CN105720157A - Gallium nitride-based micro-nano cone structure light-emitting diode and preparation method thereof - Google Patents
Gallium nitride-based micro-nano cone structure light-emitting diode and preparation method thereof Download PDFInfo
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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
- H01L33/20—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
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- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
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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
- H01L33/20—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
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
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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
- H01L33/26—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
- H01L33/325—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen characterised by the doping materials
Abstract
The invention provides a gallium nitride-based micro-nano cone structure light-emitting diode, which comprises a substrate and an epitaxial layer, wherein the epitaxial layer is arranged on the substrate; the epitaxial layer comprises an n-type gallium nitride layer; the n-type gallium nitride layer comprises an insulating medium layer; a plurality of micro-nano holes which are etched to the n-type gallium nitride layer are formed in the insulating medium layer; a plurality of n-type gallium nitride micro-nano cones which extend to the insulating medium layer grow in the micro-nano holes; and a multi-quantum well layer is arranged on the conical surfaces of the micro-nano cones. The invention provides a preparation method of the light-emitting diode. The gallium nitride-based micro-nano cone structure light-emitting diode is obtained through the preparation method. The structure can achieve the long wavelength light-emitting diode and can also be applied to the fields of a phosphor-free single-chip white light-emitting diode and the like.
Description
Technical field
The invention belongs to technical field of semiconductors, further to a kind of gallium nitrate based micro-nano wimble structure light emitting diode with and preparation method thereof.
Background technology
From 20 end of the centurys since Japanese Scientists makes a breakthrough in nitride semi-conductor material growth, the research of III-nitride semiconductor material and device obtains rapid development, and high efficiency short wavelength is blue, green light LED has also been succeeded in developing and industrialization.But, traditional gallium nitride based light emitting diode is all adopt planar structure, its quantum trap growth, in polar surface, is incorporated to difficulty etc. owing to there is quantum confinement Stark effect and indium component, it is difficult to realize high efficiency long emission wavelength diode and unstressed configuration powder Single chip white light emitting diode.
At present, the method realizing white light LEDs mainly has two kinds: a kind of is that the colour mixture that is mutually combined of multiple monochromatic LED is produced white light, but, the difference all to some extent such as material system belonging to each monochromatic light LED, driving voltage, temperature and light decay rate, and need many set circuit design to control electric current respectively, in this way easily cause difficult design, cost increase；Another kind is to excite yellow fluorescent powder to realize by blue-ray LED, the blue light part that LED sends is for excitated fluorescent powder, a part passes through from fluorescent material gap, blue light that gold-tinted and the LED that fluorescent material produces sends and the quasi-white light that produces blue and white, but, this single flap-type LED collocation fluorescent material produces the method for white light also can produce inevitable energy loss, i.e. Stokes energy loss, and penalty values is 10%～30%.
Additionally, due to existing gallium nitrate based LED SQW exists indium component is incorporated to the problem of difficulty, and the emission wavelength of LED is determined by the structure of active area SQW, and therefore current gallium nitride based LED is mainly the indigo plant of shorter wavelength, green light LED.Realize nitride long wavelength Huang, red-light LED is also one of current research direction tried to explore in the world.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of gallium nitrate based micro-nano wimble structure light emitting diode and preparation method, to overcome problems described above.
For achieving the above object, the present invention provides a kind of gallium nitrate based micro-nano wimble structure light emitting diode, and including the epitaxial layer on substrate and substrate, described epitaxial layer includes n-type gallium nitride layer, wherein:
Described n-type gallium nitride layer includes insulating medium layer, described insulating medium layer has the multiple micro-nano holes being etched to described n-type gallium nitride layer；
In described micro-nano hole, growth is extended down to the micro-nano cone of n-type gallium nitride on insulating medium layer outside having, and is provided with multiple quantum well layer on the conical surface of described micro-nano cone.
A kind of specific embodiments according to the present invention, described dielectric layer material is silicon dioxide or silicon nitride.
A kind of specific embodiments according to the present invention, described multiple quantum well layer also includes p-type gallium nitride layer.
A kind of specific embodiments according to the present invention, described multiple quantum well layer is the In in 1～10 cyclexGa1-xN/GaN SQW, wherein 0.1 < x < 0.5.
It addition, the preparation method that the present invention also provides for a kind of gallium nitrate based micro-nano wimble structure light emitting diode, comprise the following steps:
(1) selecting substrate, at Grown epitaxial layer, described epitaxial layer includes n-type gallium nitride layer；
(2) on described n-type gallium nitride layer, grow insulating medium layer, subregion on described insulating medium layer is performed etching, forms the multiple micro-nano holes being etched to described n-type gallium nitride layer；
(3) growing n-type gallium nitride in described multiple micro-nano holes, forms the micro-nano cone of n-type gallium nitride grown on insulating medium layer；
(4) on the conical surface of described micro-nano cone, multiple quantum well layer is grown.
A kind of specific embodiments according to the present invention, in above-mentioned preparation method, described etching particularly as follows: on insulating medium layer rotary coating photoresist, then one layer of compact arranged colloid micro-nano ball is arranged on a photoresist, then exposure imaging obtains micro-nano graph, recycling dry etching or wet etching on a photoresist, transfers on insulating medium layer by the micro-nano graph on photoresist, after cutting through mask layer, obtain the multiple micro-nano holes connected with n-type gallium nitride layer.
A kind of specific embodiments according to the present invention, in above-mentioned preparation method, described multiple quantum well layer is InxGa1-xN/GaN structure, the cycle is 1～10, In in SQWxGa1-xThe In component of N material can be controlled by temperature or trimethyl indium flow, and the value of x is 0.1～0.5.
A kind of specific embodiments according to the present invention, in above-mentioned preparation method, includes growth p-type gallium nitride layer on described multiple quantum well layer, and the doped chemical of described p-type gallium nitride layer is magnesium, and p-type GaN growth thickness is 50～500nm.
A kind of specific embodiments according to the present invention, in above-mentioned preparation method, described micro-nano ball is polymer microsphere or transparent inorganic-oxide microsphere.
By above technical scheme, the gallium nitrate based micro-nano wimble structure light emitting diode of the present invention and having the beneficial effects that of preparation method:
(1) by arranging nanocone structures, overcome the energy loss that the Quantum Confined Stark effect adopting planar structure in prior art causes, improve energy efficiency；
(2) by the mole of indium component in SQW on increase cone semi-polarity face, long emission wavelength can namely be realized；
(3) by the aperture of mask in change selective area growth and the width of MQW and indium component doping, this gallium nitrate based micro-nano wimble structure both can realize indigo plant, green, yellow, red light emitting diodes, it is also possible to for fields such as unstressed configuration powder Single chip white lights.
Accompanying drawing explanation
Fig. 1 is the embodiments of the invention 1 sample in cross section schematic diagrams for colloid micro ball photoetching.
Fig. 2 is embodiments of the invention 1 colloid micro ball 21 schematic cross-section after self assembly on surface positive photoetching rubber 15 in Fig. 1 sample.
Fig. 3 is the n-type gallium nitride MOCVD selective area growth template schematic cross-section obtained after embodiments of the invention 1 utilize the development of colloid micro ball photolithographic exposure.
Fig. 4 is the gallium nitride wimble structure LED schematic cross-section obtained after embodiments of the invention 1 carry out MOCVD selective area growth on n-type gallium nitride template.
Fig. 5 is the scanning electron microscope plane graph that embodiments of the invention 1 finally grow the light emitting diode of a kind of gallium nitrate based micro-nano wimble structure obtained.
Detailed description of the invention
In the present invention, " micro-nano hole " refers to the hole that internal diameter is 100-3000nm；" micro-nano cone " refers to that size is 300-5000nm, and geometry is bottom area pyramidal structure big, that area reduces gradually to top, for instance can be circular cone, triangular pyramid, rectangular pyramid, pentagonal pyramid, hexagonal pyramid etc.." on ... growth " and " ... on ... growth " term refers to grow other layer on destination layer, contacts or noncontact between this destination layer with other layer.Such as, described multiple quantum well layer grows p-type gallium nitride layer, refers to that multiple quantum well layer directly contacts with p-type gallium nitride layer, or on multiple quantum well layer, first grow electronic barrier layer, regrowth p-type gallium nitride layer.It should be noted that " on ", " under " relative to reference frame, whether be inverted unrelated with light emitting diode entirety.
The present invention provides a kind of gallium nitrate based micro-nano wimble structure light emitting diode, including the epitaxial layer on substrate and substrate, described epitaxial layer includes n-type gallium nitride layer, wherein said n-type gallium nitride layer includes insulating medium layer, described insulating medium layer has the multiple micro-nano holes being etched to described n-type gallium nitride layer；In described micro-nano hole, growth is extended down to the micro-nano cone of n-type gallium nitride on insulating medium layer outside having, and includes multiple quantum well layer on the conical surface of described micro-nano cone.
The preparation method also providing for a kind of gallium nitrate based micro-nano wimble structure light emitting diode, comprises the following steps:
(1) selecting substrate, at Grown epitaxial layer, described epitaxial layer includes n-type gallium nitride layer, it is characterised in that
(2) on described n-type gallium nitride layer, grow insulating medium layer, subregion on described insulating medium layer is performed etching, forms the multiple micro-nano holes being etched to described n-type gallium nitride layer；
(3) growing n-type gallium nitride in described micro-nano hole, forms the micro-nano cone of n-type gallium nitride grown on insulating medium layer；
(4) on the conical surface of described micro-nano cone, multiple quantum well layer is grown.
Selection for substrate, it is possible to be sapphire or silicon substrate, it is preferred to use Sapphire Substrate.
Growth for epitaxial layer, preferably, available metal-organic chemical vapor deposition equipment growing system growth epitaxial buffer layer, involuntary doped gallium nitride layer, n-type gallium nitride layer, then utilize plasma enhanced chemical vapor deposition at n-type gallium nitride layer Epitaxial growth dielectric mask layer.
For multi-quantum pit structure, it is preferred that multiple quantum well layer is InxGa1-xN/GaN structure, the cycle is 1～10, In in SQWxGa1-xThe In component of N material can be controlled by temperature or trimethyl indium flow, and the value of x is 0.1～0.5.
For etching mode, it is preferable that rotary coating photoresist on insulating medium layer, then arrange one layer of compact arranged colloid micro-nano ball, then exposure imaging on a photoresist, obtain micro-nano graph on a photoresist；Then utilize dry etching or wet etching, the micro-nano graph on photoresist is transferred on dielectric mask layer, after cutting through mask layer, obtain the n-type gallium nitride template having graphic mask；Colloid micro-nano ball can be polymer microsphere, for instance polystyrene microsphere；Or it is transparent inorganic-oxide microsphere, such as silicon dioxide microsphere.Microsphere diameter can be 500～5000nm.Dry etching means can be inductively coupled plasma etching (InductivelyCoupledPlasma, or reactive ion etching (ReactiveIonEtching ICP), RIE), wet etching can utilize buffering etching liquid etching (BufferedOxideEtchant, BOE) solution.Require that etching depth is equal to or slightly greater than mask layer thickness, reach n-type gallium nitride layer surface.After etching, the graphic aperture of mask layer is 100～5000nm.
Preferably, in the n-type micro-nano gallium nitride pyramid structure of gallium nitride graphics template Epitaxial growth, then epitaxial growth MQW, electronic barrier layer, p-type gallium nitride layer successively on micro-nano gallium nitride pyramid.N-type gallium nitride cone growth conditions is: growth temperature 800～1200 DEG C, reaction chamber pressure is 100～600Torr, and the response time is 30～3600 seconds.
One preferred embodiment of the present invention is: the preparation method of gallium nitrate based micro-nano wimble structure light emitting diode comprises the following steps:
(1) on sapphire or silicon substrate, utilize metal-organic chemical vapor deposition equipment growing system epitaxial buffer layer successively, involuntary doped gallium nitride layer, n-type gallium nitride layer, then utilize plasma enhanced chemical vapor deposition at n-type gallium nitride layer Epitaxial growth dielectric mask layer；
(2) rotary coating photoresist on dielectric mask layer, then arranges one layer of compact arranged colloid micro-nano ball, then exposure imaging on a photoresist, obtains micro-nano graph on a photoresist；
Utilize dry etching or wet etching, the micro-nano graph on photoresist is transferred on dielectric mask layer, after cutting through mask layer, obtain the n-type gallium nitride template having graphic mask；
(3) n-type GaN growth conditions is regulated, at the n-type micro-nano gallium nitride wimble structure of gallium nitride graphics template Epitaxial growth, then epitaxial growth MQW, electronic barrier layer, p-type gallium nitride layer successively on micro-nano gallium nitride is bored.
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail.
Embodiment 1
The present embodiment provides the light-emitting diodes tube preparation method of a kind of gallium nitrate based micro-nano wimble structure, comprises the following steps:
Step 1: utilize the mode epitaxial growth buffer 11 successively of metal-organic chemical vapor deposition equipment, not intentionally doped gallium nitride layer 12, n-type gallium nitride layer 13 in Sapphire Substrate 10, then plasma enhanced chemical vapor deposition (PECVD) is utilized to grow one layer of 100～1000nm silicon dioxide insulator dielectric film passivation layer 14, rotary coating positive photoetching rubber 15 on 14 afterwards, as shown in Figure 1.
Step 2: utilizing spin-coating method or czochralski method self assembly arrangement monolayer polystyrene microsphere 21 on positive photoetching rubber 15, diameter is 100～5000nm.
Step 3: the sample (as shown in Figure 2) completing polystyrene microsphere 21 is placed under litho machine and exposes 1～300 second, then microsphere is removed, sample after exposure is immersed in developer solution and develops 1～120 second, stripper is utilized to remove photoresist after having developed, namely obtaining the n-type gallium nitride template for choosing growth, aperture size is 100～3000nm.
Step 4: the n-type gallium nitride template (as shown in Figure 3) prepared is placed in MOCVD system and carries out selective area growth, set n-type gallium nitride cone growth conditions as growth temperature 800～1200 DEG C, reaction chamber pressure is 100～600Torr, and the response time is 30～3600 seconds.Then the In being sequentially depositing 1～10 cycle on 41 is bored at n-type gallium nitridexGa1-xN/GaN SQW 42, finally grows the p-type gallium nitride 43 of 50～500nm, as shown in Figure 4.Fig. 5 is the scanning electron microscope plane graph of the light emitting diode finally growing the gallium nitrate based micro-nano wimble structure obtained.
The above; being only the detailed description of the invention in the present invention, but protection scope of the present invention is not limited thereto, any people being familiar with this technology is in the technical scope that disclosed herein; the conversion that can readily occur in or replacement, all should be encompassed in comprising within scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (9)
1. a gallium nitrate based micro-nano wimble structure light emitting diode, including the epitaxial layer on substrate and substrate, described epitaxial layer includes n-type gallium nitride layer, it is characterised in that
Described n-type gallium nitride layer includes insulating medium layer, described insulating medium layer has the multiple micro-nano holes being etched to described n-type gallium nitride layer；
In described micro-nano hole, growth is extended down to the micro-nano cone of n-type gallium nitride on insulating medium layer outside having, and is provided with multiple quantum well layer on the conical surface of described micro-nano cone.
2. gallium nitrate based micro-nano wimble structure light emitting diode according to claim 1, it is characterised in that described dielectric layer material is silicon dioxide or silicon nitride.
3. gallium nitrate based micro-nano wimble structure light emitting diode according to claim 1, it is characterised in that also include p-type gallium nitride layer on described multiple quantum well layer.
4. gallium nitrate based micro-nano wimble structure light emitting diode according to claim 1, it is characterised in that described multiple quantum well layer is the In in 1～10 cyclexGa1-xN/GaN SQW, wherein 0.1 < x < 0.5.
5. the preparation method of a gallium nitrate based micro-nano wimble structure light emitting diode, it is characterised in that comprise the following steps:
(1) selecting substrate, at Grown epitaxial layer, described epitaxial layer includes n-type gallium nitride layer；
(2) on described n-type gallium nitride layer, grow insulating medium layer, subregion on described insulating medium layer is performed etching, forms the multiple micro-nano holes being etched to described n-type gallium nitride layer；
(3) growing n-type gallium nitride in described micro-nano hole, forms the micro-nano cone of n-type gallium nitride grown on insulating medium layer；
(4) on the conical surface of described micro-nano cone, multiple quantum well layer is grown.
6. the preparation method of gallium nitrate based micro-nano wimble structure light emitting diode according to claim 5, it is characterized in that, described etching particularly as follows: on insulating medium layer rotary coating photoresist, then one layer of compact arranged colloid micro-nano ball is arranged on a photoresist, then exposure imaging obtains micro-nano graph on a photoresist, recycling dry etching or wet etching, micro-nano graph on photoresist is transferred on insulating medium layer, after cutting through mask layer, obtain the multiple micro-nano holes connected with n-type gallium nitride layer.
7. the preparation method of gallium nitrate based micro-nano wimble structure light emitting diode according to claim 5, it is characterised in that described multiple quantum well layer is InxGa1-xN/GaN structure, the cycle is 1～10, In in SQWxGa1-xThe In component of N material can be controlled by temperature or trimethyl indium flow, and the value of x is 0.1～0.5.
8. the preparation method of gallium nitrate based micro-nano wimble structure light emitting diode according to claim 5, it is characterized in that, including growth p-type gallium nitride layer on described multiple quantum well layer, the doped chemical of described p-type gallium nitride layer is magnesium, and p-type GaN growth thickness is 50～500nm.
9. the preparation method of gallium nitrate based micro-nano wimble structure light emitting diode according to claim 6, it is characterised in that described micro-nano ball is polymer microsphere or transparent inorganic-oxide microsphere.
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| CN108389941A (en) * | 2018-04-08 | 2018-08-10 | 中国科学院半导体研究所 | It is aobvious to refer to adjustable unstressed configuration powder Single chip white light LED component and preparation method thereof |
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| CN109904292A (en) * | 2019-02-01 | 2019-06-18 | 中国科学院半导体研究所 | Single chip white light LED and preparation method thereof based on pyramid-like type dual wavelength structure |
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| CN114270542A (en) * | 2019-06-25 | 2022-04-01 | 艾利迪公司 | Optoelectronic device comprising a three-dimensional semiconductor element and method for manufacturing said device |
| CN111048635A (en) * | 2019-12-27 | 2020-04-21 | 广东省半导体产业技术研究院 | Chip preparation method and chip structure to be stripped |
| CN111048635B (en) * | 2019-12-27 | 2021-06-18 | 广东省半导体产业技术研究院 | Chip preparation method and chip structure to be stripped |
| CN115305571A (en) * | 2022-08-11 | 2022-11-08 | 江苏第三代半导体研究院有限公司 | Gallium oxide epitaxial structure and preparation method thereof |
| CN115305571B (en) * | 2022-08-11 | 2023-07-21 | 江苏第三代半导体研究院有限公司 | Gallium oxide epitaxial structure and preparation method thereof |
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