CN100338733C - Group III nitride semiconductor crystal, production method thereof and group III nitride semiconductor epitaxial wafer - Google Patents
Group III nitride semiconductor crystal, production method thereof and group III nitride semiconductor epitaxial wafer Download PDFInfo
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- CN100338733C CN100338733C CNB038050781A CN03805078A CN100338733C CN 100338733 C CN100338733 C CN 100338733C CN B038050781 A CNB038050781 A CN B038050781A CN 03805078 A CN03805078 A CN 03805078A CN 100338733 C CN100338733 C CN 100338733C
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Abstract
A method for producing a Group III nitride semiconductor crystal includes a first step of supplying a Group III raw material and a Group V raw material at a V/III ratio of 0 to 1,000 to form and grow a Group III nitride semiconductor on a heated substrate and a second step of vapor-phase-growing a Group III nitride semiconductor crystal on the substrate using a Group III raw material and a nitrogen raw material.
Description
The cross reference of related application
The application is the application of submitting to according to 35U.S.C. § 111 (a), according to 35U.S.C. § 119 (e) (1), requires the application purpose priority in the provisional application sequence number 60/367,719 of application on March 28th, 2002 according to 35U.S.C. § 111 (b).
Technical field
The present invention relates to III group-III nitride semiconductor (the III group-III nitride semiconductor is represented by InGaAlN) crystal and the manufacture method thereof of good crystallinity, the III group-III nitride semiconductor crystal is used to make light-emitting diode (LED), laser diode (LD), electronic device etc., and relating to III group-III nitride semiconductor epitaxial wafer, it has the III group-III nitride semiconductor crystal layer that forms on the III group-III nitride semiconductor crystal.Specifically, the present invention relates to make the method for III group-III nitride semiconductor crystal, this method goes for the III group-III nitride semiconductor crystal that the epitaxial growth crystallinity is good on Sapphire Substrate.
Background technology
The III group-III nitride semiconductor has corresponding to the direct transition type band gap from visible light to the ultraviolet light zone, and can realize efficiently luminous.Therefore, it can form LED or LD.And, for example, because the piezoelectric effect characteristic of III nitride-based semiconductor two-dimensional electron occurs on the heterojunction boundary between aluminium gallium nitride alloy (AlGaN) and the gallium nitride (GaN).Therefore, may provide electronic device with the characteristic that can not obtain by conventional III-V compound semiconductor.
But the III group-III nitride semiconductor is difficult to be grown to monocrystalline, because the decomposition pressure of nitrogen is up to 2 under the growth temperature of monocrystalline, and 000atm.Therefore, different with the III-V compound semiconductor, the single crystalline substrate of III group-III nitride semiconductor at present can not be as the substrate that uses for epitaxial growth.As the substrate that uses for epitaxial growth, use by as sapphire (Al
2O
3) substrate that constitutes of the dissimilar materials of monocrystalline or carborundum (SiC) monocrystalline.
Between this foreign substrate and epitaxially grown III group-III nitride semiconductor crystal, there is big lattice mismatch thereon.For example, at sapphire (Al
2O
3) and gallium nitride (GaN) between have 16% lattice mismatch, between SiC and gallium nitride, have 6% lattice mismatch.When having so big lattice mismatch, be difficult to epitaxial growth crystal on substrate usually.Even grow, can not obtain the crystal of good crystallinity.Therefore, passing through metal organic chemical vapor deposition (MOCVD) method under the situation of epitaxial growth III group-III nitride semiconductor on sapphire single-crystal or the SiC single crystalline substrate, usually the method that adopts is the low temperature buffer layer that at first deposit is made of aluminium nitride (AlN) or AlGaN on substrate, epitaxial growth III group-III nitride semiconductor crystal thereon at high temperature then, as Japan Patent 3,026,087 and the flat 4-297023 of JP-A (term " JP-A " is " a uncensored disclosed Japanese patent application " as used herein) disclosed.
Except the growing method of using low temperature buffer layer, for example, at Applied Physics LettersP.Kung etc.,
66, 2958 (1995) and the flat 9-64477 of JP-A a kind of growing method is disclosed, under the high growth temperature about 900 to 1,200 ℃, on substrate, form the AlN layer, then growing gallium nitride thereon.
Using under the situation of sapphire as substrate the above-mentioned low temperature buffer layer of common following formation.
At first, at the growth apparatus that is used for the MOCVD method Sapphire Substrate is heated to 1,000 to 1,200 ℃ high temperature, to remove oxide-film etc. from the surface.Then, reduce the temperature of growth apparatus, under the temperature about 400 to 600 ℃, provide raw material organic metal and nitrogenous source than simultaneously, deposit low temperature buffer layer on substrate by V/III with 3,000 to 10,000.Here, V/III is than the ratio that is the molal quantity of the molal quantity of the molecule that comprises III family element of feeding reative cell by MOCVD method growth III-V compound semiconductor time the and the molecule that comprises V group element.For example, under the situation of using TMGa and ammonia growing gallium nitride, this is than being the ratio that feeds the molal quantity of the molal quantity of the TMGa in the reative cell and ammonia.After this, stop that raw material are organometallic to be provided, the temperature of the growth apparatus that raises once more is with the heat treatment of the crystallization that is called low temperature buffer layer, the III of epitaxial growth target then group-III nitride semiconductor crystal.
Be used under 400 to 600 ℃ of temperature of deposit low temperature buffer layer, as the raw material organic metal and the nitrogenous source of parent material, it is insufficient especially to carry out ground as the thermal decomposition of the ammonia of nitrogenous source.Thus, the low temperature buffer layer that deposit is not further handled under this low temperature comprises many defectives.And, owing to parent material reacts at low temperatures, polymerization reaction take place between organometallic alkyl of raw material and undecomposed nitrogenous source, its reactant and other impurity also are contained in the crystal of low temperature buffer layer in large quantities.
In order to eliminate these defect and impurities, be called the heat treatment step of the crystallization of low temperature buffer layer.The step of crystallization resilient coating is included in the low temperature buffer layer that comprises many impurity and defective near heat treatment under the high temperature of the epitaxial growth temperature of III group-III nitride semiconductor crystal, removes impurity and defective thus.
Thus, in the growing method of using low temperature buffer layer, underlayer temperature must be reduced to about 500 ℃ of the temperature that is used for grown buffer layer for 1,200 ℃ from the temperature that is used for thermal purification, then within a short period of time with about 500 ℃ be elevated to as annealing temperature near 1,000 ℃ temperature range.At this moment, usually, follow the temperature change of cooling to need for a long time, and the unexpected increase of temperature need lot of energy.
And all temps process that is applied to substrate makes substrate warpage, and the substrate of warpage may break or fine fisssure.In addition, the influence of the warpage of substrate is the crystal layer of growth thereon, and special in the manufacturing of LED structure, emission wavelength in the substrate plane or emissive porwer become inhomogeneous.
Except this growing method of using low temperature buffer layer, a kind of growing method is disclosed, 900 to 1, height about 200 ℃ growth temperature forms AlN down on substrate, then thereon growing gallium nitride (for example, referring to, Applied Physics Letters, P.Kung etc.
66, 2958 (1995)).In the disclosure, having set forth the X ray swing curve that can make (0002) face by this method is the extraordinary crystal of 30arc sec.But,, find to have very high column, and in crystal, comprise the great number of grains border by the gallium nitride film of this technology manufacturing according to the test that the inventor carries out.This crystal produces highdensity threading dislocation from substrate to the surface.Therefore, even made device architecture, the characteristic that can not obtain as luminescent device and electronic device.
The growing method of using the AlN layer of at high temperature making also has been described among the flat 9-64477 of this external JP-A.This patent disclosure has been set forth the preferably monocrystalline of good crystallinity of the III group-III nitride semiconductor crystal made.Although the inventor has carried out duplicate test, make good use of can not the grow crystal of device architecture that characteristic can be provided of single crystal AlN growth for Thin Film method by using making of in this patent disclosure, illustrating.This is because when the single crystalline layer of good crystallinity is used as resilient coating, and the initial period of the growth of the III group-III nitride semiconductor of growing thereon, the migration of growth atom can not be carried out smoothly, and two-dimensional growth takes place hardly.
Thus, can not obtain to have the III group-III nitride semiconductor crystal of the high crystalline that is enough to make device, and not use the grow method of III group-III nitride semiconductor crystal of the AlN resilient coating of growth at high temperature at present usually.
An object of the present invention is to provide the method for making the III group-III nitride semiconductor crystal, the method that this method can replace using low temperature buffer layer and many temperature ranges need be set, or use high temperature AlN layer and the problematic method of crystal mass, and can form high-quality III group-III nitride semiconductor crystal by the step in the relative minimizing variations in temperature.
Another object of the present invention provides the method for making the III group-III nitride semiconductor crystal, this method can be on Sapphire Substrate the high-quality III group-III nitride semiconductor crystal of epitaxial growth.
Another object of the present invention provides the III group-III nitride semiconductor epitaxial wafer that can be advantageously used in LED, electronic device etc.
Summary of the invention
The invention provides a kind of method of the III of manufacturing group-III nitride semiconductor crystal, comprise with 0 to 1,000 V/III is than providing III family raw material and V family raw material forming on hot substrate and the first step of growth III group-III nitride semiconductor, and second step of using III family's raw material and nitrogen raw material vapor phase growth III group-III nitride semiconductor crystal on substrate.
In the method, substrate is sapphire (Al
2O
3) substrate.
In the method, the III family raw material that provide in first step comprise Al at least.
In the method, in second step on substrate the III group-III nitride semiconductor crystal of vapor phase growth comprise GaN.
In the method, at least one of the first step and second step, grow by metal organic chemical vapor deposition (MOCVD) method.
In the method, the nitrogen raw material that use in second step are ammonia (NH
3).
In the method, the III group-III nitride semiconductor that forms in first step is an island crystal grain.
In the method, the III group-III nitride semiconductor that forms in first step is a column crystal.
As just now in the described method, on substrate, form and the growth column crystal, so that the side of column crystal is approximately perpendicular to the surface of substrate.
The present invention also provides a kind of method of the III of manufacturing group-III nitride semiconductor crystal, be included in and form an III group-III nitride semiconductor on the hot substrate, and on an III group-III nitride semiconductor, form the 2nd III group-III nitride semiconductor crystal, wherein an III group-III nitride semiconductor is the aggregate of column crystal or island crystal.
In the method, on substrate, form and the growth column crystal, so that each side of column crystal is approximately perpendicular to the surface of substrate.
The present invention also provides a kind of III group-III nitride semiconductor crystal, by any one manufacturing of said method.
The present invention also provides a kind of III group-III nitride semiconductor epitaxial wafer, has the III group-III nitride semiconductor crystal layer that forms on described III group-III nitride semiconductor crystal just now.
The method according to this invention, wherein as mentioned above in first step with 1,000 or littler V/III ratio raw material are provided, to form the aggregate of column or island crystal, can make the III group-III nitride semiconductor crystal that can bring characteristic to device.
By on the III group-III nitride semiconductor crystal, forming III group-III nitride semiconductor crystal layer, and on crystal layer, be formed for making the epitaxial wafer of LED or electronic device, can obtain various high quality devices.
Description of drawings
Fig. 1 shows the epitaxial wafer sectional view with epitaxial layer structure of the light emitting semiconductor device that is used for embodiment according to the present invention 5;
Fig. 2 shows the plane graph of the electrode structure of same light emitting semiconductor device.
Embodiment
Method of the present invention is used to make the III group-III nitride semiconductor crystal, this method comprises with 1,000 or littler V/III provide III family and V family raw material than (comprising that V/III is than the situation that is 0), with the first step of formation on hot substrate and growth III group-III nitride semiconductor, and second step of using III family's raw material and nitrogen raw material vapor phase growth III group-III nitride semiconductor crystal on substrate.This manufacture method of the III group-III nitride semiconductor crystal by having first and second steps can form the III group-III nitride semiconductor crystal of good crystallinity on substrate.In the present invention, the III group-III nitride semiconductor is expressed as InGaAlN.
The V/III ratio be 1,000 or the III group-III nitride semiconductor crystal made under than condition of littler low V/III in, the stoichiometric proportion of V group element in the crystal and III family element is not 1: 1, and III family element moves to superfluous side so that the excess metal attitude to be provided.In this III group-III nitride semiconductor crystal layer, there is superfluous III family element with metallic crystal or drop.Therefore, when growth III group-III nitride semiconductor crystal on crystal layer, the migration of the initial period of growth is very effective in can carry out horizontal two-dimensional growth.But this machine-processed details is not known.
Be preferred for the good III group-III nitride semiconductor of growing with little V/III than the AlN film of making, in the flat 9-64477 of JP-A, also be illustrated.But this patent disclosure has been set forth the preferably monocrystalline of good crystallinity of the III group-III nitride semiconductor crystal that forms.The inventor has carried out duplicate test and analysis, and finds that the aggregate of column crystal or island crystal more successfully is used as resilient coating than single crystal film.This is because metallic crystal or drop have entered the granule boundary that exists in comprising the layer of column crystal or island crystal, and is easy to generate more excess metal crystal.But its details is not known.
This method of comparing with the conventional method of using low temperature buffer layer has reduced the occasion that heats up or lower the temperature, and therefore can shorten technology and reduce power consumption.Thus, can reduce manufacturing process and cost.And by the little variation of temperature, the warpage of substrate can be suppressed to minimum value, and device can have good characteristic uniformity.In addition, compare, can make the crystal that device has been produced characteristic with the growing method of the AlN layer of growth under the use high temperature that has illustrated.
In the present invention, glass, SiC, Si, GaAs, sapphire etc. can be used as substrate.Specifically, the substrate that uses among the present invention sapphire (Al preferably
2O
3).Using sapphire is favourable as substrate, because can obtain high-quality substrate with very low cost.
For the planar orientation of Sapphire Substrate, can use m face, a face, c face etc., in these planar orientations, preferred c face ((0001) face).And the vertical axis on the substrate surface is preferably from＜0001〉direction tilts to specific direction.In addition, the substrate of Shi Yonging preferably stood preliminary treatment before first step in the present invention, as organic cleaning or etching, because substrate surface can be maintained at constant attitude.
Can comprise trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, trimethyl gallium, triethyl-gallium, tributyl gallium, trimethyl indium, triethylindium, tributyl indium and cyclopentadiene indium as the raw-material example of III family that provides in the first step of the present invention.The optimal seeking of raw and processed materials of III family comprises Al at least, as trimethyl aluminium, triethyl aluminum and tri-butyl aluminum, have high decomposition temperature because comprise the nitride of aluminium, even and provide thus and at high temperature also take place hardly to decompose or the effect of distillation, and crystal is grown on the substrate easily.
In first step of the present invention, provide V family raw material simultaneously with III family raw material, to form the III group-III nitride semiconductor as ammonia, alkylamine and hydrazine.In the present invention, when III family raw material were provided in first step, the V/III ratio was set as 1,000 or littler, preferably is made as 500 or littler, more preferably is made as 100 or littler.By the V/III ratio is set like this, provide easy manufacturing to have the effect of the compound semiconductor crystal of more excess metals.
In the present invention, the V/III ratio can be 0, that is, the raw-material amount of V family that provides can be 0.Although the raw-material amount of V family of having a mind to provide is 0,, in the case, must use the nitrogen that adheres to the wall or the end face of reative cell or adhere to the material production of pedestal by decomposition to form the III group-III nitride semiconductor.At this moment, must suitably control the component and the amount of wall or end face that adheres to reative cell or the material that adheres to pedestal.More particularly, by after growth is finished, adjusting the temperature cure in time or the reative cell or, controlling these by stopping to cure itself.In addition, also adjust and be known as time or the temperature in the step that heat cleans or stop step itself, this step is to use the routine techniques under the situation that the low temperature buffer method grows.
For example, formerly after the growth, carrying out 10 minutes heat under 600 ℃ cleans, do not cure, after this only feed the first step of metallic compound, substrate is heated to 1,000 ℃, and carry out follow-up second step of grown crystal, the III group-III nitride semiconductor crystal that can make thus.
Another condition of the III group-III nitride semiconductor crystal that is used to obtain, the V/III ratio is made as 0 in first step, is to use N
2As carrier gas with use by a small amount of decomposing N under near 1,000 ℃ temperature
2Nitrogen (N) atom that produces is as the method for nitrogenous source.
For the atmosphere gas in the first step of the present invention, can use gas maybe can use its mist separately as hydrogen, rare gas or nitrogen.Under the situation of nitrogen as atmosphere gas, as mentioned above, nitrogen is sometimes also as raw gas.
Pressure when carrying out first step in the atmosphere from 1,000 to 1 * 10
5Pa, preferred 1 * 10
5Pa or littler, more preferably 1 * 10
4Pa or littler.When the pressure in the first step was low, the surface of the III nitride semiconductor layer with excess metal of manufacturing became smooth.This provides the effect on the surface of the 2nd III nitride semiconductor layer that planarization easily will grow on flat surfaces.
In the present invention, underlayer temperature when carrying out first step and the underlayer temperature when carrying out second step do not have concrete regulation, but the underlayer temperature in first step preferably is equal to or higher than the underlayer temperature in follow-up second step.When carrying out first step under the temperature of the underlayer temperature in being equal to or higher than second step, advantageously carry out the decomposition of organo-metallic compound molecule effectively and do not have sneaking in the crystal of formation as the impurity of undecomposed alkyl, wherein the organo-metallic compound molecule is an III family raw gas.
In first step of the present invention, the III group-III nitride semiconductor forms island crystal grain.More particularly, form the aggregate of island crystal grain, wherein assemble island crystal grain densely with 1 to 500nm width and about 5 to 100nm height.By the III group-III nitride is formed the island crystal, in crystal layer, produce a large amount of grain boundaries.This provides metallic crystal or drop to stay easily in the border so that the effect of the more excess metal layer of crystal layer conduct.Crystal layer also can have wherein, and the distribution of island crystal is not the structure that densification like this and substrate surface appear at intergranule.In the case, according to the selective growth effect, the surface is scattered with the different zone of crystal growth rate, and reduces the density of threading dislocation.As a result, can make more favourable crystal.
Alternatively, in first step of the present invention, the III group-III nitride semiconductor forms column crystal.More particularly, form the column crystal that gathers columnar grain with 0.1 to 100nm width and about 10 to 500nm height.By the III group-III nitride is formed column crystal, in crystal layer, produce a large amount of granule boundaries.This provides metallic crystal or drop to stay easily in the border so that the effect of the more excess metal layer of crystal layer conduct.
In second step of the present invention, use III family's raw material and nitrogen raw material vapor phase growth III group-III nitride semiconductor crystal on substrate, wherein in first step, formed the III group-III nitride.The III group-III nitride semiconductor crystal of growth is GaN preferably, because in the III group-III nitride semiconductor, GaN carries out two-dimensional growth easily and forms smooth crystal film easily.When in a single day making the smooth crystal film of becoming reconciled with GaN, it is easy to use the III group-III nitride semiconductor crystal layer with various components to make semiconductor device structure thereon.
In of the present invention first or second step or two steps, can use metal organic chemical vapor deposition (MOCVD) method and vapour phase epitaxy (VPE) method as method of vapor-phase growing.In these methods, preferred MOCVD method is because for example can adjust the raw-material decomposition rate of III family and growth rate is suitable.And, according to the MOCVD method, can on crystal, make the various device architectures of characteristic, and flat substrate not taken out from reative cell.
Under the situation by MOCVD method growth III group-III nitride semiconductor crystal in second step, preferably from 950 to 1,200 ℃ of underlayer temperatures, and atmosphere pressures preferably from 1,000 to 1 * 10
5Pa.
The nitrogen optimal seeking of raw and processed materials of using in second step is ammonia (NH
3), because ammonia is easy-to-handle gas, the many ammonia products on the market are available, with and cost low.As III family raw material, can use trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, trimethyl gallium, triethyl-gallium, tributyl gallium, trimethyl indium, triethylindium, tributyl indium and encircle penta 2 rare indiums.In second step during growth III group-III nitride semiconductor crystal, V/III is than preferably from 500 to 20,000.
According to the manufacture method of the III group-III nitride semiconductor crystal that comprises above-mentioned first and second steps of the present invention, can on substrate, form the III group-III nitride semiconductor crystal of uniformity height and good crystallinity by the technology in short-term that reduces power consumption.When further on above-mentioned III group-III nitride semiconductor crystal, forming III group-III nitride semiconductor crystal layer, can make the III group-III nitride semiconductor epitaxial wafer with laminated construction, it is used to make light-emitting diode, laser diode, electronic device etc.
Below with reference to the present invention of example more detailed description.
Example 1:
The following describes the method for the present invention of making gallium nitride base compound semiconductor crystal.
In example 1, first step be on Sapphire Substrate, feed comprise by the gas that obtains with 1: 2 mixed in molar ratio trimethyl aluminium (TMAl) steam and trimethyl gallium (TMGa) steam with comprise ammonia (NH
3) the processing of gas, second step is the processing of growing gallium nitride when feeding TMGa and ammonia.Carry out two processing on Sapphire Substrate, to make the GaN layer that constitutes by gallium nitride.In the condition of using in first step, the V/III ratio is about 85.
The sample that comprises this GaN layer according to following operation by the manufacturing of MOCVD method.
Before introducing Sapphire Substrate,, decompose more to prevent it thus by the inner material that forms and grow of the heating reative cell that nitrogenize had before been grown in same equipment in the gas that comprises ammonia and hydrogen.This reative cell is made by quartz.Waiting after reative cell is cooled to normal temperature, reative cell is placed in the RF coil of induction heater.Introduce Sapphire Substrate in the chamber and be placed on the pedestal of making by carbon that is used to heat in the glove box with nitrogen purge.Introduce after the sample, feed nitrogen to purify the inside of reative cell.
Feed nitrogen more than 10 minutes, after this start induction heater, in the time more than 10 minutes, underlayer temperature is elevated to 1,170 ℃.Substrate is remained on 1,170 ℃ temperature, and under this state, kept 9 minutes, feed hydrogen and nitrogen simultaneously, clean with the heat of carrying out substrate surface.
In hot cleaning process, by comprising parent material, promptly the vessel catheter (bubbler) of trimethyl gallium (TMGa) and trimethyl aluminium (TMAl) feeds hydrogen carrier gas, to begin foaming.Here, conduit is connected to reative cell.The heating bath that serviceability temperature is regulated is adjusted to constant temperature with each bubbler.When growth step began, the TMGa steam and the TMAl steam that will produce by bubbling fed conduit to disinfection unit together with carrier gas, and are discharged into the system outside by disinfection unit.
Heat clean finish after, with the valve closing of nitrogen carrier gas, and hydrogen becomes and is provided to unique gas in the reative cell.
After changing carrier gas, underlayer temperature is reduced to 1,150 ℃.Confirming that temperature stabilization after 1,150 ℃, opens the valve of ammonia conduit, ammonia is being fed in the chamber beginning.Then, change the duct valve of TMGa and TMAl simultaneously, and the gas that will comprise TMGa steam and TMAl steam is provided in the reative cell, on Sapphire Substrate, forms and the first step of growth III family nitride semiconductor with beginning.By the flow speed controller that is used to bubble that is provided with in conduit, the TMGa that provides of control and TMAl were with 2: 1 mixed in molar ratio, and the V/III ratio of adjusting ammonia amount to 85.
After handling 6 minutes, change the duct valve of TMGa and TMAl simultaneously, to stop to provide the gas that comprises TMGa steam and TMAl steam in reative cell.Then, also stop to provide ammonia, and system was kept 3 minutes at this state.
After annealing 3 minutes, change the duct valve of ammonia, and begin once more to provide ammonia in the chamber.Fed ammonia 4 minutes, and in this process, adjust flow velocity in the conduit of TMGa with flow speed controller.After 4 minutes, change the valve of TMGa, to begin providing TMGa in reative cell, begin the growth of GaN thus.
The growing GaN layer about more than 1 hour after, the duct valve that changes TMGa stops growing thus to stop to provide raw material to reative cell.
After the growth of finishing the GaN layer, stop to feed the electric current of induction heater, and in the time more than 20 minutes, underlayer temperature is reduced to normal temperature.In temperature decline process, the atmosphere of reative cell inside is made of the ammonia, nitrogen and the hydrogen that are similar in the growth course, but confirming that underlayer temperature is reduced to after 300 ℃, stops to provide ammonia and hydrogen.After this, underlayer temperature is reduced to normal temperature, feeds nitrogen simultaneously, then sample is fetched in the air.
By those steps, the perparation of specimen wherein has the excess metal III family nitride semiconductor layer of column structure in Sapphire Substrate in formation, and forms the thick not Doped GaN layer of 2 μ m thereon.The substrate that takes out presents the color of the black that has metalloid.This show with the interface of substrate on the III nitride semiconductor layer that forms be in the stoichiometry of excess metal.Growing surface is a minute surface.
Go up the unadulterated GaN layer of measuring by the said method growth at X ray swing curve (XRC).In measurement, with Cu β line x ray generator as light source, and to measuring as (0002) face of the plane of symmetry with as (10-12) face of asymmetric faces.Usually, under the situation of gallium nitride-based compound semiconductor, the half-breadth of the XRC of (0002) face spectrum is as smooth (planarization (mosaicity)) index, and (10-12) half-breadth of the XRC spectrum of face as the index of dislocation density (distortion).
Measurement result is, the unadulterated GaN layer by method manufacturing of the present invention demonstrates 230 seconds half-breadth of (0002) face and (10-12) 350 seconds half-breadth of face.
And, use conventional atomic force microscope (AFM) to observe the outermost surface of GaN layer, the result does not observe the growth depression from the teeth outwards, and has confirmed that the surface has good pattern.
Observe the cross section of this sample by transmission electron microscope (TEM), the result confirms between Sapphire Substrate and gallium nitride layer at the interface, has a large amount of grain boundaries at the direction AlN film perpendicular to substrate surface almost.Film thickness is 5 to 50nm for the distance between about 60nm and the grain boundary.This layer comprises the aggregate of the column crystal that height over width is longer.According to elementary analysis, this film comprises about 20% Ga.
Example 2:
In example 2, the growth time of the III group-III nitride semiconductor in first step is 2 minutes, by testing with example 1 step much at one.In addition, in the case, the wafer of taking-up has minute surface and is colourless and transparent.
By the cross section of transmission electron microscope (TEM) observation sample, the result confirms to exist island AlN crystal grain on the interface between Sapphire Substrate and the gallium nitride layer.According to elementary analysis, this crystal grain comprises about 15% Ga.
Except stopping technology before the growing gallium nitride layer and taking out sample, carrying out the growth identical with the technology of this experiment from the growth room, the perparation of specimen thus.Observe the pattern on surface by atomic force microscope (AFM), the result has round hexagonal configuration when being scattered with from top the inspection and has the aluminum nitride grain of trapezoid cross section.
Example 3:
In example 3, Sapphire Substrate is introduced into reative cell, and do not cure before the growth after before testing, and feed the first step of the gas that comprises trimethyl aluminium (TMAl) steam and feed TMGa and ammonia with second step of growing gallium nitride, on Sapphire Substrate, to make the GaN layer that comprises gallium nitride.The V/III ratio of Xi Wanging is 0 in this example, but owing to adhere to the material breakdown of reative cell wall or end face, the minor N atom is provided on the substrate.
Use the manufacturing of MOCVD method to comprise the sample of this GaN layer according to following operation.
Sapphire Substrate introduced the reative cell of making by quartz in the RF coil place induction heater.In with the glove box of nitrogen purge, Sapphire Substrate is placed on the pedestal of making by carbon that is used to heat, after introducing sample, feeds nitrogen to purify the inside of reative cell.
Feed nitrogen more than 10 minutes, after this start induction heater, in the time more than 10 minutes, underlayer temperature is elevated to 600 ℃.Substrate is remained on 600 ℃ temperature, and under this state, kept 9 minutes, feed hydrogen simultaneously.
In this process, by comprising parent material, promptly the vessel catheter (bubbler) of trimethyl gallium (TMGa) and trimethyl aluminium (TMAl) feeds hydrogen carrier gas, to begin foaming.Here, conduit is connected to reative cell.The heating bath that serviceability temperature is regulated is adjusted to constant temperature with each bubbler.When growth step began, the TMGa steam and the TMAl steam that will produce by bubbling fed conduit to disinfection unit together with carrier gas, and are discharged into the system outside by disinfection unit.
After this, close the valve of nitrogen carrier gas, and begin to provide hydrogen in reative cell.
Then change carrier gas, underlayer temperature is elevated to 1,150 ℃.Confirming temperature stabilization after 1,150 ℃, changing the duct valve of TMAl, and the gas that will comprise the TMAl steam is provided in the reative cell.At this moment, owing to adhere to the material breakdown of the wall or the end face of reative cell, provide small amount of N simultaneously to substrate with TMAl.
After handling 9 minutes, change the duct valve of TMAl, stopping to provide the gas that comprises the TMAl steam in reative cell, and system was kept 3 minutes at this state.
After annealing 3 minutes, change the duct valve of ammonia, and begin once more to provide ammonia in the chamber.
Fed ammonia 4 minutes, and in this process, with the flow velocity in the conduit of flow speed controller adjustment TMGa.After 4 minutes, change the valve of TMGa, to begin providing TMGa in reative cell, begin the growth of GaN thus.
The growing GaN layer about more than 1 hour after, change the duct valve of TMGa, to stop to provide raw material, stop growing thus to reative cell.
After the growth of finishing the GaN layer, stop to feed the electric current of induction heater, and in the time more than 20 minutes, underlayer temperature is reduced to normal temperature.In temperature decline process, the atmosphere of reative cell inside is made of the ammonia, nitrogen and the hydrogen that are similar in the growth course, but confirming that underlayer temperature is reduced to after 300 ℃, stops to provide ammonia and hydrogen.After this, underlayer temperature is reduced to normal temperature, feeds nitrogen simultaneously, then sample is fetched in the air.
By these steps, the perparation of specimen wherein forms on Sapphire Substrate in first step and has the excess metal III nitride semiconductor layer of column structure, and forms the thick not Doped GaN layer of 2 μ m thereon.Be similar to example 1, the substrate of taking-up presents the color of the black that has metalloid.These show with the interface of substrate on the III nitride semiconductor layer that forms be in the stoichiometry of excess metal.Growing surface is a minute surface.
On XRC, measure unadulterated GaN layer by the said method growth.In measurement, Cu β line x ray generator is used as light source, and to measuring as (0002) face of the plane of symmetry with as (10-12) face of asymmetric faces.Measurement result is, the unadulterated GaN layer by method manufacturing of the present invention demonstrates 200 seconds half-breadth of (0002) face and (10-12) 330 seconds half-breadth of face.
And, use conventional atomic force microscope (AFM) to observe the outermost surface of GaN layer, the result does not observe the growth depression from the teeth outwards, and has confirmed that the surface has good pattern.
Observe the cross section of this sample by transmission electron microscope (TEM), the result confirms between Sapphire Substrate and gallium nitride layer at the interface, has a large amount of grain boundaries at the direction AlN film perpendicular to substrate surface almost.Film thickness is 10 to 50nm for the distance between about 20nm and the granule boundary.This layer comprises the aggregate of the column crystal that height over width is longer.According to elementary analysis, this film comprises about 5% Ga.
Example 4:
In example 4, first step is that nitrogen is fed the processing that comprises by the gas that obtains with 2: 1 mixed in molar ratio trimethyl aluminium (TMA4) steam and trimethyl indium (TMGa) steam as carrier gas on Sapphire Substrate, and second step is the processing of Grown GaN layer when feeding TMGa and ammonia.Carry out two processing on Sapphire Substrate, to make the GaN layer that constitutes by gallium nitride.In first step, decomposed on a small quantity and a spot of nitrogen-atoms is provided as the nitrogen of carrier gas.
The sample that comprises this GaN layer according to following operation by the manufacturing of MOCVD method.
Before introducing Sapphire Substrate,, decompose more to prevent it thus by the heating material that nitrogenize adheres to the reative cell inside of before having grown in same equipment in the gas that comprises ammonia and hydrogen.This reative cell is made by quartz.Waiting after reative cell is cooled to normal temperature, reative cell is placed in the RF coil of induction heater.Introduce Sapphire Substrate in the chamber and be placed on the pedestal of making by carbon that is used to heat in the glove box with nitrogen purge.Introduce after the sample, feed nitrogen to purify the inside of reative cell.
Feed nitrogen more than 10 minutes, after this start induction heater, in the time more than 10 minutes, underlayer temperature is elevated to 1,170 ℃.Substrate is remained on 1,170 ℃ temperature, and under this state, kept 9 minutes, feed hydrogen simultaneously, clean with the heat of carrying out substrate surface.
In hot cleaning process, by comprising parent material, promptly the vessel catheter (bubbler) of trimethyl gallium (TMGa), trimethyl aluminium (TMAl) and trimethyl indium (TMIn) feeds hydrogen carrier gas, to begin foaming.Here, conduit is connected to reative cell.The heating bath that serviceability temperature is regulated is adjusted to constant temperature with each bubbler.When growth step began, TMGa steam, TMAl steam and the TMIn steam that will produce by bubbling fed conduit to disinfection unit together with carrier gas, and are discharged into the system outside by disinfection unit.
Heat clean finish after, close the valve of hydrogen carrier gas and the valve that provides of nitrogen be provided, become nitrogen with the gas that will be provided in the reative cell.
After changing carrier gas, underlayer temperature is reduced to 1,150 ℃.Confirming that temperature stabilization after 1,150 ℃, changes the duct valve of TMIn and TMAl simultaneously, and the gas that will comprise TMIn steam and TMAl steam is provided in the reative cell, to begin that the III group-III nitride semiconductor is sticked to first step on the Sapphire Substrate.By the flow speed controller that is used to bubble that is provided with in conduit, the TMIn that provides of control and TMAl were with 1: 2 mixed in molar ratio.
After handling 6 minutes, change the duct valve of TMIn and TMAl simultaneously, stopping to provide the gas that comprises TMIn steam and TMAl steam in reative cell, and system was kept 3 minutes at this state.
After annealing 3 minutes, the duct valve that changes ammonia also begins to provide ammonia in the chamber once more.
Fed ammonia 4 minutes, and in this process, adjust flow velocity in the conduit of TMGa with flow speed controller.After 4 minutes, change the valve of TMGa, beginning providing TMGa in the chamber, and the growth of beginning GaN.
The growing GaN layer about more than 1 hour after, change the duct valve of TMGa, stopping to provide raw material, and stop growing to reative cell.
After the growth of finishing the GaN layer, stop to feed the electric current of induction heater, and in the time more than 20 minutes, underlayer temperature is reduced to normal temperature.In temperature decline process, the atmosphere of reative cell inside is made of the ammonia, nitrogen and the hydrogen that are similar in the growth course, but confirming that underlayer temperature is reduced to after 300 ℃, stops to provide ammonia and hydrogen.After this, underlayer temperature is reduced to normal temperature, feeds nitrogen simultaneously, then sample is fetched in the air.
By these steps, the perparation of specimen, wherein formation has the excess metal III family nitride semiconductor layer of column structure on Sapphire Substrate, and forms the thick unadulterated GaN layer of 2 μ m thereon.The substrate that takes out is colourless and transparent.Growing surface is a minute surface.
On XRC, measure unadulterated GaN layer by the said method growth.In measurement, Cu β line x ray generator is used as light source, and to measuring as (0002) face of the plane of symmetry with as (10-12) face of asymmetric faces.
Measurement result is, the unadulterated GaN layer by method manufacturing of the present invention demonstrates 350 seconds half-breadth of (0002) face and (10-12) 400 seconds half-breadth of face.
And, use conventional atomic force microscope (AFM) to observe the outermost surface of GaN layer.As a result, do not observe the growth depression from the teeth outwards, and confirmed that the surface has good pattern.
Observe the cross section of this sample by transmission electron microscope (TEM), the result confirms between Sapphire Substrate and gallium nitride layer at the interface, has a large amount of grain boundaries at the direction AlN film perpendicular to substrate surface almost.Film thickness is 5 to 50nm for the distance between about 10nm and the grain boundary.This layer comprises the aggregate of the column crystal that height over width is longer.
Example 5:
In example 5, the method for the method manufacturing gallium-nitride-based compound semiconductor light emitting element that uses III group-III nitride semiconductor crystal of the present invention is described.
In example 5, use the condition identical to make GaN crystal smooth and low-mix silicon with example 3, and further form III group-III nitride semiconductor crystal layer thereon, with final generation epitaxial wafer as shown in Figure 1, this wafer has the epitaxial layer structure that is used for light emitting semiconductor device.That is, epitaxial wafer has such structure, wherein forms the excess metal AlN layer 8 with column structure by the growing method identical with example 3 on the Sapphire Substrate 9 with c face, after this from the layer below the substrate side sequential cascade.These layers comprise: the GaN layer 7 of the low-mix silicon that 2 μ m are thick has 1 * 10
17Cm
-3Electron concentration, the thick height of 1.8 μ m is mixed the GaN layer of silicon, has 1 * 10
19Cm
-3Electron concentration, the In that 100 are thick
0.1Ga
0.9N cover layer 5 has 1 * 10
17Cm
-3Electron concentration, by 70 thick six GaN barrier layers 3 and four thick unadulterated In of 20
0.2Ga
0.8The multi-quantum pit structure 20 that N trap layer 4 constitutes, this multi-quantum pit structure starts from the GaN barrier layer and ends at the GaN barrier layer, the unadulterated Al that 30 are thick
0.2Ga
0.8N diffusion impervious layer 2, and the thick GaN layer 1 of mixing Mg of 0.15 μ m, this layer has 8 * 10
17Cm
-3Hole concentration.
Fig. 2 shows the plane graph of the electrode structure of the light emitting semiconductor device of making in the example 5.
Be manufactured on the wafer that has epitaxial loayer in the above-mentioned light emitting semiconductor device structure by the MOCVD method according to following operation.
Form on the Sapphire Substrate have the AlN layer 8 of column structure after, adopt the operation identical with example 3.
After formation on the Sapphire Substrate had the AlN layer 8 of column structure, the flow velocity with in the conduit of flow speed controller adjustment TMGa fed ammonia simultaneously continuously.In addition, begin Si
2H
6Feed conduit.When beginning to grow the GaN layer of low-mix Si, with Si
2H
6Feed conduit to disinfection unit together with carrier gas, and be discharged into the system outside by disinfection unit.After this, change TMGa and Si
2H
6Valve, to begin to provide TMGa and Si
2H
6In the chamber and begin the growth of low-doped GaN.Growing GaN layer about 1 hour is more than 15 minutes.Check and control the SiH of feeding in advance
4Amount has 1 * 10 to provide
17Cm
-3The GaN layer of low-mix Si of electron concentration.
Therefore, form the GaN layer 7 of the thick low-mix Si of 2 μ m.
On the GaN layer 7 of this low-mix Si, the high n type GaN layer 6 of mixing Si of growth.After the GaN layer of growth low-mix Si, stop to provide TMGa and Si
2H
6In the chamber 1 minute.In this process, change the Si that feeds
2H
6Amount.Check and adjust the amount of feeding in advance, have 1 * 10 to provide
19Cm
-3The height of electron concentration mix the GaN layer of Si.Provide ammonia in the chamber and do not change flow velocity continuously.Restart to provide TMGa and Si after 1 minute
2H
6, grow more than 1 hour.By this operation, form the GaN layer that the thick height of 1.8 μ m is mixed Si.
After the growth height is mixed the GaN layer 6 of Si, change TMGa and Si
2H
6Valve and stop to provide these raw material in the chamber.When continuing to feed ammonia, change valve so that carrier gas is become nitrogen from hydrogen.After this underlayer temperature is reduced to 800 ℃ from 1,160 ℃.
In the process of the variations in temperature in waiting room, change the Si that provides
2H
6Amount.Check and adjust the amount of feeding in advance, have 1 * 10 to provide
17Cm
-3The InGaN cover layer of mixing Si of electron concentration.Provide ammonia in the chamber and do not change flow velocity continuously.
Begin in advance carrier gas is fed in the bubbler of trimethyl indium (TMIn) and triethyl-gallium (TEGa).When beginning tectal growth step, with Si
2H
6Gas and the TMIn steam that produces by bubbling and TEGa steam feed conduit to disinfection unit together with carrier gas, and are discharged into the system outside by disinfection unit.
After this, when chamber interior in stable condition, change TMIn, TEGa and Si simultaneously
2H
6Valve and begin to provide these raw material in the chamber.This provides and keeps about In that mixes Si more than 10 minutes with formation
0.1Ga
0.9 N cover layer 5 has the thickness of 100 .
Then, change TMIn, TEGa and Si
2H
6Valve, and stop to provide these raw material.
Then, make by GaN barrier layer 3 and In
0.2Ga
0.8The multi-quantum pit structure 20 that N trap layer constitutes.In the manufacturing of multi-quantum pit structure, mixing the In of Si
0.1Ga
0.9At first form GaN barrier layer 3 on the N cover layer 5, and on the GaN barrier layer that forms thus, form In
0.2Ga
0.8N trap layer 4.Repeat this structure 5 times with stacked each layer and at 5In
0.2Ga
0.8Form the 6GaN barrier layer on the N trap layer, on the both sides of multi-quantum pit structure 20, to finish structure with GaN barrier layer 3.
More particularly, finish the In that mixes Si
0.1Ga
0.9After the tectal growth of N, stopping this providing more than 30 seconds, and in the flow velocity and kind of the pressure in not changing underlayer temperature, chamber, carrier gas, the valve that changes TEGa is to provide TEGa in the chamber then.After providing TEGa more than 7 minutes, change valve once more stopping to provide TEGa, and finish the growth on GaN barrier layer.As a result, form the thick GaN barrier layer 3 of 70 .
In the process on growing GaN barrier layer, adjust to than 2 times of mole flow velocity of tectal growth to the flow velocity of the TMIn of disinfection unit feeding conduit.
After the growth of finishing the GaN barrier layer, stop to provide III family raw material more than 30 seconds, and in the flow velocity and kind of the pressure in not changing underlayer temperature, chamber, carrier gas, the valve that changes TEGa and TMIn is to provide TEGa and TMIn in the chamber.Provide TEGa and TMIn more than 2 minutes after, change valve once more stopping to provide TEGa and TMIn, and finish In
0.2Ga
0.8The growth of N trap layer.As a result, form the thick In of 20
0.2Ga
0.8N trap layer 4.
Finish In
0.2Ga
0.8After the growth of N trap layer, stop to provide III family raw material more than 30 seconds, and in the flow velocity and kind of the pressure in not changing underlayer temperature, chamber, carrier gas, begin to provide TEGa in the chamber, and regrow the GaN barrier layer.
Repeat this operation 5 times to make five GaN barrier layers and five In
0.2Ga
0.8N trap layer.At last In
0.2Ga
0.8Further form the GaN barrier layer on the N trap layer.
Ending to form unadulterated Al on this quantum well structure 20 on GaN barrier layer
0.2Ga
0.8N diffusion impervious layer 2.
Begin in advance the carrier gas feeding is comprised in the bubbler of trimethyl aluminium (TMAl).When beginning the growth step of diffusion impervious layer, the TMAl steam that will produce by bubbling feeds conduit to disinfection unit together with carrier gas, and is discharged into the portion that begins outside the system by disinfection unit.
After waiting indoor pressure stability, the valve that changes TEGa and TMAl is to begin providing these raw material in the chamber.After this, grow about more than 3 minutes.Then, stop to provide TEGa and TMAl to stop unadulterated Al
0.2Ga
0.8The growth of N diffusion impervious layer.As a result, form the thick unadulterated Al of 30
0.2Ga
0.8N diffusion impervious layer 2.
This this unadulterated Al
0.2Ga
0.8Form the GaN layer 1 of mixing Mg on the N diffusion impervious layer.
Stop to provide TEGa and TMAl and finishing unadulterated Al
0.2Ga
0.8After the growth of N diffusion impervious layer, in the time more than 2 minutes, underlayer temperature is elevated to 1,060 ℃.And, carrier gas is become hydrogen.
Begin in advance the carrier gas feeding is comprised bis-cyclopentadienyl magnesium (Cp
2Mg) in the bubbler.When beginning to mix the growth step of GaN layer of Mg, will be by the Cp that bubbles and produce
2The Mg steam feeds conduit to disinfection unit together with carrier gas, and is discharged into the portion that begins outside the system by disinfection unit.
After changing temperature and pressure and waiting pressure stability in the chamber, change TMGa and Cp
2The valve of Mg, and begin to provide these raw material in the chamber.Adjust and check the Cp of feeding in advance
2The Mg amount has 8 * 10 to provide
17Cm
-3The GaN cover layer of mixing Mg of hole concentration.After this, carrying out this grows about more than 6 minutes.Then, stop TMGa and Cp
2Mg provides, and mixes the growth of the GaN layer of Mg with termination.As a result, form the thick GaN layer 1 of mixing Mg of 0.15 μ m.
After the growth of finishing the GaN layer of mixing Mg, stop electric current being fed induction heater, and in the time more than 20 minutes, underlayer temperature is reduced to normal temperature.Be reduced to 300 ℃ process from growth temperature, the carrier gas in the reative cell only is made of nitrogen, and feeds the NH of 1% volume
3When confirming that underlayer temperature is reduced to 300 ℃, stop to feed NH
3, and atmosphere gas becomes and has only nitrogen.After confirming that underlayer temperature is reduced to normal temperature, wafer is fetched in the air.
By this operation, make epitaxial wafer with the epitaxial loayer that is used for light emitting semiconductor device.Here, although do not activate the annealing in process of p type charge carrier, the GaN layer of mixing Mg demonstrates P-type conduction.
Then, use the light-emitting diode of epitaxial wafer manufacturing as a kind of light emitting semiconductor device, wherein epitaxial wafer comprises the Sapphire Substrate that is laminated with epitaxial layer structure thereon.
By known photoetching on the surface 14 of the GaN layer of mixing Mg of the wafer of making, formation has and comprises from face side with the p electrode engagement pad 12 of the structure of the sequential cascade of titanium, aluminium and gold layer and the printing opacity p electrode 13 that is connected to pad and only is made of gold, to form the p lateral electrode.
Then, this wafer stands dry etching, mixes the GaN layer of Si with the height that exposes in the part 11 that forms the n lateral electrode, and forms the n electrode 10 that comprises four layers of Ni, Al, Ti and Au on the part of exposing.By this processing, on wafer, form each and have the electrode of shape as shown in Figure 2.
On wafer, form after p side and the n lateral electrode, grind and polish the back side of Sapphire Substrate, so that minute surface to be provided.Then, wafer is cut into the square chip that the length of side is 350 μ m, chip is placed on the lead frame, electrode and is connected to lead frame with gold wire up, finishes luminescent device thus.
When feeding forward current between the p side of the light-emitting diode of making thus and n lateral electrode, the forward voltage of 20mA electric current is 3.0V.And, luminous by the observation of printing opacity p lateral electrode, the result, emission wavelength is that 470nm and transmitting power are 6cd.Use does not have the scattering of light-emitting diode from these characteristics of the chip acquisition light-emitting diode of the almost whole surface cutting of the wafer of manufacturing.
Industrial applicibility:
When using the manufacture method of III group-III nitride semiconductor crystal of the present invention, reduced heat up or The situation of cooling. Therefore, shortened required time of this technology and reduced power consumption. This can To reduce manufacturing process and cost. And, by the little variation of temperature, can suppress the warpage of substrate And can obtain the crystal property of good uniformity.
Consequently, when the manufacture method system of using by III group-III nitride semiconductor crystal of the present invention When the gallium nitride-based compound semiconductor made is made light emitting semiconductor device, can make and have high brightness And at wafer plane internal characteristic uniform light emitting diode almost.
In addition, according to the method for the invention described above, with the routine side that uses the AlN that at high temperature grows Method is compared, and it is little and the device knot that has demonstrated device property can be provided to make column and dislocation density The crystal of structure.
Claims (13)
1. method of making the III group-III nitride semiconductor crystal, comprise with 0 to 1000 V/III than providing III family raw material and V family raw material on hot substrate, forming and the first step of growth III group-III nitride semiconductor, and second step of using III family's raw material and nitrogen raw material vapor phase growth III group-III nitride semiconductor crystal on described III group-III nitride semiconductor.
2. according to the process of claim 1 wherein that substrate is sapphire Al
2O
3Substrate.
3. according to the method for claim 1 or 2, the III family raw material that wherein provide in first step comprise Al at least.
4. according to the process of claim 1 wherein that in second step III group-III nitride semiconductor crystal of vapor phase growth comprises GaN on described III group-III nitride semiconductor.
5. according to the process of claim 1 wherein at least one of the first step and second step, grow by metal organic chemical vapor deposition MOCVD method.
6. according to the process of claim 1 wherein that the nitrogen raw material that use are ammonia NH in second step
3
7. according to the process of claim 1 wherein that the III group-III nitride semiconductor that forms is an island crystal grain in first step.
8. according to the process of claim 1 wherein that the III group-III nitride semiconductor that forms is a column crystal in first step.
9. method according to Claim 8 wherein forms on substrate and the growth column crystal, so that the side of column crystal is approximately perpendicular to the surface of substrate.
10. method of making the III group-III nitride semiconductor crystal, be included in and form an III group-III nitride semiconductor on the hot substrate, and on an III group-III nitride semiconductor, form the 2nd III group-III nitride semiconductor crystal, wherein an III group-III nitride semiconductor is the aggregate of column crystal or island crystal.
11., wherein on substrate, form and the growth column crystal, so that each side of column crystal is approximately perpendicular to the surface of substrate according to the method for claim 10.
12. an III group-III nitride semiconductor crystal is by any one the method manufacturing according to claim 1 to 11.
13. an III group-III nitride semiconductor epitaxial wafer has the III group-III nitride semiconductor crystal layer that forms on the III group-III nitride semiconductor crystal according to claim 12.
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|---|---|---|---|
| JP2002038841A JP3656606B2 (en) | 2002-02-15 | 2002-02-15 | Method for producing group III nitride semiconductor crystal |
| JP38841/2002 | 2002-02-15 |
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| US7935955B2 (en) | 2004-01-26 | 2011-05-03 | Showa Denko K.K. | Group III nitride semiconductor multilayer structure |
| JP2005244202A (en) * | 2004-01-26 | 2005-09-08 | Showa Denko Kk | Group iii nitride semiconductor laminate |
| JP4901115B2 (en) | 2004-03-04 | 2012-03-21 | 昭和電工株式会社 | Gallium nitride semiconductor device |
| WO2005086241A1 (en) | 2004-03-04 | 2005-09-15 | Showa Denko K.K. | Gallium nitride-based semiconductor device |
| WO2005088738A1 (en) | 2004-03-12 | 2005-09-22 | Showa Denko K.K. | Group iii nitride semiconductor light-emitting device, forming method thereof, lamp and light source using same |
| WO2005091391A1 (en) | 2004-03-18 | 2005-09-29 | Showa Denko K.K. | Group iii nitride semiconductor light-emitting device and method of producing the same |
| WO2005109478A1 (en) * | 2004-05-12 | 2005-11-17 | Showa Denko K.K. | P-type group iii nitride semiconductor and production method thereof |
| JP2006229219A (en) * | 2004-05-12 | 2006-08-31 | Showa Denko Kk | P-type group iii nitride semiconductor and production method thereof |
| JP4833616B2 (en) * | 2004-09-13 | 2011-12-07 | 昭和電工株式会社 | Method for producing group III nitride semiconductor |
| US7652299B2 (en) | 2005-02-14 | 2010-01-26 | Showa Denko K.K. | Nitride semiconductor light-emitting device and method for fabrication thereof |
| DE112006000562B4 (en) * | 2005-03-09 | 2021-02-18 | Toyoda Gosei Co., Ltd. | Nitride semiconductor lighting component and method for its production |
| JP4707712B2 (en) * | 2005-04-01 | 2011-06-22 | シャープ株式会社 | Manufacturing method of p-type nitride semiconductor and semiconductor device manufactured using the method |
| JP4432827B2 (en) | 2005-04-26 | 2010-03-17 | 住友電気工業株式会社 | Group III nitride semiconductor device and epitaxial substrate |
| US7951617B2 (en) | 2005-10-06 | 2011-05-31 | Showa Denko K.K. | Group III nitride semiconductor stacked structure and production method thereof |
| JP2007220745A (en) * | 2006-02-14 | 2007-08-30 | Showa Denko Kk | Manufacturing method of p-type group iii nitride semiconductor |
| CN101438429B (en) | 2006-05-10 | 2011-04-27 | 昭和电工株式会社 | III nitride compound semiconductor laminated structure |
| JP5250856B2 (en) | 2006-06-13 | 2013-07-31 | 豊田合成株式会社 | Method for manufacturing gallium nitride compound semiconductor light emitting device |
| JP2009123718A (en) | 2007-01-16 | 2009-06-04 | Showa Denko Kk | Group iii nitride compound semiconductor element and its manufacturing method, group iii nitride compound semiconductor light-emitting element and its manufacturing method, and lamp |
| JP4993627B2 (en) * | 2009-03-24 | 2012-08-08 | 古河機械金属株式会社 | Method for manufacturing group III nitride semiconductor layer |
| CN103460359A (en) * | 2011-04-05 | 2013-12-18 | 住友电气工业株式会社 | Method for manufacturing nitride electronic devices |
| JP5948698B2 (en) * | 2012-04-13 | 2016-07-06 | パナソニックＩｐマネジメント株式会社 | Ultraviolet light emitting device and manufacturing method thereof |
| JP6442957B2 (en) * | 2014-09-29 | 2018-12-26 | 日亜化学工業株式会社 | Manufacturing method of nitride semiconductor template |
| CN107039250B (en) * | 2016-02-03 | 2018-08-21 | 中晟光电设备（上海）股份有限公司 | A kind of method of the material of growing gallium nitride on a sapphire substrate, gallium nitride material and application thereof |
| JP7429522B2 (en) * | 2019-11-22 | 2024-02-08 | 住友化学株式会社 | Group III nitride multilayer substrate and semiconductor device |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2003243302A (en) | 2003-08-29 |
| KR100692267B1 (en) | 2007-03-12 |
| CN1639393A (en) | 2005-07-13 |
| TWI221638B (en) | 2004-10-01 |
| KR100659520B1 (en) | 2006-12-20 |
| JP3656606B2 (en) | 2005-06-08 |
| TW200307313A (en) | 2003-12-01 |
| KR20060079259A (en) | 2006-07-05 |
| KR20040079443A (en) | 2004-09-14 |
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