CN105470357B - Semiconductor devices in AlN templates, the preparation method of AlN templates and AlN templates - Google Patents
Semiconductor devices in AlN templates, the preparation method of AlN templates and AlN templates Download PDFInfo
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- CN105470357B CN105470357B CN201511029761.0A CN201511029761A CN105470357B CN 105470357 B CN105470357 B CN 105470357B CN 201511029761 A CN201511029761 A CN 201511029761A CN 105470357 B CN105470357 B CN 105470357B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L33/12—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 stress relaxation structure, e.g. buffer layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L33/005—Processes
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L33/005—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L33/04—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
- H01—ELECTRIC ELEMENTS
- 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
- H01L33/26—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
Abstract
The invention discloses the semiconductor devices in a kind of AlN templates, the preparation method of AlN templates and AlN templates, belong to technical field of semiconductors.AlN templates include：Substrate and the AlN films deposited on substrate, the AlN films include the first AlN layers deposited on substrate, first in AlN layers mixed with oxygen, and from the first AlN layers with substrate interface to the first AlN layers surface direction, the content of the first oxygen in AlN layers gradually increases.Semiconductor devices includes：AlN templates and nitride semiconductor layer, the AlN templates include substrate and the AlN films deposited over the substrate, and the nitride semiconductor layer is deposited on the AlN films, and AlN templates are foregoing AlN templates.Method includes：Substrate is provided；Depositing Al N thin film on substrate；The AlN films include the first AlN layers deposited on substrate, the first in AlN layers mixed with oxygen, and from the first AlN layers with substrate interface to the first AlN layers surface direction, the content of the first oxygen in AlN layers gradually increases.
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly to a kind of AlN templates, the preparation method of AlN templates and AlN moulds
Semiconductor devices on plate.
Background technology
At present, most of GaN base blue light-emitting diode (English：Light emitting diode, abbreviation：LED) with
GaN base white light LEDs use Sapphire Substrate.Since sapphire and GaN material always exist lattice mismatch and thermal mismatch problem, and
Only have smaller lattice between AlN materials and GaN material, Sapphire Substrate to mismatch, therefore indigo plant is placed to using AlN as buffer layer
Between jewel substrate and GaN.Specifically, an AlN buffer layers are first grown on a sapphire substrate, AlN templates are made, then in AlN
GaN epitaxy is grown in template, LED epitaxial wafer is made.
In the implementation of the present invention, inventor has found that the prior art has at least the following problems：
The lattice constant of AlN buffer layers is less than GaN and sapphire, when growing GaN epitaxy in AlN templates, after causing
Continuous GaN epitaxy accumulates larger compression, and in the quantum well structure in growing GaN epitaxy, epitaxial wafer is in warped state, makes
Quantum well structure growth temperature it is uneven, epitaxial wafer wavelength uniformity is poor, so as to cause that can not carry out the outer of high yield
Prolong the volume production of piece.Fig. 1 shows the luminescence generated by light (English of the LED epitaxial wafer based on 4 inches of AlN templates：
Photoluminescence, abbreviation：PL) Wavelength distribution (English：Mapping) figure, from figure 1 it will be seen that epitaxial wafer edge (A
Point) wavelength is 458nm, epitaxial wafer center (B points) wavelength is 468nm, and the wavelength difference of center and peripheral is up to 10nm, the wavelength of full wafer
Standard variance reaches 4.18nm, and the epitaxial wafer requirement standard of wavelength variance of qualification is 2nm, therefore the epitaxial wafer is not up to qualified want
It asks.
The content of the invention
In order to solve, when growing GaN epitaxy in existing AlN templates, to cause compression in GaN epitaxy excessive, epitaxial wafer
There is the problem of larger warpage, epitaxial wafer wavelength uniformity is poor, an embodiment of the present invention provides a kind of AlN templates, AlN moulds
Semiconductor devices in the preparation method of plate and AlN templates.The technical solution is as follows：
In a first aspect, provide a kind of AlN templates, the AlN films that deposit including substrate and over the substrate,
The AlN films include the first AlN layers deposited over the substrate, the described first in AlN layers mixed with oxygen, and from
Described first AlN layers with the substrate interface to the described first AlN layers surface direction, the described first oxygen in AlN layers
Content gradually increases.
In the first embodiment of first aspect, the described first AlN layers be laminated by several AlN sublayers, and from institute
State the first AlN layers with the substrate interface to the described first AlN layers surface direction, oxygen in several AlN sublayers
Content successively increases；Oxygen in the single AlN sublayers is equally distributed, alternatively, the oxygen in the single AlN sublayers
It is uneven distribution.
In the second embodiment of first aspect, the quantity of the AlN sublayers is 1~50, the thickness of the AlN sublayers
For 1~10nm.
In the 3rd embodiment of first aspect, the thickness of the AlN films is 1nm~1000nm；It is thin in the AlN
In film, the molar ratio of oxygen atom and nitrogen-atoms is not more than 50%.
In the 4th embodiment of first aspect, the AlN films also include deposited on the first AlN layers the
Two AlN layers, the described 2nd in AlN layers mixed with oxygen, the described 2nd oxygen in AlN layers is equally distributed；And from the first AlN
To the described 2nd AlN layers, the content of oxygen gradually increases layer；Described 2nd AlN layers thickness be more than 1nm.
In the 5th embodiment of first aspect, the described 2nd AlN layers thickness be 3nm~5nm.
Second aspect provides the semiconductor devices in a kind of AlN templates, including AlN templates and nitride semiconductor layer,
The AlN templates include substrate and the AlN films deposited over the substrate, and the nitride semiconductor layer is deposited on described
On AlN films, the AlN templates are foregoing AlN templates.
The third aspect provides a kind of preparation method of AlN templates, the described method includes：
Substrate is provided；
Depositing Al N thin film over the substrate；The AlN films include the first AlN layers deposited over the substrate, institute
The first is stated in AlN layers mixed with oxygen, and from the described first AlN layers with the substrate interface to the described first AlN layers surface side
To the content of the described first oxygen in AlN layers gradually increases.
In the first embodiment of the third aspect, depositing Al N thin film over the substrate, including：
The substrate is arranged in vacuum environment, and the substrate is toasted；Baking time is 1~15 minute,
Baking temperature is 300~900 degrees Celsius, and baking pressure is less than 10-7Torr；
After completing baking, Ar, N are being mixed with2And O2Atmosphere or be mixed with Ar, N2With the gas of oxygen-containing gas
Under atmosphere, Al targets are sputtered, to deposit the AlN films over the substrate；Meanwhile in deposition process, gradually
Increase the O2Or the flow of the oxygen-containing gas；Depositing temperature is 400~800 degrees Celsius, deposition pressure be 1~
10mTorr, sputtering power are 1KW~10KW, a length of 10 seconds~1000 seconds during sputtering.
In the second embodiment of the third aspect, the method further includes：
As the O being passed through2Or the flow of oxygen-containing gas is when reaching target flow, the O that current time is kept to be passed through2It is or oxygenous
The flow of body is constant, until deposition terminates.
The advantageous effect that technical solution provided in an embodiment of the present invention is brought is：
By mixing O atom in AlN layers the first, a part of O atom can substitute N atoms in AlN, another part O atom
Interstitial atom can be formed.Since O atom radius ratio N atoms are big, this part displacement O atom and calking O atom can all make AlN brilliant
Lattice generate certain distortion, increase the lattice constant of AlN films, this will make AlN films and the lattice of follow-up GaN epitaxial film normal
Number is closer, so as to be conducive to reduce the compression in GaN material, the warpage of epitaxial wafer, Jin Ergai when improving grown quantum trap
The kind wavelength uniformity based on AlN template upper epitaxial layers.Experiments have shown that the O of incorporation is more, wavelength uniformity is better, still,
Excessive O is mixed in AlN films can be so that the crystal quality of AlN films in itself declines, and then it is thin to influence follow-up GaN epitaxy
The crystal quality of film, it is impossible to embody the good advantage of AlN template crystal quality.And by from the first AlN layers with substrate interface to the
The direction on one AlN layers of surface, the content of the first oxygen in AlN layers gradually increases, in this way, first being mixed in AlN films less
Oxygen, then gradually increase the content of incorporation oxygen, before it is less mix oxygen amount AlN films can be made to possess preferable crystal quality, from
And embody the advantage that GaN epitaxial film crystal quality is good in AlN templates；More oxygen amount of mixing will make the lattice of AlN films below
Constant is more nearly with follow-up GaN epitaxial film, reduces the compression in follow-up GaN epitaxial film, so as to improve LED epitaxial wafer
Wavelength uniformity.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only some embodiments of the present invention, for
For those of ordinary skill in the art, without creative efforts, other are can also be obtained according to these attached drawings
Attached drawing.
Fig. 1 is the PL wavelength mapping of the LED epitaxial wafer provided by the invention prepared based on existing 4 inches of AlN templates
Figure；
Fig. 2 is a kind of structure diagram for AlN templates that first embodiment of the invention provides；
Fig. 3 is a kind of structure diagram for AlN templates that second embodiment of the invention provides；
Fig. 4 is a kind of structure diagram for AlN templates that third embodiment of the invention provides；
Fig. 5 is a kind of flow chart of the preparation method for AlN templates that fourth embodiment of the invention provides；
Fig. 6 is the structure diagram of the semiconductor devices in a kind of AlN templates that fifth embodiment of the invention provides；
Fig. 7 is the PL wavelength mapping figures for 4 inches of LED epitaxial wafer that fifth embodiment of the invention provides.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
Fig. 2 shows a kind of AlN templates that first embodiment of the invention provides, as shown in Fig. 2, the AlN templates include lining
Bottom 10 and the AlN films deposited over the substrate 10.Wherein, which includes the first AlN layers 11 deposited over the substrate 10,
Mixed with oxygen (O) in first AlN layers 11.And from the first AlN layers 11 and 10 interface of substrate to the direction on the surface of the first AlN layers 11,
The content of oxygen in first AlN layers 11 gradually increases.
Wherein, substrate 10 includes but not limited to Si, SiC, sapphire, ZnO, GaAs, GaP, MgO, Cu and W substrate.
The O atom mixed in first AlN layers 11, a part can substitute N atoms in AlN, and another part can form calking original
Son.Since O atom radius ratio N atoms are big, this part displacement O atom and calking O atom all can generate AlN lattices certain
Distortion increases the lattice constant of AlN films, this will make the lattice constant of AlN films and follow-up GaN epitaxial film closer, from
And be conducive to reduce the compression in GaN material, the warpage of epitaxial wafer when improving grown quantum trap, and then improve based on AlN moulds
The wavelength uniformity of plate upper epitaxial layer.Experiments have shown that the O of incorporation is more, wavelength uniformity is better, still, is mixed in AlN films
Entering excessive O can be so that the crystal quality of AlN films in itself declines, and then influences the crystal matter of follow-up GaN epitaxial film
Amount, it is impossible to embody the good advantage of AlN template crystal quality.And by from the first AlN layers 11 and 10 interface of substrate to the first AlN layers
The direction on 11 surface, the content of the oxygen in the first AlN layers 11 gradually increase, in this way, first being mixed in AlN films less
Oxygen, then gradually increase the content of incorporation oxygen, before it is less mix oxygen amount AlN films can be made to possess preferable crystal quality, so as to
Embody the advantage that GaN epitaxial film crystal quality is good in AlN templates；It is more below that mix oxygen amount normal by the lattice for making AlN films
Number is more nearly with follow-up GaN epitaxial film, reduces the compression in follow-up GaN epitaxial film, so as to improve LED epitaxial wafer
Wavelength uniformity.
Also, in AlN films in a manner that doping oxygen gradually increases, the AlN template surface oxygen component highests of preparation,
The oxidation resistance that AlN templates are stored for a long time can be so improved, improves the stability and uniformity of AlN templates in volume production.
Specifically, physical vapour deposition (PVD) (English may be employed：Physical Vapor Deposition, abbreviation：PVD)
Technique or electron beam evaporation process depositing Al N thin film over the substrate 10.The oxygen mixed in AlN films can be derived from AlN films
Film forming procedure in the oxygen or oxygen-containing gas that mix.Oxygen-containing gas includes but not limited to hydrogen oxide (H2O), carbon monoxide
(CO), carbon dioxide (CO2), nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), nitrogen trioxide (N2O3)、
Dinitrogen tetroxide (N2O4) and dinitrogen pentoxide (N2O5)。
Wherein, from the first AlN layers 11 and the direction at 10 interface of substrate to the surface of the first AlN layers 11, the first AlN layers 11
The content of oxygen can increase in a continuously variable manner or increased in a manner of interval variation, can also be with
The mode that consecutive variations and interval variation two ways combine is increased.
During realization, in the film forming procedure of AlN films, can control incorporation oxygen or oxygen-containing gas flow at any time
It is incremented by, for example is incremented by linearly over time, in this way, the content of the oxygen in the first AlN layers 11 is to increase in a continuously variable manner.Class
As, the oxygen of incorporation or the flow of oxygen-containing gas in the film forming procedure of AlN films, can be increased at interval of certain time,
In this way, the content of the oxygen in the first AlN layers 11 is increased in a manner of interval variation.Similar, it can be in the film forming of AlN films
In the process, the oxygen or the flow of oxygen-containing gas that control mixes in a period of time are incremented by any time, control and mix in another a period of time
The oxygen or the flow of oxygen-containing gas entered increases at interval of certain time, in this way, the content of the oxygen in the first AlN layers 11 is to incite somebody to action
The mode that consecutive variations and interval variation two ways combine increases.
Wherein, the thickness of AlN films can be 1nm~1000nm.In AlN films, mole of oxygen atom and nitrogen-atoms
Than being not more than 50%.
Increase mode by control the content of the oxygen in AlN films and the content of oxygen, can be given birth to subsequent GaN epitaxy
Long technique is flexibly arranged in pairs or groups complementation, can all realize that preferable LED epitaxial wafer wavelength is uniform on different GaN epitaxy growth techniques
Property.
When realizing, which is suitable for growth GaN epitaxy, such as GaN base LED is made.
Fig. 3 shows a kind of AlN templates that second embodiment of the invention provides.In the present embodiment, will implement to first
The first AlN layers 11 in example are introduced.As shown in figure 3, the first AlN layers 11 are laminated by several AlN sublayers 31, and from
One AlN layers 11 and the direction at 10 interface of substrate to the surface of the first AlN layers 11, the content of the oxygen in several AlN sublayers 31 be by
What layer increased.
Wherein, from the first AlN layers 11 and 10 interface of substrate to the direction on the surface of the first AlN layers 11, single AlN sublayers 31
In oxygen content be it is constant, i.e., the oxygen in single AlN sublayers 31 be it is equally distributed, at this moment, the oxygen in the first AlN layers 11
Content be to be increased in a manner of interval variation.Alternatively, from the first AlN layers 11 and 10 interface of substrate to the table of the first AlN layers 11
The direction in face, the content of the oxygen in single AlN sublayers 31 is gradual change (such as incremental), i.e., the oxygen in single AlN sublayers 31 is
Uneven distribution, at this moment, the content of the oxygen in the first AlN layers 11 is to increase in a continuously variable manner.Alternatively, from first
AlN layers 11 and 10 interface of substrate to the surface of the first AlN layers 11 direction, in several AlN sublayers 31, a part of AlN sublayers 31
In the content of oxygen be constant, the content of the oxygen in another part AlN sublayers 31 is incremental, at this moment, in the first AlN layers 11
The content of oxygen be to be increased in a manner that consecutive variations and interval variation two ways are combined.
Wherein, the thickness of any two AlN sublayers 31 may be the same or different.
Optionally, the quantity of AlN sublayers 31 is that the thickness of 1~50, AlN sublayers 31 is 1~10nm.
Preferably, the quantity of AlN sublayers 31 is that the thickness of 5~10, AlN sublayers 31 is 2~5nm.
As preferred embodiment, the oxygen in single AlN sublayers 31 is equally distributed.When in single AlN sublayers 31
Oxygen be that will make every AlN sublayers 31 that there is certain thickness when being uniformly distributed, it is preferable in 1-10nm per layer thickness, preferably
For 2-5nm.It is certain thickness to mix oxygen AlN sublayers 31, AlN films will be made to have sufficient time and thickness to discharge what oxygen atom was brought
Stress, while realize preferable AlN crystalline films layer crystal weight.
Fig. 4 shows a kind of AlN templates that third embodiment of the invention provides.As shown in figure 4, the AlN templates include lining
Bottom 10 and the AlN films deposited over the substrate 10.Wherein, AlN films include 11 He of the first AlN layers stacked above one another on substrate
2nd AlN layers 12.
Wherein, the structure for the first AlN layers 11 that the structure of the first AlN layers 11 is described with first embodiment or second embodiment
Identical, details are not described herein.
Wherein, in the 2nd AlN layers 12 mixed with oxygen, the oxygen in the 2nd AlN layers 12 is equally distributed, and from the first AlN layers
11 to the 2nd AlN layers 12, the content of oxygen gradually increase.The thickness of 2nd AlN layers 12 is more than 1nm.
Preferably, the thickness of the 2nd AlN layers 12 is 3nm~5nm.
By the way that the surface layer of AlN films is arranged to the 2nd AlN layers 12 that thickness is more than 1nm, the oxygen in the 2nd AlN layers 12 is
It is equally distributed, this can cause AlN templates surface layer stress state keep to greatest extent stablize with it is consistent, it is ensured that different batches
The AlN template stress stabilities produced are controllable, and the steady of stress in follow-up GaN epitaxial layer is advantageously implemented in batch production
It is fixed, so as to realize that batch grows the stability contorting of medium wavelength uniformity to greatest extent.
Fig. 5 shows a kind of preparation method for AlN templates that fourth embodiment of the invention provides, suitable for first to the 3rd
The AlN templates that any embodiment provides in embodiment.As shown in figure 5, this method comprises the following steps.
Step 501 provides substrate.
The substrate can be Si, SiC, sapphire, ZnO, GaAs, GaP, MgO, Cu and W substrate.Preferably, which is
Sapphire Substrate.
Step 502, on substrate depositing Al N thin film.
Wherein, AlN films include the first AlN layers deposited on substrate, the first in AlN layers mixed with oxygen, and from the first AlN
Layer and substrate interface to the first AlN layers surface direction, the content of the first oxygen in AlN layers gradually increases.
Exemplified by using PVD process over the substrate 10 depositing Al N thin film, the deposition process of AlN films is introduced, this is heavy
Product process includes step 5021 and step 5022.
Substrate is arranged in vacuum environment, and substrate is toasted by step 5021；Baking time is 1~15 minute,
Baking temperature is 300~900 degrees Celsius, and baking pressure is less than 10-7Torr。
Specifically, first, substrate is positioned on the pallet of SiC materials, and pallet is put into PVD sputtering machine tables, and passed
It send to board deposition chambers.Secondly, after substrate is put into, deposition chambers are vacuumized, started while vacuumizing to lining
Bottom carries out heat temperature raising.Base vacuum is evacuated to less than 10-7During Torr, by heating temperature stabilization at 300~900 degrees Celsius, to lining
Bottom is toasted, and baking time is 1~15 minute.
Step 5022 after completing baking, is being mixed with Ar, N2And O2Atmosphere or be mixed with Ar, N2With it is oxygenous
Under the atmosphere of body, Al targets are sputtered, with depositing Al N thin film on substrate；Meanwhile in deposition process, gradually
Increase O2Or the flow of oxygen-containing gas；Depositing temperature be 400~800 degrees Celsius, deposition pressure be 1~10mTorr, sputtering power
For 1KW~10KW, a length of 10 seconds~1000 seconds during sputtering.
Wherein, during the sputtering a length of AlN films sedimentation time.Sputtering power and sputtering duration influence the thickness of AlN films
Degree, when sputtering power is 1KW~10KW, when a length of 10 seconds~1000 seconds during sputtering, the thickness of AlN films is 1~1000nm.
Specifically, after completing baking, Ar, N are passed through2And O2(O2It can be substituted by oxygen-containing gas).Wherein, Ar：N2Flow
Than that can be 1：3~1：10, the O that initial time is passed through2Flow can be Ar and N2The two flow sum 0.1%, 0.2% or
Person 0.5%.In deposition process, Ar, N2And O2PVD deposition chamber pressure maintains 1 by the total gas couette of three~
10mTorr is preferred.Meanwhile substrate heating temperature is set to depositing temperature, preferable deposition temperature range is taken the photograph for 400~800
Between family name's degree.After depositing temperature stablizes 10~60 seconds, shielding power supply is opened, Al targets are sputtered, will served as a contrast at this time
Deposition is mixed with the AlN crystalline membranes of oxygen on bottom.Wherein, sputtering power may be set to 1KW~10KW depending on the requirement of sedimentation rate, splash
It penetrates duration and regards the different set of AlN crystalline membrane thickness as 10 seconds~1000 seconds.Meanwhile in the deposition process of AlN crystalline membranes
In, gradually increase the O being passed through2Flow.The O being passed through2The mode that increases of flow can continuously increase, such as linear increment,
In this way, the content of the oxygen in the AlN films of deposition is consecutive variations.It can also be that interval is increased that this, which increases mode, such as rank
Ladder is incremented by, in this way, the AlN films of deposition are stepped construction, and the content of the oxygen in AlN films is interval variation.This increases
Mode, which can also be, continuous to be increased and interval is increased to combine and increased, for example first linear increment is increased stepwise again.
Assuming that direction of the content of the oxygen in the AlN films of deposition from substrate/AlN film interfaces to the surface of AlN films
It is increased stepwise, then, in depositing Al N thin film, 5~10 layers can be divided to grow AlN films, oxygen is uniformly distributed in every layer, 5~
The successively gradual change of the content of oxygen in 10 layers.By taking AlN films include 6 AlN sublayers as an example, in depositing Al N thin film, it can set
The sputtering power of Al targets is 3KW；1st AlN sublayer is to the 6th AlN sublayer, a length of 10 seconds during the deposition of each AlN sublayers,
The deposition thickness of so each AlN sublayers is about 4nm.Also, the O being passed through during 1 AlN sublayer of growth regulation2Flow is Ar, N2Stream
The 0.5% of sum is measured, the oxygen flow being passed through during the 2nd to 6 AlN sublayer thereafter is grown and is sequentially adjusted in as Ar and N2Flow sum
1%th, 3%, 5%, 10%, 15%.It is thick for 24nm overall thickness is thus prepared, point 6 layers of progress oxygen doping amount layering gradual change
AlN templates.
Assuming that the AlN films of deposition be in oxygen side of the content from substrate/AlN film interfaces to the surface of AlN films
To linear increment, then, in depositing Al N thin film, it can linearly increase the flow of the oxygen being passed through or oxygen-containing gas.For example,
In the deposition process of AlN crystalline membranes, the sputtering power of Al targets can be set as 2KW, a length of 100 seconds during sputtering, at this time
The thickness of AlN crystalline membranes is about 25nm.Meanwhile in this 100 seconds, by O2Flow is by Ar and N210% line of the two flow sum
Property is incremented to Ar and N2The 12% of the two flow sum.
Optionally, AlN films also include the 2nd AlN layers deposited on the first AlN layers, the 2nd in AlN layers mixed with oxygen, the
Oxygen in two AlN layers is equally distributed；And from the first AlN layers to the 2nd AlN layers, the content of oxygen gradually increases；2nd AlN layers
Thickness be more than 1nm.Then, which further includes step 5023.
Step 5023, as the O being passed through2Or the flow of oxygen-containing gas is when reaching target flow, the O that current time is kept to be passed through2
Or the flow of oxygen-containing gas is constant, until deposition terminates.
By this step 5023, the 2nd AlN layers can be deposited, the 2nd AlN layers of thickness is at least above 1nm.Optionally,
2nd AlN layers of thickness is 3 to 5nm.For example, it is assumed that entire deposition process maintains 300 seconds (sputtering duration)；Sputtering power is
4KW, the O that initial time is passed through2Flow is Ar, N2The 0.2% of flow sum.In first 285 seconds, the O that will be passed through2Flow is Ar, N2
12% linear increment of flow sum is to 10%, in latter 15 seconds, keeps O2Flow is Ar and N2The 10% of flow sum is constant, continues
Sputtering 15 seconds, will obtain surface layer is that about 3nm mixes oxygen amount and keeps the stable 2nd AlN layers of AlN templates.
2nd AlN layers by cause AlN templates surface layer stress state keep to greatest extent stablize with it is consistent, it is ensured that no
The AlN template stress stabilities produced with batch are controllable, and stress in follow-up GaN epitaxial layer is advantageously implemented in batch production
Stabilization, so as to greatest extent realize batch grow medium wavelength uniformity stability contorting.
After deposition, pallet is spread out of into deposition chambers, to get to required AlN templates after being cooled down to sample.
Fig. 6 shows the semiconductor devices in a kind of AlN templates that fifth embodiment of the invention provides, as shown in fig. 6, should
Semiconductor devices includes AlN templates 61 and nitride semiconductor layer 62.AlN templates 61 include substrate 611 and deposit on substrate
AlN films 612, nitride semiconductor layer 62 is deposited on AlN films 612.
Wherein, which can be the AlN templates that first embodiment, second embodiment or 3rd embodiment provide,
Details are not described herein.The preparation method of the AlN templates 61 may refer to fourth embodiment.
Wherein, which can include stacked above one another the single-layer or multi-layer n-type on AlN films 612
Nitride layer 621, single-layer or multi-layer nitride multiple quantum well active layer 622, single-layer or multi-layer p-type nitride layer 623 and nitrogen
Compound contact layer (not shown).Wherein, the quantum barrier layer in nitride multiple quantum well active layer 622 includes In；P-type nitride
Layer 623 includes one or more layers electronic barrier layer for including Al；Nitride contact layer includes n-type and p-type nitride contact layer, n
For forming n-electrode, n-type nitride contact layer is located on single-layer or multi-layer n-type nitride layer 621 type nitride contact layer；P-type
For forming p-electrode, p-type nitride contact layer is located in single-layer or multi-layer p-type nitride layer 623 nitride contact layer.
Optionally, which can be GaN base LED epitaxial layers.Preferably, GaN base LED epitaxial layers bag
Include the first high-temperature gan layer being sequentially laminated on AlN films, the second high-temperature gan layer, n-type GaN layer, multiple quantum well active layer, p
Type AlGaN electronic barrier layers, p-type GaN layer and p-type InGaN contact layers.
During realization, metallo-organic compound chemical gaseous phase deposition (English may be employed in GaN base LED epitaxial layers：Metal-
Organic Chemical Vapor Deposition, abbreviation：MOCVD) technique is grown.
Specifically, the growth temperature of the first high-temperature gan layer is 950~1050 degrees Celsius, preferable for 1000 degrees Celsius, raw
Long pressure is 50~600Torr, and the thickness of the first high-temperature gan layer is 0.5~3 micron.
The growth temperature of second high-temperature gan layer is 1020-1100 degrees Celsius, and preferable is 1060 degrees Celsius, growth pressure
For 50~600Torr, 0.2~3 micron of the thickness of the second high-temperature gan layer.Wherein, Si or light can not be mixed in the second high-temperature gan layer
Mix Si.When adulterating Si, Si doping concentrations are not more than 2 × 1018cm-3, preferable Si doping concentrations are 8 × 1017cm-3。
The growth temperature of n-type GaN layer is 1020-1100 degrees Celsius, preferable for 1060 degrees Celsius, growth pressure for 50~
600Torr, the thickness of n-type GaN layer is 0.5~3 micron, and n-type is realized by mixing Si, and Si doping concentrations are 2 × 1018~5 ×
1019cm-3, preferable Si doping concentrations are 1 × 1019cm-3。
In multiple quantum well active layer, Quantum Well is InGaN Quantum Well, and wherein In contents can control depending on the needs of different wave length
1~30%, as In contents control In in 3%, the blue-ray LED that wavelength is 450nm contains in purple LED that wavelength is 390nm
Amount control is 13%, and In contents are controlled 20% in the green light LED that wavelength is 520nm.The thickness of Quantum Well is 1~5nm, compared with
The thickness of good Quantum Well is 3nm.The material that quantum is built is AlGaN, and Al content is can be controlled in no more than 30%, the thickness that quantum is built
It spends for 3~50nm, the thickness that preferable quantum is built is 12nm.The quantity of Quantum Well pair is 1~20, is preferably 10 quantum
Trap pair.
The growth temperature of p-type AlGaN electronic barrier layers is 800~950 degrees Celsius, and Al content can be controlled in 10~30%, p
The thickness of type AlGaN electronic barrier layers is 10~50nm, and the thickness of preferable p-type AlGaN electronic barrier layers is 25nm.P-type is led to
Incorporation Mg realizations are crossed, the doping concentration of Mg is 1 × 1018~1 × 1020cm-3。
The growth temperature of p-type GaN layer is 800~950 degrees Celsius, and the thickness of p-type GaN layer is 20~500nm, preferable P
The thickness of type GaN layer is 70nm.P-type realizes that the doping concentration of Mg is 1 × 10 by mixing Mg18~1 × 1020cm-3。
In p-type InGaN contact layers, In contents are can be controlled in no more than 20%, the thickness of p-type InGaN contact layers for 0.5~
10nm.P-type realizes that p-type doping concentration is higher by mixing Mg, so that follow-up chip manufacture forms Ohmic contact, Mg doping
Concentration is 5 × 1019~1 × 1022cm-3。
During realization, can 4 inches or 6 inches of AlN templates be prepared by the method that fourth embodiment provides, then using upper
It states MOCVD techniques and GaN base LED epitaxial layers is grown on 4 inches or 6 inches of AlN templates, obtain 4 inches or 6 inches of LED extensions
Piece.Fig. 7 shows the PL wavelength mapping figures of 4 inches of LED epitaxial wafer, from figure 7 it can be seen that the center (E points) of the epitaxial wafer
Wavelength is close to 460nm, and edge (F points) wavelength of epitaxial wafer is close to 462nm, and center and peripheral wavelength difference is 2nm or so, full wafer
Standard of wavelength variance is 1.71nm, with the LED epitaxial wafer prepared based on existing AlN templates (standard of wavelength variance is 4.18nm)
It compares, standard of wavelength variance is reduced close to 2.5nm, and wavelength uniformity obtains the improvement of essence.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modifications, equivalent replacements and improvements are made should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of AlN templates, the AlN films that deposit including substrate and over the substrate, which is characterized in that
The AlN films include the first AlN layers deposited over the substrate, the described first in AlN layers mixed with oxygen, and from described
First AlN layers with the substrate interface to the described first AlN layers surface direction, the content of the described first oxygen in AlN layers
Gradually increase.
2. AlN templates according to claim 1, which is characterized in that the described first AlN layers by several AlN sublayers be stacked and
Into, and from the described first AlN layers with the substrate interface to the described first AlN layers surface direction, several AlN sublayers
In the content of oxygen successively increase；Oxygen in the single AlN sublayers is equally distributed, alternatively, single AlN
Oxygen in layer is uneven distribution.
3. AlN templates according to claim 2, which is characterized in that the quantity of the AlN sublayers is 1~50, the AlN
The thickness of sublayer is 1~10nm.
4. AlN templates according to claim 1, which is characterized in that the thickness of the AlN films is 1nm~1000nm.
5. AlN templates according to claim 1, which is characterized in that the AlN films are additionally included in the described first AlN layers
The 2nd AlN layers of upper deposition, the described 2nd in AlN layers mixed with oxygen, the described 2nd oxygen in AlN layers is equally distributed；And from
Described first AlN layers to the described 2nd AlN layers, the content of oxygen gradually increases；Described 2nd AlN layers thickness be more than 1nm.
6. AlN templates according to claim 5, which is characterized in that the described 2nd AlN layers thickness be 3nm~5nm.
7. the semiconductor devices in a kind of AlN templates, including AlN templates and nitride semiconductor layer, the AlN templates include lining
Bottom and the AlN films deposited over the substrate, the nitride semiconductor layer are deposited on the AlN films, and feature exists
In,
The AlN templates are AlN templates according to any one of claims 1 to 6.
8. a kind of preparation method of AlN templates, which is characterized in that the described method includes：
Substrate is provided；
Depositing Al N thin film over the substrate；The AlN films include the first AlN layers deposited over the substrate, and described the
Mixed with oxygen in one AlN layers, and from the described first AlN layers with the substrate interface to the described first AlN layers surface direction, institute
The content for stating the first oxygen in AlN layers gradually increases.
9. according to the method described in claim 8, it is characterized in that, depositing Al N thin film over the substrate, including：
The substrate is arranged in vacuum environment, and the substrate is toasted；Baking time is 1~15 minute, baking
Temperature is 300~900 degrees Celsius, and baking pressure is less than 10-7Torr；
After completing baking, Ar, N are being mixed with2And O2Atmosphere or be mixed with Ar, N2With the atmosphere of oxygen-containing gas
Under, Al targets are sputtered, to deposit the AlN films over the substrate；Meanwhile in deposition process, gradually increase
The O2Or the flow of the oxygen-containing gas；Depositing temperature is 400~800 degrees Celsius, and deposition pressure is in 1~10mTorr, is splashed
Power is penetrated as 1KW~10KW, a length of 10 seconds~1000 seconds during sputtering.
10. according to the method described in claim 9, it is characterized in that, the method further includes：
As the O being passed through2Or the flow of oxygen-containing gas is when reaching target flow, the O that current time is kept to be passed through2Or oxygen-containing gas
Flow is constant, until deposition terminates.
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| CN106025026B (en) * | 2016-07-15 | 2018-06-19 | 厦门乾照光电股份有限公司 | It is a kind of for AlN buffer layers of light emitting diode and preparation method thereof |
| DE102017119931A1 (en) * | 2017-08-30 | 2019-02-28 | Osram Opto Semiconductors Gmbh | Optoelectronic semiconductor component |
| CN109192827B (en) * | 2018-07-27 | 2020-12-22 | 华灿光电（浙江）有限公司 | Gallium nitride-based light emitting diode epitaxial wafer and growth method thereof |
| CN109638117B (en) * | 2018-11-29 | 2021-06-11 | 华灿光电（浙江）有限公司 | AlN template, epitaxial wafer structure and manufacturing method |
| CN109671819B (en) * | 2018-11-30 | 2020-05-19 | 华灿光电（浙江）有限公司 | GaN-based light emitting diode epitaxial wafer and preparation method thereof |
| CN109888070A (en) * | 2019-01-22 | 2019-06-14 | 华灿光电（浙江）有限公司 | AlN template, LED epitaxial slice and its manufacturing method |
| CN109888063B (en) * | 2019-01-23 | 2020-07-07 | 华灿光电（浙江）有限公司 | Preparation method of AlN template and gallium nitride-based light-emitting diode epitaxial wafer |
| CN112768614A (en) * | 2020-12-28 | 2021-05-07 | 华灿光电（浙江）有限公司 | Quantum dot light-emitting diode and preparation method thereof |
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