CN106876532B - The UV LED and its manufacturing method of a kind of high light-emitting rate, high reliability - Google Patents
The UV LED and its manufacturing method of a kind of high light-emitting rate, high reliability Download PDFInfo
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L33/005—Processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices having potential barriers 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 electrodes
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Abstract
The invention discloses a kind of high light-emitting rates, the ultraviolet semiconductor light emitting diode of high reliability, including a LED chip, graphene transparency conducting layer, metal conducting layer and conductive reflective are successively arranged in the LED chip in p-type layer, graphene transparency conducting layer is characterized in that it is stacked by the graphene repeatedly shifted, forms Ohmic contact between the graphene transparency conducting layer and metal conducting layer and p-type layer.The graphene transparency conducting layer repeatedly shifted is repeatedly shifted by single-layer or multi-layer graphene, and the metal conducting layer is formed on graphene layer or between multi-layer graphene.The present invention reduces surface resistance, improves luminous efficiency by repeatedly shifting stacked graphene；Metal conducting layer formation process of the invention, the 2min that anneals under the conditions of 400 DEG C in nitrogen, oxygen mix atmosphere make contact resistivity be down to 4.3*10‑4Ω·cm‑2, while the reflecting layer Al reflectivity in 450nm being made to maintain 90%.
Description
Technical field
The invention belongs to photoelectron technical field, it is related to a kind of ultraviolet semiconductor luminescent device and its manufacturing method.
Background technique
UV LED has that small in size, the service life is long, high-efficient, environmentally friendly, energy-efficient potential advantages, in Industrial Solid
Change, disinfection, Water warfare, medical treatment and biochemistry, high-density optical record etc. replace existing mercury lamp, gas laser etc. purple
Outer light source has important application prospect and the wide market demand.LED device is divided into formal dress, upside-down mounting and vertical junction
Structure.
Upside-down mounting and vertical structure can be had the advantage that by the way that metallic conductive reflective layer is added by metallic conductive reflective layer
As current extending, spread electric current more evenly from electrode to active area；It is higher that heat is directly transferred to thermal conductivity simultaneously
Substrate, then by radiator heat-dissipation, thermal resistance is more much smaller than positive assembling structure therefore more potential and application value.
The ultraviolet LED of upside-down mounting and vertical structure need to use the p-type ohmic contact metal layer of high reflection, to improve device light
Effect.It is all greatly reduced in common high reflection metal ohmic contact such as Ag of visible light wave range etc. in the reflectivity of ultraviolet band, it is main
Want in metal only Al in ultraviolet band still have higher reflectivity.It is connect however, Al and p-GaN or p-AlGaN cannot form ohm
Touching.It using Al as the method for high reflection layer is covered on Al in p-GaN the or p-AlGaN Ohmic contact of electrically conducting transparent, this
In kind technology, needs Ohmic contact caused by the effective diffusion for stopping Al to electrically conducting transparent ohmic contact layer and be destroyed.Specially
Sharp CN104810455A uses the electrically conducting transparent ohmic contact layer of graphene-Ag composite construction, wherein graphene, which has, to be stopped to make
With, can promote its reliability in turn, but its there are the following problems: graphene first exists between farmland there are multidomain structure
Gap, Al can pass through gap and migrate, and especially at 100 DEG C or more, meeting fast degradation causes its diffusion, destroy p Ohmic contact,
It makes a big impact to device reliability；Al and graphene adherency are poor simultaneously, are easy to peel off, can solve Al currently without technology
With the sticking problem of graphene, to significantly limit the preparation of flip device.
Summary of the invention
Aiming at the shortcomings in the prior art, the main object of the present invention is to provide for a kind of with high-transmission rate, bottom surface electricity
Resistance, high reflection, good p-type Ohmic contact UV LED.Another object of the present invention is to provide for a kind of system
Make the method for the UV LED.
To realize the present invention provide high light-emitting rate, high reliability UV LED purpose, what the present invention used
Technical solution are as follows:
A kind of UV LED device of high light-emitting rate, high reliability, including mainly by n-layer, quantum well layer and p
The epitaxial structure layer of type layer composition, is successively arranged P-contact layer, graphene photic zone and conductive reflective, the Europe in p-type layer
Nurse contact layer part blanket p-type layer surface covers ratio less than 30%, and the graphene photic zone is by the graphene heap that repeatedly shifts
It is folded to form, between the P-contact layer and p-type layer, be all Ohmic contact between P-contact layer and graphene photic zone；
Preferably, the ohmic contact layer includes the Ag perhaps Au perhaps alloy structure or more of Ni or above-mentioned metal
Layer structure；
Preferably, described to constitute between euphotic at least two layers of the graphene of graphene also comprising the insertion gold of part covering
Belong to layer, which covers ratio and be lower than 10%；Preferably, it is described insertion metal conducting shell be tile Ag or Au nano dot or
Person's nano wire；It is further preferred that the partial size of Ag or Au nano dot described in the metal inserting layer be 10nm~1 μm, Ag or
The diameter of Au nano wire is 5~100nm, length is 5~100 μm；
Preferably, the conductive reflective is with a thickness of 0.1~3 μm, and the conductive reflective has high electric conductivity
And reflectivity, the preferred Al of conducting reflective layer material.
Another purpose to realize the present invention, the technical solution adopted by the present invention are as follows:
High light-emitting rate, high reliability UV LED device manufacturing method, include the following steps:
Step S1, epitaxial structure layer is grown on substrate, and epitaxial layer successively includes p-type layer, n-layer and quantum well layer；
Step S2, processing is performed etching etc. for the epitaxial structure layer, forms n contact hole；
Step S3, P-contact layer is formed by evaporation or sputtering, and annealing in p-type layer；
Step S4, it stacks to form graphene photic zone by repeatedly shifting graphene in P-contact layer；
Step S5, pass through evaporation high reflecting metal conductive reflective on graphene photic zone, it is preferred that the high reflection
Conductive metal layer is 150nm or more aluminium；
Step S6, the area n ohmic contact layer is prepared on n contact hole；
Step S7, p, n-electrode are respectively formed on the area p high reflecting metal conductive layer and the area n ohmic contact layer
Preferably, P-contact layer described in step S3 is that Ag, Au, Ni single layer of 1~5nm or above-mentioned metallic multilayer structures exist
Nitrogen or nitrogen are formed with short annealing in oxygen mix atmosphere, and accumulation of metal after annealing, coverage rate is reduced to 30% or less；
Or step S3 is comprised the steps of: step S3a, Ag, Au, Ni, ITO of 3~100nm of evaporation or sputtering
Single-layer or multi-layer forms round or polygon metal dots array, metal spot diameter or right by photoetching and corrosion or stripping technology
Angular length degree is 2~10 μm, and adjacent metal dot center distance is twice or more of metal spot diameter or diagonal length；Step S3b,
The short annealing in nitrogen or nitrogen and oxygen mix atmosphere；
Preferably, step S4 is comprised the following steps: on S4a, transfer single-layer or multi-layer graphene to P-contact layer；S4b,
There are also insertion metal layer on transfer graphene, insertion metal layer is Ni, Au or Ti of 1-2nm or the alloy of above-mentioned metal
Structure or multilayered structure；S4c, S4a~S4b or S4a is repeated, shifts the number of plies needed for reaching；In addition, the insertion metal of step S4b
The subsequent technique of layer further includes short annealing under nitrogen atmosphere.
Compared with prior art, the invention has the advantages that
(1) present invention stops the ability of Al diffusion also to greatly reinforce by repeatedly transfer graphene, improves connecing for device
Touching, reflecting properties and reliability；
(2) P contact layer covers ratio less than 30%, guarantees there is very high light transmission rate while it forms Ohmic contact；
(3) preferred embodiment improves stone by increasing insertion metal layer between graphene layer and between graphene and Al
Electric connection between black alkene layer, and solve the problems, such as the poor adhesion of graphene Yu the reflecting layer Al.
In summary to make the ultraviolet semiconductor luminescent device to be formed that there is high-transmission rate, external amount compared with the prior art
Characteristics, cut-in voltage are low, thermal diffusivity is good, high reliability for sub high-efficient, light extraction efficiency is high, good p-type Ohmic contact etc..
Detailed description of the invention
Fig. 1 is the structural schematic diagram that graphene upside-down mounting GaN base UV LED chip is repeatedly shifted in the embodiment of the present invention 1；
Fig. 2 is the structure directly annealed in the embodiment of the present invention 2 and repeatedly shift graphene upside-down mounting GaN base UV LED chip
Schematic diagram；
Fig. 3 is the multiple transfer graphene upside-down mounting GaN base UV LED chip of the metal layer containing insertion in the embodiment of the present invention 3
Structural schematic diagram；
Fig. 4 is the structural schematic diagram of P-contact layer.
Specific embodiment
Understand to make the objectives, technical solutions, and advantages of the present invention clearer, is described in detail with reference to embodiments.
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Embodiment 1
Referring to Fig.1, this GaN base ultraviolet LED structure is mainly by Sapphire Substrate 101, and the epitaxial layer grown on substrate,
Contact electrode composition.Up from substrate, epitaxial layer successively includes: AlN buffer layer 102, n-AlGaN electronic shell 103, quantum well layer
104, p-type layer 105.After epitaxial growth, epitaxial layer is etched out table top and n contact hole, and mesa surfaces are former epi-layer surface, n
Contacting hole surface is n-AlGaN layers.P-contact layer 106 is disposed on table top, the graphene repeatedly shifted stacks the stone to be formed
Black alkene photic zone 107 and conductive reflective 108 and p-type electrode 109 collectively form the reflective ohmic contact electrode of p-type layer.
Wherein, P-contact layer 106 is metal dots array, and metal spot diameter or diagonal length are 2~10 μm, adjacent metal dot center distance
It is twice or more of metal spot diameter or diagonal length.N-shaped Ohm contact electrode 110 is provided in n contact hole.
The manufacturing step of the GaN base UV LED chip described further below:
Step S1: in Sapphire Substrate 101, using MOCVD technique, successively grown epitaxial layer, epitaxial layer successively include
AlN buffer layer 102, n-AlGaN electronic shell 103, InGaN/AlGaN multiple quantum well layer 104, AlGaN p-type layer 105.
Step S2, n-AlGaN layers are etched to from p-AlGaN layers by lithography and etching technique, formed n-AlGaN table top and
N contact hole；
Step S3a, the Ag for evaporating 3nm forms round or polygon metal dots array, metal by photoetching and etching process
Spot diameter or diagonal length are 2~10 μm, adjacent metal dot center distance be twice of metal spot diameter or diagonal length or with
On, with the distribution of Fig. 4 lattice-like, wherein 41 be metal dots, 42 be p-type layer；
Step S3b, the short annealing in nitrogen；
Contact layer can be replaced Ag, Au, Ni, ITO single layer or more of 3~100nm of evaporation or sputtering in above step S3a
Layer, annealing can be replaced the short annealing in nitrogen and oxygen mix atmosphere in step S3b.
Step S4, it stacks to form graphene photic zone 107 by the graphene repeatedly shifted in P-contact layer；Specifically such as
Under:
Graphene transfer method can be wet process transfer either dry method transfer, and wet process is displaced through poly- using organic material
The etched the matrix method of methyl methacrylate (PMMA) or dimethione (PDMS) as transfer medium, dry method use
Roll To Roll either pressure sintering (Hot pressing) (bibliography: Efficient Transfer of Large-
Area Graphene Films onto Rigid Substrates by Hot Pressing.(2012).Acs Nano 6
(6): 5360-5365.).Preferably using wet process be displaced through using organic material polymethyl methacrylate (PMMA) as
The etched the matrix method of transfer medium, is transferred to contact layer for monoatomic layer or polyatom layer graphene, then carries out again next time
Transfer, transfer number are controlled at 2-5 times, preferably 3 times, form graphene photic zone 107.
Step S5, conductive reflective 108 is formed by evaporation high reflecting metal on graphene photic zone, it is preferred that institute
Stating high reflection conductive metal layer is 150nm or more aluminium；
Step S6, the area n ohmic contact layer is prepared on n contact hole with the method for photoetching, removing, annealing, contact material is
Ti/Al, Cr/Al or Cr/Au；
Step S7, SiO2 passivation layer is deposited in sample surfaces with PECVD method, on the passivation layer with photoetching, caustic solution
The metal layer under p, n-electrode is exposed in aperture；Utilize electron beam evaporation or sputtering sedimentation electrode metal, preferably Ti (50nm)/Au
(1000nm) forms p, n metal electrode 109,110 in conjunction with photoetching, stripping means above passivation layer opening；
Step S8, further, epitaxial wafer is thinned, sliver, forms single chip.
The present embodiment is stopping the ability of Al diffusion also to greatly reinforce by repeatedly transfer graphene, improves connecing for device
Touching, reflecting properties and reliability；It is distributed simultaneously by being lithographically formed the dot matrix of P-contact layer, covers P-contact layer part, cover
Ratio is covered less than 25%, guarantees there is very high light transmission rate while it forms Ohmic contact.
Embodiment 2
Referring to Fig. 2, this GaN base ultraviolet LED structure is mainly by Sapphire Substrate 201, and the epitaxial layer grown on substrate,
Contact electrode composition.Up from substrate, epitaxial layer successively includes: AlN buffer layer 202, n-AlGaN electronic shell 203, quantum well layer
204, p-type layer 205.After epitaxial growth, epitaxial layer is etched out table top and n contact hole, and mesa surfaces are former epi-layer surface, n
Contacting hole surface is n-AlGaN layers.P-contact layer 206 is disposed on table top, the graphene repeatedly shifted stacks the stone to be formed
Black alkene photic zone 207 and conductive reflective 208 and p-type electrode 209 collectively form the reflective ohmic contact electrode of p-type layer.
Wherein P-contact layer 206 is the metal dots of random distribution, is provided with N-shaped Ohm contact electrode 210 in n contact hole.
The present embodiment and the difference of the structure and technique of embodiment 1 are as described below:
P-contact layer in embodiment 1 is Ag, Au, Ni, ITO single-layer or multi-layer of 3~100nm of evaporation or sputtering, passes through light
It carves and forms round or polygon metal dots array with corrosion or stripping technology.Metal dots array is being formed after photoetching and corrosion
Later, further short annealing forms P-contact layer in nitrogen or nitrogen and oxygen mix atmosphere.
Embodiment 2 and 1 structure of embodiment the difference is that: embodiment 2 does not form P-contact layer rule as shown in Figure 4 and arranges
The metal dots array of cloth, but aggregation forms random metal dots after being annealed by thin metal layer.The metal be Ag, Ni or
Au, metal layer thickness is 1~3nm before annealing, and accumulation of metal forms the metal dots of nano-scale after annealing, and metal dot coverage is low
In 30%.
Embodiment 2 and 1 technique of embodiment the difference is that: 2 step S3 of embodiment are as follows:
Step S3a, the Ag of 3nm is evaporated；
Step S3b, the short annealing in nitrogen；
Contact layer can be replaced Ag, Au, Ni single-layer or multi-layer of 1~3nm of evaporation or sputtering in above step S3a, step
Annealing can be replaced the short annealing in nitrogen and oxygen mix atmosphere in rapid S3b.
Other processing steps are identical with embodiment 1.
Embodiment 3
Referring to Fig. 3, this GaN base ultraviolet LED structure is mainly by Sapphire Substrate 301, and the epitaxial layer grown on substrate,
Contact electrode composition.Up from substrate, epitaxial layer successively includes: AlN buffer layer 302, n-AlGaN electronic shell 303, quantum well layer
304, p-type layer 305.After epitaxial growth, epitaxial layer is etched out table top and n contact hole, and mesa surfaces are former epi-layer surface, n
Contacting hole surface is n-AlGaN layers.P-contact layer 306 is disposed on table top, the graphene repeatedly shifted stacks the stone to be formed
Black alkene photic zone 307, wherein 307a, 307b, 307c are the graphene of transfer, and there are also insertion metal layers on transfer graphene
308 (308a, 308b, 308c), conductive reflective 309 and p-type electrode 310, collectively form the reflective ohmic contact of p-type layer
Electrode.Wherein N-shaped Ohm contact electrode 311 is provided in n contact hole.
The production method of embodiment 3 and 1 structure of embodiment the difference is that: increase in graphene layer be inserted into step s 4
Metal layer 308 (308a, 308b, 308c).It is comprised the following steps in step S4:
On S4a, transfer single-layer or multi-layer graphene to P-contact layer；
S4b, there are also insertion metal layer, Ni, Au or Ti that insertion metal layer is 1-2nm, Huo Zheshang on transfer graphene
State the alloy structure or multilayered structure of metal；
S4c, S4a~S4b or S4a is repeated, shifts the number of plies needed for reaching.
In addition, the subsequent technique of the insertion metal layer of step S4b further includes nitrogen atmosphere or argon gas and hydrogen mixed gas atmosphere
In lower short annealing.
Other processing steps are identical with embodiment 1.
The present embodiment can improve graphite by increasing insertion metal layer between graphene layer and between graphene and Al
Electric connection between alkene layer, and improve the adhesiveness of graphene Yu the reflecting layer Al.
In front in 3 embodiments, it is all made of the inverted structure for going out light from Sapphire Substrate side, greatly reduces light
Loss, increases light emission rate；Stop the ability of Al diffusion also to greatly reinforce using the method for repeatedly transfer graphene simultaneously, makes it
It is more likely formed Ohmic contact, improves reliability, in addition to this three above embodiment also all has low turn-on voltage, height heat dissipation
The advantages that property, external quantum efficiency is high.
It is above only the preferred embodiment of the present invention in conjunction with attached drawing described embodiment, and not to guarantor of the invention
The restriction of range is protected, any improvement done based on spirit of that invention all ought to be within that scope of the present invention.
Claims (6)
1. the UV LED device of a kind of high light-emitting rate, high reliability, including mainly by n-layer, quantum well layer and p-type
The epitaxial structure layer of layer composition, P-contact layer, graphene photic zone and conductive reflective, feature are successively arranged in p-type layer and is existed
In the P-contact layer part blanket p-type layer surface, ratio is covered less than 30%, the graphene photic zone is by the stone that repeatedly shifts
Black alkene stacks, between the P-contact layer and p-type layer, between P-contact layer and graphene photic zone all be Ohmic contact；Institute
State the insertion metal layer between euphotic at least two layers of the graphene of graphene also comprising part covering, insertion metal layer covering
Ratio is formed with insertion metal layer lower than 10% between multi-layer graphene and between graphene and conductive reflective, described to insert
Enter Ag the or Au nano dot or Ag or Au nano wire that metal layer is tiling, Ag or Au nano dot described in the insertion metal layer
Partial size be 10nm~1 μm, the diameter of Ag or Au nano wire is 5~100nm, length is 5~100 μm.
2. the UV LED device of high light-emitting rate according to claim 1, high reliability, it is characterised in that described
P-contact layer includes the Ag perhaps Au perhaps alloy structure or multilayered structure of Ni or above-mentioned metal.
3. the UV LED device of a kind of high light-emitting rate according to claim 1, high reliability, it is characterised in that
The conductive reflective is with a thickness of 0.1~3 μm, and the conductive reflective has high electric conductivity and reflectivity, conductive anti-
It penetrates layer material and is selected from Al.
4. as described in any one of claim 1-3 high light-emitting rate, high reliability UV LED device manufacturer
Method, which comprises the steps of:
Step S1, epitaxial structure layer is grown on substrate, and epitaxial structure layer successively includes p-type layer, n-layer and quantum well layer；
Step S2, processing is performed etching for the epitaxial structure layer, forms n contact hole；
Step S3, P-contact layer is formed by evaporation or sputtering, and annealing in p-type layer；
Step S4, it stacks to form graphene photic zone by repeatedly shifting graphene in P-contact layer；
Wherein, the step S4 is comprised the following steps:
On S4a, transfer single-layer or multi-layer graphene to P-contact layer；
S4b, there are also insertion metal layers on transfer graphene, are inserted into metal layer as Ni, Au or Ti or above-mentioned gold of 1-2nm
The alloy structure or multilayered structure of category；
S4c, S4a~S4b or S4a is repeated, shifts the number of plies needed for reaching；
In addition, the subsequent technique of the insertion metal layer of step S4b further includes short annealing under nitrogen atmosphere；
Step S5, on graphene photic zone by evaporation high reflecting metal conductive reflective, the conductive reflective is 150nm
Above aluminium；
Step S6, the area n ohmic contact layer is prepared on n contact hole；
Step S7, p, n-electrode are respectively formed in the area p high reflecting metal conductive reflective and the area n ohmic contact layer.
5. the manufacturing method of the UV LED device of a kind of high light-emitting rate according to claim 4, high reliability,
It is characterized by: Ag, Au, Ni single layer or above-mentioned metallic multilayer structures that P-contact layer described in step S3 is 1~5nm are in nitrogen
Or nitrogen is formed with short annealing in oxygen mix atmosphere, accumulation of metal after annealing, coverage rate is reduced to 30% or less.
6. the manufacturing method of the UV LED device of a kind of high light-emitting rate according to claim 4, high reliability,
It is characterized by:
Step S3 is comprised the steps of:
Step S3a, Ag, Au, Ni, ITO single-layer or multi-layer of 3~100nm of evaporation or sputtering passes through photoetching and corrodes or remove work
Skill forms round or polygon metal dots array, and metal spot diameter or diagonal length are 2~10 μm, adjacent metal dot center distance
It is twice or more of metal spot diameter or diagonal length；
Step S3b, the short annealing in nitrogen or nitrogen and oxygen mix atmosphere.
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