer of the face N p-type is grown:
Use MOCVD technique growth thickness for the N of 700- 2000nm in the place that III group iii nitride layer of N-shaped is etched away
III group iii nitride layer of face p-type, is maintained 850 DEG C for reaction chamber temperature later, in H2Under atmosphere, anneal 10min；
6) depositing electrode；
Using the method depositing n-type electrode on III group iii nitride layer of N-shaped respectively of splash-proofing sputtering metal, in III group-III nitride of p-type
Layer depositing p-type electrode, completes element manufacturing.
The present invention has the advantage that
1. the luminescent layer of tradition LED is quantum well structure, need to grow III group-III nitride film of multilayer, LED of the invention
Luminescent layer is one layer of III group iii nitride layer of the face N, is shone using the transoid farmland in III group-III nitride film of the face N, i.e., the present invention utilizes
Transoid farmland shines instead of quantum well structure, simplifies device architecture.
2. the present invention reduces process flow since structure is simple, fabrication cycle is shortened.
Detailed description of the invention
Fig. 1 is structural schematic diagram of the invention；
Fig. 2 is the growth course schematic diagram of structure of the invention.
Specific embodiment
The present invention will be further described below with reference to the accompanying drawings.
Referring to Fig.1, device architecture of the invention includes: the face c Al2O3Substrate layer, high-temperature AlN nucleating layer, the nitridation of III race of the face N
Nitride layer and electrode.The high-temperature AlN nucleating layer is located at the face c Al2O3On substrate layer, with a thickness of 20-50nm；III race of the face N nitridation
Nitride layer is located on high-temperature AlN nucleating layer, with a thickness of 700-2000nm；III group iii nitride layer of the face N includes III race of the face N N-shaped
III group iii nitride layer of nitride layer and the face N p-type, wherein p-type III group iii nitride layer in the face N is located at III group iii nitride layer of the face N N-shaped
The right；Electrode includes n-type electrode and p type electrode, is located on III group iii nitride layer of III group iii nitride layer of N-shaped and p-type.
III group iii nitride layer of the face N sends out different colours for being used as luminescent layer using GaN or AlN or AlGaN material
Light.
Referring to Fig. 2, the present invention provides preparation based on the face c Al2O3The three of the light emitting diode of III group-III nitride of the face N of substrate
Kind embodiment.
Embodiment 1 is prepared a kind of based on the face c Al2O3The UV LED of the face the N GaN of substrate.
Step 1, it is heat-treated.
By the face c Al2O3Substrate is placed in metal organic chemical vapor deposition MOCVD reaction chamber, and the vacuum degree of reaction chamber is dropped
Low to less than 2 × 10-2Torr；It is passed through hydrogen to reaction chamber again, makes MOCVD chamber pressure 20Torr, silicon is arrived
Temperature is 900 DEG C, and the heat treatment of 5min is carried out to substrate base.
Step 2, high-temperature ammonolysis.
Substrate after heat treatment is placed in the reaction chamber that temperature is 1000 DEG C, the ammonia that flow is 3000sccm is passed through, holds
Continuous 3min is nitrogenized.
Step 3, high-temperature AlN nucleating layer is grown, such as Fig. 2 (a).
It uses MOCVD technique under conditions of reaction chamber temperature is 950 DEG C on substrate after nitridation, while being passed through flow
The silicon source that ammonia and flow for 3000sccm are 20sccm, growth thickness is 20nm under conditions of keeping pressure to be 20Torr
High-temperature AlN nucleating layer.
Step 4, the face N n-type GaN layer is grown.
4a) using MOCVD technique while to be passed through flow under conditions of reaction chamber temperature is 950 DEG C on AlN nucleating layer
For the ammonia of 2500sccm, the silicon source that the gallium source and flow that flow is 150sccm are 10sccm is keeping pressure to be 20Torr's
Under the conditions of growth thickness be 700nm the face N n-type GaN layer, such as Fig. 2 (b)；
4b) using photoetching process etch away sections n-type GaN layer to high-temperature AlN nucleating layer, such as Fig. 2 (c).
Step 5, the face N p-type GaN layer is grown, such as Fig. 2 (d).
Use MOCVD technique under conditions of reaction chamber temperature is 950 DEG C in the place that n-type GaN layer is etched away, simultaneously
It is passed through the ammonia that flow is 2500sccm, the magnesium source that the gallium source and flow that flow is 150sccm are 100sccm is keeping pressure
The face the N p-type GaN layer for being 700nm for growth thickness under conditions of 20Torr, is maintained 850 DEG C for reaction chamber temperature later, in H2
Under atmosphere, anneal 10min.
Step 6, depositing electrode, such as Fig. 2 (e).
Using the method depositing n-type electrode in n-type GaN layer respectively of splash-proofing sputtering metal, in p-type GaN layer depositing p-type electrode,
Complete the production to uv-LED device.
Embodiment 2, preparing emission wavelength is 200nm based on the face c Al2O3The extreme ultraviolet light-emitting diodes of the face the N AlN of substrate
Pipe LED.
Step 1, heat treatment.
By the face c Al2O3Substrate is placed in metal organic chemical vapor deposition MOCVD reaction chamber, and the vacuum degree of reaction chamber is dropped
Low to less than 2 × 10-2Torr；It is passed through hydrogen to reaction chamber again, makes MOCVD chamber pressure 200Torr, by silicon
It is 1000 DEG C to temperature, the heat treatment of 7min is carried out to substrate base.
Step 2, high-temperature ammonolysis.
Substrate after heat treatment is placed in the reaction chamber that temperature is 1050 DEG C, the ammonia that flow is 3500sccm is passed through, holds
Continuous 4min is nitrogenized.
Step 3 grows high-temperature AlN nucleating layer, such as Fig. 2 (a).
It uses MOCVD technique under conditions of reaction chamber temperature is 1050 DEG C on substrate after nitridation, while being passed through stream
The silicon source that the ammonia and flow that amount is 3500sccm are 30sccm, growth thickness is under conditions of keeping pressure to be 200Torr
The high-temperature AlN nucleating layer of 40nm.
Step 4 grows N-shaped AlN layers of the face N.
4.1) using MOCVD technique while to be passed through stream under conditions of reaction chamber temperature is 1050 DEG C on AlN nucleating layer
Amount is the ammonia of 3000sccm, and the silicon source that the silicon source and flow that flow is 200sccm are 15sccm is in holding pressure
Growth thickness is N-shaped AlN layers of the face N of 1200nm under conditions of 200Torr, such as Fig. 2 (b)；
4.2) again using AlN layers of photoetching process etch away sections N-shaped to high-temperature AlN nucleating layer, such as Fig. 2 (c).
Step 5 grows p-type AlN layers of the face N, such as Fig. 2 (d).
Use MOCVD technique under conditions of reaction chamber temperature is 1050 DEG C in AlN layers of place being etched away of N-shaped, together
When be passed through flow be 3000sccm ammonia, the magnesium source that the silicon source and flow that flow is 200sccm are 150sccm, keep press
P-type AlN layers of the face N that growth thickness is 1200nm under conditions of power is 200Torr, is maintained 850 DEG C for reaction chamber temperature later,
In H2Under atmosphere, anneal 10min.
Step 6, depositing electrode, such as Fig. 2 (e).
Using the method depositing n-type electrode on N-shaped AlN layer respectively of splash-proofing sputtering metal, in AlN layers of depositing p-type electrode of p-type,
Complete the production of extreme ultraviolet LED component.
Embodiment 3, preparing emission wavelength is 280nm based on the face c Al2O3The face the N Al of substrate0.43Ga0.57The deep ultraviolet of N
Light emitting diode.
Step A, by the face c Al2O3Substrate is placed in metal organic chemical vapor deposition MOCVD reaction chamber, by the true of reaction chamber
Reciprocal of duty cycle drops below 2 × 10-2Torr；It is passed through hydrogen to reaction chamber again, makes MOCVD chamber pressure 760Torr, by substrate
Being heated to temperature is 1200 DEG C, and the heat treatment of 10min is carried out to substrate base.
Substrate after heat treatment is placed in the reaction chamber that temperature is 1100 DEG C by step B, and being passed through flow is 4000sccm's
Ammonia continues 5min and is nitrogenized, completes high-temperature ammonolysis.
Step C uses on the substrate after nitridation MOCVD technique under conditions of reaction chamber temperature is 1100 DEG C, simultaneously
It is passed through the ammonia that flow is 4000sccm and the silicon source that flow is 40sccm, is grown under conditions of keeping pressure to be 760Torr
With a thickness of the high-temperature AlN nucleating layer of 50nm, such as Fig. 2 (a).
Step D, using MOCVD technique to be passed through simultaneously on AlN nucleating layer under conditions of reaction chamber temperature is 1100 DEG C
Flow is the ammonia of 3500sccm, and flow is the silicon source of 250sccm, and the gallium source and flow that flow is 250sccm are 20sccm's
Silicon source, the face the N N-shaped Al that growth thickness is 2000nm under conditions of keeping pressure to be 760Torr0.43Ga0.57N layers, such as Fig. 2
(b)；Again using AlGaN layers of photoetching process etch away sections N-shaped to high-temperature AlN nucleating layer, such as Fig. 2 (c).
Step E uses MOCVD technique in reaction chamber temperature for 1100 DEG C of item in AlN layers of place being etched away of N-shaped
Under part, while it being passed through the ammonia that flow is 3500sccm, flow is the silicon source of 250sccm, gallium source and the stream that flow is 250sccm
Amount is the magnesium source of 180sccm, the face the N p-type that growth thickness is 2000nm under conditions of keeping pressure to be 760Torr
Al0.43Ga0.57N layers；Reaction chamber temperature is maintained 850 DEG C later, in H2Under atmosphere, anneal 10min, such as Fig. 2 (d).
Step F is heavy in p-type AlGaN layer using the method depositing n-type electrode in N-shaped AlGaN layer respectively of splash-proofing sputtering metal
Product p-type electrode, completes the production of deep ultraviolet LED component, such as Fig. 2 (e).
Above description is only three specific examples of the invention, does not constitute any limitation of the invention, it is clear that for this
It, all may be without departing substantially from the principle of the present invention, structure after understand the content of present invention and principle for the professional in field
In the case of, various modifications and variations in form and details are carried out, but these modifications and variations based on inventive concept are still
Within the scope of the claims of the present invention.
Claims (4)
1. one kind is based on the face c Al2O3The preparation method of the light emitting diode of III group-III nitride of the face N of substrate, includes the following steps:
1) it is heat-treated:
By the face c Al2O3Substrate is placed in metal organic chemical vapor deposition MOCVD reaction chamber, and the vacuum degree of reaction chamber is reduced to
Less than 2 × 10-2Torr；It is passed through hydrogen to reaction chamber again, it, will under the conditions of MOCVD chamber pressure is reached for 20-760Torr
Silicon is 900-1200 DEG C to temperature, and keeps 5-10min, completes the heat treatment to substrate base；
2) high-temperature ammonolysis:
Substrate after heat treatment is placed in the reaction chamber that temperature is 1000-1100 DEG C, is passed through the ammonia that flow is 3000-4000sccm
Gas continues 3-5min and is nitrogenized；
3) high-temperature AlN nucleating layer is grown:
It uses MOCVD technique under conditions of reaction chamber temperature is 950-1100 DEG C on substrate after nitridation, while being passed through stream
The silicon source that the ammonia and flow that amount is 3000-4000sccm are 20-40sccm, the high-temperature AlN that growth thickness is 20-50nm are nucleated
Layer；
4) III group iii nitride layer of the face N N-shaped is grown:
Use MOCVD technique growth thickness for III group iii nitride layer of the face N N-shaped of 700-2000nm on high-temperature AlN nucleating layer, then
Using III group iii nitride layer of photoetching process etch away sections N-shaped to high-temperature AlN nucleating layer；
5) III group iii nitride layer of the face N p-type is grown:
Use MOCVD technique growth thickness for the face the N p-type of 700-2000nm in the place that III group iii nitride layer of N-shaped is etched away
III group iii nitride layer；Reaction chamber temperature is maintained 850 DEG C later, in H2Under atmosphere, anneal 10min；
6) depositing electrode:
It is heavy in III group iii nitride layer of p-type using the method depositing n-type electrode on III group iii nitride layer of N-shaped respectively of splash-proofing sputtering metal
Product p-type electrode, completes element manufacturing.
2. according to the method described in claim 1, wherein growing high-temperature AlN nucleating layer, work using MOCVD technique in step 3)
Skill condition is as follows:
Chamber pressure is 20-760Torr,
Temperature is 950-1100 DEG C,
Ammonia flow is 3000-4000sccm,
Silicon source flow is 20-40sccm.
3. according to the method described in claim 1, wherein growing III group-III nitride of the face N N-shaped using MOCVD technique in step 4)
Layer, process conditions are such as
Chamber pressure is 20-760Torr,
Temperature is 950-1100 DEG C,
Ammonia flow is 2500-3500sccm,
III race's element source flux is 150-250sccm,
Silicon source flow is 10-20sccm.
4. according to the method described in claim 1, wherein growing III group-III nitride of the face N p-type using MOCVD technique in step 5)
Layer, process conditions are as follows:
Chamber pressure is 20-760Torr,
Temperature is 950-1100 DEG C,
Ammonia flow is 2500-3500sccm,
III race's element source flux is 150-250sccm,
Magnesium source flux is 100-180sccm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1995796A2 (en) * | 2001-10-09 | 2008-11-26 | Sumitomo Electric Industries, Ltd. | Single crystal GaN substrate and laser diode produced thereon |
| CN101901756A (en) * | 2010-06-24 | 2010-12-01 | 西安电子科技大学 | MOCVD Growth Method of Polar c-plane GaN Thin Films on C-plane Al2O3 Substrate |
| CN105098017A (en) * | 2015-08-18 | 2015-11-25 | 西安电子科技大学 | N surface yellow-light LED material based on c-surface sapphire substrate and manufacturing method thereof |
| CN105140365A (en) * | 2015-08-18 | 2015-12-09 | 西安电子科技大学 | C-surface sapphire substrate-based Ga polar yellow light-emitting diode (LED) material and fabrication method thereof |
-
2017
- 2017-03-31 CN CN201710206927.4A patent/CN107134512B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1995796A2 (en) * | 2001-10-09 | 2008-11-26 | Sumitomo Electric Industries, Ltd. | Single crystal GaN substrate and laser diode produced thereon |
| CN101901756A (en) * | 2010-06-24 | 2010-12-01 | 西安电子科技大学 | MOCVD Growth Method of Polar c-plane GaN Thin Films on C-plane Al2O3 Substrate |
| CN105098017A (en) * | 2015-08-18 | 2015-11-25 | 西安电子科技大学 | N surface yellow-light LED material based on c-surface sapphire substrate and manufacturing method thereof |
| CN105140365A (en) * | 2015-08-18 | 2015-12-09 | 西安电子科技大学 | C-surface sapphire substrate-based Ga polar yellow light-emitting diode (LED) material and fabrication method thereof |
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