CN106480492A - Method for producing group III nitride semiconductor monocrystalline - Google Patents
Method for producing group III nitride semiconductor monocrystalline Download PDFInfo
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- CN106480492A CN106480492A CN201610727174.7A CN201610727174A CN106480492A CN 106480492 A CN106480492 A CN 106480492A CN 201610727174 A CN201610727174 A CN 201610727174A CN 106480492 A CN106480492 A CN 106480492A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
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Abstract
The invention provides for the method for producing group III nitride semiconductor monocrystalline, which is designed to grow the semiconductor monocrystal with degree of reproducibility.Method for producing group III nitride semiconductor monocrystalline adds seed crystal substrate, Ga and Na, and growth group III nitride semiconductor monocrystalline in including to crucible.In the growth of group III nitride semiconductor monocrystalline, using the reaction of measurement apparatus detection Ga and Na.In the case that the temperature of crucible is adjusted in 80 DEG C to 200 DEG C of the first temperature range, Ga and Na reacts.After measurement apparatus detect Ga and Na reaction, the temperature of crucible is increased to the growth temperature of group III nitride semiconductor monocrystalline.
Description
Technical field
The technical scheme of this specification relates to produce the side of group III nitride semiconductor monocrystalline by flux growth metrhod
Method.
Background technology
By vapor growth method, such as metal-organic chemical vapor deposition (MOCVD) and hydride gas-phase epitaxy
(HVPE)；Molecular beam epitaxy (MBE)；Semiconductor crystal is produced with liquid phase epitaxy.A kind of liquid phase epitaxial technique is fluxed using Na
The flux growth metrhod of agent.
In the general procedure of flux growth metrhod, gallium nitride (GaN) layer is formed in the substrates such as sapphire substrates, be consequently formed
Seed crystal substrate, and semiconductor monocrystal is to be grown in seed crystal substrate in the melt.By seed crystal substrate, the raw material of semiconductor monocrystal
It is positioned in crucible with flux, and then, growth semiconductor monocrystal is while control reaction chamber temperature and pressure.Disclose
Nitrogen is (public see, for example Japanese patent application from the technology of gas and liquid phase interfacial migration to melt by stirring melt
Open [0003rd] section, the table 1 of (JP) No. 2010-168236th number etc.).
When semiconductor monocrystal is grown by flux growth metrhod, semiconductor monocrystal is grown not according to growth conditions sometimes.Very
To when semiconductor monocrystal can grow, it is also difficult to obtain uniform semiconductor monocrystal in the whole surface of seed crystal substrate.Half
The repeatability of conductor monocrystalline is sometimes unstable.That is, semiconductor monocrystal easily stably will never be grown.
Content of the invention
Technical solution of the present invention has been completed the solution to involved the problems referred to above in routine techniques.Therefore, this
One purpose of bright technical scheme is to provide the method for producing group III nitride semiconductor monocrystalline with high reproducibility.
Therefore, in the first aspect of technical solution of the present invention, there is provided for producing group III nitride semiconductor list
Brilliant method, methods described add seed crystal substrate, Ga and Na, and growth group III nitride semiconductor in including to crucible
Monocrystalline.In growth of the group III nitride semiconductor monocrystalline under predetermined growth temperature, it is adjusted to be below in crucible temperature
In the case of in 500 DEG C of the first temperature range, Ga and Na reacts.After the reaction of Ga and Na, the temperature of crucible is raised
Growth temperature to group III nitride semiconductor monocrystalline.
The second aspect of technical solution of the present invention relates to produce the one of the method for group III nitride semiconductor monocrystalline
The reaction of individual specific embodiment, wherein Ga and Na is the fine grain dispersion state of Ga-Na alloy.
First temperature range is preferably 80 DEG C to 400 DEG C, and further preferred 80 DEG C to 200 DEG C.The invention of the present invention
People has found to realize the fine grain dispersion of Ga and Na reaction in the melt, i.e. Ga-Na alloy before semiconductor growing
State greatly helps generation or the melt back in growth period core.In routine techniques, there is no high quality crystal and be because
Before growth, the fine grain growing amount of Ga-Na alloy is few.When the temperature is maintained at a below in the range of 500 DEG C or is heated up
When speed reduces in the temperature range, the alloying of Ga and Na is promoted.Afterwards, by the temperature is increased to growth
Temperature and grow semiconductor come realize high quality crystal growth.The fine grained of substantial amounts of Ga-Na alloy is even at 80 DEG C to 400
Produce within the temperature range of DEG C.However, certainly a large amount of fine graineds can be produced within the temperature range of 80 DEG C to 200 DEG C so that
The semiconductor crystal of first water can be grown.
A third aspect of the present invention relates to one of the method for production group III nitride semiconductor monocrystalline specifically in fact
Scheme is applied, wherein passes through the measurement for detecting the reaction of the Ga in the first and second aspect of technical solution of the present invention and Na
The reaction of device detection Ga and Na.
In the method for producing group III nitride semiconductor monocrystalline, Ga is fully reacted with Na.Ga-Na alloy is equal
Disperse evenly in the melt.It is formed on the surface of whole seed crystal substrate group III nitride semiconductor single crystalline uniform.Partly lead
Body monocrystalline also has high yield.When the reaction of Ga and Na is insufficient, continue heat treatment in the first temperature range until true
Fixed sufficiently reaction.In order to promote the reaction of Ga and Na, can proceed as follows：The time of prolongation heat treatment, stirring, change
Pressure and control furnace atmosphere.
The fourth aspect of technical solution of the present invention relates to produce the one of the method for group III nitride semiconductor monocrystalline
Individual specific embodiment, wherein measurement apparatus are to pass through in the third aspect of technical solution of the present invention to launch X-ray to crucible
X-ray finder inside detection crucible.The measurement apparatus are by receiving X-ray detection Ga and Na through crucible transmission
Reaction.
5th aspect of technical solution of the present invention relates to produce the one of the method for group III nitride semiconductor monocrystalline
Individual specific embodiment, wherein measurement apparatus have measurement crucible internal temperature and detect the technology of the present invention side with differential thermal analysis
The temperature measurement unit of the Ga in the third aspect of case and Na reaction.
6th aspect of technical solution of the present invention relates to produce the one of the method for group III nitride semiconductor monocrystalline
Individual specific embodiment, wherein in the growth of group III nitride semiconductor monocrystalline, adjusts the temperature of crucible with the present invention
The first of technical scheme keeps at least 30 minutes to the 5th aspect in the first temperature range.
7th aspect of technical solution of the present invention relates to produce the one of the method for group III nitride semiconductor monocrystalline
Individual specific embodiment, wherein described in the first to the 5th aspect of technical solution of the present invention, the temperature of crucible is raised from room temperature
Heating rate to the temperature when the reaction of Ga and Na is completed is increased to life less than the temperature of the crucible after the reaction
The heating rate of long temperature.
Technical solution of the present invention disclosed in this specification provides the III-th family for production with degree of reproducibility
The method of nitride semiconductor single-crystal.
Description of the drawings
When considered in conjunction with the accompanying drawings and described in detail below with reference to preferred embodiment, technical solution of the present invention various
Other purposes, feature and many bonus are better understood with and more easily recognize, wherein：
Fig. 1 is the schematic diagram of the group III nitride semiconductor monocrystalline of embodiment 1 to 3；
Fig. 2 is to illustrate the crystal growth equipment for producing the group III nitride semiconductor monocrystalline of embodiment 1
Structure schematic diagram；
Fig. 3 illustrates the schematic diagram for forming the method for seed crystal substrate, and the seed crystal substrate is used for producing embodiment 1
The method of group III nitride semiconductor monocrystalline；
Fig. 4 is to be shown in the method for the group III nitride semiconductor monocrystalline for producing embodiment 1 and 2 to be wrapped
The figure of the rotation mode of crucible in the growth of the semiconductor monocrystal for including；
Fig. 5 is to be shown in the temperature in the method for the group III nitride semiconductor monocrystalline for producing embodiment 1 and 2
Write music the figure of line；
Fig. 6 is the figure for illustrating the temperature curve when being tested to produce group III nitride semiconductor monocrystalline；
Fig. 7 is to illustrate earthenware in the method for producing group III nitride semiconductor monocrystalline in the embodiment described in which
The sketch map (part 1) of Ga and Na in crucible；
Fig. 8 is to illustrate earthenware in the method for producing group III nitride semiconductor monocrystalline in the embodiment described in which
The sketch map (part 2) of Ga and Na in crucible；
Fig. 9 is to illustrate earthenware in the method for producing group III nitride semiconductor monocrystalline in the embodiment described in which
The sketch map (third portion) of Ga and Na in crucible；
Figure 10 is to illustrate to make in the method for producing the group III nitride semiconductor monocrystalline of embodiment 2
The schematic diagram of the structure of crystal growth equipment；
Figure 11 is the schematic diagram of the structure of the vertical semiconductor device for illustrating embodiment 3；
Figure 12 is the schematic diagram of the structure of the Lateral-type semiconductor device for illustrating embodiment 3；And
Figure 13 is the schematic diagram of the structure of the semiconductor light-emitting apparatus for illustrating embodiment 3.
Specific embodiment
The specific embodiment of description of the drawings technical solution of the present invention will be further referenced.The embodiment is related to
Based on the method that flux growth metrhod produces group III nitride semiconductor monocrystalline, and the semiconductor dress produced by methods described
Put.The merely illustrative purpose of these key elements described in the embodiment is given, and technical solution of the present invention is not
It is limited to the embodiment.The thickness of per layer schematically shown in accompanying drawing does not simultaneously correspond to actual value in fact.
Embodiment 1
1. semiconductor monocrystal
Fig. 1 shows the crystal CR of embodiment 1.As shown in figure 1, crystal CR have sapphire substrates 11, cushion 12,
GaN layer 13 and monocrystalline CR1.Monocrystalline CR1 is formed by group III nitride semiconductor.Monocrystalline CR1 is by removing indigo plant from crystal CR
Jewel substrate 11 and other layers are obtained.
2. crystal growth equipment
The structure of 2-1. crystal growth equipment
Fig. 2 shows the crystal growth equipment 1000 of the crystal CR of production embodiment 1.Crystal growth equipment 1000 passes through
The flux growth metrhod of Na is used for growing group III nitride semiconductor monocrystalline in growth substrate.As shown in Fig. 2 crystal growth sets
Standby 1000 with air supply pipe 1210, blast pipe 1220, heat guard 1230, reative cell 1240, pressure vessel 1250, rotating disk 1270,
Rotating shaft 1280, engine 1310, control unit of engine 1320, x-ray irradiation unit 1400, X-ray receiving unit 1500, temperature
Degree measuring unit 1600, reaction determining unit 1700, heater H and heater control unit 1800.
As shown in Fig. 2 in crystal growth equipment 1000, crucible 1260 can be placed on rotating disk 1270.Crucible 1260
Can be with rotating disk 1270 while rotating.Pivot corresponds to rotating shaft 1280.The rotary speed of crucible 1260 can be by adjusting
The rotation of engine 1310 is adjusted.In crystal growth equipment 1000, in addition to the rotation, crucible 1260 can also be carried out
Vibration is waved, so as to stir raw material.
Pressure vessel 1250 is applied to receiving reative cell 1240.Pressure vessel 1250 is made up of the material of such as SUS.Without
Say, it is also possible to using other materials.Reative cell 1240 is applied to receiving crucible 1260 and provides bar to the growth of semiconductor monocrystal
Part.
Arranging air supply pipe 1210 is used for nitrogen (N2) supply to reative cell 1240.Arranging blast pipe 1220 is used for nitrogen
Gas (N2) discharge from reative cell 1240.The internal pressure of reative cell 1240 can be adjusted by this two pipes.Heating is set
Device H is with the inside of heated pressure container 1250 and the inside of reative cell 1240.Heater H can also control the interior of reative cell 1240
Portion's temperature.Heat guard 1230 is used as can prevent heat from the diffusion inside of reative cell 1240 to its outside component.Can supply
Any gas in addition to nitrogen, such as Ar, to control pressure or atmosphere in stove.
Rotating disk 1270 is used as the base for arranging crucible 1260 thereon.Therefore, rotating disk 1270 is arranged in reative cell 1240.
Crucible 1260 is made up of aluminum oxide.Or crucible 1260 can by transmission X-ray and have heat resistance other materials make.Rotating shaft
1280 support rotating disk 1270 and transmit the power of engine 1310 to rotating disk 1270.Rotating shaft 1280 receives the driving of engine 1310
Power and as pivot.
Engine 1310 is used as the Rotary-drive member for rotating shaft 1280.The control of control unit of engine 1320 is sent out
The rotation of motivation 1310.Control unit of engine 1320 controls the direction of the rotation of engine 1310 and the rotation of engine 1310
Speed, and increase and reduce the rotary speed of engine 1310.In other words, control unit of engine 1320 is according to hereafter institute
The rotation of the rotary mode control crucible 1260 that states.
X-ray irradiation unit 1400 is applied to generation X-ray and uses X-ray X1 irradiation crucible 1260 on rotating disk 1270.X
Ray receiving unit 1500 is applied to X-ray X2 received through the transmission of crucible 1260.X-ray receiving unit 1500 is by passing through earthenware
The X-ray that crucible 1260 is transmitted forms radioscopic image.
Temperature measurement unit 1600 is applied to the internal temperature of measurement crucible 1260.Reaction determining unit 1700 is applied to base
The reactiveness of Ga and Na is determined in the radioscopic image obtained by X-ray receiving unit 1500.Reaction determining unit 1700 by
The temperature of the crucible 1260 measured by temperature measurement unit 1600 carries out differential thermal analysis.
Heater control unit 1800 is applied to the heat levels of control heater H.1800 basis of heater control unit
The heat levels of the reactiveness control heater H of the Ga observed by X-ray receiving unit 1500 and Na.Heater control unit
The heat levels of the temperature control heater H of the crucible 1260 that 1800 bases are measured by temperature measurement unit 1600.
Crystal growth equipment 1000 can have the device of monitoring furnace atmosphere.This device includes gas monitor, example
As four polar form mass spectrographs and oxygen concentration testing meter.
The operation of 2-2. crystal growth equipment
Crystal growth equipment 1000 is monitored the state in crucible 1260 and grows monocrystalline CR1 in crucible 1260.Using X
X ray irradiation x unit 1400, X-ray receiving unit 1500 and temperature measurement unit 1600 are monitored.
Observation of the 2-2-1. by X-ray
The X-ray X1 irradiation of x-ray irradiation unit 1400 contains the crucible 1260 of raw material.X-ray receiving unit 1500 connects
Receive X-ray X2 transmitted through crucible 1260.X-ray receiving unit 1500 carries out the image procossing of passed through X-ray X2.X
Ray image can show respectively on display etc..Therefore, X-ray receiving unit 1500 can export instantaneous continually varying
Radioscopic image.
X-ray receiving unit 1500 can monitor the reactiveness of Ga and Na in crucible 1260.Crystal growth equipment 1000
Or operator determines whether Ga and Na reacts.Operator determines that by visual inspection X-ray Ga and Na reacts.When being obtained
Radioscopic image when being close to the image shown in Ga and Na reaction photo, the reaction determining unit 1700 of crystal growth equipment 1000
Determine that Ga and Na reacts, also, when the radioscopic image for being obtained keeps off the image shown in Ga and Na reaction photo, determine
Ga is not reacted with Na.
2-2-2. differential thermal analysis
Temperature measurement unit 1600 measures the internal temperature of crucible 1260.The reaction of crystal growth equipment 1000 determines single
Unit 1700 obtains the reference temperature value of the measurement temperature value of crucible 1260 and the setting value based on heater control unit 1800.
Reference temperature value can be pre-stored within memory etc..Reaction determining unit 1700 is determined in crucible 1260 by differential thermal analysis
Whether Ga and Na there occurs reaction.
3. the method for being used for producing group III nitride semiconductor monocrystalline
3-1. forms seed crystal substrate
Then, the method for producing semiconductor monocrystal will be described.As shown in figure 3, the system by description template 10
Standby.Template 10 be for by flux growth metrhod grow semiconductor monocrystal seed crystal substrate.First, sapphire substrates 11 are provided.Logical
MOCVD is crossed, and cushion 12 is formed on the c- face of sapphire substrates 11.Cushion 12 is formed by the material of such as AlN.Cushion
Can be formed by TiN or GaN.Free-standing GaN crystal is used as template 10.
On cushion 12, GaN layer 13 is formed, thus prepares template 10.Cushion 12 and GaN layer 13 are used as seed layer.So
And, when using GaN self-supporting substrate (wafer), it is not necessary to form cushion 12.GaN layer 13 is (for the GaN in the embodiment
Layer) can also be formed by AlGaN, InGaN or AlInGaN.Under some growth conditions, GaN layer 13 is experienced back in flux
Molten.In this case, a part for GaN layer 13 is dissolved in flux.
3-2. grows semiconductor monocrystal
Then, semiconductor single crystal layer is formed in template 10 by the flux growth metrhod as liquid phase epitaxy type.Table 1 is illustrated
For growing the raw material of semiconductor monocrystal.Carbon ratio can change in the range of 0mol% to 2.0mol%.That is,
Flux optionally or can not include carbon.Value shown in table 1 is only example, and can use other values.
In addition to these elements, doped chemical can be added.
Semiconductor monocrystal to be grown is group III nitride semiconductor monocrystalline, such as GaN.First, template 10 and 1 institute of table
The raw material for showing is weighed in the glove box of control dew point and oxygen concentration.Subsequently, template 10 and Ga and Na are added earthenware
In crucible 1260.Then, crucible 1260 is placed on the rotating disk 1270 of reative cell 1240.Afterwards, pressure vessel 1250 is carried out
Vacuumize, and then improve the pressure and temperature in container.When crucible 1260 rotates, semiconductor monocrystal is grown.In office
When wait, it is possible to use any stirring means.Therefore, semiconductor monocrystal can be grown in the case of not stirring.In growth period
Between can be changed to whether stirring.
Table 1
| Raw material | Material quantity |
| Ga | 1g |
| Na | 1.4g |
| C | 0mol% to 2.0mol% (with regard to Na) |
Table 2 is shown in crucible for growing the condition of semiconductor monocrystal.The growth temperature of semiconductor monocrystal is adjusted to,
For example, 870 DEG C, and pressure is adjusted to, for example, 3MPa.Growth time is for about 20 hours to 200 hours.
Table 2
| Temperature | About 700 DEG C to 900 DEG C |
| Pressure | 3MPa to 10MPa |
| Mixing speed | 0rpm to 100rpm |
| Growth time | 20 hours to 200 hours |
4. the rotary mode of crucible
The rotary mode of the crucible 1260 used in embodiment 1 is shown in Figure 4.As shown in figure 4, the rotation of crucible 1260
Pattern includes that rotated forward and reversely rotate is alternately repeated.In this manual, the rotary speed of crucible 1260 is forward
Represented with symbol "+", and represented with symbol "-" on reversely.
As shown in figure 4, agitation phases include boost phase A1, constant speed rotary (forward direction) stage A2, decelerating phase A3, acceleration
Stage A4, constant speed rotary (reverse) stage A5 and decelerating phase A6.In the growth of semiconductor monocrystal, continuously carry out this and follow
Ring.Term as used herein " acceleration " refers to the absolute value of the rotary speed for increasing crucible 1260, and term " deceleration " is referred to
Reduce the absolute value of the rotary speed of crucible 1260.
In boost phase A1, rotary speed ω of crucible 1260 increases to rotary speed ω 1.Rank is rotated forward in constant speed
In section A2, crucible 1260 is rotated with constant speed ω 1.In decelerating phase A3, rotary speed ω of crucible 1260 is from rotary speed ω 1
Reduce.In boost phase A4, rotary speed ω of crucible 1260 increases to rotary speed-ω 1.The stage is reversely rotated in constant speed
In A5, crucible 1260 is rotated with constant speed-ω 1.In decelerating phase A6, rotary speed ω of crucible 1260 is from rotary speed-ω 1
Reduce.
5. the temperature curve of melt
Fig. 5 is the figure of the temperature curve of melt in the crucible 1260 for be shown in embodiment 1.As shown in figure 5, in embodiment party
In case 1, in the first stage during K1, the internal temperature of crucible 1260 is adjusted to the first temperature range J1.First stage, K1 was
20 minutes to 70 minutes.Preferably, first stage K1 is 30 minutes to 60 minutes.First temperature range J1 is 80 DEG C to 200 DEG C.
That is, the temperature of crucible 1260 is maintained at 30 minutes or longer in the first temperature range J1.
As mentioned below, when the internal temperature of crucible 1260 is in the first temperature range J1, Ga and Na reacts.Assume Ga
React with each other with Na, so as to form the fine grained of Ga-Na alloy.That is, the fine grained completed as Ga-Na alloy of reaction
Dispersion state.When Ga is equably mixed with Na while when Ga and Na reacts, equably growing uniform semiconductor crystal.
Therefore, in the first stage during K1, the temperature of crucible 1260 is adjusted in the first temperature range J1.
After the reaction of Ga and Na is fully carried out, heater control unit 1800 increased the temperature of heater H.By earthenware
The temperature of crucible 1260 is increased to the growth temperature of semiconductor monocrystal.
Therefore, in the first stage during K1 in the first temperature range J1 Ga and Na react, and monocrystalline CR1 is at 700 DEG C
Or grow under higher growth temperature.
It is found through experiments：The life of reactiveness of the Ga and Na in the first temperature range J1 and subsequently GaN at high temperature
There is close relationship between length.When crucible 1260 has been heated above the first temperature range J1 and in the first temperature range J1
During interior insufficient reaction, GaN crystal may not grow or crystal may abnormality growth.Therefore, have well again to grow
The GaN of existing property, preferably after Ga and Na generation fully reaction in the first temperature range J1, crucible 1260 is heated to high temperature.
The detection of 6.Ga and Na reaction
In the growth of semiconductor monocrystal, Ga and Na are placed in crucible 1260, and grow III-th family nitride
Semiconductor monocrystal.Measurement apparatus are used for the reaction of detection Ga and Na when group III nitride semiconductor monocrystalline is grown.Following article
Described in, under the temperature of crucible 1260 is adjusted in 80 DEG C to 200 DEG C of the first temperature range J1, Ga and Na reacts.Surveying
After the reaction of amount device detection Ga and Na, the temperature of crucible 1260 is increased to the life of group III nitride semiconductor monocrystalline
Long temperature.The growth temperature of group III nitride semiconductor monocrystalline is 700 DEG C to 950 DEG C.
6-1.X axial observation device
The measurement apparatus be for being observed by launching X-ray by crucible 1260 and observe the internal X-ray of crucible 1260
Device.As shown in Fig. 2 the measurement apparatus have x-ray irradiation unit 1400, X-ray receiving unit 1500 and reaction determining
Unit 1700.The X-ray X1 irradiation crucible 1260 of x-ray irradiation unit 1400.X-ray X2 through crucible 1260 is penetrated by X
Line receiving unit 1500 is received.Reaction determining unit 1700 detects the reaction of Ga and Na by receiving X-ray X2.Or operator
Determine that Ga and Na reacts by the radioscopic image for being obtained.
6-2. differential thermal analysis
Measurement apparatus have temperature measurement unit 1600 and reaction determining unit 1700.Temperature measurement unit 1600 measures earthenware
The internal temperature of crucible 1260.Then, reaction determining unit 1700 is using the temperature value that measured by temperature measurement unit 1600 and pre-
Fixed reference value carries out differential thermal analysis.When the difference of measured temperature value and reference value exceedes predetermined threshold value, determine Ga with
Na reacts.When measured temperature value carries out time integral with the difference of reference value, and integrated value exceedes predetermined integral reference value
When, it may be determined that the reaction of Ga and Na is completed.After the reaction of Ga and Na is completed, preferably the temperature of crucible 1260 is increased to
The growth temperature of semiconductor monocrystal.
6-3. temperature control
When group III nitride semiconductor monocrystalline is grown, the temperature of crucible 1260 is preferably in the first temperature range J1
Kept at least 30 minutes, so as to be sufficiently carried out the reaction of Ga and Na.
6-4. other
In order to the reaction of Ga and Na is detected, the change that the internal state of crucible 1260 is produced can be obtained due to reaction.
In principle, it is possible to the method using such as resistance measurement.
7. test
The experiment for carrying out is described below.In this experiment, under various temperature curves, semiconductor single-crystal growth is in seed crystal
In substrate.
Fig. 6 is to illustrate the figure for growing the temperature curve of semiconductor monocrystal.In online L1, in the first stage during K1,
The temperature of crucible 1260 is in the first temperature range J1.The first temperature range J1 is reached and through the first stage in the temperature
After K1, the temperature of crucible 1260 is lifted.In this case, when the temperature of crucible 1260 is for about 100 DEG C, start Ga and Na
Reaction.Ga and Na reacts and fully disperses.That is, it appears that the fine grained of the alloy of Ga and Na is effectively disperseed.
Monocrystalline CR1 is grown in the whole surface of template 10.
In the line L2 of Fig. 6, the temperature of crucible 1260 more sharp rises than line L1.The stage of 1260 temperature of crucible is
In one temperature range J1, more shorter than line L1.However, when temperature is in the range of 200 DEG C to 300 DEG C, the temperature of crucible 1260
Rising is gentle.In this case, Ga and Na does not fully react, and monocrystalline CR1 is not almost grown in template 10.
In the line L3 of Fig. 3, the temperature of crucible 1260 more sharp rises than line L1.The stage of 1260 temperature of crucible is
In one temperature range J1, more shorter than line L1.In this case, Ga and Na does not fully react.Monocrystalline CR1 does not almost grow
In template 10.
It is therefore contemplated that it is important that gradually rising the temperature of crucible 1260 in the first temperature range J1 such that it is able to make
Ga is fully reacted with Na.In order to equably grow monocrystalline CR1 in the whole surface of template 10, it is believed that it is important that after making reaction
Ga and Na (i.e. the fine grained of the alloy of Ga and Na) fully disperse.
Then the radioscopic image obtained by X-ray receiving unit 1500 will be described.Fig. 7 is an immediately proceeding at temperature
The radioscopic image of the crucible 1260 after degree rising.In this stage, Ga and Na both of which is not melted.Therefore, in the figure 7,
Na is placed on Ga.
Fig. 8 is the radioscopic image in the crucible 1260 when the temperature of crucible 1260 is near 100 DEG C.The fusing point of Na is for about
97.7℃.The fusing point of Ga is for about 29.8 DEG C.Therefore, near 100 DEG C, Na starts melting, and Ga and Na reacts.In fig. 8,
Ga is mixed with Na.
In fig .9, in template 10, Ga and Na reacts.The fine grained of the Ga-Na alloy obtained by the reaction is uniform
Be arranged in template 10.When the reaction of Ga and Na proceeds to the stage, monocrystalline CR1 equably grows.On the other hand, described
Reaction stopped in the stage of Fig. 7, did not grow monocrystalline CR1.
The result of experiment shows that the reaction of Ga and Na proceeds to as shown in Figure 9 as temperature curve (the line L1) using Fig. 6
State, and equably produce monocrystalline CR1.As temperature curve (line L2 and the line L3) using Fig. 6, the reaction of Ga and Na is such as
Stop in the state of shown in Fig. 7, and do not produce monocrystalline CR1.
8. change programme
8-1. temperature control
In embodiment 1, observe in the radioscopic image obtained by X-ray receiving unit 1500 Ga with
After the mixture of Na is completed, the temperature of crucible 1260 is increased to the growth temperature of semiconductor monocrystal.K1 phase in the first stage
Between, the temperature of crucible 1260 is adjusted in the first temperature range J1.After first stage K1, can be by crucible 1260
Temperature be increased to growth temperature.
In differential thermal analysis, when reference temperature value is integrated over time with the difference of measured temperature value, and integrated value
During more than predetermined integrated reference value, it may be determined that the reaction of Ga and Na is completed.In this case, determining unit 1700 is reacted
It is integrated being calculated and determined whether reaction completes.Afterwards, the temperature of crucible 1260 is increased to growth temperature.
8-2. group III nitride semiconductor monocrystalline
In embodiment 1, GaN semiconductor monocrystal is formed.However, this production method can apply to other ii I
The growth of nitride semiconductor single crystal.For example, it is possible to produce AlXInYGa(1-X-Y)N (0≤X, 0≤Y, X+Y≤1).This
In the case of, add extra raw material in needing to crucible 1260.
The growth of many semiconductor monocrystals of 8-3.
In embodiment 1, a semiconductor monocrystal is grown by single crucible.However, it is also possible to big by having
The single crucible of diameter produces multiple semiconductor monocrystals, causes the raising of productivity.
8-4. rotary mode
The rotary mode of crucible 1260 is not necessarily limited to that a kind of pattern shown in Fig. 4.Other rotary modes can be used.
9. the summary of embodiment
As described above, in embodiment 1, that is, it is used in the method for produce group III nitride semiconductor monocrystalline, passes through
Flux growth metrhod grows semiconductor monocrystal.The temperature of crucible 1260 is adjusted in the first temperature range J1 during K1 in the first stage
Interior.The temperature of crucible 1260 is gradually risen during K1 in the first stage, and Ga is fully reacted with Na.Measurement apparatus detection Ga and Na's
Reaction.Reacted Ga and Na is fully disperseed.Therefore, monocrystalline CR1 can equably be grown in the whole table of seed crystal substrate
On face.Therefore, in the method for producing III-th family semiconductor monocrystal, semiconductor monocrystal has high yield.
Note, the merely illustrative purpose of embodiment 1 is given.Much less, those skilled in the art can be
Embodiment is altered or modified in the case of without departing from its spirit.For example, in embodiment 1, by metal-organic chemical gas
Mutually deposition (MOCVD) forms cushion 12 and GaN layer 13 in template 10.However, it is also possible to using vapor phase growth techniques for example
Hydride gas-phase epitaxy (HVPE), physical method such as molecular beam epitaxy (MBE) and other similar technology.
Embodiment 2
Technical solution of the present invention based on the discovery that：When the reaction for realizing Na and Ga at a temperature of less than growth temperature
Afterwards, when growth temperature being increased to the growth temperature for growing group III nitride semiconductor, high-quality and uniform crystalline substance are obtained
Body.The reaction of Na and Ga is the fine grain dispersion state of Ga-Na alloy.When realizing fine grain point of Ga-Na alloy
Prose style free from parallelism state and by the temperature be increased to growth group III nitride semiconductor monocrystalline growth temperature after Ga-Na close
When gold becomes liquid in temperature-rise period, flat high quality crystal is obtained.In embodiment 1, the fine grained of Ga-Na alloy
Dispersion state detected using X-ray or in differential thermal analysis.
Therefore, if realizing the fine grain dispersion state of Ga-Na alloy before crystal growth, this can be realized
The target of inventive technique scheme.Heating curve shown in Fig. 5 and 6 and the dispersion of the Ga-Na alloy using X-ray detection
Relation between state can be stored by experiment.From result, Ga-Na can be realized only by optimum temperature rise curve
The dispersion state of alloy.That is, can be by the temperature of heating curve or wherein described melt less than growth temperature
The dispersion state of Ga-Na alloy is realized in time period in the range of the predetermined low temperature level of degree.
Embodiment 2 is the temperature before growing under growth temperature only by control group III nitride semiconductor
An example of the reaction of Ga and Na is completed in the first temperature range.
Figure 10 shows the crystal growth equipment 1010 of embodiment 2.Crystal growth equipment 1010 and the crystalline substance shown in Fig. 2
The difference of bulk-growth equipment 1000 be only in that pressure vessel 1250 be one-piece type without being separated into top or bottom,
And there is no x-ray irradiation unit 1400, X-ray receiving unit 1500 and reaction determining unit 1700.
In embodiment 2, the temperature of reative cell 1240 is being maintained at 95 DEG C while when emptying, raw material will be included
Crucible 1260 is placed in reative cell 1240.Subsequently, 30 handkerchiefs were adjusted to the pressure of reative cell 1240 in 2.5 hours.Also
Be to say, the temperature of crucible 1250 maintained at 95 DEG C 2.5 hours (stage K1) of holding, as Fig. 5 and 6 curve L4 shown in.This
Afterwards, the temperature is increased to growth temperature with 10 DEG C/min of heating rate, and crystal is grown under growth temperature.
In figure 6, when with the short time by 80 DEG C to 200 DEG C of low temperature range and by material under temperature curve L2 and L3
When the temperature of material (i.e. melt) is increased to growth temperature, high-quality and uniform crystal will not be obtained.That is, needing at least
The low-temperature condition of certain time is realizing the fine grain dispersion state of Ga-Na alloy.When with high speed by low-temperature condition,
Even if the melt is maintained above under the temperature of the temperature range or growth temperature also realizing thin of Ga-Na alloy
The dispersion state of grain, so as to cause Ga to separate with Na.
Conversely, work as the temperature is increased to by said temperature scope with the long time under temperature curve L1 or L4
During growth temperature, high-quality and uniform semiconductor crystal is obtained.When in the heating curve of melt by low temperature range when
Between section be 30 minutes or more when, realize the fine grain dispersion state of Ga-Na alloy.In the fine grain of Ga-Na alloy
After dispersion state is completed, it is not necessary to by the extra time section of low temperature range.Even if being prolonged by the stage of low temperature range
It is long that also there is no problem.However, the longer production time is not preferred.Normally, the time period for increasing low temperature range is 30
Minute was to 3 hours.When the time period is oversize, the meltage of minimizing nitrogen, and increase the melt back of seed crystal, thus make semiconductor crystal
Quality deterioration.
In the heating curve of melt, the time period K1 in 80 DEG C to 200 DEG C of low temperature range is preferred for the temperature of melt
For predetermined value.Temperature can be stopped raise and be maintained in low temperature range.The temperature of melt is low at 80 DEG C to 200 DEG C
Time period K1 in warm scope can be by making from room temperature to 200 DEG C of heating rate less than the liter from 200 DEG C to growth temperature
Warm speed is controlling.From room temperature to 200 DEG C of heating rate be preferably lower than or equal to 10 DEG C/min.From 200 DEG C to growth temperature
Heating rate be preferably 5 DEG C/min to 20 DEG C/min.In the temperature curve L1 and L4 of Fig. 6, heating rate is walked at two
Change in rapid.However, which can change in multiple steps.For example, the temperature-rise period under 10 DEG C/min of heating rate
In, the temperature can be kept for 30 minutes respectively at 95 DEG C, 150 DEG C, 200 DEG C and 250 DEG C.Retention time is in each holding temperature
Can be different under degree.
In figure 6, when the time by the temperature range less than or equal to 400 DEG C being 30 minutes or longer, Ga- is realized
The fine grained of Na alloy is evenly dispersed in the state in melt.The alloy becomes liquid at 400 DEG C.When wherein big in realization
The fine grained of the Ga-Na alloy of amount is equably increased to the mistake of growth temperature by Ga-Na alloy after scattered state in temperature
When becoming liquid in journey, improve the degree of crystallinity of growth semiconductor.The present invention based on the discovery that：By wherein a large amount of in realization
Ga-Na alloy fine grained obtain liquid Ga-Na alloy before equably by scattered state after, by growth temperature
Degree is lower to be grown semiconductor to obtain high quality crystal.Therefore, it is however generally that, when the temperature range less than 500 DEG C must remain long
Between to realize the fine grain dispersion state of Ga-Na alloy.
Embodiment 3
Embodiment 1 and 2 refers to the method for producing group III nitride semiconductor monocrystalline.Embodiment 3 is to instigate
With the group III nitride semiconductor monocrystalline as self-supporting substrate semiconductor device.
1. vertical semiconductor device
Figure 11 shows the power device 100 according to embodiment 2.Power device 100 is vertical semiconductor device.Work(
Rate device 100 has the drain electrode D1 as shown in Figure 11 bottom, and the gate electrode G1 as shown in Figure 11 top and source electrode S1.
Power device 100 is with multiple group III nitride semiconductor layers.As shown in figure 11, in addition to former electrodes,
Power device 100 also has substrate 110, n-layer 120, p-type layer 130, n-layer 140 and dielectric film 150.N-layer 120 is with n+
GaN layer 121 and n-GaN layer 122, which is sequentially arranged in substrate 110.Source electrode S1 is contacted with n-layer 140, and is leaked electricity
Pole D1 is contacted with substrate 110.
2. self-supporting substrate
Substrate 110 is the self-supporting substrate produced by the crystal CR of embodiment 1 and 2.As used herein term is " certainly
Support substrate " includes disk like substrate (wafer), and substrate of acquisition etc. after device isolation.Sapphire substrates 11 and other
Part is removed from crystal CR.Removing can be carried out by known technology such as laser lift-off.The two of the monocrystalline CR1 for so obtaining
Individual surface is all polished or experiences similar process, thus obtains substrate 110.Substrate 110 can be provided with projection or its
His shape.Or, it is also possible to monocrystalline CR1 at least one side is polished, rather than polishing both surfaces.After crystal growing process
Cooling period, it is possible to use thermal strain is peeled off to substrate 110.
3. change programme
3-1. Lateral-type semiconductor device
Embodiment 2 refers to vertical semiconductor device.However, the self-supporting substrate of embodiment 2 can apply to as
Lateral-type semiconductor device 200 shown in Figure 12.Semiconductor device 200 shown in Figure 12 is HFET.Semiconductor device 200 has
Substrate 210, cushion 220, first vector mobile layer 230, Second support mobile layer 240, carrier supply layer 250, dielectric film
260th, drain electrode D2, source electrode S2 and gate electrode G2.Substrate 210 is by being processed to obtain to monocrystalline CR1.
3-2. semiconductor light-emitting apparatus
Or, the self-supporting substrate of embodiment 2 can be applicable to the semiconductor light-emitting apparatus 300 shown in Figure 13.As above institute
State, the monocrystalline CR1 obtained by the production method of embodiment 1 and 2 can be applicable to multiple semiconductor devices.Semiconductor light emitting is filled
300 are put with substrate 310, semiconductor layer, p-electrode P3 and n-electrode N3.Substrate 310 be by being processed to obtain to monocrystalline CR1
?.
Semiconductor layer is prevented layer 340, N-shaped coating 350, is lighted by cushion 320, n-contact layer 330, N-shaped electrostatic breakdown
Layer 360, p-type coating 370 and P type contact layer 380 constitute, and which is formed on the first type surface of substrate 310 in order.P-electrode P3 and p
Type contact layer 380 contacts, and n-electrode N3 is contacted with n-contact layer 330.
Claims (11)
1. a kind of method for producing group III nitride semiconductor monocrystalline, methods described include：
Add seed crystal substrate, Ga and Na, and growth group III nitride semiconductor monocrystalline in crucible,
Wherein, under predetermined growth temperature in the growth of the group III nitride semiconductor monocrystalline,
The temperature adjustment of the crucible is in the first temperature range less than 500 DEG C in the case of, react Ga and Na；With
And
After the reaction of Ga and Na, the temperature of the crucible is increased to the life of the group III nitride semiconductor monocrystalline
Long temperature.
2. the method for producing group III nitride semiconductor monocrystalline according to claim 1, wherein described Ga and Na
Reaction for Ga-Na alloy fine grain dispersion state.
3. the method for producing group III nitride semiconductor monocrystalline according to claim 1, wherein described first temperature
Degree scope is 80 DEG C to 400 DEG C.
4. the method for producing group III nitride semiconductor monocrystalline according to claim 2, wherein described first temperature
Degree scope is 80 DEG C to 400 DEG C.
5. the method for producing group III nitride semiconductor monocrystalline according to claim 1, wherein described first temperature
Degree scope is 80 DEG C to 200 DEG C.
6. the method for producing group III nitride semiconductor monocrystalline according to claim 2, wherein described first temperature
Degree scope is 80 DEG C to 200 DEG C.
7. the method for producing group III nitride semiconductor monocrystalline according to claim 1, wherein described Ga and Na
Reaction by the measurement apparatus for detecting the reaction of the Ga and Na detecting.
8. the method for producing group III nitride semiconductor monocrystalline according to claim 7, wherein described measurement dress
It is X-ray finder to put, and the X-ray finder passes through to launch, to the crucible, the inside that X-ray observes the crucible,
And by receiving the reaction of Ga and Na described in the X-ray detection through the crucible transmission.
9. the method for producing group III nitride semiconductor monocrystalline according to claim 7, wherein described measurement dress
Put with the temperature measurement unit for measuring the crucible internal temperature, and the reaction of the Ga and Na is detected with differential thermal analysis.
10. the method for producing group III nitride semiconductor monocrystalline according to any one of claim 1 to 9, its
In in the growth of the group III nitride semiconductor monocrystalline, adjust the temperature of the crucible to fall into first temperature
In the range of kept at least 30 minutes.
11. methods for producing group III nitride semiconductor monocrystalline according to any one of claim 1 to 9, its
Described in the temperature of crucible be increased to the heating rate of the temperature when the reaction of the Ga and Na is completed less than described from room temperature
After reaction, the temperature of the crucible is increased to the heating rate of the growth temperature.
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| US20120125255A1 (en) * | 2009-06-04 | 2012-05-24 | Mitsubishi Chemical Corporation | Method and apparatus for producing crystal of metal nitride of group 13 of the periodic table |
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| JPS61151089A (en) * | 1984-12-21 | 1986-07-09 | Sumitomo Electric Ind Ltd | Production of single crystal |
| JPH06102589B2 (en) * | 1985-02-14 | 1994-12-14 | 株式会社東芝 | Single crystal manufacturing method and manufacturing apparatus |
| JP4048476B2 (en) * | 2001-05-22 | 2008-02-20 | 株式会社リコー | III-nitride crystal manufacturing apparatus with observation function and nitride crystal manufacturing method |
| RU2296189C2 (en) * | 2001-06-06 | 2007-03-27 | АММОНО Сп.з о.о. | Method and apparatus for producing three-dimensional monocrystalline gallium-containing nitride (variants) |
| JP5310611B2 (en) * | 2002-11-26 | 2013-10-09 | 株式会社リコー | Group III nitride crystal manufacturing method |
| JP2010037189A (en) * | 2008-07-08 | 2010-02-18 | Sumitomo Electric Ind Ltd | Apparatus and method for growing crystal |
| DE112012003278B4 (en) * | 2011-08-10 | 2018-08-23 | Ngk Insulators, Ltd. | Films of nitrides of Group 13 elements and layered bodies incorporating them |
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| US20040262630A1 (en) * | 2003-05-29 | 2004-12-30 | Matsushita Electric Industrial Co., Ltd. | Group III nitride crystals usable as group III nitride substrate, method of manufacturing the same, and semiconductor device including the same |
| CN101558188A (en) * | 2007-03-14 | 2009-10-14 | 松下电器产业株式会社 | Process for producing group iii elment nitride crystal, and group iii element nitride crystal |
| US20120125255A1 (en) * | 2009-06-04 | 2012-05-24 | Mitsubishi Chemical Corporation | Method and apparatus for producing crystal of metal nitride of group 13 of the periodic table |
| CN103305903A (en) * | 2013-05-16 | 2013-09-18 | 西安交通大学 | Method for preparing GaN crystal by high-nitrogen pressure flux-crucible descending process |
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