CN102828251B - Method for preparing aluminum nitride single crystal material - Google Patents
Method for preparing aluminum nitride single crystal material Download PDFInfo
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- CN102828251B CN102828251B CN201210332652.6A CN201210332652A CN102828251B CN 102828251 B CN102828251 B CN 102828251B CN 201210332652 A CN201210332652 A CN 201210332652A CN 102828251 B CN102828251 B CN 102828251B
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Abstract
The invention relates to a method for preparing an aluminum nitride single crystal material, comprising the following steps: preparing a III-nitride nucleation layer on a substrate; preparing a III-nitride crystallization layer on the III-nitride nucleation layer; preparing a stress covariation layer on the III-nitride crystallization layer; preparing a III-nitride self-decomposing decoupling layer on the stress covariation layer; preparing a first III-nitride template layer on the III-nitride self-decomposing decoupling layer; preparing a second III-nitride template layer on the first III-nitride template layer; preparing an aluminum nitride thick-film monocrystalline material layer on the second III-nitride template layer; and preparing an aluminum nitride single crystal wafer substrate material by adopting an intermediate process. The method can be used for providing low-cost large-size aluminum nitride single crystal wafer substrate material to study and produce ultraviolet and deep-ultraviolet semiconductor optoelectronic devices, thereby having very good practical value and marketing prospect.
Description
Technical field
The present invention relates to a kind of semiconductor single crystal material preparation method, specifically a kind of aluminum-nitride single crystal material preparation method.
Background technology
Along with the widespread use of third generation semiconductor gallium nitride (GaN) material at field of photoelectric devices is promoted, greatly promote the research and development of super semiconductor material with wide forbidden band aluminium nitride (AlN).Since 2006, Japanese NTT company developed first AlN base deep ultraviolet (wavelength 210nm) photodiode (LED), became the new study hotspot of semiconductor applications based on the short wavelength UV of AlN and high Al contents AlGaN material and deep UV (ultraviolet light) electrical part.But utilize foreign substrate (as sapphire, silicon carbide and silicon) extension preparation method as adopted similar GaN base photoelectric device, due to required growth temperature higher (at least 1300 DEG C), the lattice mismatch born, thermal stresses and surface and interface problem will be more outstanding.Optimal mode adopts AlN monocrystal material to carry out photoelectric device preparation as homo-substrate, this makes it possible to effectively to eliminate the large mismatch problems of AlN and high Al contents AlGaN base device and develop high performance device.Therefore, AlN monocrystal material technology of preparing becomes the study hotspot that semiconductor material preparation field is new in recent years.AlN monocrystal material has using value of crucial importance and considerable economic benefit.
At present, the conventional preparation technology for AlN monocrystal material has three kinds: metal-organic chemical vapor deposition equipment (MOCVD), halide gas phase extension (HVPE), physical vapor transport (PVT).The relative merits of three kinds of techniques are as follows:
(1) MOCVD technique: be the mode adopting chemosynthesis, utilize metallic aluminium organic compound (as TMAl) as aluminium source, ammonia (NH3), as nitrogenous source, foreign substrate such as high temperature (1200-1600 DEG C) sapphire, silicon carbide etc. is carried out AlN thin-film material synthesis preparation.Its advantage is: 1) can prepare large-area AlN thin film single crystal material.Area is determined by the size of foreign substrate and growth room, and current maximum area can reach diameter 6 inches; 2) can preparing growth, to obtain various meticulous mismatch stress adjusted and controlled and have very even curface.This and the MOCVD process materials speed of growth are more closely related.Its shortcoming is: the high density dislocation (109-10/cm2) that the stress 1) being difficult to overcome hetero epitaxy generation causes, rete bend and be full of cracks problem.The thicker problem of the larger rete of area is more outstanding; 2) the MOCVD process materials speed of growth comparatively slow (hundreds of nanometer thickness per hour).Be not suitable for the commercialization AlN monocrystalline substrate material preparing hundreds of micron thickness.
(2) HVPE technique: be also the mode adopting chemosynthesis, utilize metallic aluminium halogenide (as AlCl or AlCl3) as aluminium source, ammonia (NH3), as nitrogenous source, foreign substrate such as high temperature (1200-1600 DEG C) sapphire, silicon carbide etc. is carried out AlN thick-film material synthesis preparation.Its advantage is: 1) also can prepare big area AlN monocrystal material.Area is also by the decision of foreign substrate and growth room's size, and current maximum area still only has 2 inches diameter; 2) the HVPE speed of growth is very fast, can prepare the AlN thick film monocrystal material (tens and even hundreds of micron thickness) used as substrate, and better can suppress the increment (dislocation desity 106-7/cm2) of break-through dislocation.Its shortcoming is: 1) be difficult to direct heteroepitaxial growth and obtain surfacing and have higher crystalline quality materials.The AlN thin film single crystal material often needing MOCVD technique to prepare is the template of nucleation and crystallization growth.Due to needs two equipment, cause material produce cost high; 2) rete that the more difficult stress overcoming hetero epitaxy generation causes bends and be full of cracks problem.Cause being difficult to obtain complete large-area without supporting al N thick film monocrystal material from the stripping of heterojunction substrate, the larger rete of area is more thick more outstanding, and finished material rate is low is not suitable for commercialization popularization.
(3) PVT technique: be the atmosphere adopting the mode of physical evaporation condensation high-purity AlN powder stock high temperature (1900-2400 DEG C) physical evaporation to be gone out Al and N, then on the seed crystal with certain temperature gradient condensation growing AIN body monocrystal material.Its advantage is: 1) Material growth speed fast (hundreds of micron thickness per hour).If any large size AlN seed crystal can prepare low-dislocation-density (102-4/cm2) can commercialization large size AlN body monocrystal material; 2) equipment build and maintenance cost low.Large-scale production is very easy to after technical maturity.Its shortcoming is: 1) prepare growth without seed crystal and to be easy to get polycrystalline or large grain size material (crystal particle scale mm-scale or less).What need to combine preparation by MOCVD and HVPE two kinds of techniques is that seed crystal expands and grows brilliant size without supporting al N thick film monocrystal material; 2) Material growth temperature very high (1900-2400 DEG C), controls requirements at the higher level to the material of growth room and structure and thermograde.Although PVT technique prepares the energy consumption of growing AIN body monocrystalline and current sapphire body monocrystal material is prepared close, but due to its economic benefit considerable (at present every sheet 2 inches of AlN single-chip prices more than 5,000 dollars), its practical value and market outlook are expected most.
Summary of the invention
The object of the invention is preparing the technical deficiency in aluminum-nitride single crystal material for conventional MOCVD, HVPE, PVT technique, a kind of not only practical but also the aluminum-nitride single crystal material preparation method that can reduce costs are provided.
The invention provides a kind of aluminum-nitride single crystal material preparation method, it is characterized in that, comprise following steps:
Step 1 a: substrate is inserted in the growth room of metal-organic chemical vapor deposition equipment-halide gas phase extension recombining process equipment;
Step 2: adopt mocvd process, substrate is prepared a group III-nitride nucleating layer;
Step 3: heated up by substrate heating temperature, adopts mocvd process, group III-nitride nucleating layer is prepared a group III-nitride crystallizing layer;
Step 4: the Heating temperature changing substrate, adopts mocvd process, group III-nitride crystallizing layer is prepared a stress covariant layer;
Step 5: adopt mocvd process, changes the Heating temperature of substrate, stress covariant layer is prepared a group III-nitride self-decomposition solution coupling layer;
Step 6: adopt mocvd process, changes the Heating temperature of substrate, and group III-nitride self-decomposition solution coupling layer prepares one first group III-nitride template layer;
Step 7: the Heating temperature of substrate is heated up, the indium component in group III-nitride self-decomposition solution coupling layer raises with temperature and separates out, and forms porous loose structure between stress covariant layer and the first group III-nitride template layer;
Step 8: adopt mocvd process, heats up substrate heating temperature, and the first group III-nitride template layer prepares one second group III-nitride template layer;
Step 9: heated up by substrate heating temperature, adopts halide gas phase epitaxy technique, the second group III-nitride template layer is prepared an aluminium nitride thick film monocrystalline material layer;
Step 10: substrate heating temperature is dropped to room temperature with the rate of temperature fall of 5 to 50 DEG C/min, realize aluminium nitride thick film monocrystal material from peeling off from substrate, and take out thick film monocrystalline material layer from metal-organic chemical vapor deposition equipment-halide gas phase extension recombining process equipment in growth room;
Step 11: top aluminium nitride thick film monocrystalline material layer being inserted the tungsten crucible of the body monocrystalline material growth indoor of physical vapor transport equipment as seed crystal, inserts in the tungsten crucible of body monocrystalline material growth indoor of physical vapor transport equipment using high purity silicon nitride aluminium powder form as raw material;
Step 12: the Heating temperature of physical vapor transport device body monocrystalline material growth indoor is warmed up to 1900 to 2400 DEG C, by heating the thermograde regulation and control of warm area up and down, keep the seed crystal warm area of the aluminium nitride thick film monocrystal material above tungsten crucible lower than tungsten crucible inside aluminum nitride powder powder stock warm area 30 to 100 DEG C, adopt physical vapor transport technique, with thick film monocrystalline material layer for seed crystal prepares growing aluminum nitride body monocrystal material;
Step 13: the body monocrystalline material growth room Heating temperature of physical vapor transport equipment is dropped to room temperature and take out aluminum nitride body monocrystal material, through cutting, grinding, polishing prepares aluminum-nitride single crystal sheet substrate material.
The present invention utilizes the MOCVD-HVPE recombining process MOCVD and HVPE two kinds of techniques being integrated in same reaction chamber, the transition metal IVB group-III nitride stress covariant layer having appropriate crystal lattice constant and a thermal expansivity by design preparation overcomes stress that hetero epitaxy produces and causes the bending and be full of cracks problem of rete, particularly thermal expansivity is combined with the group III-nitride self-decomposition solution coupling layer comprising indium component than heterogeneous single crystalline substrate and all large transition metal IVB group-III nitride stress covariant layer of aluminium nitride, prepared aluminium nitride thick film monocrystal material can be realized complete from peeling off heterogeneous single crystalline substrate, and then provide big area seed crystal for follow-up PVT technique expands aluminum nitride body single crystal growing size.The present invention can provide low cost large size aluminum-nitride single crystal sheet substrate material for development and production ultraviolet and deep ultraviolet semiconductor photoelectric device, has extraordinary practical value and marketing prospect.
Accompanying drawing explanation
For further illustrating concrete technology contents of the present invention, be described in detail as follows below in conjunction with embodiment and accompanying drawing, wherein:
Fig. 1 adopts MOCVD-HVPE recombining process to prepare aluminium nitride thick film monocrystal material structural representation.
Embodiment
Refer to shown in Fig. 1, the invention provides a kind of aluminum-nitride single crystal material preparation method, it is characterized in that, comprise following steps:
Step 1 a: substrate 1 is inserted in the growth room of metal-organic chemical vapor deposition equipment-halide gas phase extension recombining process equipment, described substrate 1 is the heterogeneous single crystalline substrate of high-melting-point, and its fusing point is higher than 1300 DEG C and have the sapphire of good lattice match relation, silicon carbide or gallium nitride material with aluminium nitride;
Step 2: adopt mocvd process, prepare a group III-nitride nucleating layer 2 on substrate 1, described group III-nitride nucleating layer 2 is GaN, AlN or AlGaN material, and preparation temperature is 300 to 700 DEG C, and thickness is 5 to 500nm;
Step 3: substrate 1 Heating temperature is heated up, adopt mocvd process, group III-nitride nucleating layer 2 is prepared a group III-nitride crystallizing layer 3, described group III-nitride crystallizing layer 3 is GaN, AlN or AlGaN material, the Heating temperature of substrate 1 rises to 900 to 1200 DEG C, and the thickness of group III-nitride crystallizing layer 3 is 10 to 1000nm;
Step 4: the Heating temperature changing substrate 1, adopt mocvd process, group III-nitride crystallizing layer 3 is prepared a stress covariant layer 4, for coordinating the lattice mismatch stress that produces in subsequent nitride template layer or aluminium nitride thick-film material preparation process and thermal stresses.Described stress covariant layer 4 is transition metal IVB group-III nitride stress covariant layers, its material is TiN, ZrN, HfN, TiZrN, TiHfN, ZrHfN or TiZrHfN, its thermal expansivity is higher than high-melting-point single crystalline substrate 1 and aluminium nitride, the Heating temperature changing substrate 1 is low temperature 300 to 700 DEG C, and the thickness of stress covariant layer 4 is 10 to 1000nm;
Step 5: adopt mocvd process, change the Heating temperature of substrate 1, stress covariant layer 4 is prepared a group III-nitride self-decomposition solution coupling layer 5, coordinate the lattice mismatch stress that produces in subsequent nitride template layer or aluminium nitride thick-film material preparation process and thermal stresses for auxiliary stress covariant layer 4, and terminate temperature-fall period and the acting in conjunction of stress covariant layer 4 impels aluminium nitride thick film from substrate 1 from peeling off at Material growth.The material of described group III-nitride self-decomposition solution coupling layer 5 is In
xga
1-xn, In
xal
1-xn or In
xal
yga
1-x-yn, its indium component x is 0.05 to 0.9, and change the Heating temperature to 300 of substrate 1 during preparation to 700 DEG C, the thickness of group III-nitride self-decomposition solution coupling layer 5 is 5 to 500nm;
Step 6: adopt mocvd process, change the Heating temperature of substrate 1, group III-nitride self-decomposition solution coupling layer 5 prepares a group III-nitride template layer 6, the material of the first described group III-nitride template layer 6 is GaN, AlN or AlGaN, change the Heating temperature to 300 of substrate during preparation to 700 DEG C, the first group III-nitride template layer 6 thickness is 5 to 500nm;
Step 7: the Heating temperature of substrate 1 is heated up, the indium component in group III-nitride self-decomposition solution coupling layer 5 raises with temperature and separates out, and forms porous loose structure between stress covariant layer 4 and the first group III-nitride low temperature template layer 6;
Step 8: adopt mocvd process, substrate 1 Heating temperature is heated up, first group III-nitride template layer 6 prepares one second group III-nitride template layer 7, the material of the second described group III-nitride high temperature template layer 7 is GaN, AlN or AlGaN, intensification back substrate Heating temperature is 900 to 1200 DEG C, and the second group III-nitride high temperature template layer 7 thickness is 200 to 2000nm;
Step 9: substrate 1 Heating temperature heated up, adopts halide gas phase epitaxy technique, the second group III-nitride template layer 7 is prepared an aluminium nitride thick film monocrystalline material layer 8;
Step 10: substrate 1 Heating temperature is dropped to room temperature with the rate of temperature fall of 5 to 50 DEG C/min.Thermal expansivity due to stress covariant layer 4 compares substrate 1 and aluminium nitride is all large, the thermal stresses that temperature-fall period produces discharges first transferring in stress covariant layer 4, because above it being the porous loose structure of group III-nitride, the two acting in conjunction, just achieves aluminium nitride thick film monocrystal material 8 complete from peeling off from substrate 1 with the joint portion of porous loose structure at power covariant layer 4.Take out without supporting aluminium nitride thick film monocrystalline material layer 8 in metal-organic chemical vapor deposition equipment-halide gas phase extension recombining process equipment growth room;
Step 11: top aluminium nitride thick film monocrystalline material layer 8 being inserted the tungsten crucible of the body monocrystalline material growth indoor of physical vapor transport equipment as seed crystal, inserts in the tungsten crucible of body monocrystalline material growth indoor of physical vapor transport equipment using high purity silicon nitride aluminium powder form as raw material;
Step 12: the Heating temperature of physical vapor transport device body monocrystalline material growth indoor is warmed up to 1900 to 2400 DEG C, by heating the thermograde regulation and control of warm area up and down, keep the seed crystal warm area of the aluminium nitride thick film monocrystal material above tungsten crucible lower than tungsten crucible inside aluminum nitride powder powder stock warm area 30 to 100 DEG C, adopt physical vapor transport technique, with aluminium nitride thick film monocrystalline material layer 8 for seed crystal prepares growing aluminum nitride body monocrystal material;
Step 13: the body monocrystalline material growth room Heating temperature of physical vapor transport equipment is dropped to room temperature and take out aluminum nitride body monocrystal material, through cutting, grinding, polishing prepares aluminum-nitride single crystal sheet substrate material.
Above-mentioned semiconductor single crystal material preparation method can provide low cost large size low-dislocation-density aluminum-nitride single crystal sheet substrate material for development and production ultraviolet and deep ultraviolet semiconductor photoelectric device.
A kind of aluminum-nitride single crystal material preparation method of the present invention, compares existing conventional nitridation aluminium monocrystal material method.There is following features and beneficial effect:
(1) MOCVD-HVPE recombining process is adopted, the film forming layer that the stress that the transition metal IVB group-III nitride stress covariant layer having appropriate crystal lattice constant and thermal expansivity by design preparation overcomes hetero epitaxy generation is made bends and be full of cracks problem, particularly thermal expansivity is combined than heterogeneous single crystalline substrate and all large transition metal IVB group-III nitride stress covariant layer of aluminium nitride and the group III-nitride self-decomposition solution coupling layer the comprising indium component porous loose structure be decomposed to form that heats up, prepared aluminium nitride thick film monocrystal material can be realized complete from peeling off and then obtaining unsupported aluminium nitride thick film monocrystal material heterogeneous single crystalline substrate,
(2) big area utilizing MOCVD-HVPE recombining process to prepare is seed crystal without support aluminium nitride thick film monocrystal material; size and the raising quality of material grown of PVT process high-temperature growing aluminum nitride body monocrystal material can be expanded, and then lay the foundation for follow-up large size aluminum nitride body monocrystal material PVT Process Planning modelling prepares production.
(3) technological merit of MOCVD, HVPE, PVT tri-kinds of techniques is organically combined, not only greatly reduce aluminum-nitride single crystal material and prepare production cost, be also easy to large-scale production.
Introduce the above-mentioned aluminum-nitride single crystal material preparation method of preparation below.Should be appreciated that, preparation method described below is only the specific examples preparing aluminum-nitride single crystal material of the present invention.Those skilled in the art can the present invention instruct under as required and other factors make change.
Embodiment 1:
The technical process adopting sapphire (a-Al2O3) material to prepare aluminium nitride (AlN) thick film monocrystal material and aluminium nitride (AlN) body monocrystal material as heterogeneous single crystalline substrate is as follows:
Step 1: by the a-Al of 2 inches diameter
2o
3monocrystalline substrate material 1 is inserted in the growth room of MOCVD-HVPE recombining process equipment;
Step 2: adopt golden MOCVD technique, with the substrate heating temperature of 550 DEG C, the thick GaN low temperature nucleation layer 2 of low-temperature growth one 30nm on sapphire single crystal substrate material;
Step 3: substrate heating temperature is risen to 1050 DEG C, adopt MOCVD technique, on GaN low temperature nucleation layer 2, high temperature prepares a 500nm thick GaN high temperature crystallization layer 3;
Step 4: substrate heating temperature is down to 600 DEG C, adopts MOCVD technique, low-temperature growth one 50nm thick TiN stress covariant layer 4 on GaN high temperature crystallization layer 3;
Step 5: adopt MOCVD technique, with the substrate heating temperature of 600 DEG C, the In of the thick indium component x=0.15 of low-temperature growth one 30nm on TiN stress covariant layer 4
0.15ga
0.85n self-decomposition solution coupling layer 5;
Step 6: adopt MOCVD technique, with the substrate heating temperature of 600 DEG C, at In
0.15ga
0.85the GaN low temperature template layer 6 that on N self-decomposition solution coupling layer 5, low-temperature growth one 100nm is thick;
Step 7: substrate heating temperature is slowly warming up to 1050 DEG C of high temperature with the temperature rise rate of 10 DEG C/min, In
0.15ga
0.85indium component in N self-decomposition solution coupling layer 5 raises with temperature and separates out, and between TiN thermal stresses covariant layer 4 and GaN low temperature template layer 6, form the porous loose structure of GaN;
Step 8: adopt MOCVD technique, with the substrate heating temperature of 1050 DEG C, GaN low temperature template layer 6 is prepared the GaN high temperature template layer 7 of a thick 1000nm;
Step 9: substrate heating temperature is risen to 1350 DEG C, adopt HVPE technique, on GaN high temperature template layer 7, high temperature prepares one 100 μm of thick AlN thick film monocrystal materials 8;
Step 10: substrate heating temperature is dropped to room temperature with the rate of temperature fall of 30 DEG C/min, realizes AlN thick film monocrystal material 8 from a-Al
2o
3from peeling off on substrate 1, and take out without supporting al N thick film monocrystal material 8 in MOCVD-HVPE recombining process equipment growth room.
Step 11: top AlN thick film monocrystal material 8 being inserted the tungsten crucible of the body monocrystalline material growth indoor of PVT equipment as seed crystal, inserts in the tungsten crucible of body monocrystalline material growth indoor of PVT equipment using high-purity AlN powder as raw material;
Step 12: the Heating temperature of PVT device body monocrystalline material growth indoor is heated to 2350 DEG C, by heating the thermograde regulation and control of warm area up and down, keep the seed crystal warm area of the AlN thick film monocrystal material above tungsten crucible lower than tungsten crucible inside AlN powder stock warm area 70 DEG C, adopt PVT technique, with AlN thick film monocrystal material for seed crystal high temperature preparation growth 10mm thick AlN body monocrystal material;
Step 13: the body monocrystalline material growth room Heating temperature of PVT equipment is dropped to room temperature and take out AlN body monocrystal material, through cutting, grinding, polishing prepares AlN single-chip substrate material.
Embodiment 2
The technical process adopting silicon carbide (6H-SiC) material to prepare aluminium nitride (AlN) thick film monocrystal material and AlN body monocrystal material as heterogeneous single crystalline substrate is as follows:
Step 1: 2 inches diameter 300 micron thickness 6H-SiC monocrystalline substrate material 1 is inserted in the growth room of MOCVD-HVPE recombining process equipment;
Step 2: adopt MOCVD technique, with the substrate heating temperature of 650 DEG C, the thick AlN low temperature nucleation layer 2 of low-temperature growth one 20nm on 6H-SiC monocrystalline substrate material;
Step 3: substrate heating temperature is risen to 1300 DEG C, adopts MOCVD technique high temperature on AlN low temperature nucleation layer 2 to prepare a 300nm thick AlN high temperature crystallization layer 3;
Step 4: substrate heating temperature is down to 650 DEG C, adopts MOCVD technique, low-temperature growth one 50nm thick HfN stress covariant layer 4 on AlN high temperature crystallization layer 3;
Step 5: adopt MOCVD technique, with the substrate heating temperature of 650 DEG C, the In of the thick indium component x=0.25 of low-temperature growth one 20nm on HfN stress covariant layer 4
0.25al
0.75n self-decomposition solution coupling layer 5;
Step 6: adopt MOCVD technique, with the substrate heating temperature of 650 DEG C, at In
0.25al
0.75the AlGaN low temperature template layer 6 that on N self-decomposition solution coupling layer 5, low-temperature growth one 50nm is thick;
Step 7: substrate heating temperature is slowly warming up to 1300 DEG C of high temperature with the temperature rise rate of 15 DEG C/min, In
0.25al
0.75indium component in N self-decomposition solution coupling layer 5 raises with temperature and separates out, and between HfN stress covariant layer 4 and AlGaN low temperature template layer 6, form the porous loose structure of AlN;
Step 8: adopt MOCVD technique, with the substrate heating temperature of 1300 DEG C, AlGaN low temperature template layer 6 is prepared the AlN high temperature template layer 7 of a thick 1500nm;
Step 9: substrate heating temperature is risen to 1450 DEG C, adopts HVPE technique high temperature on AlN high temperature template layer 7 to prepare one 200 μm of thick AlN thick film monocrystal materials 8;
Step 10: substrate heating temperature is dropped to room temperature with the rate of temperature fall of 50 DEG C/min, realizes AlN thick film monocrystal material 8 from peeling off from 6H-SiC substrate 1, and takes out without supporting al N thick film monocrystal material 8 in MOCVD-HVPE recombining process equipment growth room.
Step 11: top AlN thick film monocrystal material 8 being inserted the tungsten crucible of the body monocrystalline material growth indoor of PVT equipment as seed crystal, inserts in the tungsten crucible of body monocrystalline material growth indoor of PVT equipment using high-purity AlN powder as raw material;
Step 12: the Heating temperature of PVT device body monocrystalline material growth indoor is heated to 2300 DEG C, by heating the thermograde regulation and control of warm area up and down, keep the seed crystal warm area of the AlN thick film monocrystal material above tungsten crucible lower than tungsten crucible inside AlN powder stock warm area 60 DEG C, adopt PVT technique, with AlN thick film monocrystal material for seed crystal high temperature preparation growth 20mm thick AlN body monocrystal material;
Step 13: the body monocrystalline material growth room Heating temperature of PVT equipment is dropped to room temperature and take out AlN body monocrystal material, through cutting, grinding, polishing prepares AlN single-chip substrate material.
Embodiment 3
The technical process adopting gan (GaN) material to prepare aluminium nitride thick film monocrystal material and aluminum nitride body monocrystal material as heterogeneous single crystalline substrate is as follows:
Step 1: the GaN monocrystalline substrate material 1 of 2 inches diameter 200 micron thickness is inserted in the growth room of MOCVD-HVPE vapour phase epitaxy recombining process equipment;
Step 2: adopt MOCVD technique, with the substrate heating temperature of 550 DEG C, low-temperature growth one 50nm thick ZrN stress covariant layer 4 on GaN monocrystalline substrate material 1;
Step 5: adopt MOCVD technique, with the substrate heating temperature of 550 DEG C, the In of the thick In component x=0.3 of low-temperature growth one 30nm on ZrN thermal stresses covariant layer 4
0.3ga
0.7n self-decomposition solution coupling layer 5;
Step 6: adopt MOCVD technique, with the substrate heating temperature of 550 DEG C, at In
0.3ga
0.7low-temperature growth one 50nm thick GaN low temperature template layer 6 on N self-decomposition solution coupling layer 5;
Step 7: substrate heating temperature is slowly warming up to 1100 DEG C of high temperature with the temperature rise rate of 20 DEG C/min, In
0.3ga
0.7in component in N self-decomposition solution coupling layer 5 raises with temperature and separates out, and between ZrN stress covariant layer 4 and GaN low temperature template layer 6, form the porous loose structure of GaN;
Step 8: adopt MOCVD technique, with the substrate heating temperature of 1100 DEG C, GaN low temperature template layer 6 is prepared the GaN high temperature template layer 7 of a thick 500nm;
Step 9: substrate heating temperature is risen to 1500 DEG C, adopt HVPE technique, on GaN high temperature template layer 7, high temperature prepares one 300 μm of thick AlN thick film monocrystal materials 8;
Step 10: substrate heating temperature is dropped to room temperature with the rate of temperature fall of 25 DEG C/min, realizes AlN thick film monocrystal material 8 from peeling off GaN substrate 1, and takes out without supporting al N thick film monocrystal material 8 in MOCVD-HVPE recombining process equipment growth room.
Step 11: top AlN thick film monocrystal material 8 being inserted the tungsten crucible of the body monocrystalline material growth indoor of PVT equipment as seed crystal, inserts in the tungsten crucible of body monocrystalline material growth indoor of PVT equipment using high-purity AlN powder as raw material;
Step 12: the Heating temperature of PVT device body monocrystalline material growth indoor is heated to 2250 DEG C, by heating the thermograde regulation and control of warm area up and down, keep the seed crystal warm area of the AlN thick film monocrystal material above tungsten crucible lower than tungsten crucible inside AlN powder stock warm area 50 DEG C, adopt PVT technique, with AlN thick film monocrystal material for seed crystal high temperature preparation growth 30mm thick AlN body monocrystal material;
Step 13: the body monocrystalline material growth room Heating temperature of PVT equipment is dropped to room temperature and take out AlN body monocrystal material, through cutting, grinding, polishing prepares AlN single-chip substrate material.
Finally it should be noted that above example only in order to technical scheme of the present invention to be described but not to be limited.Although with reference to given example to invention has been detailed description, those of ordinary skill in the art can modify to technical scheme of the present invention or equivalent replacement as required, and does not depart from the spirit and scope of technical solution of the present invention.
Claims (8)
1. an aluminum-nitride single crystal material preparation method, is characterized in that, comprises following steps:
Step 1 a: substrate is inserted in the growth room of metal-organic chemical vapor deposition equipment-halide gas phase extension recombining process equipment;
Step 2: adopt mocvd process, substrate is prepared a group III-nitride nucleating layer;
Step 3: heated up by substrate heating temperature, adopts mocvd process, group III-nitride nucleating layer is prepared a group III-nitride crystallizing layer;
Step 4: the Heating temperature changing substrate, adopt mocvd process, group III-nitride crystallizing layer is prepared a stress covariant layer, described stress covariant layer is transition metal IVB group-III nitride stress covariant layer, its material is TiN, ZrN, HfN, TiZrN, TiHfN, ZrHfN or TiZrHfN, and its thermal expansivity is higher than high-melting-point single crystalline substrate and aluminium nitride;
Step 5: adopt mocvd process, changes the Heating temperature of substrate, stress covariant layer is prepared a group III-nitride self-decomposition solution coupling layer;
Step 6: adopt mocvd process, changes the Heating temperature of substrate, and group III-nitride self-decomposition solution coupling layer prepares one first group III-nitride template layer;
Step 7: the Heating temperature of substrate is heated up, the indium component in group III-nitride self-decomposition solution coupling layer raises with temperature and separates out, and forms porous loose structure between stress covariant layer and the first group III-nitride template layer;
Step 8: adopt mocvd process, heats up substrate heating temperature, and the first group III-nitride template layer prepares one second group III-nitride template layer;
Step 9: heated up by substrate heating temperature, adopts halide gas phase epitaxy technique, the second group III-nitride template layer is prepared an aluminium nitride thick film monocrystalline material layer;
Step 10: substrate heating temperature is dropped to room temperature with the rate of temperature fall of 5 to 50 DEG C/min, realize aluminium nitride thick film monocrystal material from peeling off from substrate, and take out thick film monocrystalline material layer from metal-organic chemical vapor deposition equipment-halide gas phase extension recombining process equipment in growth room;
Step 11: top aluminium nitride thick film monocrystalline material layer being inserted the tungsten crucible of the body monocrystalline material growth indoor of physical vapor transport equipment as seed crystal, inserts in the tungsten crucible of body monocrystalline material growth indoor of physical vapor transport equipment using high purity silicon nitride aluminium powder form as raw material;
Step 12: the Heating temperature of physical vapor transport device body monocrystalline material growth indoor is warmed up to 1900 to 2400 DEG C, by heating the thermograde regulation and control of warm area up and down, keep the seed crystal warm area of the aluminium nitride thick film monocrystal material above tungsten crucible lower than tungsten crucible inside aluminum nitride powder powder stock warm area 30 to 100 DEG C, adopt physical vapor transport technique, with thick film monocrystalline material layer for seed crystal prepares growing aluminum nitride body monocrystal material;
Step 13: the body monocrystalline material growth room Heating temperature of physical vapor transport equipment is dropped to room temperature and take out aluminum nitride body monocrystal material, through cutting, grinding, polishing prepares aluminum-nitride single crystal sheet substrate material.
2. aluminum-nitride single crystal material preparation method according to claim 1, substrate wherein described in step 1 is the heterogeneous single crystalline substrate of high-melting-point, and its fusing point is higher than 1300 DEG C and have the sapphire of good lattice match relation, silicon carbide or gallium nitride material with aluminium nitride.
3. aluminum-nitride single crystal material preparation method according to claim 1, the group III-nitride nucleating layer wherein described in step 2 is GaN, AlN or AlGaN material, and preparation process substrate heating temperature is 300 to 700 DEG C, and thickness is 5 to 500nm.
4. aluminum-nitride single crystal material preparation method according to claim 1, group III-nitride crystallizing layer wherein described in step 3 is GaN, AlN or AlGaN material, the Heating temperature of substrate rises to 900 to 1200 DEG C, and the thickness of group III-nitride crystallizing layer is 10 to 1000nm.
5. aluminum-nitride single crystal material preparation method according to claim 1, the Heating temperature of wherein said change substrate is 300 to 700 DEG C, and the thickness of stress covariant layer is 10 to 1000nm.
6. aluminum-nitride single crystal material preparation method according to claim 1, the material of the group III-nitride self-decomposition solution coupling layer wherein described in step 5 is In
xga
1-xn, In
xal
1-xn or In
xal
yga
1-x-yn, its indium component x is 0.05 to 0.9, and change the Heating temperature to 300 of substrate during preparation to 700 DEG C, the thickness of group III-nitride self-decomposition solution coupling layer is 5 to 500nm.
7. aluminum-nitride single crystal material preparation method according to claim 1, the material of the first group III-nitride template layer wherein described in step 6 is GaN, AlN or AlGaN, change the Heating temperature to 300 of substrate during preparation to 700 DEG C, the first group III-nitride template layer thickness is 5 to 500nm.
8. aluminum-nitride single crystal material preparation method according to claim 1, the material of the second group III-nitride template layer wherein described in step 8 is GaN, AlN or AlGaN, substrate heating temperature is warming up to 900 to 1200 DEG C, and the second group III-nitride template layer thickness is 200 to 2000nm.
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| CN103489968B (en) * | 2013-09-09 | 2015-11-18 | 中国科学院半导体研究所 | AlInGaN is utilized to make the method for epitaxy of gallium nitride film |
| CN103849853B (en) * | 2014-02-21 | 2016-06-08 | 中国科学院半导体研究所 | Alleviate the method for stress between silicon substrate and gallium nitride film in MOCVD technique |
| CN104178807A (en) * | 2014-08-06 | 2014-12-03 | 上海世山科技有限公司 | Method for obtaining self-supporting gallium nitride substrates by using thermal decomposition characteristics |
| CN109728138B (en) * | 2018-12-30 | 2020-07-28 | 广东省半导体产业技术研究院 | Aluminum nitride self-supporting substrate and preparation method thereof |
| CN111129111A (en) * | 2019-12-10 | 2020-05-08 | 深圳市汇芯通信技术有限公司 | Semiconductor device, method of manufacturing the same, and integrated circuit |
| CN112687523B (en) * | 2020-12-23 | 2022-11-22 | 广东省科学院半导体研究所 | Preparation method of III nitride template |
| WO2024048766A1 (en) * | 2022-08-31 | 2024-03-07 | 株式会社Gaianixx | Crystal, multilayer structure, element, electronic device, electronic appliance, and system |
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