CN108242420A - A kind of GaN layer transfer monocrystal thin films preparation method based on silicon foreign substrate - Google Patents
A kind of GaN layer transfer monocrystal thin films preparation method based on silicon foreign substrate Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 169
- 239000010703 silicon Substances 0.000 title claims abstract description 169
- 239000000758 substrate Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000010409 thin film Substances 0.000 title claims abstract description 34
- 239000010408 film Substances 0.000 claims abstract description 104
- 230000012010 growth Effects 0.000 claims abstract description 98
- 239000013078 crystal Substances 0.000 claims abstract description 94
- 230000004888 barrier function Effects 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910002704 AlGaN Inorganic materials 0.000 claims description 4
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000009616 inductively coupled plasma Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910002601 GaN Inorganic materials 0.000 description 120
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 120
- 239000004065 semiconductor Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 238000003491 array Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 229910017107 AlOx Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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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
- H01L33/005—Processes
- H01L33/0093—Wafer bonding; Removal of the growth substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
- H01L2221/68386—Separation by peeling
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention provides a kind of GaN layer transfer monocrystal thin films preparation method based on silicon foreign substrate, and the preparation method includes at least：First, a silicon substrate is provided, the silicon substrate is etched and forms silicon column array；Secondly, the barrier layer of selective epitaxial growth can be realized in the silicon substrate and the formation of silicon column array surface；Then, the barrier layer of the silicon column array top is removed, seed crystal of the silicon column array top exposed as subsequent growth；Then in the seed crystal face selective epitaxial growth buffer layer；Then continuous GaN film layer is formed in the buffer-layer surface selective epitaxial growth；The transfer GaN film layer is finally peeled away, remaining silicon substrate and silicon column array are recycled for the step 4).The preparation of high quality, large area, inexpensive GaN single crystal film can be realized by the preparation method of the present invention, so as to promote the commercial Application of GaN electronic devices.
Description
Technical field
The present invention relates to technical field of semiconductor material preparation, more particularly to a kind of GaN layer based on silicon foreign substrate
Shift monocrystal thin films preparation method.
Background technology
With the development of society, the progress of science and technology, semi-conducting material plays extremely important in modern revolution of science and technology
Role.Be known as the gallium nitride (GaN) of third generation semi-conducting material representative, be after with semiconductor silicon (Si) and germanium (Ge) for representative
First generation semi-conducting material and with GaAs (GaAs) and indium phosphide (InP) for the second generation semi-conducting material of representative after,
Develop a kind of very rapid novel semiconductor material in the past 10 years.Compared with first and second generation semiconductor, third generation semiconductor material
Material have energy gap is wider, breakdown voltage bigger, thermal conductivity are more preferable, dielectric constant smaller, saturated electrons rate higher, it is corrosion-resistant,
Outstanding advantages of radioresistance, chemical stability and thermal stability are good.It is to make light emitting diode, laser diode, ultraviolet detection
The preferred material of device and high temperature, high frequency and high power device is known as being most important semi-conducting material after silicon, is 21 century
The economic developments pillars such as the new and high technologies such as power electronics, microelectronics, photoelectron and national defense industry, information industry and energy industry
Industry continues the key basic material depended on for existence and development.
High-melting-point and high dissociation pressure due to GaN, GaN bulk growths are extremely difficult, at present still can not be in industry
Middle acquisition GaN circular wafers, therefore the preparation of GaN semiconductor devices depends on heterogeneous wafer substrate epitaxial growing film at present
Method carry out.But usually cause heterogeneous there are bigger lattice mismatch and thermal mismatching between GaN material and foreign substrate
Often there is very high dislocation density, these dislocations strongly limit GaN base electronic device in the GaN film material that extension obtains
Performance and quality.
At present, commercialized GaN base device is substantially heteroepitaxial growth, and substrate used mainly has sapphire
(Al2O3), silicon carbide (SiC), silicon (Si) etc., the problem of the following aspects is primarily present using foreign substrate growth GaN：
(1) mismatch problems between the coefficient of thermal expansion between GaN material and substrate.If the heat of GaN epitaxy film and substrate is swollen
Swollen coefficient has big difference, and cracking is easily generated in thin film growth process, but also can reduce the reliability of GaN base device, special
It is other for high power device, because junction temperature is higher when device works, coefficient of thermal expansion difference is easy to that different zones is caused to dissipate greatly
Heat is uneven, causes the damage of device.
(2) lattice mismatch issue between GaN material and substrate.Larger lattice mismatch can be in extension between epitaxial layer and substrate
Larger residual stress is generated in layer, occurs a large amount of lattice defects in the film, causes film crystal of poor quality, and then influences device
Part performance.
(3) when hetero-epitaxy gives birth to GaN film, usually since the factors such as stress generate warpage, it is unfavorable for large area film
Preparation.
In addition, when preparing GaN base LED component, in order to enhance device light extraction efficiency, it is necessary to portion or external system in the chip
The scattering center of light is made, weakens total reflection of the light in interface, matte usually is carried out to chip surface, substrate.But GaN materials
Expect that chemical stability is very high, wet-method etching difficulty is big, and the cost of manufacture for leading to GaN base LED component is also higher.
Si substrates compared with sapphire, SiC substrate there is cheap, large size single crystal to be easy to get (6 inches, 8 English
Very little, 12 inch substrates have commercial offers) advantage, and the electrical and thermal conductivity of Si is good, and epitaxial growth is in the future on Si substrates
The important channel that realization GaN single crystal film is cheap, prepared by large area, and Si Grown GaN films are expected to realize
Photoelectron and microelectronics it is integrated.But the lattice mismatch of Si substrates and GaN be up to 20% and thermal mismatching be up to 34% (Si heat be swollen
Swollen coefficient：3.59×10-6/ DEG C, GaN coefficient of thermal expansion：5.45×10-6/℃；Si lattice constantsGaN lattice constants), the GaN film for growing high quality is extremely difficult, easily generates high dislocation density, film warpage, cracking etc. and asks
Topic.In addition, Ga metals have the problem of melt back corrosion to Si substrates, cause epitaxial growth control condition harsh.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of based on silicon foreign substrate
GaN layer shifts monocrystal thin films preparation method, and lattice mismatch in the existing foreign substrate technologies of GaN is solved using discrete heterogeneous seed crystal
With the technological difficulties of thermal mismatching, improving crystal quality and passing through the repeatable substrate technology utilized reduces cost.
In order to achieve the above objects and other related objects, the present invention provides a kind of GaN layer transfer based on silicon foreign substrate
Monocrystal thin films preparation method, the preparation method include at least：
1) silicon substrate is provided, the silicon substrate is etched and forms silicon column array；
2) barrier layer of selective epitaxial growth can be realized in the silicon substrate and the formation of silicon column array surface；
3) barrier layer of the silicon column array top is removed, the silicon column array top exposed is as subsequent growth
Seed crystal；
4) in the seed crystal face grown buffer layer；
5) it grows to form continuous GaN film layer in the buffer-layer surface；
6) stripping is shifted the GaN film layer, remaining silicon substrate and silicon column array and is recycled for the step 4).
Preferably, by controlling in the silicon column array diameter of silicon column and the silicon column array in the silicon substrate
Surface accounting rate realizes the use ratio of foreign substrate when controlling the GaN film layer epitaxially grown, reaches quasi- homo-substrate
Epitaxial growth effect
Preferably, for the ease of obtaining the distance between continuous GaN film, silicon column no more than 10 microns, otherwise from
Scattered seed crystal needs long-time lateral growth that can just be merged into continuous monocrystal thin films.
Preferably, in the step 1), in order to which silicon column is made to have machinery stripping of enough mechanical strengths convenient for follow-up GaN film
From transfer, 50% of diameter not less than silicon column length of silicon column end face is advisable.
Preferably, in the step 1), in order to realize that Seed crystal substrate heteroepitaxial growth reaches quasi- homo-substrate effect, silicon
Surface of silicon product ratio, which is no more than 5%, shared by column is advisable, to reduce actual ratio of the foreign substrate on epitaxial film.
Preferably, in the step 1), the process for forming silicon column array is：
1-1), mask is formed in the surface of silicon；
1-2), the mask is patterned using photoetching process；
1-3), using inductively coupled plasma dry etch process, in forming periodic silicon column on the silicon substrate
Array；
1-4), the mask is removed.
Preferably, it in the step 2), is formed using thermal oxidation technology in the silicon substrate and silicon column array surface
SiO2The alternatively barrier layer of property epitaxial growth.
Preferably, in the step 4), because of the metallorganic and SiO of aluminium2It easily reacts to be formed at high temperature and be not easy
Aluminum oxide (the AlO of gasificationX), in order to realize selective growth of the AlN and AlGaN buffer layers on seed crystal, using the halogen of aluminium
Compound is silicon source, epitaxial growth AlN or AlGaN buffer layer, and adds in HCl gases and improve growth selectivity.
Preferably, the thickness range of the buffer layer is 10~30nm.
Preferably, the step 5) growth forms continuous GaN film layer process and includes：
In early growth period, GaN pyramid-like shape crystal grain is formed on the buffer layer, wherein, each described seed crystal pair
The pyramid-like shape crystal grain should be formed；
With the progress of growth, the pyramid-like shape crystal grain is grown up along pyramid inclined-plane lateral growth, adjacent later
The pyramid-like shape grain mergin ultimately forms continuous GaN film layer.
Preferably, the front surface of the GaN film layer forms textured surfaces structure or flat surfaces, the GaN film layer
Rear surface formed textured surfaces structure.
Preferably, if forward and backward two surface of the GaN film layer is respectively formed textured surfaces structure, rear surface matte rises and falls
Degree is less than front surface matte waviness.
Preferably, the GaN film layer is shifted using the method stripping of vacuum suction machinery stripping in the step 6).
Preferably, in the step 6), after the silicon substrate and silicon column array reuse certain number, described
The barrier layer is thickened using atomic layer chemical vapor deposition growing method before the transfer of GaN film layer mechanical stripping, restores institute
State the repeatable usability of silicon substrate and silicon column array
As described above, the transfer monocrystal thin films preparation method of the GaN layer based on silicon foreign substrate of the present invention, has with following
Beneficial effect：
1st, the surface occupation rate when the diameter and silicon column array of control silicon column on female substrate, makes the seed crystal at the top of silicon column
In the space occupancy very hour of substrate plane, such as less than 5%, when seed crystal at the top of silicon column is only as GaN film growth
Initial nucleation site, because of the intrinsic behavior of the anisotropy of crystal growth, the seed crystal of early stages of development various discrete passes through different
Matter is epitaxially-formed polyhedron-shaped GaN micromeritics, and subsequent film growth is grown up using these micromeritics as crystal seed
Single continuous monocrystal thin films are merged into, because the partial dislocation that heteroepitaxial growth is formed can exist with GaN micromeritics on seed crystal
Anisotropic growth in each crystal plane direction grows up and disappears, i.e., subsequent film growth is homo-substrate growth behavior, this
For sample in entire GaN epitaxial film growth course, the actual use ratio of foreign substrate is very small, is equal to same using GaN standards
Matter substrate carries out GaN single crystal thin film epitaxial growth, can greatly improve the crystal quality of GaN epitaxial film in this way.
2nd, after GaN micromeritics being epitaxially-formed on silicon seed array, due to the anisotropic intrinsic spy of crystal growth
Property, this GaN micromeritics is with polyhedral surface form, and then subsequently epitaxial growing is using these polyhedrons as growth front table
Face makes grain growth grow up and merges into single monocrystalline continuous film, these polyhedral surfaces are not polar surfaces (0001), non-
Polar surfaces epitaxial growth is not in crystal polarity reversion farmland, has superior crystal property.
3rd, when the GaN micromeritics, which is grown up, merges into single monocrystal thin films, the gap between adjacent silicon column is retained
Come, i.e., only connected between GaN film and silicon substrate by silicon column, other places are gap, these gaps contribute to release GaN thin
Stress, warpage that can be to avoid GaN film layer, fragmentation caused by thermal mismatching between film layer and silicon substrate.Meanwhile because growth
The GaN film layer of acquisition is only connect with silicon substrate by silicon column, and silicon materials are big relative to GaN material brittleness, therefore GaN is thin
Film layer is removed from silicon substrate more easily by mechanical tension and is shifted.
4th, when the GaN micromeritics is grown up through anisotropic growth merges into continuous film, the front and rear surfaces of film are equal
The textured surfaces structure orderly for the period, can be by controlling the growth of film fast in subsequent film thickens growth course
Rate makes front surface continue to keep suede structure or become flat surfaces, and the rear surface of film cannot be filled because of reactant air source
It assigns to and reaches, matte pattern when still keeping the film just to be closed to be formed.
5th, after the GaN film stripping transfer obtained in growth, the SiO on silicon column and its periphery2Coating completely retains, silicon core
Only exposed at the top of silicon column, i.e. silicon seed array substrate completely remains, therefore remaining seed crystal array substrate can weigh
It is multiple to utilize, so as to reduce the manufacturing cost of GaN film.
6th, after the Seed crystal substrate reuses certain number, because of the corrasion of metal, SiO2Mask layer has one
Fixed is thinned, and can be thickened before the GaN film removes transfer using atomic layer chemical vapor deposition growing method (ALD)
SiO2Layer restores the reusing of seed crystal array.
Description of the drawings
Fig. 1~Fig. 4, which is that the present invention is based on the GaN layers of silicon foreign substrate, to shift what monocrystal thin films preparation method step 1) was presented
Structure diagram.
Fig. 5 is that the present invention is based on the structures that the GaN layer of silicon foreign substrate shifts the presentation of monocrystal thin films preparation method step 2)
Schematic diagram.
Fig. 6 is that the present invention is based on the structures that the GaN layer of silicon foreign substrate shifts the presentation of monocrystal thin films preparation method step 3)
Schematic diagram.
Fig. 7 is that the present invention is based on the structures that the GaN layer of silicon foreign substrate shifts the presentation of monocrystal thin films preparation method step 4)
Schematic diagram.
Fig. 8~Figure 12 is to shift monocrystal thin films preparation method step 5) the present invention is based on the GaN layer of silicon foreign substrate to present
Structure diagram.
Figure 13 is that the present invention is based on the structures that the GaN layer of silicon foreign substrate shifts the presentation of monocrystal thin films preparation method step 6)
Schematic diagram.
Component label instructions
101 silicon substrates
102 periodical columnar arrays masks
103 silicon column arrays
104 barrier layers
105 seed crystals
106 buffer layers
107 GaN pyramid-like shape crystal grain
108 GaN film layers
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Please refer to attached drawing.It should be noted that the diagram provided in the present embodiment only illustrates the present invention in a schematic way
Basic conception, component count, shape when only display is with related component in the present invention rather than according to actual implementation in schema then
Shape and size are drawn, and kenel, quantity and the ratio of each component can be a kind of random change during actual implementation, and its component cloth
Office's kenel may also be increasingly complex.
The present invention provides a kind of GaN layer transfer monocrystal thin films preparation method based on silicon foreign substrate, the preparation method
Including at least following steps：
Step 1 is first carried out, as shown in Figure 1 to 4, provides a silicon substrate 101, etches the silicon substrate 101 and forms silicon
Column array 103.
As an example, as shown in Figure 1, the silicon substrate 101 selects monocrystalline silicon (111) crystal face substrate.
In the step, the process for forming silicon column array 103 is：
1-1) mask is formed in 101 surface of silicon substrate；
1-2), as shown in figures 2 a and 2b, the mask is patterned using uv-exposure photoetching process, forms periodical column
Array mask 102；Wherein, Fig. 2 a are vertical view, and Fig. 2 b are side view.
1-3), it as shown in figure 3, using inductively coupled plasma dry etch process, is formed on the silicon substrate 101
Periodic silicon column array 103；
1-4), as shown in figure 4, the removal periodical columnar arrays mask 102.For example, institute is removed using acetone solution
State mask 102.
As an example, for the ease of obtaining continuous GaN film layer, between the silicon column of the silicon column array 103, distance is not
Preferably more than 10 μm, otherwise follow-up discrete seed crystal needs long-time lateral growth that can just be merged into continuous GaN single crystal film.
As an example, the silicon column end face diameter of the silicon column array 103 is not less than the 50% of 103 length of silicon column array
It is advisable, to ensure that the silicon column there are enough mechanical strengths, convenient for the mechanical stripping transfer of the follow-up GaN film layer and lining
Bottom is cleaned.
As an example, the surface area that the surface area of the silicon column array 103 accounts for the silicon substrate is advisable no more than 5%, with
Realize that Seed crystal substrate heteroepitaxial growth reaches quasi- homo-substrate effect.
In the present embodiment, 2 μm of the diameter selected as of the silicon column, 4 μm of height, the spacing between silicon column is 10 μm.
Secondly step 2 is performed, as shown in figure 5, forming barrier layer in the silicon substrate 101 and 103 surface of silicon column array
104。
As an example, SiO is formed in the silicon substrate 101 and 103 surface of silicon column array using thermal oxidation technology2As
The follow-up barrier layer 104 for realizing GaN selective epitaxial growths.
For example, can SiO be formed by dry oxygen thermal oxide2Barrier layer 104, thickness control is in 300nm.Subsequent growth GaN
Film layer, no matter using the metallorganic (such as common trimethyl gallium) of gallium or halide (such as the GaCl of gallium3) be
Gallium source can use SiO2For mask blocks layer 104, regioselectivity epitaxial growth is realized.
Then step 3 is performed, as shown in fig. 6, removing the barrier layer 104 at 103 top of silicon column array, is exposed
Seed crystal 105 of 103 top of silicon column array as subsequent growth.
As an example, barrier layer (the SiO using 103 top of selective etch technique removal silicon column array2) 104, exposure
The silicon core at 103 top of silicon column array, the seed crystal 105 that exposed silicon core is grown as subsequent selective epitaxial form seed crystal
Array.
Then step 4 is performed, as shown in fig. 7, in the 105 surface grown buffer layer 106 of seed crystal.
As an example, in seed crystal 105 surface selective vapor the epitaxial growth AlN or AlGaN as buffer layer
106.In the present embodiment, in order to avoid aluminum metal organic matter and SiO2Barrier reaction generation be not easy gasification volatilization AlOx so as to
It hinders to realize selective epitaxial growth, using halide (such as the AlCl of aluminium3) it is silicon source, and add in HCl gases and improve growth
Selectivity.Specifically, with AlCl3For silicon source, with H2For carrier gas (and mixing 1% HCl gases) or with H2Airborne 5% or so
HCl gases AlCl is obtained by aluminum melt3Reactant air source, and with excessive NH3React growing AIN buffer layer 106, AlN bufferings
The thickness control of layer 106 is in 10~30nm.
It should be noted that during grown buffer layer 106, strong corrasion during due to HCl gas high temperature can be used for pressing down
Forming core processed promotes to realize thin membrane regions property growth selection.The AlN thin film buffer layers 106 formed in the present embodiment lose with GaN lattices
With smaller, on the one hand as the growth of follow-up GaN film layer when, prevent the buffer layer of lattice mismatch, on the other hand can prevent
Subsequent metal Ga melt backs etch the seed crystal 105 of silicon column array top.
Then step 5 is performed, as shown in Fig. 8~Figure 12, grows to form continuous GaN on 106 surface of buffer layer
Film layer 108.
As an example, using the method for metal-organic chemical vapor deposition equipment (MOCVD) on 106 surface of buffer layer
Growth forms continuous GaN film layer 108.
In the present embodiment, with trimethyl gallium (Ga (CH3)3) and NH3For air source, reaction growth GaN single crystal is thin at 1100 DEG C
Film layer 108.
In the step, growth forms continuous GaN film layer 108 and includes procedure below：
In early growth period, attached drawing 8 is please referred to, discrete seed crystal carries out independent growths, because of the anisotropy row of crystal growth
For, Polyhedral centrum only is formed in air-flow front end, so as to form pyramid-like shape crystal grain 107, wherein, each seed crystal 105 is right
A pyramid-like shape crystal grain 107 (forming GaN micromeritics array) should be formed；
Then, attached drawing 9 is please referred to, with the progress of growth, crystal grain 107 continues to grow up, in the side for carrying airflow direction,
Also there is polyhedron crystal face in crystal grain 107；
10~Figure 11 of attached drawing is please referred to, as crystal grain 107 continues to grow up, crystal grain 107 is long along pyramid inclined-plane lateral growth
Greatly, neighboring die 107 merges, and ultimately forms continuous GaN single crystal film layer 108；
Attached drawing 12 is please referred to, it, can by controlling the growth rate of film as the growth of GaN single crystal film layer 108 thickens
The front surface of continuous single crystal film (one side far from silicon substrate) to be controlled to keep the textured surfaces structure or shape of pyramid-like shape
Into flat surfaces, and on the other hand, in rear surface (close to the one side of silicon substrate), because of the anisotropic properties of crystal growth,
There are textured surfaces structure, but due to the crystal grain shadow effect of itself, in the gap between neighboring die 107, gas
Source cannot fully be arrived at, and reactant degree of supersaturation is low, and with growing up for crystal grain 107, shadow effect gradually enhances, neighboring die
Reactant degree of supersaturation is lower and lower in gap between 107, grows on the crystal face of the back of the body airflow direction of crystal grain 107 and gradually slows down,
Therefore when crystal grain 107 grows up closure for single continuous GaN film layer 108, the matte waviness of film rear surface is less than film
Front surface matte waviness, the position that film is connected with silicon column are the high point of rear surface matte.
The two-sided or single side of the GaN single crystal film layer 108 forms spontaneous suede structure, which forms follow-up LED
The window texture of device reduces the manufacturing process steps of GaN device, obtains excellent performance.
In the present embodiment, the two sides of the GaN single crystal film layer 108 is respectively formed textured surfaces structure, and the GaN single crystal
The matte waviness of 108 rear surface of film layer is less than front surface matte waviness.
It should also be noted that, since the ratio of silicon chip substrate area entire shared by control silicon seed array is less than 5%, silicon
Seed crystal is intended only as the initial nucleation site of GaN film growth, because of the intrinsic behavior of the anisotropy of crystal growth, early growth period rank
The seed crystal of section various discrete forms polyhedron-shaped GaN micromeritics by heteroepitaxial growth, and subsequent film growth is with this
Crystal grain, which for crystal seed grow up, slightly merges into single continuous monocrystal thin films, because of the part of heteroepitaxial growth formation on seed crystal
Dislocation can grow up with anisotropic growth of the GaN micromeritics in each crystal plane direction and be disappeared, i.e., subsequent film growth
Homo-substrate growth behavior, in this way in entire GaN epitaxial film growth course, the actual use amount of foreign substrate also less than
5% so that the effect of foreign substrate epitaxial growth of the present invention, which is equal to, to be carried out using the quasi- homo-substrates of GaN outside GaN single crystal film
The dislocation density in epitaxial film can be greatly reduced in epitaxial growth, improve the crystal quality of GaN epitaxial film.
After GaN micromeritics is epitaxially-formed on silicon seed array, due to the anisotropic intrinsic characteristic of crystal growth,
This GaN micromeritics has polyhedral surface form, and then subsequently epitaxial growing makes using these polyhedrons as growth leading surface
Grain growth, which is grown up, merges into single monocrystalline continuous film, these polyhedral surfaces are not polar surfaces (0001)；It is and traditional
GaN epitaxial film growth, either with Si (111), Al2O3(0001) or SiC (0001) chip is substrate, before growth
All it is polarity (0001) crystal face along face, is susceptible to polarity reversion farmland in the film, influences subsequent device performance, need good
Good growing surface polarity control means.Therefore, the present invention is apolar surfaces epitaxial growth, is not in crystal polarity reversion
Farmland has superior crystal property.In addition, using initial GaN micromeritics polyhedron (pyramid-like shape crystal grain 107) surface as
Growth front surface, the thickness direction of film and film growth front surface normal direction are inconsistent, can substantially eliminate because of crystalline substance
The dislocation that lattice mismatch and thermal mismatching are formed, make most dislocations all locals with silicon column connection near, so as to substantially carry
The GaN film crystal quality that high extension obtains.
In addition, when 107 array of GaN crystal grain grows up and merges into single monocrystal thin films 108, the sky between adjacent silicon column
Gap is retained, i.e., is only connected between GaN film layer 108 and silicon substrate 101 by silicon column, and other places are gap, these
Gap helps to eliminate between GaN film layer 108 and silicon substrate 101 stress caused by thermal mismatching, can be to avoid GaN film
108 layers of warpage and fragmentation.
Finally perform step 6, as shown in figure 13, the GaN film layer 108 is shifted in stripping, remaining silicon substrate 101 and
Silicon column array 103 is recycled for the step 4).
As an example, the method stripping transfer GaN film layer 108 using the stripping of vacuum suction machinery.
Only connected between GaN film layer 108 and silicon substrate 101 by silicon column since growth obtains, and silicon materials relative to
GaN material brittleness is big, and therefore, GaN film layer 108 is easily removed from silicon substrate 101 by mechanical tension and shifted, and can pass through control
The applying mode of mechanical tension makes fracture position be in the junction of silicon column and GaN film layer 108.
After the GaN film layer 108 is shifted in stripping, the SiO on silicon column array 103 and its periphery2Barrier layer 104 is completely protected
Stay, silicon core it is exposed also only at the top of silicon column, i.e., silicon seed array substrate can be remained completely, therefore remaining seed crystal battle array
Row substrate can be reused directly, so as to reduce the manufacturing cost of GaN film layer 108.It if it is desired, can be to remaining seed
Brilliant array substrate carries out lye etching removal mechanical damage, then reuses.When Seed crystal substrate reuses certain number
Afterwards, because of the corrasion of metal, SiO2Barrier layer have it is certain be thinned, can be before the transfer of GaN film layer mechanical stripping
SiO is thickened using atomic layer chemical vapor deposition growing method (ALD)2Barrier layer enhances the repeatable usability of seed crystal array.
In conclusion the present invention provides a kind of GaN layer transfer monocrystal thin films preparation method based on silicon foreign substrate, it is described
Preparation method includes at least：First, a silicon substrate is provided, the silicon substrate is etched and forms silicon column array；Secondly, it is served as a contrast in the silicon
Bottom and the formation of silicon column array surface can realize the barrier layer of selective epitaxial growth；Then, the silicon column array top is removed
The barrier layer in portion, seed crystal of the silicon column array top exposed as subsequent growth；Then it is grown in the seed crystal face
Buffer layer；Then it grows to form continuous GaN film layer in the buffer-layer surface；The transfer GaN film layer is finally peeled away,
Remaining silicon substrate and silicon column array are recycled for the step 4).It can be realized by the preparation method of the present invention high-quality
The preparation of amount, large area, inexpensive GaN single crystal film, so as to promote the commercial Application of GaN electronic devices.
So the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of GaN layer transfer monocrystal thin films preparation method based on silicon foreign substrate, which is characterized in that the preparation method is extremely
Include less：
1) silicon substrate is provided, the silicon substrate is etched and forms silicon column array；
2) barrier layer of selective epitaxial growth can be realized in the silicon substrate and the formation of silicon column array surface；
3) barrier layer of the silicon column array top, seed of the silicon column array top exposed as subsequent growth are removed
It is brilliant；
4) in the seed crystal face selective epitaxial growth buffer layer；
5) continuous GaN film layer is formed in the buffer-layer surface selective epitaxial growth；
6) stripping is shifted the GaN film layer, remaining silicon substrate and silicon column array and is recycled for the step 4).
2. the GaN layer transfer method for manufacturing thin film according to claim 1 based on silicon foreign substrate, which is characterized in that logical
The surface accounting rate for controlling the diameter of silicon column in the silicon column array and the silicon column array in the silicon substrate is crossed, realizes control
The use ratio of foreign substrate when making the GaN film layer epitaxially grown, reaches quasi- homo-substrate epitaxial growth effect.
3. the GaN layer transfer monocrystal thin films preparation method according to claim 1 based on silicon foreign substrate, feature exist
In：In the step 1), the process for forming silicon column array is：
1-1), mask is formed in the surface of silicon；
1-2), the mask is patterned using photoetching process；
1-3), using inductively coupled plasma dry etch process, in forming periodic silicon column array on the silicon substrate；
1-4), the mask is removed.
4. the GaN layer transfer monocrystal thin films preparation method according to claim 1 based on silicon foreign substrate, feature exist
In：In the step 2), SiO is formed in the silicon substrate and silicon column array surface using thermal oxidation technology2Alternatively property
The barrier layer of epitaxial growth.
5. the GaN layer transfer monocrystal thin films preparation method according to claim 1 based on silicon foreign substrate, feature exist
In：In the step 4), using the halide of aluminium as silicon source, and HCl gases, epitaxial growth AlN are added in reaction atmosphere
Or AlGaN is as buffer layer.
6. the GaN layer transfer monocrystal thin films preparation method based on silicon foreign substrate according to claim 1 or 5, feature
It is：The thickness range of the buffer layer is 10~30nm.
7. the GaN layer transfer monocrystal thin films preparation method according to claim 1 based on silicon foreign substrate, feature exist
In：Step 5) the growth forms continuous GaN film layer process and includes：
In early growth period, GaN pyramid-like shape crystal grain is formed on the buffer layer, wherein, each described seed crystal corresponds to shape
Into the pyramid-like shape crystal grain；
With the progress of growth, the pyramid-like shape crystal grain is grown up along pyramid inclined-plane lateral growth, and adjacent later is described
Pyramid-like shape grain mergin ultimately forms continuous GaN film layer.
8. the transfer monocrystal thin films preparation method of the GaN layer based on silicon foreign substrate according to claim 1 or 7, feature
It is：The front surface of the GaN film layer forms textured surfaces structure or flat surfaces, the GaN film according to growth rate
The rear surface of layer forms textured surfaces structure.
9. the GaN layer transfer monocrystal thin films preparation method according to claim 1 based on silicon foreign substrate, feature exist
In：The GaN film layer is only connect with the silicon substrate by silicon column, and silicon materials are big relative to GaN material brittleness, described
The GaN film is shifted using the stripping of vacuum suction machinery in step 6).
10. the GaN layer transfer monocrystal thin films preparation method according to claim 9 based on silicon foreign substrate, feature exist
In：In the step 6), after the silicon substrate and silicon column array reuse certain number, in GaN film layer machinery
The barrier layer is thickened using atomic layer chemical vapor deposition growing method before stripping transfer, restores the silicon substrate and silicon column
The repeatable usability of array.
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| CN110783168A (en) * | 2018-07-25 | 2020-02-11 | 乂馆信息科技(上海)有限公司 | Preparation method of HEMT device with three-dimensional structure |
| CN110783170A (en) * | 2018-07-25 | 2020-02-11 | 乂馆信息科技(上海)有限公司 | Method for stripping semiconductor film and transferring substrate |
| WO2021012826A1 (en) * | 2018-07-25 | 2021-01-28 | 乂馆信息科技(上海)有限公司 | Method for stripping semiconductor thin film and transferring same to substrate |
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| CN110783168B (en) * | 2018-07-25 | 2022-07-01 | 乂馆信息科技(上海)有限公司 | Preparation method of HEMT device with three-dimensional structure |
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