CN108615672B - Preparation method of semiconductor crystalline film and semiconductor crystalline film - Google Patents
Preparation method of semiconductor crystalline film and semiconductor crystalline film Download PDFInfo
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Abstract
The invention provides a method for preparing high-quality phase gallium oxide semiconductor crystal on a sapphire substrateThe method comprises depositing a gallium oxide semiconductor crystal film on a sapphire substrate by chemical vapor deposition, wherein the phase gallium oxide semiconductor crystal film comprises a nucleation layer and a body layer, the nucleation layer is a pure-phase gallium oxide crystal film or a gallium oxide crystal film mixed with β phase, the body layer is a pure-phase gallium oxide semiconductor crystal film, the growth temperature of the nucleation layer is lower than that of the body layer, and the body layer may or may not contain a dopant2O3High defect density, and high quality of Ga2O3The crystalline film greatly expands the application range of the gallium oxide semiconductor material.
Description
Technical Field
The invention belongs to the field of semiconductor thin film materials, and mainly relates to-Ga with a semiconductor function2O3A method for preparing a crystalline film and the crystalline film prepared thereby.
Background
The power electronic device is made of the semiconductor material with wide forbidden band width, so that the working efficiency and the high-voltage resistance of the device can be effectively improved. Ga2O3The material has an ultra-wide forbidden band width of 4.7-5.4 eV, and the corresponding Baliga quality factor is far higher than that of the materials such as Si (1.1eV), 4H-SiC (3.3eV), GaN (3.4eV) and the like which are commercialized at present. Thus, Ga is2O3The semiconductor material is applied to electronic devices, especially high-power electronic devices, and has better device performance than Si, SiC and GaN.
Ga2O3Has β, α, gamma, five phases, of which β is the stable phase, next to α2O3A.J. Green (IEEEElectron Device Letters 37,902-2O3However, the β -Ga2O3 thin film requires a gallium oxide homogeneous substrate for preparation, which is high in cost and serious in heat dissipation problem of the prepared deviceThough CN106415845A discloses a stacked structure having excellent crystallinity and a semiconductor device having the stacked structure and excellent in mobility, the gallium oxide obtained in this patent application is α -Ga2O3Thin films, and α -Ga2O3Has poor stability of β -Ga2O3and-Ga2O3To a problem of (a).
If high quality-Ga can be realized2O3The preparation of the film can effectively overcome the current β -Ga2O3And α -Ga2O3Problems in the thin film preparation technique, but high quality-Ga is currently available2O3On the one hand, the most stable phase due to gallium oxide is β -Ga2O3Therefore, pure β -phase Ga is often obtained by adopting unreasonable preparation mode2O3Or β phase and phase mixed Ga2O3Rather than pure-phase Ga2O3Patents CN103469173B and CN103489967B disclose a method for preparing gallium oxide epitaxial film and a gallium oxide epitaxial film, which is prepared by using trimethyl gallium or triethyl gallium as gallium source and gaseous oxygen-containing substance as oxygen source, but only β -Ga can be prepared2O3Pure phase-Ga is not obtained2O3. On the other hand, the current phase Ga is due to the lack of a homogeneous substrate2O3Only by growth on foreign substrates, which tend to introduce a large number of defects.
Therefore, there is a need for a method for producing Ga-Al alloy2O3Scheme for heteroepitaxial growth to solve the problem of growing-Ga on a hetero-substrate2O3High defect density to obtain high quality-Ga2O3A semiconductor crystalline film.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides high-quality-Ga based on a sapphire substrate2O3A method for preparing a semiconductor crystalline film.
The invention also provides the-Ga prepared by the preparation method2O3A semiconductor crystalline film.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method for preparing semiconductor crystal film, forming a nucleation layer on a sapphire substrate by chemical vapor deposition, and forming a main body layer on the nucleation layer; the nucleation layer is a pure-phase gallium oxide crystalline film or a gallium oxide crystalline film mixed with a phase beta, and the main body layer is a pure-phase gallium oxide crystalline film; the growth temperature of the main body layer is higher than that of the nucleation layer; the preparation method comprises the following steps:
s1: feeding the sapphire substrate onto a reaction chamber tray, and rotating the tray;
s2: heating the reaction chamber to 500-650 ℃; introducing supplementary carrier gas into the reaction chamber, and controlling the pressure of the reaction chamber to be 20-400 Torr;
s3: respectively immersing bubbling bottles provided with an organic metal source and an oxygen source in a constant-temperature water tank, and controlling the flow and the pressure of the bubbling bottles through a mass flow meter and a pressure meter;
s4: after the temperature of the reaction chamber is stable, simultaneously introducing carrier gas into bubbling bottles of the organic metal source and the oxygen source, and allowing the carrier gas to flow into the reaction chamber; controlling the reaction time to grow Ga of 10-300nm on the surface of the sapphire substrate2O3A semiconductor crystal film;
s5: stopping introducing the organic metal source under the condition that other conditions are unchanged, and then raising the temperature to 600-800 ℃;
s6: after the temperature is stable, introducing the carrier gas carrying the organic metal source into the reaction chamber again; adjusting the reaction time and continuously growing 0.5-10 um-Ga2O3A semiconductor crystal film;
s7: keeping supplementary argon gas to be introduced into the reaction chamber, stopping introducing carrier gas carrying the organic metal source and the oxygen source into the reaction chamber, and stopping growing; and cooling to room temperature, and then sampling to obtain the product.
Preferably, the organometallic source is triethyl gallium, and the organometallic source may also use trimethyl gallium as an auxiliary gallium source.
Preferably, the oxygen source is water, and oxygen and laughing gas can also be used as auxiliary oxygen sources.
Preferably, S6: after the temperature is stable, introducing the carrier gas carrying the organic metal source into the reaction chamber again; adjusting the reaction time and continuously growing 0.5-10 um-Ga2O3A semiconductor crystal film;
preferably, the nucleation and body layers contain a dopant; the dopant is one or more of seven elements of tin, silicon, germanium, magnesium, zinc, iron and nitrogen.
The sapphire is pure alumina single crystal, the conventional sapphire substrate has four crystal faces of c, m, a and r, and the sapphire is defined as c-plane sapphire; more specifically, the actual surface of the sapphire substrate can have an off-angle of 0-10 degrees with the c-plane, and the off-angle of 0.2-2 degrees is preferred in the invention; the thickness of the substrate can be 100-1000 μm, and the thickness is preferably 350-500 μm; the shape of the substrate is not particularly limited, and a circular shape is preferable.
The carrier gas is not particularly limited as long as it is an inert gas or a gas that does not react with the organometallic source, and nitrogen or argon is preferable.
The invention adopts the hetero-epitaxial growth based on the sapphire substrate to obtain high-quality Ga2O3A semiconductor crystalline film. The object of the present invention is to prepare high quality-Ga having semiconductor characteristics2O3Crystalline film of said Ga2O3The semiconductor crystal film includes a nucleation layer and a body layer, wherein the body layer functions as a semiconductor and thus the body layer must be pure-Ga2O3The thickness is preferably 0.5-10 um; the nucleation layer is grown in a sequence prior to the body layer, introduced to improve the crystalline quality of the subsequent body layer, and preferably 10-300nm thick.
Ga of the invention2O3The semiconductor crystal film is deposited and grown by adopting a chemical vapor deposition method; in particular, the chemical vapor deposition process encompasses various specific forms including plasma enhanced chemical vapor deposition, metalorganic chemical vapor deposition, low pressure chemical vapor deposition, atomic layer deposition, and the like.
In the adoption ofWhen the CVD method is used for depositing the film, some carbon and hydrogen impurities are additionally and unintentionally introduced, the process is called unintentional doping, the doping agent is not the impurity introduced by the unintentional doping, the doping is the process of artificially and intentionally introducing impurities in the growing process, and the concentration of the impurity elements in the crystallized film is 1 × 1016～1×1021cm-3And (3) a range. These dopants include one or more of tin, silicon, germanium, magnesium, zinc, iron, nitrogen in combination with one or more of the seven elements: wherein tin, silicon and germanium are n-type dopant, and can be made into-Ga2O3The semiconductor crystal film has electron conductivity; mg, Zn and N are p-type dopants, and may be made of-Ga2O3The semiconductor crystal film has hole conducting capability; iron is a compensating dopant which can make-Ga2O3The semiconductor crystal film forms high-resistance state, high-resistance state-Ga2O3The semiconductor crystal film can be used for preventing the leakage breakdown of the device in a power device. In order to introduce these dopants, a mixture of any one or more of the following is added to the reactants: tetrakis (dimethylamino) tin is used for tin doping, tetramethyltin is used for tin doping, tetraethyltin is used for tin doping, silane is used for silicon doping, germane is used for germanium doping, magnesium metallocene is used for magnesium doping, diethyl zinc is used for zinc doping, ferrocene is used for iron doping, and ammonia is used for nitrogen doping.
In the stacked structure, the body layer functions as a semiconductor, and thus, the doping is mainly performed on the body layer, but the doping of the nucleation layer is not particularly limited. It should be noted that the bulk layer itself may be a laminate structure: by doping, the bulk layer is not meant only a single layer of dopant-free Ga2O3Semiconductor crystalline film, or single layer dopant-containing Ga2O3A semiconductor crystal film; the bulk layer may be undoped-Ga2O3Semiconductor crystalline film and-Ga containing any one or more dopants2O3Crystalline films, in any number and order. Whether doped or not, whether the number of layers and the order of the stack, provided that all the stacks except the nucleation layer are pureThe term "bulk layer" is used herein to refer to a layer that is not a bulk layer.
The invention has the beneficial effects that:
the invention prepares high-quality-Ga with semiconductor characteristics by controlling the preparation process2O3Crystalline film of said Ga2O3The semiconductor crystal film includes a nucleation layer and a body layer, wherein the body layer functions as a semiconductor and thus the body layer must be pure-Ga2O3(ii) a The nucleation layer is grown in a sequence prior to the body layer, and is introduced to improve the crystalline quality of the subsequent body layer. The invention solves the problem of growing-Ga on a heterogeneous substrate2O3High defect density, and high quality of Ga2O3And crystallizing the film.
Drawings
FIG. 1 contains high-quality-Ga2O3The stacked structure of the semiconductor crystal film is shown schematically.
FIG. 2 example 1 wherein-Ga2O3Transmission spectrum of the semiconductor crystal film.
FIG. 3 example 1 of Ga2O3An X-ray diffraction pattern of the semiconductor crystalline film.
FIG. 4 example 1 of Ga2O3The (0004) plane X-ray diffraction rocking curve of the semiconductor crystal film.
FIG. 5 example 1 wherein-Ga2O3The surface appearance of the semiconductor crystal film by an atomic force microscope.
FIG. 6 contains high quality N-type-Ga2O3The stacked structure of the semiconductor crystal film is shown schematically.
FIG. 7 contains high quality-Ga2O3The stack structure of the semiconductor PN junction is shown schematically.
Fig. 8 is an X-ray diffraction pattern of the gallium oxide thin film prepared in comparative example 1.
FIG. 9 is a transmission electron microscope surface topography of the gallium oxide thin film prepared in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to the embodiments.
Example 1:
preparation of high quality-Ga-containing Metal Organic Chemical Vapor Deposition (MOCVD) method2O3A stacked structure of semiconductor crystal films.
Step 1: selecting a clean sapphire substrate with a surface having a 0.2-degree deviation angle with a c-plane and a thickness of 430 mu m.
Step 2: the substrate was fed into the reaction chamber of the MOCVD equipment and the tray was rotated at a rotation speed of 750 rpm in preparation for epitaxial growth of a gallium oxide film.
And step 3: the temperature of the reaction chamber is raised to 600 ℃; at the same time, the reaction chamber was purged with 10slm of supplemental argon and the pressure of the reaction chamber was controlled at 80Torr by a pressure control system.
And 4, step 4: immersing the bubbling bottle filled with the triethyl gallium and the deionized water into two constant-temperature water tanks, controlling the temperature of the bubbling bottle to be 25 ℃ and 25 ℃ through the constant-temperature water tanks, and controlling the pressure of the two bubbling bottles to be 320Torr and 280Torr through a mass flow meter and a pressure meter.
And 5: after the temperature of the reaction chamber is stabilized at 600 ℃, simultaneously introducing argon carrier gas into bubbling bottles of triethyl gallium and deionized water, and allowing the carrier gas to flow into the reaction chamber, wherein the flow rates are 80sccm and 800sccm respectively; the growth time is controlled, and 50nm of undoped Ga grows on the surface of the substrate2O3A semiconductor crystalline film.
Step 6: the introduction of triethyl gallium was suspended and the temperature was then raised to 640 ℃ while the other conditions were unchanged.
And 7: after the temperature is stabilized at 640 ℃, introducing the carrier gas carrying the triethyl gallium into the reaction chamber again, and controlling the flow at 80 sccm; regulating the growth time to grow 400nm undoped-Ga on the surface of the substrate2O3A semiconductor crystalline film.
And 8: keeping supplementary argon gas to be introduced into the reaction chamber, and stopping introducing all argon gas carrier gas into the reaction chamber; directly cooling to room temperature, sampling to obtain high-quality Ga2O3And preparing an epitaxial film.
See FIG. 1 for high quality-Ga-containing2O3The stacked structure of the semiconductor crystal film is shown schematically. In this example, the nucleation layer Ga2O3Thickness of the crystalline film was 50nm, bulk layer-Ga2O3The thickness of the crystalline film was 400 nm.
Referring to FIG. 2, the transmission spectrum of the gallium oxide film of this example shows that the film has an optical band gap of 4.9eV, and still has 88% transmittance at 300 nm.
Referring to FIG. 3, which is an X-ray diffraction pattern of the gallium oxide thin film of this example, the diffraction peak position in the pattern indicates that the gallium oxide thin film prepared in this example is Ga in pure phase2O3A semiconductor crystalline film.
Referring to FIG. 4, the rocking curve of the (0004) plane of the gallium oxide film of this example has a full width at half maximum of only 540 arcseconds, indicating that the film has a high crystalline quality.
Referring to FIG. 5, the surface morphology of the gallium oxide film of this example using an atomic force microscope shows atomic layer steps on the surface, indicating that-Ga prepared in this example2O3The semiconductor crystal film has high crystal quality.
Example 2:
MOCVD preparation of high quality tin-doped-Ga2O3A stacked structure of semiconductor crystal films.
Step 1: selecting a clean sapphire substrate with a surface having a 0-degree deviation angle with a c-plane and a thickness of 100 mu m.
Step 2: the substrate was fed into the reaction chamber of the MOCVD equipment and the tray was rotated at a rotation speed of 700 rpm in preparation for epitaxial growth of a gallium oxide film.
And step 3: the temperature of the reaction chamber is raised to 500 ℃; while 8slm of argon was introduced into the reaction chamber, the pressure in the reaction chamber was controlled at 20Torr by a pressure control system.
And 4, step 4: immersing the bubbling bottle filled with the triethyl gallium, the deionized water and the tetra (dimethylamino) tin in three constant-temperature water tanks, controlling the temperature of the bubbling bottle to be 25 ℃, 25 ℃ and 2 ℃ through the constant-temperature water tanks, and controlling the pressure of the three bubbling bottles to be 320Torr, 280Torr and 440Torr through a mass flow meter and a pressure gauge.
And 5: after the temperature of the reaction chamber is stable, simultaneously introducing argon carrier gas into the bubbling bottles of the triethyl gallium and the deionized water, and allowing the argon carrier gas to flow into the reaction chamber, wherein the flow rates are 70sccm and 700sccm respectively; controlling the growth time to grow 10nm of undoped Ga on the surface of the substrate2O3A semiconductor crystalline film.
Step 6: the other conditions were not changed, the introduction of triethyl gallium was suspended and the temperature was then raised to 600 ℃.
And 7: after the temperature is stabilized at 600 ℃, introducing the carrier gas carrying the triethyl gallium into the reaction chamber again, and controlling the flow at 70 sccm; regulating the growth time to grow the non-doped-Ga of 500nm on the surface of the substrate2O3A semiconductor crystalline film.
And 8: keeping other conditions unchanged, and introducing argon carrier gas into a bubbling bottle of tetra (dimethylamino) tin by taking argon as carrier gas, and allowing the argon carrier gas to flow into the reaction chamber, wherein the flow of the carrier gas is 5 sccm; the growth time is controlled, and 500nm of-Ga containing tin dopant is grown on the surface of the substrate material2O3A semiconductor crystalline film.
And step 9: keeping supplementary argon gas to be introduced into the reaction chamber, and stopping introducing all argon gas carrier gas into the reaction chamber; directly cooling to room temperature, and sampling to finish the preparation of the high-quality gallium oxide epitaxial film.
Referring to FIG. 6, this example contains high quality N-type-Ga2O3The stacked structure of the semiconductor crystal film is shown schematically.
Example 3:
MOCVD preparation of high quality-Ga-containing materials2O3A stacked structure of semiconductor PN junctions.
Step 1: selecting a clean sapphire substrate with a surface having a 2-degree deviation angle with a c-plane and a thickness of 1000 mu m.
Step 2: the substrate was fed into the reaction chamber of the MOCVD equipment and the tray was rotated at 900 rpm in preparation for epitaxial growth of a gallium oxide film.
And step 3: the temperature of the reaction chamber is raised to 650 ℃; while introducing 12slm of argon gas into the reaction chamber, the pressure in the reaction chamber was controlled at 400Torr by a pressure control system.
And 4, step 4: immersing the bubbling bottle filled with the triethyl gallium, the deionized water, the tetra (dimethylamino) tin, the magnesium diclomentate and the ferrocene into five constant-temperature water tanks, controlling the temperature of the bubbling bottle to be 25 ℃, 2 ℃, 5 ℃ and 5 ℃ through the constant-temperature water tanks, and controlling the pressure of the five bubbling bottles to be 320Torr, 280Torr, 440Torr and 440Torr through a mass flow meter and a pressure meter.
And 5: after the temperature of the reaction chamber is stabilized at 600 ℃, simultaneously introducing argon carrier gas into the bubbling bottles of the triethyl gallium and the deionized water, and allowing the carrier gas to flow into the reaction chamber, wherein the carrier gas flow is 90sccm and 900sccm respectively; controlling the growth time to grow 300nm of undoped Ga on the surface of the substrate2O3A semiconductor crystalline film.
Step 6: the introduction of triethyl gallium was suspended and the temperature was brought to 800 ℃ while the other conditions were unchanged.
And 7: after the temperature is stabilized at 800 ℃, introducing the carrier gas carrying the triethyl gallium into the reaction chamber again, and controlling the flow at 90 sccm; regulating the growth time to grow the non-doped-Ga of 500nm on the surface of the substrate2O3A semiconductor crystalline film.
And 8: keeping other conditions unchanged, similarly taking argon as a carrier gas, introducing the argon carrier gas into the ferrocene bubbling bottle, and allowing the argon carrier gas to flow into the reaction chamber, wherein the flow rate is 1 sccm; controlling the growth time, and growing 500nm of-Ga containing iron dopant on the surface of the substrate material2O3A semiconductor crystalline film.
And step 9: keeping other conditions unchanged, and stopping introducing the argon carrier gas carrying the ferrocene into the reaction chamber; similarly, argon is used as carrier gas, argon carrier gas is introduced into a bubbling bottle of tetra (dimethylamino) tin, and the argon carrier gas flows into the reaction chamber, wherein the flow rate of the carrier gas is 5 sccm; the growth time is controlled, and 500nm of-Ga containing tin dopant is grown on the surface of the substrate material2O3A semiconductor crystalline film.
Step 10: the temperature was reduced to 620 ℃ and kept stable, keeping the other conditions unchanged.
Step 11: keeping other conditions unchanged, and stopping introducing carrier gas argon with tetra (dimethylamino) tin into the reaction chamber; similarly, argon is used as carrier gas, argon carrier gas is introduced into the bubbling bottle of the magnesium metallocene, and the argon carrier gas flows into the reaction chamber, wherein the flow rate is 2 sccm; controlling the growth time, and growing 200nm of-Ga containing magnesium dopant on the surface of the substrate material2O3A semiconductor crystalline film.
Step 12: keeping supplementary argon gas to be introduced into the reaction chamber, and stopping introducing all argon gas carrier gas into the reaction chamber; directly cooling to room temperature, and sampling to finish the preparation of the high-quality gallium oxide epitaxial film.
Referring to FIG. 7, the present example contains high quality-Ga2O3The stack structure of the semiconductor PN junction is shown schematically.
Example 4:
preparation of high quality-Ga-containing Metal Organic Chemical Vapor Deposition (MOCVD) method2O3A stacked structure of semiconductor crystal films.
Step 1: selecting a clean sapphire substrate with a surface having a deviation angle of 10 degrees with a c-plane and a thickness of 350 mu m.
Step 2: the substrate was fed into the reaction chamber of the MOCVD equipment and the tray was rotated at a rotation speed of 750 rpm in preparation for epitaxial growth of a gallium oxide film.
And step 3: the temperature of the reaction chamber is raised to 600 ℃; at the same time, the reaction chamber was purged with 10slm of supplemental argon and the pressure of the reaction chamber was controlled at 80Torr by a pressure control system.
And 4, step 4: immersing the bubbling bottle filled with the triethyl gallium and the deionized water into two constant-temperature water tanks, controlling the temperature of the bubbling bottle to be 25 ℃ and 25 ℃ through the constant-temperature water tanks, and controlling the pressure of the two bubbling bottles to be 320Torr and 280Torr through a mass flow meter and a pressure meter.
And 5: after the temperature of the reaction chamber is stabilized at 600 ℃, simultaneously introducing argon carrier gas into bubbling bottles of triethyl gallium and deionized water, and allowing the carrier gas to flow into the reaction chamber, wherein the flow rates are 80sccm and 800sccm respectively; control ofGrowing the non-doped Ga with the growth time of 300nm on the surface of the substrate2O3A semiconductor crystalline film.
Step 6: the introduction of triethyl gallium was suspended and the temperature was then raised to 640 ℃ while the other conditions were unchanged.
And 7: after the temperature is stabilized at 640 ℃, introducing the carrier gas carrying the triethyl gallium into the reaction chamber again, and controlling the flow at 80 sccm; regulating the growth time to grow 10um non-doped-Ga on the surface of the substrate2O3A semiconductor crystalline film.
And 8: keeping supplementary argon gas to be introduced into the reaction chamber, and stopping introducing all argon gas carrier gas into the reaction chamber; directly cooling to room temperature, sampling to obtain high-quality Ga2O3And preparing an epitaxial film.
Example 5:
preparation of high quality-Ga-containing Metal Organic Chemical Vapor Deposition (MOCVD) method2O3A stacked structure of semiconductor crystal films.
Step 1: selecting a clean sapphire substrate with a surface having a 0.2-degree deviation angle with a c-plane and a thickness of 500 mu m.
Step 2: the substrate was fed into the reaction chamber of the MOCVD equipment and the tray was rotated at a rotation speed of 750 rpm in preparation for epitaxial growth of a gallium oxide film.
And step 3: the temperature of the reaction chamber is raised to 600 ℃; at the same time, the reaction chamber was purged with 10slm of supplemental argon and the pressure of the reaction chamber was controlled at 80Torr by a pressure control system.
And 4, step 4: immersing the bubbling bottle filled with the triethyl gallium and the deionized water into two constant-temperature water tanks, controlling the temperature of the bubbling bottle to be 25 ℃ and 25 ℃ through the constant-temperature water tanks, and controlling the pressure of the two bubbling bottles to be 320Torr and 280Torr through a mass flow meter and a pressure meter.
And 5: after the temperature of the reaction chamber is stabilized at 600 ℃, simultaneously introducing argon carrier gas into bubbling bottles of triethyl gallium and deionized water, and allowing the carrier gas to flow into the reaction chamber, wherein the flow rates are 80sccm and 800sccm respectively; the growth time is controlled, and 50nm of undoped Ga grows on the surface of the substrate2O3Semiconductor crystalAnd (3) a membrane.
Step 6: the introduction of triethyl gallium was suspended and the temperature was then raised to 640 ℃ while the other conditions were unchanged.
And 7: after the temperature is stabilized at 640 ℃, introducing the carrier gas carrying the triethyl gallium into the reaction chamber again, and controlling the flow at 80 sccm; regulating the growth time to grow 400nm undoped-Ga on the surface of the substrate2O3A semiconductor crystalline film.
And 8: keeping supplementary argon gas to be introduced into the reaction chamber, and stopping introducing all argon gas carrier gas into the reaction chamber; directly cooling to room temperature, sampling to obtain high-quality Ga2O3And preparing an epitaxial film.
Comparative example 1:
compared with the embodiment 1, the nucleation layer is not provided, and the specific preparation steps are as follows:
step 1: selecting a clean sapphire substrate with a surface having a 0.2-degree deviation angle with a c-plane and a thickness of 430 mu m.
Step 2: the substrate was fed into the reaction chamber of the MOCVD equipment and the tray was rotated at a rotation speed of 750 rpm in preparation for epitaxial growth of a gallium oxide film.
And step 3: the temperature of the reaction chamber is raised to 640 ℃; at the same time, the reaction chamber was purged with 10slm of supplemental argon and the pressure of the reaction chamber was controlled at 80Torr by a pressure control system.
And 4, step 4: immersing the bubbling bottle filled with the triethyl gallium and the deionized water into two constant-temperature water tanks, controlling the temperature of the bubbling bottle to be 25 ℃ and 25 ℃ through the constant-temperature water tanks, and controlling the pressure of the two bubbling bottles to be 320Torr and 280Torr through a mass flow meter and a pressure meter.
And 5: after the temperature of the reaction chamber is stabilized at 640 ℃, simultaneously introducing argon carrier gas into bubbling bottles of triethyl gallium and deionized water, and allowing the carrier gas to flow into the reaction chamber, wherein the flow rates are 80sccm and 800sccm respectively; the growth time is controlled, and 400nm of Ga without doping is grown on the surface of the substrate2O3A semiconductor crystalline film.
Step 6: keeping supplementary argon gas to be introduced into the reaction chamber, and stopping introducing all argon gas carrier gas into the reaction chamber; directly cooling to room temperatureSampling to finish Ga2O3And preparing an epitaxial film.
Referring to FIG. 8, which is an X-ray diffraction pattern of the gallium oxide thin film of this comparative example, the diffraction peak positions in the pattern indicate that the gallium oxide thin film prepared in this example is Ga in pure phase2O3A semiconductor crystalline film.
Referring to fig. 9, the surface morphology of the gallium oxide thin film of this comparative example is a transmission electron microscope, and it can be seen from the morphology that the sample has poor film forming characteristics, poor crystalline quality, and large surface undulations.
Combining FIGS. 8 and 9, it is shown that pure-phase Ga can be grown on a sapphire substrate without introducing a nucleation layer2O3A semiconductor crystal film, but the crystal quality and film forming characteristics of the thin film are poor.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A method for producing a semiconductor crystalline film, characterized in that,
forming a nucleation layer on the sapphire substrate by adopting a chemical vapor deposition method, and then forming a body layer on the nucleation layer; the nucleation layer is a pure-phase gallium oxide crystalline film or a gallium oxide crystalline film mixed with a phase beta, and the main body layer is a pure-phase gallium oxide crystalline film; the growth temperature of the main body layer is higher than that of the nucleation layer; the preparation method comprises the following steps:
s1: feeding the sapphire substrate onto a reaction chamber tray, and rotating the tray;
s2: heating the reaction chamber to 500-650 ℃; introducing supplementary carrier gas into the reaction chamber, and controlling the pressure of the reaction chamber to be 20-400 Torr;
s3: respectively immersing bubbling bottles provided with an organic metal source and an oxygen source in a constant-temperature water tank, and controlling the flow and the pressure of the bubbling bottles through a mass flow meter and a pressure meter;
s4: after the temperature of the reaction chamber is stable, simultaneously introducing carrier gas into bubbling bottles of the organic metal source and the oxygen source, and allowing the carrier gas to flow into the reaction chamber; controlling the reaction time to grow Ga of 10-300nm on the surface of the sapphire substrate2O3A semiconductor crystal film;
s5: stopping introducing the organic metal source under the condition that other conditions are unchanged, and then raising the temperature to 600-800 ℃;
s6: after the temperature is stable, introducing the carrier gas carrying the organic metal source into the reaction chamber again; adjusting the reaction time and continuously growing 0.5-10 mu m of-Ga2O3A semiconductor crystal film;
s7: keeping supplementary carrier gas to be introduced into the reaction chamber, stopping introducing the carrier gas carrying the organic metal source and the oxygen source into the reaction chamber, and stopping growing; and cooling to room temperature, and then sampling to obtain the product.
2. A method for producing a crystalline semiconductor film according to claim 1, wherein said organometallic source is triethyl gallium.
3. The method for producing a crystalline semiconductor film according to claim 1, wherein the oxygen source is water.
4. The method for producing a crystalline semiconductor film according to claim 1, wherein the ratio of S6: after the temperature is stable, introducing the carrier gas carrying the organic metal source into the reaction chamber again; adjusting the reaction time and continuously growing 0.5-5 mu m of-Ga2O3A semiconductor crystalline film.
5. The method for producing a crystalline semiconductor film according to claim 1, wherein the nucleation layer and the body layer contain a dopant; the dopant is one or more of seven elements of tin, silicon, germanium, magnesium, zinc, iron and nitrogen.
6. The method of claim 1, wherein the actual surface of the sapphire substrate and the c-plane of sapphire have an off-angle of 0 ° to 10 °.
7. The method for manufacturing a semiconductor crystalline film according to claim 6, wherein the actual surface of the sapphire substrate and the c-plane of sapphire form an off-angle of 0.2 ° to 2 °.
8. The method of manufacturing a crystalline semiconductor film according to claim 1, wherein the sapphire substrate has a thickness of 100 to 1000 μm.
9. The method of manufacturing a crystalline semiconductor film according to claim 8, wherein the sapphire substrate has a thickness of 350 to 500 μm.
10. A crystalline semiconductor film produced by the method for producing a crystalline semiconductor film according to any one of claims 1 to 9.
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| WO2020217563A1 (en) * | 2019-04-24 | 2020-10-29 | 日本碍子株式会社 | Semiconductor film |
| CN110429026B (en) * | 2019-08-15 | 2022-05-06 | 西安电子科技大学 | Method for opening graphene band gap |
| CN110828589B (en) * | 2019-11-17 | 2021-08-03 | 金华紫芯科技有限公司 | Flexible solar blind ultraviolet photoelectric detector and preparation method thereof |
| CN111916341B (en) * | 2020-08-19 | 2022-10-18 | 深圳第三代半导体研究院 | Gallium oxide thin film crystal growth method |
| KR102509541B1 (en) * | 2021-01-08 | 2023-03-14 | 한국세라믹기술원 | Gallium oxide thin film using phase-transition domain alignment buffer layer and method of manufacturing the same |
| CN113517174B (en) * | 2021-06-07 | 2023-08-08 | 西安电子科技大学 | epsilon-Ga 2 O 3 Method for preparing film and epsilon-Ga 2 O 3 Film and method for producing the same |
| CN114141909B (en) * | 2021-11-26 | 2023-09-29 | 北京铭镓半导体有限公司 | Method for growing gallium oxide films with different crystal orientations on sapphire substrate and preparation method of ultraviolet light detector based on film |
| CN115838971B (en) * | 2023-02-14 | 2023-06-13 | 楚赟精工科技(上海)有限公司 | Gallium oxide film and preparation method thereof |
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