CN1619843A - Method of growing trigroup nitride semiconductor hetero crystal structure on silicon base material - Google Patents
Method of growing trigroup nitride semiconductor hetero crystal structure on silicon base material Download PDFInfo
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Abstract
A method for forming three-group nitride semiconductor hetero epitaxy structure contains using a (111) crystal orientation surface monocrystalline silicon substrate with formed double-layer buffer structure having monocrystalline silicon layer which is formed by introducing active nitrogen electric slurry and thermal nitridation, then another buffer layer of monocrystalline aluminium nitride layer or other three-group nitride layer is grown on monocrystalline nitride layer in epitaxy mode, then gallium nitride layer or three-group nitride semiconductor hetero epitaxy structure is grown on monocrystalline nitride layer in the same mode.
Description
Technical field
The present invention is relevant for a kind of semiconductor structure, more particularly a kind of on silicon base material the method for growth group iii nitride semiconductor hetero crystal structure.
Background technology
Semiconductor light-emitting-diode (LED; Light-emitting diode) structure comprises a ground, a luminous hetero crystal structure and pair of electrodes at least in order to order about led lighting.Its ground can be transparent or opaque.In the application of short wavelength's semiconductor light-emitting-diode, its main ray structure is with gallium nitride (GaN; Gallium nitride) compound is its material, and its ground can be transparent and a ground such as a sapphire ground for insulating., be before the lumination of light emitting diode hetero crystal structure forms generally in the method that solves Macrolattice mismatch (lattice mismatch) between epitaxial of heap of stone and the insulation ground, on the sapphire ground, grow up a resilient coating or nucleating layer.In the middle of these methods, resilient coating is used for controlling the formation of epitaxial nucleation of heap of stone and in order to reduce the generation of epitaxial defective of heap of stone.
Group iii nitride semiconductor layer (as the alloy of gallium nitride, indium nitride, aluminium nitride and these nitride) has become the selection of main materials used on many photovoltaic applications, particularly have the panchromatic smooth territory or the light-emitting diode of white light source and blue laser diode (LDs; Laser diode).Some nearest research reports pointed out once that except the material that is used as photovoltaic applications, III-nitride will become widely used semi-conducting material.At present, using more widely for III-nitride is to be used as luminescent layer, but has for the shortcoming that is short of the lattice match ground based on the luminescent layer of nitride in the brilliant mistake that forms of heap of stone becomes.Aluminium oxide (Al
2O
3Sapphire) and carborundum (SiC; Silicon carbide) is two main normal growth ground materials that use.Yet except having very big lattice degree of not matching, the insulation characterisitic of sapphire can make the processing procedure of element of nitride, and comparatively difficulty and cost are higher.In others, high price and the silicon carbide whisker fenestra with finite size size make based on the application of the ground of carborundum comparatively difficult.Under the contrast, it is the microelectric technique of main material and every new function that can be provided by group iii nitride semiconductor with silicon at present that the gallium nitride (GaN-on-Si) of growth on silicon base material crystal technique of heap of stone can be integrated.
For the heterogeneous building crystal to grow technology of gallium nitride on silicon base material, point out that in the literature aluminum nitride buffer layer can provide excellent result, but make that the gallium nitride growth light-emitting diode also has experimental results show that of high brightness luminescent on silicon base material.Yet aluminium and silicon material meltability each other under the growth temperature conditions of aluminum nitride buffer layer (577 ℃ of the temperature of eutectic point of silicon, aluminium, growth temperature are about 820 ℃) are very high.Therefore, nitrogenize aluminium and the silicon material inside interdiffusion phenomenon between interface is very serious, so make epitaxial layer and silicon base material cause non-painstakingly high-dopant concentration and cause the quality of epitaxial layer to reduce.
Summary of the invention
Main purpose of the present invention is to provide the pair of lamina buffer structure to be positioned on the silicon base material, to solve at the inside phase issue of inter-diffusion that caused of aluminium nitride/silicon between interface.
Another object of the present invention is to provide the aluminium nitride/silicon nitride double-layer bumper structure that can form coincidence lattice (coincident lattices) with specific proportions lattice match, reducing the problem that lattice does not match and caused, and can be in order to the high-quality brilliant film of heap of stone of growing up.
According to above-described purpose, the invention provides a kind of buffer structure solving the problem of automatic doping (autodoping), and the problem of the inside phase counterdiffusion that interface caused between aluminium nitride/silicon when monocrystalline aluminium nitride (0001) resilient coating forms.Its method comprises the monocrystalline silicon ground that employing one has (111) surface, crystal orientation, and the surface of its ground can produce surface reconstruction to remove in native oxide by hot deaeration step.Then, be feature of the present invention, the surface, (111) crystal orientation on silicon base material forms the pair of lamina buffer structure.Its double-layer bumper structure comprises a monocrystalline silicon nitride layer and is positioned at a monocrystalline aln layer or other III-nitride layer on the monocrystalline silicon nitride layer.Then, the gallium nitride epitaxial layer can be grown up on this double-layer bumper layer.The mechanism of the double-layer bumper structure that proposes of the present invention is formed with preferable advantage for the crystalline substance heterogeneous of heap of stone with Macrolattice mismatch.In addition, for the heterogeneous building crystal to grow of the gallium nitride on the silicon material, because the lattice that has coincidence lattice constant ratio coupling and be 1: 2 and 5: 2 can be respectively formed at the interface of monocrystalline silicon nitride (0001)/monocrystalline silicon (111) and monocrystalline aluminium nitride (0001)/monocrystalline silicon nitride (0001), therefore can be in order to form high-quality double-layer bumper structure.More because the monocrystalline silicon nitride can be used as the diffusion impedance layer, therefore, the phase issue of inter-diffusion of interface can solve by this double-layer bumper structure between aluminium nitride/silicon.
In addition, the invention provides a kind of method that forms the group iii nitride semiconductor hetero crystal structure on the silicon base material that is formed on, wherein comprise the mode of utilizing hot degasification and remove and remain in residual thin oxide layer on the surface silicon ground of (111) crystal orientation, and make silicon base material reconstruct.Then, be feature of the present invention, on clean silicon base material, form the pair of lamina buffer structure.Wherein the double-layer bumper structure comprises a monocrystalline silicon nitride layer, and this monocrystalline silicon nitride layer utilization imports active nitrogen pneumoelectric and starches on cleaning (111) surface, crystal orientation to silicon base material and be positioned on the silicon base material to form a monocrystalline silicon nitride monoatomic layer.Then, a monocrystalline aluminum nitride buffer layer or other III-nitride layer are that mode with building crystal to grow is formed on the monocrystalline silicon nitride layer.Then, utilize the mode of building crystal to grow that the III-nitride hetero crystal structure is formed on the aln layer top equally.
Description of drawings
Fig. 1 is disclosed technology according to the present invention, the flow chart of each step in the method for growth group iii nitride semiconductor hetero crystal structure on the silicon base material;
Fig. 2 A to Fig. 2 D is disclosed technology according to the present invention, the rough schematic of each step in the method for growth group iii nitride semiconductor hetero crystal structure on silicon base material;
Fig. 3 is disclosed technology according to the present invention, and expression utilizes secondary ion mass spectroscopy to make the schematic diagram of silicon/aluminium element analysis near gallium nitride film/buffering/ground interface area depth bounds for having the gallium nitride film that monocrystalline aluminium nitride/monocrystalline silicon nitride double-layer bumper structure (a) and monocrystalline aluminium nitride individual layer buffer structure (b) grown up;
Fig. 4 A is disclosed technology according to the present invention, be illustrated on the surface silicon ground of (111) crystal orientation and utilize monocrystalline aluminium nitride/monocrystalline silicon nitride double-layer bumper structure and the photic fluorescence spectra of low temperature of two kinds of method gallium nitride growths of monocrystalline aluminium nitride individual layer buffer structure epitaxial of heap of stone relatively;
Fig. 4 B is disclosed technology according to the present invention, and the gallium nitride that expression is grown up with monocrystalline aluminium nitride/monocrystalline silicon nitride double-layer bumper structure is built the free exciton (FX) of epitaxial and the neutrality of the gallium nitride epitaxial of heap of stone on monocrystalline aluminium nitride individual layer buffer structure of growing up is executed sub-bound exciton (D
0The Arrhenius figure of photic fluorescence spectra peak intensity X); And
Fig. 5 is disclosed technology according to the present invention, and expression utilizes the room temperature Raman spectrum schematic diagram of monocrystalline aluminium nitride/monocrystalline silicon nitride double-layer bumper structure and the two kind gallium nitride epitaxial layers of monocrystalline aluminium nitride individual layer buffer structure growth on the surface silicon ground of (111) crystal orientation.
Symbol description among the figure:
10 silicon base materials
12 monocrystalline silicon nitride layers
14 aluminium pre-deposition atomic layers
16 monocrystalline aluminum nitride buffer layers
20 have the gallium nitride layer of gallium atomic surface polarity
Embodiment
Some embodiments of the present invention can be described in detail as follows.Yet except the embodiment of this detailed description, the present invention can also be widely implements at other embodiment, and scope of the present invention do not limited, and is as the criterion with described claim.
According to the invention provides a kind of method and structure spread (inter-diffusion) alternately with improvement inside of interface between aluminium nitride/silicon and other III-nitride/silicon problem.
III-nitride (group-III nitride) often is applied in the application of photoelectricity, microelectronics and surface acoustic wave element recently at the hetero crystal structure on the silicon base material.Has good crystalline quality except having large-sized utilizability (size of monocrystalline silicon ground can to 12 English inch), low cost and silicon base material.Silicon also has simultaneously good material behavior, as doping characteristic (n/p bipolarity and high carrier concentration), riving property (cleavable), good heat conductivity (bigger three times than sapphire approximately) with and have ripe process technique.The advantage of these silicon base materials can be used to develop the range of application of many new III-nitride materials, and the element that can use gallium nitride and silicon is integrated.Its reason is because the high-quality growth of the heterogeneous crystalline substance of heap of stone of gallium nitride on silicon is feasible, and this is because hexagonal wurtzite (hexagonal wurtzite) (0001) crystal plane causes with the characteristic that cube diamond or zincblende (cubic diamond or zinc-blende) (111) surface, crystal orientation can form lattice mismatch.
This storehouse buffer structure is made of several layers of forming, and each is formed layer and has the characteristic that can form the coincidence lattice (coincidentlattice) of specific proportions coupling between the interface of layer/layer and layer ground.In an embodiment of the present invention, the growth for the heterogeneous crystalline substance of heap of stone of high-quality III-nitride on silicon base material is to utilize to be respectively formed at beta-silicon nitride (0001)/silicon (111) (β-Si
3N
4(0001)/Si (111)) and aluminium nitride (0001)/beta-silicon nitride (0001) (AlN (0001)/β-Si
3N
4(0001)) 1: 2 of interface and 5: 2 specific proportions lattice structures are to form the double-layer bumper structure.By using the technology of this buffer structure, can solve the problem of automatic doping in an embodiment of the present invention and the problem of the inside phase counterdiffusion that between aluminium nitride/silicon, caused.Shown in the experimental result of following examples, the of heap of stone brilliant quality of gallium nitride film also can be enhanced simultaneously.
Gallium nitride film on silicon base material nearly has the 20.4 percentages lattice mismatch of (in-plane) (≡ (a (silicon)-a (gallium nitride))/a (gallium nitride) in the plane; A (gallium nitride) (0001)=3.189A; A (silicon) (111)=3.840A) and big thermal expansion coefficients mismatch.Very fortunately, the resilient coating that has a specific proportions lattice structure condition by utilization can reduce the coupling of lattice.For example, (the specific proportions lattice structure between a (aluminium nitride) (0001)=3.112A) and the silicon (111) is that its effective lattice match can be reduced to-1.3 percentages by+23.4 percentages under 5: 4 the situation at aluminium nitride (0001).Therefore, can obtain the pattern of the level and smooth heterogeneous building crystal to grow of two dimension by the reduction of lattice deformation.
The growth processing procedure uses a part Shu Leijing (MBE in the disclosed embodiment of the present invention; Molecular-beam epitaxy) device, this device also is furnished with radio frequency (rf; Radio frequency) nitrogen electricity slurry source.Basic pressure at molecular beam epitaxy growth reative cell is 6*10
-11Bristol (Torr), and the molecular beam source (MBE effusioncell) of employing high purity gallium metal and aluminum metal.Nitrogen was purified by the nitrogen purification device before importing electric slurry source.In whole building crystal to grow process, adopt identical condition to produce nitrogen electricity slurry.The flow rate that the power of rf wave is approximately 450 watts and nitrogen is 0.5sccm.Before silicon base material loads the molecular beam reative cell, use the silicon base material on chemical method for etching etching three English inch (111) surfaces, crystal orientation earlier.(111) silicon base material on surface, crystal orientation further utilizes the hot scavenging of the existing field boundary native oxide residual to remove.Therefore, (111) crystal orientation surface silicon ground by treatment step before the above can demonstrate (7*7) surface reconstruction, and by the reflective high-energy electron diffraction (RHEED when the ground temperature is 800 ℃; Reflection high-energy electron diffraction) pattern can be confirmed the surface characteristic of its silicon base material.
In addition, reflection high-energy electron diffraction pattern can be used to point out the quality and the flatness on reconstruct silicon base material surface before the building crystal to grow processing procedure.It is that the phase transfer that 875 ℃ (7*7) translates into (1*1) reconstruct obtains in temperature that the correction of its ground temperature utilizes silicon (111) surface, crystal orientation.In the present embodiment, two different resilient coating systems in the gallium nitride building crystal to grow on silicon base material (111) surface, crystal orientation relatively.It is 30 aluminum nitride buffer layers of rice how that these two resilient coating systems all comprise a thickness.Its unique difference is to be that one of them resilient coating system comprises a monocrystalline beta-silicon nitride layer (β-Si
3N
4) (its thickness is approximately 1.5nm, utilizes transmission electron microscope (transmission electron microscopy) to confirm the result of gained).The monocrystalline silicon nitride layer can utilize the hot nitrogenation of (111) crystal orientation surface silicon surface of bottom material and utilize active nitrogen pneumoelectric slurry is 900 ℃ in the ground temperature, and the time is to form under 30 seconds the condition.And thickness be 30 how rice aluminum nitride buffer layer per hour 0.12 micron growth speed and the growth temperature by 820 ℃ condition under building crystal to grow formed.In addition, grow up on resilient coating thickness be 240 how the gallium nitride epitaxial layer of rice formed by 0.08 micron speed per hour with growth speed in lower ground temperature (being about 720 ℃).After molecular beam epitaxy is grown up, continue under the condition of circulation at nitrogen electricity slurry, (when being cooled to 500 to 600 ℃) can observe the surface reconstruction pattern of (2*2) on the gallium nitride growth surface, can point out that with this this gallium nitride surface characteristic is the gallium polarity (Ga polarity) that has than dominator.
On the surface silicon ground of (111) crystal orientation, form the flow chart of the method for double-layer bumper structure with reference to figure 1 expression the present invention.Step 1 expression (111) crystal orientation surface silicon ground utilizes the ultra high vacuum heat treatment mode to remove on the native oxide of silicon base material and the surface that produces the smooth and reconstruct of atom degree.(111) surface silicon ground in crystal orientation can produce the surface reconstruction of silicon base material (7*7) by above-mentioned preparation method, and the reconstructing surface that is produced can be confirmed its characteristic 800 ℃ of ground temperature by reflective high-energy electron diffraction pattern.Step 2 expression imports the surface of high temperature (900 ℃) silicon base material and the surfaces nitrided work by (111) crystal orientation surface silicon ground in order to form a monocrystalline silicon nitride layer with active nitrogen pneumoelectric slurry.The preparation process of step 3 expression one aluminium preliminary sedimentation lamination according to the flow of aluminium molecular beams and under the condition of closing active nitrogen electricity slurry air-flow, forms the aluminium of monoatomic layer on the monocrystalline silicon nitride layer.Then, high tempering aluminium pre-deposition atomic layer is positioned at silicon nitride layer top (step 4) to form an aluminium nitride monoatomic layer.Then, carry out the building crystal to grow of aln layer to form aluminum nitride buffer layer in monocrystalline silicon nitride layer top (step 5); Last gallium nitride film (GaN film) or the formation group iii nitride semiconductor hetero crystal structure (step 6) above aluminum nitride buffer layer that on aluminum nitride buffer layer, forms tool gallium atomic polarity surface.
Then with reference to figure 2A, silicon base material 10 utilizes hot degassing processing or hydrogen-Passivation Treatment (Wet-type etching or on-the-spot nitrogen electricity slurry are handled) is to remove native oxide.Utilize the prepared silicon base material 10 of hot degassing processing step can demonstrate (7*7) surface reconstruction characteristic, and can utilize reflective high-energy electron diffraction pattern to confirm its characteristic at 800 ℃.In addition, reflective high-energy electron diffraction pattern can be pointed out quality and the flatness of reconstruct silicon face before the building crystal to grow processing procedure.It is resultant that (7*7) of correction utilization (111) crystal orientation surface silicon surface of bottom material when temperature is 875 ℃ of its ground temperature changes into the phase transfer of (1*1) surface reconstruction.
Then, be feature of the present invention, its diffused barrier layer 12 utilizes the nitrogenation on surface silicon ground 10 surfaces, (111) crystal orientation to be produced by a monocrystalline silicon nitride layer, in the silicon base material temperature is to import the active nitrogen pneumoelectric under 900 ℃ the condition to starch about 30 seconds to form the monocrystalline silicon nitride layer.In the present invention, the importing that the beta-silicon nitride of (0001) crystal face (monocrystalline silicon nitride) layer (0001) 12 can be by active nitrogen gas or utilize thermal cracking ammonia (thermally cracked NH
3) importing produce, when (111) face silicon base material 10 surfaces slightly are being higher than Si (111) phase transition temperature (being transferred to (1*1) phase by (7*7)), can producing single crystalline Si
3N
4(0001)-(4*4) surface reconstruction (with regard to the lattice parameter of (111) crystal orientation surface silicon ground, also can be described as " (8*8) " surface reconstruction).
Can demonstrate importing active nitrogen pneumoelectric slurry in reflective high-energy electron diffraction diagram is 900 ℃ and time to be under 30 seconds the condition to surface silicon ground 10 surfaces, (111) crystal orientation in temperature, the reflective high-energy electron diffraction pattern of " (8*8) " reconstruct.Reflective high-energy electron diffraction pattern is expressed two kinds of different surface atom orders on beta-silicon nitride layer (0001) 12.Wherein a kind of order meets the nitrogen adatom (adatoms) of the superiors' " (8/3*8/3) "-structure and the lattice surface cycle that another surperficial order meets " (8*8) ".Wear tunnel microtechnic (STM in scanning; Scanning Tunneling Microscopy) in the experiment, can confirm that " (8*8) " lattice period is the reconfiguration unit structure cell on beta-silicon nitride 12 surfaces of monocrystalline (0001) crystal face.
Then, the growth of aluminum nitride buffer layer 16 begins shown in Fig. 2 B and Fig. 2 C at the silicon nitride reconstructing surface that stops at the surface nitrogen atom in the double-layer bumper structural system.15 seconds aluminium of deposition in aluminium pre-deposition step, single aluminium pre-deposition atomic layer 14 forms on (111) crystal orientation surface silicon ground 10.Implement high tempering aluminium pre-deposition atomic layer then to form an aluminium nitride monoatomic layer in monocrystalline silicon nitride layer 12 tops.And aluminium nitride (0001)-(1*1) structure can be presented in the real-time reflective high-energy electron diffraction pattern.The nitrogen adatom bond of pointing out the aluminium atom and the superiors forms very level and smooth of the aluminium nitride 16 of an atomic layer and its surface.Must be noted that at this and can utilize reflective high-energy electron diffraction pattern to determine to have the integer ratio relation along the periodicity of the coincidence lattice of beta-silicon nitride (2-1-10) 12 and aluminium nitride (2-1-10) 16 directions.Then, above monocrystalline silicon nitride layer 12, form monocrystalline aluminum nitride buffer layer 16 in a building crystal to grow mode.
For relatively with the individual layer with aluminium nitride and double-deck two kinds of buffer structures (the double-buffering layer structure contains a monocrystalline silicon nitride layer on silicon base material), the thickness of aluminium resilient coating 16 all be about 30 how the temperature of rice and building crystal to grow be 0.12 micron of each hour 820 ℃ and growth speed.Then, gallium nitride epitaxial layer 20 is long on monocrystalline aluminum nitride buffer layer 16.The thickness of gallium nitride epitaxial layer 20 is 240 microns grows up (being about 720 ℃) in lower ground temperature, and its building crystal to grow speed each hour is 0.08 micron.After molecular beam epitaxy is grown up, utilize the formed gallium nitride 20 of double-layer bumper structure to be cooled to 500 ℃ to 600 ℃, and under condition, can have (2*2) reconstruct pattern of the gallium nitride layer 20 of gallium atomic surface polarity with nitrogen electricity slurry air-flow.
Same with reference to figure 2D, the invention provides a kind of light emitting diode construction with double-layer bumper structure with solution when monocrystalline aluminium nitride (0001) resilient coating is grown up, automatically doping and between aluminium nitride/silicon the problem that diffusion inside produced of interface.Have (111) surface, the crystal orientation silicon base material 10 of (lattice constant on the plane is 3.840 dusts) is provided in the present invention.Then on the silicon base material 10 on (111) surface, crystal orientation, form the pair of lamina buffer structure for feature of the present invention, this double-layer bumper structure can be improved the problem of the mutual diffusion of interface inner element in the semiconductor, wherein to comprise a monocrystalline silicon nitride layer (0001) 12 its lattice constant be 7.61 dusts to the double-layer bumper layer, and aln layer (0001) 16 its lattice constant that is positioned on the monocrystalline silicon nitride layer 12 is 3.112 dusts.
In addition, can be by the relation of finding following brilliant orientation of heap of stone in the research of reflective high-energy electron diffraction pattern and X ray diffraction:
β-Si
3N
4(0001)‖Si(111)；
β-Si
3N
4[0-110]‖Si[11-2]；β-Si
3N
4[2-1-10]‖Si[-110]andAlN(0001)‖β-Si
3N
4(0001)；AlN[0-110]‖β-Si
3N
4[0-110]；AlN[2-1-10]‖β-Si
3N
4[2-1-10]。Therefore, the c-axle of gallium nitride/aluminium nitride/beta-silicon nitride is perpendicular to the silicon base material surface in (111) crystal orientation.
Because the gallium nitride building crystal to grow is (all to contain an aluminum nitride buffer layer) in identical growth condition length on different buffer structures, therefore, in order to compare the influence of these different buffer structures to epitaxial character of heap of stone, ion microprobe (SIMS; Secondary-ion massspectroscopy), X ray diffraction, photic fluorescence spectra (PL; Photoluminescence) and Raman scattering method of measurement such as (Raman scattering) be used to these buffer structures that have/do not have a beta-silicon nitride layer of comparison to the structural property of gallium nitride epitaxial of heap of stone and the influence of optical characteristics.
Fig. 3 represents to utilize secondary ion mass spectroscopy to do the signal that silicon/aluminium element is analyzed near gallium nitride film/buffer structure/ground interface area depth bounds for having the gallium nitride film that monocrystalline aluminium nitride/monocrystalline silicon nitride double-layer bumper structure (a) and aluminium nitride individual layer buffer structure (b) grown up.Impurity can utilize the ion microprobe detecting to obtain in the distribution of growth direction.In order to study the automatic doping effect of on the surface silicon ground of (111) crystal orientation, growing up when gallium nitride, at the sample of two kinds of buffer structure systems, near the aluminium ion gallium nitride layer/aln layer and the aln layer/silicon base material interface and the ion microprobe signal of silicon ion are made depth profile in the present invention.Wherein the degree of depth of the silicon of each ion microprobe/aluminium content distribution figure all is set in (111) surface, crystal orientation of silicon base material zero point.Measurement can determine little order of magnitude nearly of situation that gallium nitride is grown up and grown up on the individual layer buffering at the silicon diffusing capacity size ratio of double-layer bumper structure (having beta-silicon nitride (0001) layer) thus.
The monocrystalline silicon nitride layer just can not limit silicon and diffuse to aln layer and gallium nitride layer, under the high development temperature of aluminum nitride buffer layer, monocrystalline silicon nitride (0001) layer can prevent that equally also aluminium from diffusing to silicon base material, and aluminium element also is lower than in the content size of silicon base material and does not comprise the nearly order of magnitude of sample that the silicon nitride diffusion suppresses layer in comprising the sample that the silicon nitride diffusion suppresses layer.Therefore, the result of ion microprobe can demonstrate in the process of high temperature growth aluminium nitride epitaxial layer and follow-up gallium nitride epitaxial layer, and the monocrystalline silicon nitride layer can effectively suppress silicon and diffuse to aln layer and gallium nitride layer and suppress aluminium and diffuse to silicon base material.
With reference to figure 4A and Fig. 4 B, the comparison of the optical characteristics of expression gallium nitride film growth on different buffer structures.Demonstrate gallium nitride film and grow up when aluminium nitride/silicon nitride/silicon (111) double-layer bumper superstructure in the photic fluorescence spectra of low temperature (6.7K), the neutrality of its gallium nitride film is executed sub-bound exciton (DoX; The halfwidth of luminous crest neutral-donor-bound exciton) is much smaller than formed gallium nitride film above aluminium nitride/silicon (111) individual layer buffer structure.The minimizing of the value of a half width of photic fluorescence spectra crest (12meV vs.20meV) with by surface defect density (7*10 that atomic force microscopy measured
8Cm
-2Vs.1.1*10
9Cm
-2) unanimity as a result, confirmed the improvement aspect the epitaxial layer crystalline quality.Interior figure in Fig. 4 A is shown in different temperatures, the main fluorescent crest location of the gallium nitride sample of growth on aluminium nitride/silicon nitride/silicon (111) is when temperature is higher than 70K, demonstrates photic fluorescence spectra crest and executes sub-bound exciton emission by neutrality and go to free exciton (free exciton; FX) emission (70k
BThe neutral silicon that levels off to is executed the localization energy (E of son to exciton
Loc), k wherein
BBe Boltzmann's constant).With respect to this characteristic, for the sample of individual layer buffer structure, its neutrality is executed the dull rising along with the increase of temperature of sub-bound exciton crest location, represents the concentration of silicon atom (Shi Zi) in this sample very big.Therefore, this and above-mentioned be consistent by the resulting result of secondary ion matter instrument.
With reference to figure 4B, be illustrated in the gallium nitride growth and execute sub-bound exciton at the D of gallium nitride film growth on the individual layer buffer structure in intensity and the neutrality of the FX of the structural fluorescence spectra of double-layer bumper
oThe Arrhenius schematic diagram of X fluorescence spectra intensity.Can get by the Arrhenius icon, FX grows up at gallium nitride can concern that obtain its value is approximately 25meV, has consistency with the result of study for the activation energy value of FX in undoped gallium nitride in the document by the match thermal activation at the structural activation energy of aluminium nitride/silicon nitride/silicon (111) double-layer bumper.In addition, neutrality is executed sub-bound exciton and can be utilized two thermal activations energy (E at the compound again activation energy of on-radiation of gallium nitride growth on aluminium nitride/silicon (111) individual layer buffering
A1And E
A2) match.The E of match gained
A1And E
A2Be equivalent to known in gallium nitride the localization energy (E of silicon impurity
Loc～6meV) and silicon execute daughter ionization in conjunction with energy (E
D～29meV).
In addition, utilize Raman scattering to measure when relatively adopting two kinds of different resilient coating systems in the present invention, grow up in the lattice quality of the gallium nitride epitaxial layer on silicon base material (111) surface, crystal orientation.The non-polarization Raman spectrum that obtains with scattering geometry backward with reference to figure 5 expression, its incident light direction is along gallium nitride c direction of principal axis ([0001]) (along growth direction), and utilizing that to have wavelength be 514.5 light sources of the Argon-Ion Laser of rice how, two kinds of Raman spectrums all can get～520cm in the part of silicon base material
-1The Raman signal.In addition, in each Raman spectrum, all have near 568cm
-1The Raman signal, this is the E of gallium nitride
2Band Raman signal.In addition, growing up partly, can obtain A in the structural gallium nitride film sample of double-layer bumper
1(LO) band (～735cm
-1) the Raman signal.This A
1(LO) the high-quality lattice of gallium nitride film sample tool of growing up on the double-layer bumper structure is represented in the existence of signal.Simultaneously, for dopant material not, A
1(LO) and E
2The strength ratio of Raman signal is 1: 3.Measure the A that gallium nitride is grown up at double-layer bumper structure gained in the present invention
1(LO) and E
2Strength ratio is 1: 3.3 (only less times greater than 3), points out that carrier concentration is only a little more than the carrier concentration of undoped gallium nitride layer.The measured result of this kind result and ion microprobe has consistency, and demonstrate and utilize aluminium nitride/silicon nitride double-layer bumper structure gallium nitride growth layer on the silicon base material on (111) surface, crystal orientation, has lower silicon concentration in the gallium nitride layer of gained, so the effect of mixing spoke reduction greatly automatically.
The above is preferred embodiment of the present invention only, is not in order to limit claim of the present invention; All other do not break away from the equivalence of being finished under the disclosed spirit and changes or modification, all should be included in the described claim.
Claims (10)
1. the method for a growth group iii nitride semiconductor hetero crystal structure on silicon base material should method of growth group iii nitride semiconductor hetero crystal structure comprise on silicon base material:
Silicon base material with (111) surface, crystal orientation is provided;
Carry out a hot nitrogenation that feeds activated nitrogen source in this silicon base material with (111) surface, crystal orientation to form a monocrystalline silicon nitride layer on this silicon base material with (111) surface, crystal orientation;
Do not carry out under the hot nitrogenation of this feeding activated nitrogen source carry out an aluminium pre-deposition step on this monocrystalline silicon nitride layer to form an aluminium pre-deposition atomic layer above this monocrystalline silicon nitride layer;
Carry out a high tempering step in this aluminium pre-deposition atomic layer to form a monocrystalline aluminium nitride monoatomic layer in this monocrystalline silicon nitride layer top; And
Carry out an aluminium nitride building crystal to grow step in this monocrystalline aluminium nitride monoatomic layer top to form a monocrystalline aluminium nitride epitaxial layer.
Form a group iii nitride semiconductor structure in this aluminium nitride epitaxial layer top.
2. as claimed in claim 1 on silicon base material the method for growth group iii nitride semiconductor hetero crystal structure, wherein above-mentioned group iii nitride semiconductor structure can be a group iii nitride semiconductor single layer structure.
3. as claimed in claim 1 on silicon base material the method for growth group iii nitride semiconductor hetero crystal structure, wherein above-mentioned group iii nitride semiconductor structure can be a group iii nitride semiconductor sandwich construction.
4. semiconductor structure with group iii nitride semiconductor hetero crystal structure, this semiconductor structure with group iii nitride semiconductor hetero crystal structure comprises:
Has (111) surface, crystal orientation silicon base material one by one;
The pair of lamina buffer structure is positioned at this silicon base material top with (111) surface, crystal orientation, and wherein this double-layer bumper layer structure comprises a diffused barrier layer and is positioned at this silicon base material top with (111) surface, crystal orientation; And
One group iii nitride semiconductor structure is positioned at this double-layer bumper layer top.
5. the semiconductor structure with group iii nitride semiconductor hetero crystal structure as claimed in claim 4, wherein the material of above-mentioned diffused barrier layer is a monocrystalline silicon nitride.
6. the semiconductor structure with group iii nitride semiconductor hetero crystal structure as claimed in claim 4, wherein above-mentioned double-layer bumper structure comprise a monocrystalline aln layer and are positioned at this diffused barrier layer top.
7. the semiconductor structure with group iii nitride semiconductor hetero crystal structure as claimed in claim 4, wherein above-mentioned double-layer bumper structure comprise a gallium nitride layer and are positioned at this diffused barrier layer top.
8. the semiconductor structure with group iii nitride semiconductor hetero crystal structure as claimed in claim 4, wherein above-mentioned double-layer bumper structure comprise a nitride indium layer and are positioned at this diffused barrier layer top.
9. the semiconductor structure with group iii nitride semiconductor hetero crystal structure as claimed in claim 4, wherein above-mentioned group iii nitride semiconductor structure are a group iii nitride semiconductor single layer structure.
10. the semiconductor structure with group iii nitride semiconductor hetero crystal structure as claimed in claim 4, wherein above-mentioned group iii nitride semiconductor structure are a group iii nitride semiconductor sandwich construction.
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| CN101861661B (en) * | 2007-10-18 | 2013-06-05 | 康宁股份有限公司 | Gallium nitride semiconductor device on SOI and process for making same |
| US8946775B2 (en) | 2012-08-22 | 2015-02-03 | Industrial Technology Research Institute | Nitride semiconductor structure |
| US9917156B1 (en) | 2016-09-02 | 2018-03-13 | IQE, plc | Nucleation layer for growth of III-nitride structures |
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| EP1209729A1 (en) * | 1999-07-07 | 2002-05-29 | Matsushita Electric Industrial Co., Ltd. | Multilayered body, method for fabricating multilayered body, and semiconductor device |
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| US8946775B2 (en) | 2012-08-22 | 2015-02-03 | Industrial Technology Research Institute | Nitride semiconductor structure |
| US9917156B1 (en) | 2016-09-02 | 2018-03-13 | IQE, plc | Nucleation layer for growth of III-nitride structures |
| US10580871B2 (en) | 2016-09-02 | 2020-03-03 | Iqe Plc | Nucleation layer for growth of III-nitride structures |
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