CN106601887B - The GaN film and preparation method thereof of growth on a glass substrate - Google Patents
The GaN film and preparation method thereof of growth on a glass substrate Download PDFInfo
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- CN106601887B CN106601887B CN201611226922.XA CN201611226922A CN106601887B CN 106601887 B CN106601887 B CN 106601887B CN 201611226922 A CN201611226922 A CN 201611226922A CN 106601887 B CN106601887 B CN 106601887B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
- H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
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- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H—ELECTRICITY
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/10—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a light reflecting structure, e.g. semiconductor Bragg reflector
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
Abstract
The invention discloses the GaN film of growth on a glass substrate, including growing aluminum metal layer on a glass substrate, the silver metal layer being grown on aluminum metal layer, the AlN buffer layer being grown on silver metal layer, the GaN buffer layer being grown on AlN buffer layer, the GaN film being grown on GaN buffer layer.The invention also discloses the preparation methods of the GaN film of above-mentioned growth on a glass substrate.The present invention has growth technique simple, the cheap advantage of preparation cost, and the GaN film defect concentration prepared is low, crystalline quality is good, and electrical and optical property is good.
Description
Technical field
The present invention relates to GaN films, in particular to grow GaN film and preparation method thereof on a glass substrate.
Background technique
Light emitting diode (LED) is used as a kind of novel solid lighting source and green light source, has small in size, power consumption
Low, environmentally friendly, long service life, high brightness, the low in calories and outstanding features such as colorful, in outdoor lighting, commercial lighting and dress
The fields such as decorations engineering all have a wide range of applications.Currently, under the increasingly severe background of global warming problem, energy is saved
The major issue that greenhouse gas emission faces jointly as the whole world is reduced in source.Based on low energy consumption, low pollution, low emission
Low-carbon economy will become the important directions of economic development.Just attract common people's in the application of lighting area, LED luminous product
Sight, LED is as a kind of novel green light source product, the necessarily trend of future development.But LED is applied at this stage
This is higher, and luminous efficiency is lower, these factors can all limit LED significantly and develop to the direction of high-efficient energy-saving environment friendly.
Group III-nitride GaN is in electricity, optics and acoustically with extremely excellent property, in recent years by extensive
Concern.GaN is direct band gap material, and sonic transmissions speed is fast, and chemical and thermal stability is good, and thermal conductivity is high, thermal expansion coefficient
Low, it is the ideal material for manufacturing efficient LED component that breakdown dielectric strength is high.Currently, the luminous efficiency of GaN base LED is now
Reached 28% and also further increased, the numerical value be significantly larger than usually used incandescent lamp (about 2%) at present or
The luminous efficiency of the lighting methods such as fluorescent lamp (about 10%).
LED will really realize extensive extensive use, need to further increase the luminous efficiency of LED chip, reduce simultaneously
The price of LED chip.Although the luminous efficiency of LED alreadys exceed fluorescent lamp and incandescent lamp, commercialization LED luminous efficiency is also
Be less than sodium vapor lamp (150lm/W), unit lumens/watt it is on the high side.Current most of GaN base LED be all based on sapphire and
Epitaxial growth is carried out in SiC substrate, large-sized sapphire and SiC substrate are expensive, cause LED manufacturing cost high.Therefore
It urgently finds the cheap substrate material of one kind and is applied to epitaxial growth GaN film.
Summary of the invention
In order to overcome the disadvantages mentioned above and deficiency of the prior art, the purpose of the present invention is to provide one kind to be grown in glass lined
GaN film on bottom, defect concentration is low, crystalline quality is good, and electrical and optical property is good.
Another object of the present invention is to provide a kind of preparation method of the GaN film of above-mentioned growth on a glass substrate,
It is simple with growth technique, the cheap advantage of preparation cost.
The purpose of the present invention is achieved through the following technical solutions:
The GaN film of growth on a glass substrate is grown in aluminum metal including growing aluminum metal layer on a glass substrate
Silver metal layer on layer, the AlN buffer layer being grown on silver metal layer, the GaN buffer layer being grown on AlN buffer layer, growth
GaN film on GaN buffer layer.
The aluminum metal layer with a thickness of 150~200 μm.
The silver metal layer is with a thickness of 100~300nm.
The AlN buffer layer thickness is 5~50nm.
The GaN buffer layer with a thickness of 50~80nm.
The degree of the GaN film is 200~300nm.
The preparation method of the GaN film of the growth on a glass substrate, comprising the following steps:
(1) glass substrate surface polished, cleaned；
(2) it the growth of aluminum metal layer: in molecular beam epitaxy system, under the conditions of underlayer temperature is 400~600 DEG C, sinks
Accumulate the aluminum metal layer with a thickness of 150~200 μm；
(3) growth of silver metal layer: in molecular beam epitaxy system, using the electron beam evaporation in molecular beam epitaxy system
Function, under the conditions of underlayer temperature is 400~600 DEG C, the deposit silver metal layer on obtained aluminum metal layer；
(4) growth of AlN buffer layer: underlayer temperature is 450~550 DEG C, is 4.0~7.2 × 10 in the pressure of reaction chamber- 5Under conditions of Pa, the speed of growth are 0.2~0.8ML/s, the deposited metal aluminium film on silver metal layer, then using nitrogen etc. from
Body component nitrogenizes the metal aluminium film, and the power in plasmon source is 300~450W, and nitrogen flow is 1~5sccm,
Nitridation time is 10~50 minutes, obtains AlN film；
(5) GaN buffer layer epitaxially grown: underlayer temperature be 450~550 DEG C, reaction chamber pressure be 6.0~7.2 ×
10-5Under conditions of Pa, line ratio V/III value are 50~60, the speed of growth is 0.4~0.6ML/s, grown on AlN buffer layer
GaN buffer layer；
(6) epitaxial growth of GaN film: molecular beam epitaxial growth technique is used, underlayer temperature is 500~600 DEG C, anti-
The pressure for answering room is 4.0~5.0 × 10-5Pa, line ratio V/III value are 30~40, the speed of growth is 0.6~0.8ML/s condition
Under, GaN film is grown on GaN buffer layer.
Step (1) described polishing, specifically:
Glass substrate surface is polished with diamond mud first, cooperates optical microphotograph sem observation substrate surface, directly
It is processed by shot blasting to after no scratch, then using the method for chemically mechanical polishing.
Step (1) described cleaning, specifically:
Glass substrate is put into deionized water and is cleaned by ultrasonic at room temperature 3~5 minutes, glass substrate surface pickup is removed
Grain, then successively pass through acetone, ethanol washing, surface organic matter is removed, is dried up with drying nitrogen.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) present invention can effectively reduce the formation of dislocation, prepare high-quality GaN film, favorably improve carrier
Radiation recombination efficiency, nitride compound semiconductor device such as semiconductor laser, light emitting diode and solar energy can be increased substantially
The performance of battery.
(2) GaN film of growth of the invention on a glass substrate, after carrying out glass substrate removal, aluminum metal layer
With as supporting layer, conduction, thermally conductive function；Silver metal layer has the function of light transmitting.It is being previously deposited aluminum metal, silver
The growth of GaN film is carried out on metal layer, is established for preparation low cost, high thermal conductivity, highly conductive, high luminescence energy photoelectric device
Basis.
(3) present invention uses glass as substrate, and glass substrate is easy to get, cheap, advantageously reduces and is produced into
This.
(4) silver metal of the invention can be used as reflecting mirror, if preparing luminescent device using the GaN, can increase substantially
Luminous efficiency；If preparing solar cell using the GaN, absorptivity can be improved, improve the photoelectric conversion efficiency of solar cell.
(5) the molecular beam epitaxial growth technique that uses of the present invention, prepared high-quality GaN film thickness be 200~
300nm；When GaN thickness reaches 200~300nm, GaN is in complete relaxed state, is conducive to the n-type doping of later period high quality
The epitaxial growth of GaN film.
(6) then the present invention carries out nitrogen treatment using one layer of metal aluminium film is deposited on silver metal layer, forms AlN
Layer, is conducive to the growth of subsequent GaN, overcomes that high-quality GaN monocrystalline can not directly to be grown in amorphous glass substrate thin
The technical problem of film；Using low temperature (450~550 DEG C) epitaxy technology, first one layer of GaN of epitaxial growth is buffered on AlN buffer layer
Layer can obtain island GaN by growing GaN buffer layer, lay the groundwork for the GaN film of next step depositing high-quality low defect,
The luminous efficiency for improving device, is expected to prepare the device of efficient LED.
(7) growth technique of the invention is unique and simple and easy, has repeatability.
(8) present invention can go out glass substrate resistant to high temperature by mixing different compositional modulations.
Detailed description of the invention
Fig. 1 is the schematic cross-section of GaN prepared by embodiment 1.
Fig. 2 is the XRD spectrum of GaN film (0002) prepared by embodiment 1.
Fig. 3 is the XRD spectrum of GaN film (10-12) prepared by embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
As shown in Figure 1, the GaN film of the growth of the present embodiment on a glass substrate, including be grown in glass substrate 10
Aluminum metal layer 11, the silver metal layer 12 being grown on aluminum metal layer, the AlN buffer layer 13 being grown on silver metal layer 12 is raw
The GaN buffer layer 14 on AlN buffer layer 13 is grown, the GaN film 15 being grown on GaN buffer layer 14.
The preparation method of the GaN film of the growth of the present embodiment on a glass substrate, comprising the following steps:
(1) selection of substrate: common glass substrate is used；
(2) substrate surface polishing, cleaning treatment；
The substrate surface polishing, specifically:
Glass substrate surface is polished with diamond mud first, cooperates optical microphotograph sem observation substrate surface, directly
It is processed by shot blasting to after no scratch, then using the method for chemically mechanical polishing；
The cleaning, specifically:
Glass substrate is put into deionized water and is cleaned by ultrasonic at room temperature 3 minutes, glass substrate surface pickup particle is removed,
Successively pass through acetone, ethanol washing again, remove surface organic matter, is dried up with high-purity drying nitrogen；
(3) growth of aluminum metal layer: in molecular beam epitaxy system, under the conditions of underlayer temperature is 400 DEG C, deposition thickness
For 150 μm of aluminium layer；
(4) growth of silver metal layer: in molecular beam epitaxy system, using the electron beam evaporation in molecular beam epitaxy system
Function, under the conditions of underlayer temperature is 400 DEG C, deposition thickness is the silver metal layer of 100nm thickness on aluminum metal layer；
(5) growth of AlN buffer layer: underlayer temperature is 500 DEG C, is 4.0 × 10 in the pressure of reaction chamber-5Pa, growth speed
Under conditions of degree is 0.2ML/s, deposition thickness is the metal aluminium film of 10nm on silver metal layer, then uses nitrogen plasmon
Source nitrogenizes the metal aluminium film, and the power in nitrogen plasmon source is 300W, nitrogen flow 1.5sccm, nitridation time
It is 10 minutes, obtains AlN film；
(6) GaN buffers layer epitaxially grown: underlayer temperature is 500 DEG C, is 6.0 × 10 in the pressure of reaction chamber-5Pa, line
Under conditions of than V/III value be 50, the speed of growth is 0.4ML/s, the GaN that growth thickness is 50nm on AlN buffer layer is buffered
Layer；
(7) epitaxial growth of GaN film: molecular beam epitaxial growth technique is used, underlayer temperature is 500 DEG C, in reaction chamber
Pressure be 4.0 × 10-5Under the conditions of Pa, line ratio V/III value are 30, speed of growth 0.6ML/s, in obtained GaN buffer layer
Upper growth thickness is the GaN film of 200nm.
Fig. 2,3 be GaN film manufactured in the present embodiment XRD spectrum, from X-ray swing curve it can be seen that, GaN
(0002) half-peak breadth (FWHM) value of X-ray swing curve is lower than 231.1arcsec, and the half-value width of GaN (10-12) is
253.2arcsec；Show that epitaxial growth on a glass substrate has gone out the GaN film of high quality.
The GaN film of growth manufactured in the present embodiment on a glass substrate is used to prepare LED: manufactured in the present embodiment
Successively the N-shaped of epitaxial growth Si doping mixes silicon GaN, In in the GaN film of growth on a glass substratexGa1-xN/GaN Multiple-quantum
Well layer, the p-type of Mg doping mix the GaN layer of magnesium, and last electron beam evaporation forms Ohmic contact.It is prepared on a glass substrate
GaN base LED component, the thickness of N-shaped GaN are about 5 μm, and the concentration of carrier is 1 × 1019cm-3；InxGa1-xN/GaN volume
The thickness of sub- well layer is about 160nm, periodicity 10, wherein InxGa1-xN well layer is 3nm, and GaN barrier layer is 13nm, and p-type mixes magnesium
GaN layer thickness be about 300nm, the concentration of carrier is 3 × 1017cm-3.Under the operating current of 20mA, LED component
Optical output power is 4.3mW, and cut-in voltage value is 3.18V.
The GaN film of growth manufactured in the present embodiment on a glass substrate is used to prepare photodetector: in this implementation
Successively epitaxial growth N-shaped mixes silicon GaN, undoped GaN, p-type and mixes magnesium in the GaN film of the growth of example preparation on a glass substrate
GaN, last electron beam evaporation form Ohmic contact and schottky junction.It is about 3 μm that wherein N-shaped, which mixes silicon GaN thickness, carrier
Concentration is 1 × 1019cm-3；Undoped GaN thickness is about 200nm, and carrier concentration is 2.2 × 1016cm-3；P-type mixes magnesium
GaN thickness is about 1.5 μm.Photodetector prepared by the present embodiment is under 1V bias, and dark current is only 65pA, and device
Under 1V bias, the maximum value of responsiveness has reached 0.92A/W at 361nm.
The GaN film of growth manufactured in the present embodiment on a glass substrate is used to prepare InGaN solar battery: at this
Successively growth has the In of component gradient in the GaN film of the growth of embodiment preparation on a glass substratexGa1-xN buffer layer, n
Type mixes silicon InxGa1-xN, InxGa1-xN multiple quantum well layer, p-type mix the In of magnesiumxGa1-xN layers, last electron beam evaporation forms ohm and connects
Touching, wherein 0 < x≤0.2.Wherein, N-shaped mixes silicon InxGa1-xN thickness is about 5 μm, and the concentration of carrier is 1 × 1019cm-3；
InxGa1-xN multiple quantum well layer, thickness are about 300nm, periodicity 20, wherein In0.2Ga0.8N well layer is 3nm, In0.08Ga0.92N
Barrier layer is 10nm.The incident photon-to-electron conversion efficiency of the solar battery that this technique is prepared at room temperature is 9.1%, and short-circuit photocurrent is close
Degree is 35mA/cm2。
Embodiment 2
The preparation method of the GaN film of the growth of the present embodiment on a glass substrate, comprising the following steps:
(1) selection of substrate: common glass substrate is used；
(2) substrate surface polishing, cleaning treatment；
The substrate surface polishing, specifically:
Glass substrate surface is polished with diamond mud first, cooperates optical microphotograph sem observation substrate surface, directly
It is processed by shot blasting to after no scratch, then using the method for chemically mechanical polishing；
The cleaning, specifically:
Glass substrate is put into deionized water and is cleaned by ultrasonic at room temperature 5 minutes, glass substrate surface pickup particle is removed,
Successively pass through acetone, ethanol washing again, remove surface organic matter, is dried up with high-purity drying nitrogen；
(3) growth of aluminum metal layer: in molecular beam epitaxy system, under the conditions of underlayer temperature is 600 DEG C, deposition thickness
For 200 μm of aluminum metal layer；
(4) growth of silver metal layer: in molecular beam epitaxy system, using the electron beam evaporation in molecular beam epitaxy system
Function, under the conditions of underlayer temperature is 600 DEG C, deposition thickness is the silver metal layer of 300nm thickness on aluminum metal layer；
(5) growth of AlN buffer layer: underlayer temperature is 550 DEG C, is 7.2 × 10 in the pressure of reaction chamber-5Pa, growth speed
Under conditions of degree is 0.2ML/s, deposition thickness is the metal aluminium film of 20nm on silver metal layer, then uses nitrogen plasmon
Source nitrogenizes the metal aluminium film, and nitrogen plasmon power is 300W, nitrogen flow 1.5sccm, nitridation time 20
Minute, obtain AlN film；
(6) GaN buffers layer epitaxially grown: underlayer temperature is 550 DEG C, is 5.0 × 10 in the pressure of reaction chamber-5Pa, line
Under conditions of than V/III value be 50, the speed of growth is 0.4ML/s, in AlN buffer growth with a thickness of the GaN buffer layer of 50nm；
(7) epitaxial growth of GaN film: molecular beam epitaxial growth technique is used, underlayer temperature is 600 DEG C, in reaction chamber
Pressure be 4.0 × 10-5Under the conditions of Pa, line ratio V/III value are 30, speed of growth 0.6ML/s, grown on GaN buffer layer
With a thickness of the GaN film of 200nm.
The GaN film test result of growth manufactured in the present embodiment on a glass substrate is similar to embodiment, herein no longer
It repeats.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. the preparation method of the GaN film of growth on a glass substrate, which comprises the following steps:
(1) glass substrate surface polished, cleaned；
(2) growth of aluminum metal layer: in molecular beam epitaxy system, under the conditions of underlayer temperature is 400~600 DEG C, deposition of thick
The aluminum metal layer that degree is 150~200 μm；
(3) growth of silver metal layer: in molecular beam epitaxy system, using the electron beam evaporation function in molecular beam epitaxy system
Can, under the conditions of underlayer temperature is 400~600 DEG C, the deposit silver metal layer on obtained aluminum metal layer；
(4) growth of AlN buffer layer: underlayer temperature is 450~550 DEG C, is 4.0~7.2 × 10 in the pressure of reaction chamber-5Pa、
Under conditions of the speed of growth is 0.2~0.8ML/s, then the deposited metal aluminium film on silver metal layer uses nitrogen plasmon
Source nitrogenizes the metal aluminium film, and the power in plasmon source is 300~450W, and nitrogen flow is 1~5sccm, nitridation
Time is 10~50 minutes, obtains AlN film；
(5) GaN buffers layer epitaxially grown: underlayer temperature is 450~550 DEG C, is 6.0~7.2 × 10 in the pressure of reaction chamber- 5Under conditions of Pa, line ratio V/III value are 50~60, the speed of growth is 0.4~0.6ML/s, GaN is grown on AlN buffer layer
Buffer layer；
(6) epitaxial growth of GaN film: molecular beam epitaxial growth technique is used, underlayer temperature is 500~600 DEG C, in reaction chamber
Pressure be 4.0~5.0 × 10-5Under the conditions of Pa, line ratio V/III value are 30~40, the speed of growth is 0.6~0.8ML/s,
GaN film is grown on GaN buffer layer.
2. the preparation method of the GaN film of growth according to claim 1 on a glass substrate, which is characterized in that step
(1) polishing, specifically:
Glass substrate surface is polished with diamond mud first, cooperates optical microphotograph sem observation substrate surface, until not having
After having scratch, then the method for using chemically mechanical polishing is processed by shot blasting.
3. the preparation method of the GaN film of growth according to claim 1 on a glass substrate, which is characterized in that step
(1) cleaning, specifically:
Glass substrate is put into deionized water and is cleaned by ultrasonic at room temperature 3~5 minutes, glass substrate surface pickup particle is removed,
Successively pass through acetone, ethanol washing again, removes surface organic matter, dried up with drying nitrogen.
4. the preparation method of the GaN film of growth according to claim 1 on a glass substrate, which is characterized in that described
Aluminum metal layer with a thickness of 150~200 μm.
5. the preparation method of the GaN film of growth according to claim 1 on a glass substrate, which is characterized in that described
Silver metal layer is with a thickness of 100~300nm.
6. the preparation method of the GaN film of growth according to claim 1 on a glass substrate, which is characterized in that described
AlN buffer layer thickness is 5~50nm.
7. the preparation method of the GaN film of growth according to claim 1 on a glass substrate, which is characterized in that described
GaN buffer layer with a thickness of 50~80nm.
8. the preparation method of the GaN film of growth according to claim 1 on a glass substrate, which is characterized in that described
The degree of GaN film is 200~300nm.
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| US6969874B1 (en) * | 2003-06-12 | 2005-11-29 | Sandia Corporation | Flip-chip light emitting diode with resonant optical microcavity |
| CN103996764A (en) * | 2014-05-30 | 2014-08-20 | 广州市众拓光电科技有限公司 | LED epitaxial wafer growing on Ag substrate and preparing method and application of LED epitaxial wafer |
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